JP6453059B2 - Liquid softener composition - Google Patents

Description

  The present invention relates to a liquid softener composition for imparting softness to a textile product suitable for home use.

  Laundry is one of the housework that is indispensable in household life, and a softener is often used as a finishing agent for adjusting the texture of textile products after the washing process. As a base material used in current softening agents, softening bases having intramolecular ester groups are used for the purpose of rapidly decomposing even when discharged into the environment and reducing the burden on the environment. It is well-known that ester groups are easily hydrolyzed in water, and it is also well-known that when soft bases having ester groups in a liquid softener composition are hydrolyzed, quality such as softness performance and storage stability tends to deteriorate. It is.

  Patent Document 1 discloses a softening agent composition containing a rapid biodegradable quaternary ammonium softening agent having an ester group in the molecule. It is disclosed that the hydrolyzability of the ester group of the softening base is suppressed by adjusting the pH of the softening agent composition. In Patent Document 2, a soft base having an ester group in the molecule includes a higher alcohol alkylene oxide addition nonionic surfactant having a relatively large number of added moles of alkylene oxide and a fatty acid ester. It is disclosed that the hydrolyzability of the ester group of the flexible base is suppressed by defining the mass ratio of the two. Patent Document 3 discloses that the soft base having an ester group in the molecule contains a specific fatty acid ester and a specific perfume, thereby suppressing the hydrolyzability of the ester group of the soft base. It is disclosed. Patent Document 4 discloses that a soft base having an ester group in the molecule contains a fatty acid triglyceride, thereby having a low content of a flammable solvent, a low melt viscosity, and a high stability in a melt state. An active pharmaceutical composition is disclosed. Patent Document 5 discloses that a softer base having an ester group in the molecule contains a larger amount of fatty acid glyceride to provide a better fabric feel.

Japanese Patent Laid-Open No. 63-6168 JP 2012-82538 A JP 2012-233281 A Special table 2013-524033 gazette Special table 2014-503701 gazette

  In the softener compositions of Patent Documents 1, 2, and 3, the effect of suppressing hydrolysis of the soft base having an ester group in the molecule is not sufficient, and the softener compositions of Patent Documents 4 and 5 include softener groups. The problem concerning the hydrolysis of the agent is not described.

  The present invention suppresses the hydrolysis of the ester group of a compound having an intramolecular ester group, which is contained as a softening base, thereby maintaining a high flexibility-imparting effect on the fiber product and having a viscosity suitable for handling. A liquid softener composition is provided.

The present invention contains the following component (A) in an amount of 1% by mass or more and 20% by mass or less, (B) the component in an amount of 0.1% by mass or more and less than 4% by mass, and water. ) Component (A) / (B) is 2 or more and 50 or less, and the pH at 30 ° C. is 2.0 or more and 4.0 or less. >
The component chosen from the following (A-1) component and (A-2) component.
(A-1) component: a component comprising a plurality of quaternary ammonium salts represented by the following general formula (1),
In the total amount of the quaternary ammonium salt represented by the general formula (1), the ratio of the compound (a1) in which R ¹ in the general formula (1) is an acyl group, and R ² and R ³ are hydrogen atoms, 10 mass% or more, 45 mass% or less,
In the total amount of the quaternary ammonium salt represented by the general formula (1), the ratio of the compound (a2) in which R ¹ and R ² in the general formula (1) are acyl groups and R ³ is a hydrogen atom is: 25 mass% or more, 70 mass% or less,
In the total amount of the quaternary ammonium salt represented by the general formula (1), the proportion of the compound (a3) in which R ¹ , R ² and R ^{3 in the} general formula (1) are acyl groups is 5% by mass or more, 40% by mass or less,
Ingredients that are

^{Wherein, R 1, R 2, R} 3 are each independently, having 16 or more carbon atoms, residues obtained by removing OH from 22 following fatty acids (referred acyl group), or a hydrogen ^{atom, R} 1, R ² and R ³ are not simultaneously a hydrogen atom, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an anion. ]
(A-2) component: a component composed of a plurality of quaternary ammonium salts represented by the following general formula (2),
In the total amount of the quaternary ammonium salt represented by the general formula (2), the proportion of the compound (a4) in which R ⁵ in the general formula (2) is an acyl group and R ⁶ is a hydrogen atom is 1% by mass or more. 40% by mass or less,
In the total amount of the quaternary ammonium salt in which the ratio of the compound (a5) in which R ⁵ and R ⁶ in the general formula (2) are the acyl group is 60% by mass or more, 99% by mass Less than,
Ingredients that are

[Wherein R ⁵ is a residue obtained by removing OH from a fatty acid having 16 to 22 carbon atoms (referred to as an acyl group), R ⁶ is the acyl group or a hydrogen atom, and R ⁷ and R ⁸ Are each independently an alkyl group having 1 to 3 carbon atoms, Q is an ethylene group or a propylene group, and X ⁻ is an anion. ]
<(B) component>
A component comprising a plurality of ester compounds of glycerin and a fatty acid having 10 to 22 carbon atoms,
The proportion of the fatty acid monoester structure is 65% by mass or less in the total amount of the ester compound,
The component whose total ratio of the fatty acid diester structure and the fatty acid triester structure is 35% by mass or more and 100% by mass or less in the total amount of the ester compound

  According to the liquid softener composition of the present invention, hydrolysis of the ester group in the compound of the component (A) serving as the softening base is suppressed, so that a high softness-imparting effect on the fiber product is stably maintained. be able to. Moreover, the liquid softening agent composition of this invention has a viscosity suitable for handling.

<Liquid softener composition>
<(A) component>
Among the components (A), the component (A-1) is a component composed of a plurality of quaternary ammonium salts represented by the following general formula (1),
In the total amount of the quaternary ammonium salt represented by the general formula (1), the ratio of the compound (a1) in which R ¹ in the general formula (1) is an acyl group, and R ² and R ³ are hydrogen atoms, 10 mass% or more, 45 mass% or less,
In the total amount of the quaternary ammonium salt represented by the general formula (1), the ratio of the compound (a2) in which R ¹ and R ² in the general formula (1) are acyl groups and R ³ is a hydrogen atom is: 25 mass% or more, 70 mass% or less,
In the total amount of the quaternary ammonium salt represented by the general formula (1), the proportion of the compound (a3) in which R ¹ , R ² and R ^{3 in the} general formula (1) are acyl groups is 5% by mass or more, 40% by mass or less,
It is a component that is.

[Wherein R ¹ , R ² and R ³ are each independently a residue obtained by removing OH from a fatty acid having 16 to 22 carbon atoms (the residue may be referred to as an acyl group), or hydrogen. R ¹ , R ² and R ³ are not hydrogen atoms at the same time, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an anion. ]

  The ratio of the compound (a1), the compound (a2), and the compound (a3) in the component (A-1) of the present invention includes the component (B) as well as the softening effect imparted to the fiber product. The storage stability of other liquid softener compositions is also affected.

The proportion of compound (a1) in component (A-1) is preferably 15% by mass or more, more preferably 20% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less. is there.
The proportion of the compound (a2) in the component (A-1) is more preferably 30% by mass or more, preferably 35% by mass or more, and preferably 70% by mass or less, more preferably 65% by mass or less. is there.
The proportion of the compound (a3) in the component (A-1) is preferably 8% 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. is there.

  The compound (a2) and the compound (a3) are effective components for the softening effect, but when the component (B) is contained, the storage stability of the liquid softening agent composition is affected. Therefore, the component (A-1) preferably has a composition in which the compound (a1) is appropriately left. Furthermore, after satisfying the above ratio, the content of the compound (a2) in the component (A-1) is larger than that of the compound (a3), more preferably the content (mass%) of the compound (a2). ) And the content (mass%) of the compound (a3) is 15 mass% or more (15 points or more).

In the general formula (1), the acyl group is preferably a residue obtained by removing OH (hydroxyl group) from a fatty acid having 16 to 18 carbon atoms. R ¹ , R ² and R ³ may each independently be RCO (where R is a hydrocarbon group having 15 to 21 carbon atoms, preferably 17 or less carbon atoms). In general formula (1), at least one of R ¹ , R ² , and R ³ is an acyl group.
Specific examples of fatty acids include stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, palm oil fatty acid, sunflower oil, soybean oil, rapeseed oil, safflower oil, cottonseed oil, corn oil, Examples include olive oil, hardened palm oil fatty acid, beef tallow fatty acid, and hardened beef tallow fatty acid.
In general formula (1), R ⁴ is preferably a methyl group or an ethyl group.
In the general formula (1), X ^- it is may be an organic or inorganic anion, a halogen ion, preferably chloride ion, 1 or more carbon atoms, 3 an alkyl sulfate ion, having 12 or more carbon atoms, the 18 following An anion selected from a fatty acid ion and a benzenesulfonate ion optionally substituted with 1 or more and 3 or less alkyl groups having 1 to 3 carbon atoms is preferred, and an alkyl sulfate having 1 to 3 carbon atoms Ester ion is more preferable, and methyl sulfate ester ion or ethyl sulfate ester ion is more preferable.

  The component (A-1) used in the present invention is a method in which a fatty acid and triethanolamine are subjected to dehydration esterification (referred to as dehydration esterification), or a fatty acid lower alkyl ester (lower alkyl is a methyl group, an ethyl group, or a propyl group) It can be obtained by subjecting an esterification reaction product obtained by a method of transesterification of triethanolamine with triethanolamine (referred to as a transesterification method) to a quaternization reaction with an alkylating agent. In order to obtain a mixture satisfying the ratios of the compound (a1), the compound (a2) and the compound (a3) of the component (A-1) of the present invention, for example, the molar ratio of fatty acid or fatty acid lower alkyl ester: triethanolamine is set. Quaternization of a mixture of triethanolamine fatty acid esters reacted at a ratio of 1.3: 1 or more, preferably 1.5: 1 or more and 2.0: 1 or less, preferably 1.9: 1 or less React.

  The fatty acid or fatty acid lower alkyl ester is preferably a fatty acid composition obtained by saponifying fat selected from beef tallow, palm oil, sunflower oil, soybean oil, rapeseed oil, safflower oil, cottonseed oil, corn oil, olive oil. From the viewpoint of the softening effect, those having a fatty acid composition obtained from beef tallow, palm oil and sunflower oil are good. Further, 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 in JP-A-8-99036 or by performing a selective hydrogenation reaction described in JP-A-8-99036. It can be manufactured by a controlling method or the like. For example, hardened beef tallow is a fatty acid derived from beef tallow saturated by hydrogenation, and may be expressed as semi-hardened as partially cured. Moreover, the fatty acid and (A) component which are excellent in ease of use, such as not only a softening effect but a low viscosity on manufacture, are arbitrarily mixed by arbitrarily mixing those prepared with the degree of curing and uncured fatty acid. It may be prepared and used.

  When a selective hydrogenation reaction is performed, a mixture of geometric isomers of unsaturated bonds is formed. In the present invention, the trans / cis molar ratio is preferably 0/100 or more, more preferably 5/95. Above, and preferably 75/25 or less, more preferably 50/50 or less.

  In the dehydration esterification method, the reaction is preferably carried out at an esterification reaction temperature of 140 ° C. or higher and 230 ° C. or lower while removing condensed water. For the purpose 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 may be selected. it can. The progress of the reaction is confirmed by measuring the acid value (AV) and saponification value (SV) by the method described in JISK0070-1992, and preferably AV is 10 mgKOH / g or less, preferably 6 mgKOH / g or less. The esterification reaction is terminated. The resulting ester compound mixture has an SV of preferably 110 mg KOH / g or more, more preferably 130 mg KOH / g or more, and preferably 210 mg KOH / g or less, more preferably 190 mg KOH / g or less.

  In the transesterification method, the reaction is preferably carried out while removing the lower alcohol produced at a temperature of 50 ° C. or higher, more preferably 100 ° C. or higher, and preferably 150 ° C. or lower. In order to accelerate the reaction, inorganic alkalis such as sodium hydroxide and potassium hydroxide, and alkoxy catalysts such as methylate and ethylate can be used. It is preferable to directly quantify the amount of the fatty acid lower alkyl ester using a gas chromatograph or the like for the progress of the reaction, and 10 area% on the gas chromatograph chart with respect to the fatty acid lower alkyl ester charged with the unreacted fatty acid lower alkyl ester. Hereinafter, the reaction is preferably terminated at 6 area% or less. The resulting ester compound mixture has an SV of preferably 110 mg KOH / g or more, more preferably 130 mg KOH / g or more, and preferably 210 mg KOH / g or less, more preferably 190 mg KOH / g or less.

  Next, the thus obtained ester compound is quaternized. As the alkylating agent used for quaternization, methyl chloride, dimethyl sulfate, diethyl sulfate and the like are 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. % Of the solution mixed in a pressure reactor such as an autoclave made of titanium, and methyl chloride is injected at a reaction temperature of 30 ° C. or higher and 120 ° C. or lower in a sealed state for reaction. At this time, since a part of methyl chloride may be decomposed to generate hydrochloric acid, it is preferable that the reaction proceeds efficiently by adding a small amount of an alkali agent. As for the molar ratio of methyl chloride to the ester compound, it is preferable to use methyl chloride at least 1 equivalent and not more than 1.5 equivalents per equivalent of amino group of the ester compound.

  The molar ratio of dimethyl sulfate and / or diethyl sulfate to the ester compound is preferably 0.9 times equivalent or more, more preferably 0.95 times dimethyl sulfate and / or diethyl sulfate relative to 1 equivalent of the amino group of the ester compound. More than equivalent, and preferably 1.1 times equivalent or less, more preferably 0.99 times equivalent or less.

  The liquid softening agent composition of this invention may contain the other reaction product produced | generated at the time of manufacture of (A-1) component. For example, as the unreacted amine that has not been quaternized, there are specifically an amine of a fatty acid triester structure and an amine of a fatty acid diester structure, and depending on the production method, an amine of a fatty acid triester structure and a fatty acid diester structure The reaction product containing 5 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the component (A-1) is obtained. On the other hand, since the amine of the fatty acid monoester structure is easily quaternized, the content in the reaction product is usually 0.5 parts by mass or less with respect to 100 parts by mass of the component (A-1). Furthermore, the triethanolamine and the quaternized product of triethanolamine which were not fatty acid esterified contained in total 0.5 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the component (A-1). 90 mass% or more is a quaternized product. Unreacted fatty acids may also be included. When a reaction product containing the component (A-1) is used, such unreacted components and side reaction components may be incorporated into the liquid softener composition as long as the effects of the present invention are not impaired.

In the case of using a mixture containing the compound (a1), the compound (a2) and the compound (a3) as the component (A-1), the compound (a1), the compound (a2), the compound (a3), and the amine compound in the mixture The ratio can be determined using a high performance liquid chromatograph (sometimes called HPLC) and a charged particle detector (sometimes called Charged Aerosol Detection, CAD) as a detector. Regarding the measurement method using CAD, “Technology and Application of Charged Particle Detector Corona CAD” (Fukushima et al., Chromatography, Vol. 32 No. 3 (2011)) can be referred to.
For example, as HPLC conditions, column: Inertsil NH2 5 μm (4.6 × 250 mm)
Mobile phase: 0.05 mass / volume% TFA hexane: MeOH: THF = 85: 10: 5 (volume ratio)
Flow rate: 0.8 mL / min from the start of measurement up to 10 minutes, uniformly increase to 1.2 mL / min from over 10 minutes to 11 minutes from the start of measurement, 1.2 mL / min from over 11 minutes to 55 minutes, 0.8 mL / min from the start of measurement to over 60 minutes to 60 minutes
Injection: 20 μL
Temperature: 25 ° C
Detection: CAD
Can be measured.

Among the components (A), the component (A-2) is a component composed of a plurality of quaternary ammonium salts represented by the following general formula (2),
In the total amount of the quaternary ammonium salt represented by the general formula (2), the proportion of the compound (a4) in which R ⁵ in the general formula (2) is an acyl group and R ⁶ is a hydrogen atom is 1% by mass or more. 40% by mass or less,
In the total amount of the quaternary ammonium salt in which the ratio of the compound (a5) in which R ⁵ and R ⁶ in the general formula (2) are the acyl group is 60% by mass or more, 99% by mass Less than,
It is a component that is.

[Wherein, R ⁵ is a residue obtained by removing OH from a fatty acid having 16 to 22 carbon atoms (the residue may be referred to as an acyl group), and R ⁶ is the acyl group or a hydrogen atom. R ⁷ and R ⁸ are each independently an alkyl group having 1 to 3 carbon atoms, Q is an ethylene group or a propylene group, and X ⁻ is an anion. ]

The compound (a4) is a compound in which R ⁵ is the acyl group and R ⁶ is a hydrogen atom, and the component (A-2) is 1% by mass or more, preferably 5% by mass or more, more preferably It is contained in an amount of 10% by mass or more and 40% by mass or less, preferably 30% by mass or less, and more preferably 25% by mass or less.
The compound (a5) is a compound in which R ⁵ and R ⁶ are the acyl groups, and the component (A-2) is 60% by mass or more, preferably 70% by mass or more, more preferably 75% by mass or more, 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 (2), 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 ⁷ and R ⁸ are alkyl groups having 1 to 3 carbon atoms, preferably a methyl group or an ethyl group.
Q is preferably an ethylene group or a propylene group, and more preferably an ethylene group.
X ^- is an organic or inorganic anion and the like, preferably a halogen ion, more preferably chloride ion, 1 to 3 carbon atoms an alkyl sulfate ion, 12 or more carbon atoms and 18 or less fatty acid ions, atoms 1 These are benzenesulfonate ions which may be substituted by 1 or more and 3 or less alkyl groups, and among them, chloro ions are preferred.

The component (A-2) is a method in which a fatty acid and a lower alkyldiethanolamine or lower alkyldipropanolamine (hereinafter, lower alkyl means a methyl group, an ethyl group or a propyl group), preferably a methyldiethanolamine is subjected to a dehydration esterification reaction ( An esterification product obtained by a transesterification reaction of fatty acid lower alkyl ester and lower alkyldiethanolamine or lower alkyldipropanolamine, preferably methyldiethanolamine (referred to as transesterification method). It can be obtained by a quaternization reaction with an agent.
The molar ratio of fatty acid or fatty acid lower alkyl ester to lower alkyldiethanolamine or lower alkyldipropanolamine, preferably methyldiethanolamine, in the reaction for obtaining an esterified product is preferably 1.2 / 1 or more, more preferably 1.3 / 1 or more. More preferably, it is 1.4 / 1 or more, and preferably 1.85 / 1 or less, more preferably 1.8 / 1 or less, and still more preferably 1.7 / 1 or less.

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 the softening effect, those obtained from beef tallow, palm oil and sunflower oil are more preferable.
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.
In addition, when the selective hydrogenation reaction is performed, a mixture of geometric isomers of unsaturated bonds is obtained. The cis / trans ratio (molar ratio) of the geometric isomers of fatty acids is such that the trans / cis molar ratio is Preferably it is 0/100 or more, more preferably 5/95 or more, and preferably 75/25 or less, more preferably 50/50 or less.

  The component (A-2) can be prepared in the same manner as the dehydration esterification method and the transesterification method of the component (A-1).

<(B) component>
The component (B) of the present invention is
A component comprising a plurality of ester compounds of glycerin and a fatty acid having 10 to 22 carbon atoms,
The proportion of the fatty acid monoester structure is 65% by mass or less in the total amount of the ester compound,
The total proportion of the fatty acid diester structure and the fatty acid triester structure is a component that is 35% by mass or more and 100% by mass or less in the total amount of the ester compound.

By using the component (B), hydrolysis of the component (A) can be suppressed. The reason why the (A) component and the (B) component coexist in water and thus the hydrolysis of the (A) component is not necessarily clear, but the present inventor thinks as follows.
The present inventor found that when the component (B) is present in the softening agent composition, the component (B) is aligned between the aggregates formed by the component (A), and the hydrophobic portion is clogged (A It is confirmed that the distance between the tertiary amino group or the quaternary ammonium group which is a hydrophilic group of the component is increased. At that time, it has also been confirmed that the amount of hydration water is reduced. Therefore, it is considered that water around the ester group close to the hydrophilic group of the component (A) is reduced and hydrolysis of the ester group is suppressed.

In addition, there exist three compounds from which esterification degree differs in the ester compound of the glycerin which comprises (B) component, and a C12-C22 fatty acid.
Of the ester compounds constituting the component (B), the fatty acid monoester structure is a compound in which one of the three hydroxyl groups of glycerin is a fatty acid and an ester. This compound may be referred to as a fatty acid monoester structure under the restriction of component (B).
In addition, among the ester compounds constituting the component (B), the fatty acid diester structure is a compound in which two of the three hydroxyl groups of glycerin are a fatty acid and an ester. This compound is sometimes referred to as a fatty acid diester structure under the restriction of component (B).
In addition, among the ester compounds constituting the component (B), the fatty acid triester structure is a compound in which three of the three hydroxyl groups of glycerin are fatty acids and esters. This compound may be referred to as a fatty acid triester structure under the restriction of component (B).

  The fatty acid is preferably 12 or more and 18 or less. Specific examples of the fatty acid include stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, coconut oil fatty acid, palm oil fatty acid, hardened palm oil fatty acid, beef tallow fatty acid, and hardened beef tallow fatty acid. Saturated fatty acids such as hardened palm oil fatty acids and hardened beef tallow fatty acids are preferred.

  The proportion of the fatty acid monoester structure in the component (B) is preferably 0% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, from the viewpoint of imparting a hydrolysis inhibiting effect. From the viewpoint of improving the decomposition suppression effect, it is 65% by mass or less, preferably 63% by mass or less, more preferably 60% by mass or less.

  The total proportion of the fatty acid diester structure and the fatty acid triester structure in the component (B) is 35% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass from the viewpoint of improving the hydrolysis inhibiting effect. From the viewpoint of the stability of the composition, it is 100% by mass or less, preferably 98% by mass or less, more preferably 96% by mass or less.

  JP-A-5-140037, JP-A-5-140038 and the like can be referred to as a method for obtaining the ester mixture as the component (B) of the present invention.

The ratio of glycerin fatty acid esters with different degrees of esterification can be measured by high performance liquid chromatography.
For example, the method (inverse gradient method) which measures on the following HPLC conditions using the high-speed HPLC apparatus ultraMate3000 (made by Dionex) is mentioned.
Column: L-column ODS 5 μm, 150 mm × 4.6 mm
Mobile phase:
A; Water B; Acetone Gradient condition: A / B (volume ratio) = 30/70 (0 min-2 min) -A / B = 7/93 (8-18 min) -A / B = 0/100 (23-27 min) ) -A / B = 30/70 (28min-38min)
Flow rate: 1.0 ml / min
Column temperature: 35 ° C
Detector: CAD ultra
Sample concentration and injection volume: 1 mg / ml acetone solution, 20 μl

  The component (B) of the present invention can be produced by an esterification reaction between glycerin and a fatty acid, or a transesterification reaction between glycerin and a fatty acid lower alkyl ester (lower alkyl is a methyl group, an ethyl group, or a propyl group) and fats and oils. Preferably, in order to obtain a mixture that satisfies the condition of component (B), the fatty acid is preferably 0.7 mol or more, more preferably 1.0 mol or more, more preferably 1.5 mol, per 1 mol of glycerin. The esterification reaction or the transesterification reaction is preferably performed so that the ratio is 3.5 mol or less, preferably 3.3 mol or less, more preferably 3.0 mol or less. As esterification reaction catalyst or transesterification reaction catalyst, carbonates such as sodium carbonate, potassium carbonate, calcium carbonate, magnesium carbonate, barium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, barium hydroxide Such as caustic, sodium oxide, potassium oxide, calcium oxide, magnesium oxide, barium oxide etc., sodium methylate, sodium ethylate, potassium methylate, potassium ethylate alcoholate, sodium acetate, potassium acetate etc. An acid catalyst selected from fatty acid soaps, acid catalysts such as phosphoric acid, phosphorous acid, hypophosphorous acid, sulfuric acid, p-toluenesulfonic acid, and benzenesulfonic acid can be used. The reaction temperature can be appropriately selected within the range of 50 ° C. or higher and 260 ° C. or lower depending on the type of catalyst. When an alkali catalyst is used, the reaction temperature is preferably 140 ° C. or higher, more preferably 160 ° C. or higher, and preferably 260 ° C. or lower, more preferably 240 ° C. or lower. When an acid catalyst is used, the reaction temperature is The temperature is preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and preferably 160 ° C. or lower, more preferably 150 ° C. or lower. Although the reaction time becomes long, a post-treatment process such as catalyst removal can be omitted, and the reaction may be performed without a catalyst.

  In order to improve the reaction rate under stirring, the reaction is usually carried out by introducing nitrogen into the reaction system under reduced pressure of about 0.01 MPa or more and 0.09 MPa or less, or at normal pressure, and water or lower alcohol produced. It is preferable to carry out while removing it outside the system. Moreover, in order to obtain a high pure component (B), when the fatty acid is reacted in an amount of 0.7 mol or more and 3.0 mol or less with respect to 1 mol of glycerin, it is preferable to carry out the deglycerin step after the esterification reaction. . When the fatty acid with respect to 1 mol of glycerol exceeds 3.0 mol and reacts at 3.5 mol or less, it is preferable to perform a defatty acid process.

  In the case of the dehydration esterification reaction, the progress of the reaction is confirmed by measuring the acid value (AV) or hydroxyl value (OHV) by the method described in JISK0070-1992. When the fatty acid is reacted at 0.7 mol or more and 3.0 mol or less with respect to 1 mol of glycerin, the AV is suitably 10 mgKOH / g or less, preferably 6 mgKOH / g or less, particularly 6 mgKOH / g or less. The esterification reaction is completed. When the fatty acid or fatty acid lower alkyl ester exceeds 1 mol and less than 3.5 mol with respect to 1 mol of glycerin, the ester is suitably used when the OHV is 10 mgKOH / g or less, preferably 5 mgKOH / g or less. To complete the reaction. In the case of a transesterification reaction, it can be confirmed using a gas chromatograph or a liquid chromatograph. The conditions of these chromatographs vary depending on the type of polyhydric alcohol or fatty acid, and the optimum conditions are appropriately selected under known conditions. can do.

After completion of the reaction, the catalyst is inactivated such as neutralization and adsorption removal, and then unreacted glycerin and fatty acid can be distilled off under reduced pressure.
As the component (B), not only a reaction product of glycerin and a fatty acid but also natural fats and oils may be used as they are. For example, coconut oil, palm oil, hardened palm oil, beef tallow, semi-cured beef tallow, hardened beef tallow and the like can be used as the component (B).

[Contents of component (A) and component (B), etc.]
Content of (A) component in the liquid softening agent composition of this invention is 1 mass% or more and 20 mass% or less. The content of the component (A) in the liquid softener composition of the present invention is preferably 5% by mass or more, more preferably 8% by mass or more, from the viewpoint that the amount used per wash can be reduced. Preferably it is 18 mass% or less, More preferably, it is 15 mass% or less.

  The content of the component (B) in the liquid softener composition of the present invention is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, more preferably 1.0% by mass or more, And preferably it is 3 mass% or less, More preferably, it is 2.5 mass% or less, More preferably, it is 2.0 mass% or less.

  In the liquid softener composition of the present invention, the mass ratio of the component (A) to the component (B) is (A) from the viewpoint of inhibiting hydrolysis of the component (A) and imparting an appropriate viscosity and a preferable appearance to the composition. ) Component / (B) component is 2 or more and 50 or less. The mass ratio of component (A) / component (B) is preferably 3 or more, more preferably 5 or more, and is preferably 40 or less, more preferably 30 or less.

[PH]
The pH of the liquid softener composition of the present invention is 2 or more, preferably 2.2 or more, and 4 or less at 25 ° C. from the viewpoint of hydrolytic stability of the component (A), preferably 3.8 or less. The pH is measured at 25 ° C. according to JIS K 3362; 2008, item 8.3.

〔viscosity〕
The viscosity of the liquid softener composition of the present invention is 30 ° C., preferably 50 mPa · s or less, more preferably 45 mPa · s or less, more preferably 40 mPa · s or less, more preferably, from the viewpoint of handleability during use. Is 35 mPa · s or less. Furthermore, the viscosity is preferably 5 mPa · s or more. Viscosity was measured with a liquid softener composition at 30 ° C. using a B-type viscometer (model number; TVB-10 manufactured by Toki Sangyo Co., Ltd., No. 2 rotor, 60 r / min), and stirred. The value 1 minute after the start is adopted.

[Optional ingredients]
The liquid softener composition of the present invention includes, as an optional component, an oil agent other than the component (B) [hereinafter referred to as the component (C)], a surfactant other than the component (A) [hereinafter referred to as the component (D)], Chelating agent (hereinafter referred to as (E) component), inorganic electrolyte (hereinafter referred to as (F) component), water-soluble organic solvent (hereinafter referred to as (G) component) and perfume composition (hereinafter referred to as (H) component) It is preferable to contain 1 or more types of components chosen from these.
In addition, the liquid softener composition of the present invention includes, as an optional component, an antioxidant, a dye, a preservative, a silicone compound, a polymer, and a pH adjuster for adjusting the pH suitable for stabilizing the component (A). Can be contained.

[(C) component: oil agent]
It is preferable that the liquid softening agent composition of this invention contains oil agents other than (B) component as (C) component. The oil agent used in the present invention is used for imparting more excellent softness performance to the textile product, and also has an effect on inhibiting hydrolysis of the component (A). Examples thereof include hydrocarbons having 14 or more carbon atoms and aliphatic alcohols, preferably octadecane, liquid paraffin, stearyl alcohol and the like. Moreover, the esterified product of a polyhydric alcohol and a fatty acid etc. are mentioned, Preferably, a pentaerythritol fatty acid ester, sorbitan fatty acid ester, etc. are mentioned. From the viewpoint of improving the softness performance, the fatty acid is preferably palmitic acid, stearic acid, or a mixture thereof. The blending amount of the component (C) oil is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 5% by mass or less, more preferably 3% by mass in the composition. % Or less.

[Component (D): Surfactant]
The liquid softener composition of the present invention preferably contains a surfactant other than the component (A) as the component (D), and is a nonionic surfactant [hereinafter referred to as the component (D1)] and (A It is more preferable to contain one or more surfactants selected from cationic surfactants (D2) other than the component [D2] [hereinafter referred to as the component (D2)].

(D1) As a nonionic surfactant of a component, 1 or more types chosen from the following (D11) and (D12) are mentioned.
(D11): Nonionic surfactant represented by the following general formula (3) R ^1g —O — [(C ₂ H ₄ O) _s (C ₃ H ₆ O) _t ] —H (3)
[Wherein, R ^1g represents an alkyl group or an alkenyl group having 8 or more, preferably 10 or more, and 18 or less, preferably 16 or less carbon atoms. s and t are average added mole numbers, s is 2 or more, preferably 10 or more, and 50 or less, preferably 40 or less, t is 0 or more, preferably 1 or more, and 5 or less, preferably Is a number of 3 or less. (C ₂ H ₄ O) and (C ₃ H ₆ O) may be random polymers or block polymers. ]
(D12): Nonionic surfactant represented by the following general formula (4)

[Wherein R ^1g represents the above-mentioned meaning. A is -N <or -CON <, u and v are each independently a number of 0 or more and 40 or less, and u + v is a number of 5 or more and 60 or less, preferably 40 or less. R ^2g and R ^3g are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

As the cationic surfactant of component (D2), one or more selected from the following (D21) to (D23) are preferable, and one or more selected from (D22) are more preferable. The salt is preferably a chlorine salt.
(D21): Di-long-chain alkyl or alkenyldimethylammonium salt having an alkyl group or alkenyl group having 10 to 22 carbon atoms (D22): Mono-long chain having an alkyl group or alkenyl group having 10 to 22 carbon atoms Alkyl or alkenyltrimethylammonium salt (D23): mono-long-chain alkyl or alkenylbenzyldimethylammonium salt in which the alkyl group or alkenyl group has 10 to 22 carbon atoms

  The softener composition of the present invention preferably contains the component (D1) as the component (D), and more preferably contains the nonionic surfactant (D11) represented by the general formula (3). preferable.

  The content of the component (D) surfactant in the composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less. In the concentration limitation of the component (D), the content of the nonionic surfactant (D11) represented by the general formula (3) is 0.5% by mass or more in the softener composition of the present invention, 1 mass% or more is preferable.

[(E) component: chelating agent]
The liquid softener composition of the present invention preferably contains a chelating agent as the component (E) in order to capture metal ions such as copper and iron and alkaline earth metal ions in water.

  The chelating agent used in the present invention is used for improving the storage stability of the liquid softening agent composition of the present invention, in addition to the purpose of capturing metal ions such as copper and iron and alkaline earth metal ions in water. It is also used to suppress discoloration of the composition and dye fading.

  Examples of the component (E) include ethylenediaminetetraacetic acid, hydroxyethylidene diphosphonic acid, L-aspartic acid diacetic acid, S, S-ethylenediamine disuccinic acid, and N-2-hydroxy, which are superior in biodegradability compared to these. Ethyliminodiacetic acid, 3-hydroxy-2,2′-iminodisuccinic acid, L-glutamic acid-N, N-diacetic acid, and methylglycine diacetic acid can be used. (E) As a component, the compound chosen from hydroxyethylidene diphosphonic acid, methylglycine diacetic acid (MGDA), and those salts is more preferable.

  In the liquid softener composition of the present invention, the component (E) is preferably 0.001% by mass or more, more preferably 0.003% by mass or more, and still more preferably 0.005% by mass in terms of acid type compound. More preferably, it is 0.0075% by mass or more, and preferably 0.1% by mass or less, more preferably 0.05% by mass or less, and still more preferably 0.03% by mass or less.

[(F) component: inorganic electrolyte]
The liquid softener composition of the present invention preferably contains an inorganic electrolyte as the component (F). The inorganic electrolyte of component (F) is preferably one that dissolves 5 g or more in 100 g of water at 20 ° C.
The inorganic electrolyte of component (F) is preferably used to adjust the softener composition to a viscosity suitable for use. For example, the component (F) includes an inorganic salt in which the cation is an ion of a substance selected from alkali metals and alkaline earth metals, and the anion is an ion of a substance selected from halogen compounds and sulfates. It is done. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium and calcium. Examples of the halogen compound include chloride, bromide, and iodide.
Specific examples of the inorganic electrolyte of component (F) include one or more inorganic electrolytes selected from sodium chloride, sodium sulfate, calcium chloride, calcium sulfate, magnesium chloride, and magnesium sulfate.

  The content of the inorganic electrolyte (F) in the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 1% by mass or less, more preferably 0.5% by mass or less.

[(G) component: water-soluble organic solvent]
The softener composition of the present invention preferably contains a water-soluble organic solvent as the component (G) from the viewpoint of the stability and viscosity of the composition. (G) As a component, the water-soluble organic solvent known to mix | blend with a softening agent is mentioned. Regarding the component (G), “water-soluble organic solvent” means that 20 g or more is dissolved in 100 g of 20 ° C. deionized water. Specific examples of the component (G) include propylene glycol, ethylene glycol, glycerin, diethylene glycol, monoethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, isopropanol, and ethanol. . One or more water-soluble organic solvents selected from ethylene glycol and ethanol are preferred. When the viscosity of the liquid softener composition is high or when it is desired to adjust the phase stability, it is preferable to use a water-soluble organic solvent. The liquid softener composition of the present invention contains the component (G) preferably 1.0% by mass or more and preferably 10% by mass or less.

[(H) component: perfume composition]
The softener composition of the present invention preferably contains a fragrance composition as the component (H) not only for the fragrance of the composition itself but also for the fragrance of the textile product. The fragrance | flavor of (H) component exists normally melt | dissolving or disperse | distributing in the liquid part of a liquid softening agent composition. (H) As a component, the microcapsule which included the fragrance | flavor can also be contained.
As the fragrance | flavor of (H) component, the various natural or synthetic | combination fragrance | flavor generally used for the softener composition and the textile product processing agent composition is mentioned. For example,
(H1) Ethers such as fatty acid ethers and aromatic ethers (excluding phenol ethers),
(H2) Oxides such as fatty acid oxides and terpene oxides,
(H3) Acetal,
(H4) Ketal,
(H5) phenol,
(H6) phenol ether,
(H7) acids such as fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, aromatic carboxylic acids,
(H8) Synthetic fragrances such as nitrogen-containing compounds such as acid amide, nitromusk, nitrile, amine, pyridine, quinoline, pyrrole and indole. Moreover, the natural fragrance | flavor from an animal and a plant is mentioned. Moreover, the mixing | blending fragrance | flavor containing a natural fragrance | flavor and / or a synthetic fragrance | flavor is mentioned. As the component (G), one or two or more of these can be mixed and used.

  As the component (H), for example, the fragrance components described in “Perfume and Flavor Chemicals” written by Motoichi Into, published in 1969 by Chemical Industry Daily, “Synthetic Fragrance Chemistry and Product Knowledge”, 1969 MONTCLAIR, STEFFEN ARCTANDER published by NJ, etc. Can be used.

  Moreover, the fragrance | flavor component which has a hydroxyl group can be used together as a silicate ester (for example, Unexamined-Japanese-Patent No. 2009-256818 description) body as a fragrance | flavor of (H) component for the purpose of the fragrance sustainability and residual fragrance property.

  In the liquid softener composition of the present invention, the component (H) is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 3.0% by mass or less, more preferably 2%. .5% by mass or less.

<(I) pH adjuster>
In the liquid softener composition of the present invention, the pH of the stock solution is adjusted to 2.0 or more and 4.0 or less at 30 ° C. in order to suppress decomposition due to hydrolysis of the quaternary ammonium compound as the component (A). . Therefore, it is preferable that the liquid softening agent composition of this invention mix | blends a pH adjuster as (I) component. Examples of the pH adjuster include a component selected from an acid agent and an alkali agent.

Examples of the acid agent include inorganic acids and organic acids. As specific examples of the inorganic acid, hydrochloric acid and sulfuric acid can be used. The organic acid of component (I) is an organic acid other than component (E). Specific examples of the organic acid (I) include monovalent or polyvalent carboxylic acids having 1 to 10 carbon atoms, or monovalent or polyvalent sulfonic acids having 1 to 20 carbon atoms. . More specifically, methylsulfuric acid, ethylsulfuric acid, p-toluenesulfonic acid, (o-, m-, p-) xylenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, formic acid, glycolic acid, citric acid, benzoic acid And salicylic acid.
Examples of the alkali agent include inorganic bases and organic bases. Specific examples of the inorganic base include sodium hydroxide and potassium hydroxide. Specific examples of the organic base include monoethanolamine, diethanolamine, and triethanolamine.

  (I) component of an acid agent or an alkali agent is mix | blended in the quantity from which the pH of a composition becomes the said range, and is restrict | limited to the quantity which does not impair stability.

[Other optional ingredients]
The softening agent composition of the present invention can contain an antioxidant. The antioxidant is, for example, an antioxidant having a phenol group in the molecule. An antioxidant having a phenol group in the molecule is used to suppress a change in the odor of the fragrance. When an antioxidant is used in combination with a fragrance, the change in odor can be suppressed, but since the antioxidant having a phenol group that has been oxidized is colored, the discoloration of the softener composition is promoted. The compounding amount of the agent is used after sufficiently confirming with the perfume component that is susceptible to oxidation and its content.
From the viewpoint of easy availability, 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol are antioxidants having a phenol group in the molecule. And one or more antioxidants selected from butylhydroxyanisole are preferred. From the viewpoint of suppressing discoloration, one or more antioxidants selected from 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol are preferable. .
The antioxidant may be blended for the storage stability of other base materials such as the component (A), and may be mixed into the softener composition of the present invention by blending the component (A). is there.

The softener composition of the present invention may contain a dye for aesthetics or for masking color or coloring derived from the substrate. Dyes are used to give consumers a high preference for softener compositions. For example, one or more dyes selected from a color index acidic red dye, a color index acidic yellow dye, and a color index acidic blue dye.
Specific examples of the color index acidic red dye include CIAcid Red 18 CIAcid Red 27, CIAcid Red 52, CIAcid Red 82, CIAcid Red 114, CIAcid Red 138, and CIAcid Red 186.
Specific examples of the color index acidic yellow dye include CIAcid Yellow 1, CIAcid Yellow 7, CIAcid Yellow 23, and CIAcid Yellow 141.
Specific examples of the color index acidic blue dye include CIAcid Blue 5, CIAcid Blue 9, and CIAcid Blue 74.

  In the present invention, dyes other than these can also be used. These dyes include alkoxylated anthraquinone polymer colorants, alkoxylated triphenylmethane polymer colorants, and alkoxylated thiophene polymer colorants.

  When the dye is used in combination with a chelating agent, discoloration of the softener composition containing the fragrance or the fragrance and the antioxidant can be suppressed. From the viewpoint of inhibiting discoloration, one or more dyes selected from a color index acidic red dye and a color index acidic yellow dye are preferred.

  The preservative used in the present invention is used to impart antiseptic properties to the softener composition. For example, biguanide compounds, isothiazoline compounds, and isothiazolinone compounds can be used. Specific examples include polyhexamethylene biguanide hydrochloride, 5-chloro-2-methyl-4-isothiazolin-3-one, 1,2-benzisothiazolin-3-one, and commercially available products such as “Proxel IB”. "," Caisson CG "," Proxel BDN "can also be used.

  The present invention may contain a silicone compound depending on the case or in order to add a new impression to the tactile sensation to the textile product. Silicone compounds are used to impart even better softness performance to textile products. For example, dimethyl silicone, polyether modified silicone, methylphenyl silicone, alkyl modified silicone, higher fatty acid modified silicone, methyl hydrogen silicone, fluorine modified silicone, epoxy modified silicone, carboxy modified silicone, carbinol modified silicone, amino modified silicone, etc. Is mentioned. From the viewpoint of the softening effect, dimethyl silicone, amino-modified silicone, and polyether-modified silicone are particularly preferable, and dimethyl silicone and amino-modified silicone are more preferable. These can be used alone or as a mixture of two or more.

  The present invention may contain a polymer compound having a structural unit obtained by polymerizing a polymerizable monomer. The polymer compound is used for adjusting the viscosity of the softening agent composition and capturing residual detergent components during the finishing of the softening agent. Specific examples of the cationic polymer include, but are not limited to, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, diethylaminopropyl. Examples include an acid neutralized product obtained by polymerizing acrylamide or diethylaminopropylmethacrylamide as a monomer and neutralizing them with an acid, or a quaternary ammonium salt quaternized with a quaternizing agent.

The acid used for neutralization of the cationic polymer is not particularly limited, but inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as citric acid, tartaric acid, toluenesulfonic acid, lactic acid, succinic acid, and glycolic acid. Can be mentioned.
The quaternizing agent for the cationic polymer is not particularly limited, but alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, diethyl sulfate, di-n-sulfate. Examples of the alkyl alkylating agent include alkylpropyl sulfate such as propyl.
The polymer is not limited to homopolymers, copolymers, block polymers and the like.

  The balance of the liquid softener composition of the present invention is water. As the water, deionized water, sterilized water in which a small amount of hypochlorite is mixed in deionized water, tap water, or the like can be used.

  The liquid softener composition of the present invention may be in an emulsion state. In the present invention, an emulsion liquid softener composition means that the compounding component forms large particles that scatter visible light in the liquid softener composition, thereby scattering visible light and making it visually turbid. Represents a liquid softener composition in a wet state. Specifically, when a glass cell having an optical path length of 10 mm is used as a measurement cell and ion-exchanged water is put into a control cell, the visible light transmittance (wavelength) of the sample measured using an ultraviolet-visible spectrophotometer. 660 nm) represents a liquid softener composition with less than 25%.

  The liquid softener composition of the present invention is suitable for textile products such as clothing, bedding, fabrics, and other fabric products.

The components used in the examples and comparative examples are shown below.
<Synthesis Example 1> (a-1) Synthesis of Component A fatty acid having an acid value of 206.9 mgKOH / g and a triethanolamine using palm oil as a raw material and a reaction molar ratio of 1.65 / 1 (fatty acid / triethanolamine) ) To obtain a condensate containing N, N-dialkanoyloxyethyl-N-hydroxyethylamine as a main component.

  Next, the amine value of this condensate was measured, and quaternization was performed using 0.95 equivalent of dimethyl sulfate to the condensate, and N, N-dialkanoyloxyethyl-N-hydroxyethyl-N-methyl was obtained. A quaternary ammonium salt mixture containing ammonium methyl sulfate as a main component and containing 10% by mass of ethanol was obtained (hereinafter referred to as (a-1)). However, the term “alkanoyl” used herein includes residues derived from unsaturated fatty acids, such as alkenoyl, in addition to saturated fatty acids, since alkanoyl is a fatty acid residue of palm oil raw material. Moreover, the preparation procedure and reaction conditions for obtaining the said condensate and (a-1) were performed according to the synthesis example 2 of Unexamined-Japanese-Patent No. 2010-209493.

  In the quaternary ammonium salt contained in (a-1), the proportion of the component (a1) was 30% by mass, the proportion of the component (a2) was 55% by mass, and the proportion of the component (a3) was 15% by mass. (A-1) has a quaternization rate of 92% by mass, and in addition to the (a1) component, the (a2) component, the (a3) component and ethanol, a tertiary amine compound of a diester structure and a triester structure , Trace amounts of triethanolamine and its quaternized product, and trace amounts of fatty acids.

<Synthesis Example 2> Synthesis of component (a-2) Fatty acid having an acid value of 205.8 mg KOH / g (palmitic acid / stearic acid / oleic acid / others = 11 mass% / 66 mass% / 20 mass% / 3 mass%) And methyldiethanolamine are subjected to a dehydration condensation reaction at a reaction molar ratio of 1.7 / 1 (fatty acid / methyldiethanolamine) to obtain a condensate containing N, N-dialkanoyloxyethyl-N-methylamine as a main component. It was. Next, the amine value of the condensate was measured, and quaternization was performed using 0.97 equivalent of methyl chloride to the condensate, and N, N-dialkanoyloxyethyl-N, N-dimethylammonium chloride was used. As a main component, a quaternary ammonium salt compound containing 10% by mass of ethanol was obtained (hereinafter referred to as (a-2)). In the quaternary ammonium salt contained in (a-2), the proportion of the component (a4) was 21% by mass, and the proportion of the component (a5) was 79% by mass. (A-2) has a quaternization rate of 95% by mass. In addition to the component (a4), the component (a5), and ethanol, a tertiary amine compound of a diester structure, a trace amount of diethanolamine and a quaternized product thereof, As well as trace amounts of fatty acids.

In addition, about (a-1) and (a-2), (a1) component, (a2) component, (a3) component, (a4) component, the ratio of (a5) component, and the analysis of other components are HPLC. The measurement was performed under the following conditions.
<HPLC conditions>
Column: Inertsil NH2 5 μm (4.6 × 250 mm) Room temperature (25 ° C.)
Mobile phase: 0.05 mass / volume% TFA (trifluoroacetic acid) Hexane: MeOH (methanol): THF (tetrahydrofuran) = 85: 10: 5 (volume ratio)
Flow rate: 0.8 mL / min from the start of measurement up to 10 minutes, uniformly increase to 1.2 mL / min from over 10 minutes to 11 minutes from the start of measurement, 1.2 mL / min from over 11 minutes to 55 minutes, 0.8 mL / min from the start of measurement to over 60 minutes to 60 minutes
Injection: 20 μL
Detection: CAD

<Synthesis Example 3> Synthesis of Component (b-2) 158 g of glycerin, fatty acid (lauric acid / myristic acid / palmitic acid / stearic acid / others = 51 mass% / 23 mass% / 7 mass% / 17 mass% / 2 mass) %) 932 g (fatty acid 2.44 mol per mol of glycerin) and NaOH 1.7 g were charged into a four-necked flask, heated while introducing nitrogen gas, and the water generated by the reaction was removed at 220 ° C. For 5 hours. It was confirmed that the acid value of the reaction product was 0.3 mgKOH / g or less and the hydroxyl value was between 32 and 38 mgKOH / g, and component (b-2) was synthesized. In (b-2), the proportion of the monoester structure was 7% by mass in the total amount of (b-2), and the total of the fatty acid diester structure and the fatty acid triester structure was 93% by mass.

<Synthesis Example 4> Synthesis of Component (c-1) 180 g of pentaerythritol, 565 g of stearic acid (1.5 mol of fatty acid with respect to 1 mol of pentaerythritol), and 0.27 g of NaOH were charged into a four-necked flask. The mixture was heated while introducing nitrogen gas into a four-necked flask, and reacted at 235 ° C. for 5 hours while removing water produced by the reaction. After confirming that the acid value of the reaction product was 1 mg KOH / g or less, and cooling to 70 ° C., the precipitated unreacted pentaerythritol was removed by pressure filtration at the same temperature, and the component (c-1) was removed. Obtained.
The obtained component (c-1) is a mixture of pentaerythritol fatty acid ester, and the ratio of each ester compound is 29% by mass of fatty acid monoester, 43% by mass of fatty acid diester, 23% by mass of fatty acid triester, and fatty acid tetraester. It was 5 mass%.
The ratio of fatty acid monoester, fatty acid diester, fatty acid triester, and fatty acid tetraester was measured under the following conditions using a high-speed GPC device HCL-8220GPC (manufactured by Tosoh Corporation).
<HPLC conditions>
Column: TSKgel G1000HXL + G2000HXL (series connection)
Mobile phase: THF (tetrahydrofuran)
Flow rate: 0.7 ml / min
Temperature: 25 ° C
Detector: RI
Sample concentration and injection volume: 1% THF solution, 20 μl

[Component (A)]
(A-1): Reaction product containing a quaternary ammonium salt mixture produced in Synthesis Example 1 above. The numerical value of (a-1) shown in the table is the content concentration in the form of (a-1). The (A) component density | concentration in (a-1) is 80 mass%.
(A-2): Reaction product containing a quaternary ammonium salt mixture produced in Synthesis Example 2 above. The numerical value of (a-2) shown in Table 3 is the content concentration in the form of (a-2). The (A) component density | concentration in (a-1) is 85 mass%.

[(B) component]
(B-1): EXCEL P-40S (manufactured by Kao Corporation): the proportion of monoester structure is 60% by mass in the total amount of the ester compound, and the total of fatty acid diester structure and fatty acid triester structure is 40 mass%)
(B-2): The reaction product produced in Synthesis Example 3 and containing an ester compound of glycerin and a fatty acid.
(B-3): Tristearin (manufactured by Wako Pure Chemical Industries, Ltd .: the proportion of monoester structure is 0% by mass in the total amount of the ester compound, and the total of fatty acid diester structure and fatty acid triester structure is 100. mass%)

[(B ′) component]
(B′-1): Excel S-95 (the proportion of the monoester structure is 90% by mass in the total amount of the ester compound, and the total of the fatty acid diester structure and the fatty acid triester structure is 10% by mass)

[Component (C)]
(C-1): Pentaerythritol stearate produced in Synthesis Example 4 above (acylation degree 1.5)

[Component (D)]
(D-1): Nonionic surfactant (polyoxyethylene lauryl ether having an average addition mole number of oxyethylene groups of 30 mol)

[(E) component]
(E-1): Trilon M liquid (manufactured by BASF Japan Ltd., methylglycine diacetate 3Na content 40% by mass)
(E-2): Cylest PH-214 (manufactured by Cylest Co., Ltd., hydroxyethylidene diphosphonic acid 4Na content 27% by mass)
The numerical values of (e-1) and (e-2) shown in Table 3 are the effective content concentrations.

[(F) component]
(F-1): Calcium chloride

[(G) component]
(G-1): Ethylene glycol

[(H) component]
(H-1): Perfume composition h1 shown in Table 1
(H-2): Perfume composition h2 shown in Table 1

[Other ingredients]
(J-1): 1,2-benzisothiazolin-3-one (Proxel BDN (manufactured by Arch Chemical Japan))
(K-1): Highly polymerized dimethicone emulsion: 60% by mass of dimethylpolysiloxane having a kinematic viscosity of 500,000 mm ² / s at 25 ° C., and the average number of added oxyethylene groups (hereinafter referred to as the average number of added EO) 5 mol of polyoxyethylene lauryl ether 1.5% by weight, average EO added mole number 23 mol of polyoxyethylene lauryl ether 4.5% by weight, lauryl sulfate sodium salt 0.1% by weight, water remaining emulsion, The average particle diameter of the dispersed particles was 500 nm (the effective amount of dimethylpolysiloxane was used so as to have the values shown in Table 2).

<Method for Producing Emulsion Liquid Softener Composition>
An emulsion liquid softener composition was prepared by mixing each component so as to have the composition shown in Table 2. Specifically, it is as follows.
In a 300 mL beaker, 90% by mass of ion-exchange water corresponding to the amount necessary for the finished mass of the emulsified liquid softening agent composition to be 200 g, (G) component, (E) component, (j− 1) was added, and the temperature of ion-exchanged water was adjusted to 60 ± 2 ° C. using a water bath. In order to dissolve these components uniformly in ion-exchanged water, stirring was performed using the following stirring blade as necessary.
Ion-exchanged water containing the above-mentioned components adjusted to a temperature of 60 ± 2 ° C. is agitated with a stirring blade (blade arranged so that the long side is in the direction of 90 degrees with reference to the rotation center axis of a stirring rod having a diameter of 5 mm. Number: 3 blades, long side / short side of blades: 3 cm / 1.5 cm, installation of blades: angle of 45 degrees with respect to the rotating surface) at a temperature of 65 ° C. with stirring (300 r / m) (B) The component or the component (B ′), the component (C), and the component (A) heated and dissolved together with the component (D) were added over 3 minutes. After completion of the addition, the mixture was stirred for 15 minutes.
(F) A 10% by mass aqueous solution of the component was added and stirred for 10 minutes. Using a 5 ° C. water bath, the contents were cooled to 30 ± 2 ° C.
Component (H) was added and stirred for 5 minutes. Next, the component (k-1) was added and stirred for 5 minutes. Ion exchange water was added so that the mass (200 g) was completed, and the mixture was stirred for 5 minutes.
In Table 2, the (A) / (B) mass ratio is shown with the component (B ′) as the component (B) for convenience. The pH was finally adjusted with an aqueous hydrochloric acid solution.

<Evaluation method>

(1) Viscosity 30 g of the liquid softening agent composition shown in Table 2 was filled in a container (glass wide-mouth standard bottle No. 6), and the temperature of the composition was adjusted to 30 ° C. Using a B-type viscometer (model number; TVB-10 manufactured by Toki Sangyo Co., Ltd., No. 2 rotor, 60 r / min), the viscosity measurement of the liquid softener composition was started at the above temperature. The later value was read (the unit of viscosity is “mPa · s”). The results are shown in Table 2. In this evaluation, the viscosity is preferably 50 mPa · s or less.

(2) (A) Component residual rate [Preservation method of liquid softening agent composition]
A storage container (glass wide-mouth standard bottle No. 6) was filled with 30 g of the liquid softener composition shown in Table 2. The storage container filled with the liquid softening agent composition was stored at 50 ± 2 ° C. for 2 months. Next, a sample that was allowed to stand for 24 hours in a room at 25 ± 2 ° C. was used as an evaluation sample.

[Measurement method of hydrolysis rate of ester group]
In order to evaluate the time-dependent hydrolysis rate of the component (A), the cation residual rate in the liquid softening agent composition was measured by the following method.
A sample stored for 2 months at −5 ° C. in the storage container described above was used as a reference sample. The residual ratio of the component (A) (monoester, diester, triester) in these samples was measured. The measurement was performed using Shimadzu LCMS-2010EV. The measurement conditions are as follows.
* Measurement condition column: Shimadzu Shim-pack XR-ODS 2.2 μm, 50 mm × 2.0 mm
Eluent:
A: Methanol added with 10 mM ammonium acetate B; Methanol added with 10 mM ammonium acetate (50%) Ethanol (50%)
Gradient condition: A / B (capacity ratio) = 50/50 (0 min) -A / B = 0/100 (3-10 min) -A / B = 50/50 (10-15 min)
Flow rate: 0.4ml / min
Injection volume: 5 μL
Column temperature: 40 ° C
Detector: MS

  Component (A) contains quaternized products of monoester, diester, triester, and triethanolamine. Since each ester is hydrolyzed, purely from the reference sample. Only the triester form can be measured for the hydrolysis rate, and the residual rate was examined. The tribody component amount in the reference sample was taken as 100%, and the proportion of the tribody remaining amount in the evaluation sample was taken as the residual ratio. In terms of commercial value, a bird body remaining ratio after storage of 60% or more is considered acceptable. The results are shown in Table 2.

* In Comparative Examples 4 and 5, precipitation of particles was observed.

Claims (4)

The following (A) component is 1 mass% or more and 20 mass% or less, (B) component is 0.1 mass% or more and less than 4 mass%, (C) component is 0.1 mass% or more and 5 mass% or less, And the mass ratio (A) / (B) of the component (A) to the component (B) is 2 or more and 50 or less, and the pH at 30 ° C. is 2.0 or more and 4.0 or less. A liquid softener composition.
<(A) component>
The component chosen from the following (A-1) component and (A-2) component.
(A-1) component: a component comprising a plurality of quaternary ammonium salts represented by the following general formula (1),
In the total amount of the quaternary ammonium salt represented by the general formula (1), the ratio of the compound (a1) in which R ¹ in the general formula (1) is an acyl group, and R ² and R ³ are hydrogen atoms, 10 mass% or more, 45 mass% or less,
In the total amount of the quaternary ammonium salt represented by the general formula (1), the ratio of the compound (a2) in which R ¹ and R ² in the general formula (1) are acyl groups and R ³ is a hydrogen atom is: 25 mass% or more, 70 mass% or less,
In the total amount of the quaternary ammonium salt represented by the general formula (1), the proportion of the compound (a3) in which R ¹ , R ² and R ^{3 in the} general formula (1) are acyl groups is 5% by mass or more, 40% by mass or less,
Ingredients that are

^{Wherein, R 1, R 2, R} 3 are each independently, having 16 or more carbon atoms, residues obtained by removing OH from 22 following fatty acids (referred acyl group), or a hydrogen ^{atom, R} 1, R ² and R ³ are not simultaneously a hydrogen atom, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an anion. ]
(A-2) component: a component composed of a plurality of quaternary ammonium salts represented by the following general formula (2),
In the total amount of the quaternary ammonium salt represented by the general formula (2), the proportion of the compound (a4) in which R ⁵ in the general formula (2) is an acyl group and R ⁶ is a hydrogen atom is 1% by mass or more. 40% by mass or less,
In the total amount of the quaternary ammonium salt in which the ratio of the compound (a5) in which R ⁵ and R ⁶ in the general formula (2) are the acyl group is 60% by mass or more, 99% by mass Less than,
Ingredients that are

[Wherein R ⁵ is a residue obtained by removing OH from a fatty acid having 16 to 22 carbon atoms (referred to as an acyl group), R ⁶ is the acyl group or a hydrogen atom, and R ⁷ and R ⁸ Are each independently an alkyl group having 1 to 3 carbon atoms, Q is an ethylene group or a propylene group, and X ⁻ is an anion. ]
<(B) component>
A component comprising a plurality of ester compounds of glycerin and a fatty acid having 10 to 22 carbon atoms,
The proportion of the fatty acid monoester structure is 65% by mass or less in the total amount of the ester compound,
The component whose sum total ratio of a fatty-acid diester structure and a fatty-acid triester structure is 35 mass% or more and 100 mass% or less in the whole quantity of the said ester compound.
<(C) component>
Pentaerythritol fatty acid ester or sorbitan fatty acid ester. Furthermore as the component (D), the liquid softener composition of claim 1 containing a nonionic surfactant (D1). Furthermore, the liquid softening agent composition of Claim 1 or 2 which contains an inorganic electrolyte as (F) component. The component (F) is an inorganic salt in which the cation is an ion of a substance selected from alkali metals and alkaline earth metals, and the anion is an ion of a substance selected from halogen compounds and sulfates. 3. The liquid softener composition according to 3 .