JP2018044256A - Liquid softener composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid softener composition, in the case a fiber product is treated, capable of imparting the excellent persistence of flavor.SOLUTION: Provided is a liquid softener composition comprising: (A) a fatty acid ester type quaternary ammonium salt having an aliphatic acid-derived acyl group, in which the aliphatic acid ratio selected from oleic acid, linolic acid and linolenic acid as aliphatic acid composing the acyl group is 60- 100 mass% of the whole aliphatic acid; (B) a flavor precursor as an ester between a specified flavor and a specified aliphatic acid ester or a specified aliphatic acid diester; and water, and whose pH at 30°C is 2.5-5.0.SELECTED DRAWING: None

Description

  The present invention relates to a liquid softener composition.

In recent years, various treatment compositions for textile products such as detergents and finishes for clothes using persistent fragrances and sustainability-imparting ingredients have been studied due to increasing awareness of laundry scents in general households. .
However, since the fiber treatment composition used in general households is processed into a fiber product through water, the fragrance imparted to the fiber product volatilizes with water at the time of drying. The fragrance is weakened by evaporating from above. In particular, when a perfume component having a strong hydrophilic property is used, the diffusion to the treated water is remarkable, so that the fiber product is hardly adsorbed and the aroma after the treatment cannot be expected.
For such a problem, for example, Patent Document 1 discloses a fabric softening composition that contains a specific long-lasting perfume composition and improves the life of the perfume on the fabric. Patent Document 2 discloses a fabric softener composition containing a specific long-lasting perfume composition and having improved perfume persistence on the laundry. In general, a main base material used for a fabric softener is a cationic surfactant, which forms a vesicle in a liquid phase and exhibits a cationic property, so that it is efficiently adsorbed to a textile product in a laundry finishing process. Therefore, the fragrance | flavor in a softening agent composition tends to adhere to a textile product via a vesicle.

Furthermore, as a technique related to a perfume having a long lasting time, a technique for generating a perfume continuously by using an ester of a perfume alcohol has been proposed.
Specifically, Patent Document 3 discloses a method for aromatizing a fabric treated with a detergent and / or fabric softener containing an ester compound of a specific fragrant alcohol and a carboxylic acid having a specific alkyl group of C7 to C24. Is disclosed.
Patent document 4 relates to skin care and personal care, a fragrance precursor composition that exhibits odoriferous properties when it comes into contact with skin containing an odorant alcohol and an ester of an acid having an optionally substituted C1-C30 alkyl or the like. Things are disclosed.

  Further, Patent Document 5 discloses a gradual process that can be used for clothing that uses a mixture of a dibasic acid monoester and / or a dibasic acid diester with ethylene glycol or propylene glycol for the purpose of maintaining the aroma for a long time. A release fragrance composition is disclosed.

Japanese National Patent Publication No. 11-504994 JP 10-507793 A Japanese National Patent Publication No. 8-502522 JP 2000-512663 A JP 2003-313580 A

  As described above, the softener composition can enhance the adhesion of the fragrance to the fiber product, but when using a hydrophilic fragrance compound such as ethyl vanillin or ethyl maltol, these hydrophilic fragrance compounds are: Since it is a fragrance compound having a relatively high solubility in water, there is a problem in scent persistence and fiber adsorption when blended with a fragrance composition for a fiber treatment agent. Furthermore, when a perfume precursor with increased oiliness, which is an ester compound of a perfume compound and a fatty acid, is used, the perfume persistence is superior to the perfume compound itself, but the perfume persistence of the treated fiber product is further improved. Is required.

  The present invention provides a liquid softener composition capable of imparting excellent scent sustainability when a textile product is treated.

The present invention relates to a liquid softener composition containing the following component (A), component (B), and water, and having a pH at 30 ° C. of 2.5 or more and 5.0 or less.
<(A) component>
A quaternary ammonium salt compound represented by the following general formula (1), wherein when the acyl group is regarded as a fatty acid, the ratio of oleic acid, linoleic acid and linolenic acid constitutes the acyl group. Quaternary ammonium salt compound which is 60% by mass or more and 100% by mass or less of fatty acid

[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 (referred to as an acyl group) or a hydrogen atom, provided that R ¹ , R ² , and R ³ are acyl groups, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an anion. ]
<(B) component>
A fragrance precursor comprising an ester of a fragrance compound having a phenol structure or a hydroxy-4-pyrone structure and an aliphatic monocarboxylic acid having 8 to 18 carbon atoms or an aliphatic dicarboxylic acid having 3 to 20 carbon atoms.

  ADVANTAGE OF THE INVENTION According to this invention, when a textile product is processed, the liquid softening agent composition which can provide the persistence of the outstanding fragrance can be provided.

[Liquid softener composition]
The liquid softening agent composition of this invention contains (A) component, (B) component, and water, and pH in 30 degreeC is 2.5 or more and 5.0 or less. Hereinafter, each component will be described.

<(A) component>
The component (A) of the present invention is a quaternary ammonium salt compound represented by the following general formula (1). When the acyl group is regarded as a fatty acid, the ratio of oleic acid, linoleic acid and linolenic acid is And a quaternary ammonium salt compound that is 60% by mass or more and 100% by mass or less of the total fatty acid constituting the acyl group.

[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 (referred to as an acyl group) or a hydrogen atom, provided that R ¹ , R ² , and R ³ are acyl groups, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an anion. ]

  The fiber product processed with the liquid softening agent composition of this invention is excellent in the persistence of fragrance. The reason is not necessarily clear, but the quaternary ammonium salt compound of component (A) mainly composed of an acyl group derived from one or more fatty acids selected from oleic acid, linoleic acid and linolenic acid is liquid at room temperature. Therefore, it is easy to incorporate the component (B) into the vesicle, suppress the decomposition of the component (B) on the dried fiber product, and the component (B) is gradually decomposed to release the fragrance compound. As a result, it is estimated that the persistence of remaining scent increases.

In the component (A) of the present invention, the proportion of one or more selected from oleic acid, linoleic acid and linolenic acid in the total fatty acids constituting the acyl group is preferably 70% by mass or more, more preferably 75% by mass. % Or more, more preferably 80% by mass or more, still more preferably 85% by mass or more, and preferably 98% by mass or less, more preferably 95% by mass or less.
(A) component, after satisfying the condition of the ratio of this fatty acid, in the total fatty acid constituting the acyl group, the ratio of oleic acid is preferably 50% by mass or more, more preferably 60% by mass or more, More preferably, it is 65% by mass or more, and preferably 100% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.

  Examples of fatty acids other than oleic acid, linoleic acid, and linolenic acid that constitute the acyl group of component (A) include stearic acid, palmitic acid, and elaidic acid.

  Since the component (A) is a quaternized product of triethanolamine fatty acid ester, it is composed of three different quaternary compounds having an acylation degree of 1, 2 or 3. The average acylation rate of the component (A) is preferably 1.3 or more, more preferably 1.5 or more, preferably from the viewpoint of flexibility, storage stability of the composition, and persistence persistence. It is 0 or less, more preferably 1.95 or less. The average degree of acylation can be adjusted by the reaction ratio between the fatty acid and triethanolamine, the reaction ratio with the alkylating agent in the quaternization, and the reaction conditions.

In the present invention, the following ratios are preferable for each ratio constituting the component (A).
The proportion of the compound having an acylation degree of 1, that is, the compound (a1) [hereinafter referred to as component (a1)] in which R ¹ in the general formula (1) is an acyl group and R ² and R ³ are hydrogen atoms is In the total amount of the quaternary ammonium salt represented by the general formula (1), it is 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and 45% by mass or less, preferably 40% by mass. % Or less, more preferably 35% by mass or less,
The proportion of the compound having an acylation degree of 2, that is, the compound (a2) [hereinafter referred to as component (a2)] in which R ¹ and R ² in the general formula (1) are acyl groups and R ³ is a hydrogen atom is In the total amount of the quaternary ammonium salt represented by the general formula (1), it is 30% by mass or more, more preferably 35% by mass or more, preferably 40% by mass or more, and 75% by mass or less, preferably 70% by mass. % Or less, more preferably 65% by mass or less, and a compound having an acylation degree of 3, that is, a compound (a3) wherein R ¹ , R ² and R ^{3 in the} general formula (1) are acyl groups (hereinafter, ( a3) component] is 5% by mass or more, preferably 8% by mass or more, more preferably 10% by mass or more in the total amount of the quaternary ammonium salt represented by the general formula (1), and 40 % By mass, preferably 30% by mass Or less, more preferably 25% by mass.

  The component (a2) and the component (a3) are effective components for the softening effect and the adsorption of the fragrance precursor to the fiber product, but affect the storage stability of the liquid softening agent composition. Therefore, it is preferable that (A) component is a composition which left the (a1) component moderately. Furthermore, after satisfying the above ratio, the content of the component (a2) in the component (A) is larger than that of the component (a3), more preferably the content (mass%) of the component (a2). The difference from the content (% by mass) of the component (a3) is 15% by mass or more, preferably 20% by mass or more, more preferably 25% by mass or more.

In general formula (1), R ⁴ is preferably a methyl group or an ethyl group.
In the general formula (1), X ⁻ is a halogen ion, preferably a chloro ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, and an alkyl group having 1 to 3 carbon atoms substituted by 1 or more and 3 or less. An anion selected from benzenesulfonic acid ions that may be present is preferable, an alkyl sulfate ion having 1 to 3 carbon atoms is more preferable, and a methyl sulfate ion or an ethyl sulfate ion is more preferable.

  The component (A) used in the present invention is a method in which a ratio of oleic acid, linoleic acid and linolenic acid is subjected to a dehydration esterification reaction with fatty acid and triethanolamine (referred to as dehydration esterification method), The esterification reaction product obtained by the transesterification reaction of alkyl ester (lower alkyl is methyl group, ethyl group, propyl group) and triethanolamine (referred to as transesterification method) is quaternized with an alkylating agent. Can be obtained. In order to obtain a mixture satisfying the ratio of the components (a1) to (a3) of the component (A) of the present invention, for example, the molar ratio of fatty acid or fatty acid lower alkyl ester: triethanolamine is preferably 1.3: A mixture of triethanolamine fatty acid esters reacted at a ratio of 1 or more, more preferably 1.5: 1 or more, and 2.0: 1 or less, preferably 1.95: 1 or less is subjected to a quaternization reaction.

  When the selective hydrogenation reaction is carried out, a mixture of geometric isomers of unsaturated bonds is formed. In the present invention, the cis / trans is 25/75 to 100/0, preferably 50/50 to 95/5. (Molar ratio) is preferred.

  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. The progress of the reaction is preferably performed by directly quantifying the amount of the fatty acid lower alkyl ester using gas chromatography or the like. The amount of unreacted fatty acid lower alkyl ester is 10 on the gas chromatography chart with respect to the fatty acid lower alkyl ester charged. It is preferable to terminate the reaction at an area% or less, particularly 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 to 50% by mass with respect to the ester compound. The mixed solution is charged in 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 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 1 to 1.5 times equivalent of methyl chloride with respect to 1 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) 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 A reaction product containing 5 to 30 parts by mass with respect to 100 parts by mass of the component (A) 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). Furthermore, the triethanolamine and the quaternized product of triethanolamine which have not been fatty acid esterified are contained in a total of 0.5 to 3 parts by mass with respect to 100 parts by mass of the component (A), of which 90% by mass or more is 4%. It is a graded product. Unreacted fatty acids may also be included. When the reaction product containing the component (A) is used, such an unreacted component and side reaction component may be contained in the liquid softener composition as long as the effects of the present invention are not impaired.

  When a mixture containing the component (a1), the component (a2) and the component (a3) is used as the component (A), the proportion of the component (a1), component (a2), component (a3), amine compound, etc. in the mixture 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.

<(B) component>
The component (B) in the present invention includes a perfume compound having a phenol structure or a hydroxy-4-pyrone structure (hereinafter also referred to as “component (b1)”), and an aliphatic monocarboxylic acid having 8 to 18 carbon atoms [hereinafter referred to as “component”] , “(B2-1) component”] or an aliphatic dicarboxylic acid having 3 to 20 carbon atoms [hereinafter also referred to as “(b2-2) component”].

[(B1) component]
The component (b1) is a fragrance compound having a phenol structure or a hydroxy-4-pyrone structure.
In the present invention, the “perfume” refers to a substance that makes a scent feel, and refers to “fragrance”. A fragrance compound refers to an individual compound that constitutes a fragrance. A fragrance compound may be a fragrance.
The pKa of the fragrance compound having a phenol structure or a hydroxy-4-pyrone structure is preferably 13 or less, more preferably 12 or less, still more preferably 11.5 or less, from the viewpoint of developing a strong scent over a long period of time. And it is preferably 7 or more, more preferably 7.5 or more.
In the present invention, pKa is an acid dissociation constant, and is represented by a negative common logarithm pKa of an equilibrium constant Ka in a dissociation reaction in which hydrogen ions are released. A smaller pKa indicates a stronger acid. For the calculation of pKa in the present invention, SPARC (SPARC Performs Automated Reasoning In Chemistry, ARChem, http://www.archemcalc.com/sparc.html) is a chemical structure-physical property calculation site constructed on the Internet. Was used.

The perfume compound having a phenol structure has a carbon number of preferably 7 or more, more preferably 8 or more, still more preferably 9 or more, and preferably from the viewpoint of sustained release of the scent over a long period of time. 14 or less, more preferably 10 or less, still more preferably 9 or less, and even more preferably 9.
Specifically, vanillin (carbon number 8, pKa 7.8), ethyl vanillin (carbon number 9, pKa 7.8), iso-eugenol (carbon number 10, pKa 9.8), benzyl salicylate (carbon number 14, pKa 9. 8), cis-3-hexenyl salicylate (carbon number 13, pKa 9.8), vanillin PGA (carbon number 11, pKa 9.8), cyclohexyl salicylate (carbon number 13, pKa 10.0), eugenol (carbon number 10, pKa10) 0.0), Zingerone (11 carbon atoms, pKa 10.0), Banitrop (11 carbon atoms, pKa 10.0), Raspberry ketone (10 carbon atoms, pKa 10.1), Methyl salicylate (8 carbon atoms, pKa 10.1), salicylic acid Hexyl (13 carbon atoms, pKa 10.1), Carvacrol (10 carbon atoms, pKa 10.5) And thymol (10 carbon atoms, pKa10.9) can be mentioned.

The fragrance compound having a hydroxy-4-pyrone structure preferably has 6 or more carbon atoms, more preferably 7 or more carbon atoms, and preferably 10 or less, more preferably 7 or less, and further 7. preferable. When the carbon number is within the above range, the scent can be gradually released over a long period of time.
Specific examples include maltol (carbon number 6, pKa11.2) and ethyl maltol (carbon number 7, pKa11.3).

Among the components (b1), the flavor selected from maltol, ethyl maltol, vanillin, ethyl vanillin, and raspberry ketone from the viewpoint of improving the storage stability of the softener composition and improving the sustained release performance. A compound is preferable, and a fragrance compound selected from ethyl maltol and ethyl vanillin is more preferable.
These fragrance | flavor compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

[Aliphatic monocarboxylic acid]
[(B2-1) component]
The component (b2-1) is an aliphatic monocarboxylic acid having 8 to 18 carbon atoms.
By using an aliphatic monocarboxylic acid having a carbon number within the above range, in the liquid softener composition, the ester bond part of the component (B) is less likely to come into contact with water, and the progress of hydrolysis is suppressed. The storage stability of the agent composition is improved. Thereby, the change of the liquid color of a liquid softening agent composition can be suppressed.
The number of carbon atoms of the aliphatic monocarboxylic acid is 8 or more, preferably 10 or more, more preferably 11 or more, still more preferably 12 or more, and molecular weight as much as possible from the viewpoint of improving the storage stability in the liquid softening agent composition. From the viewpoint of efficiently blending the component (B) and reducing the initial perfume, it is 18 or less, preferably 16 or less, more preferably 14 or less, still more preferably 12 or less, and 12 Is even more preferable.

Specific examples of the aliphatic monocarboxylic acid include enanthic acid, caprylic acid, verargonic acid, capric acid, undecyl acid, lauric acid, tridecyl acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, dimethyloctanoic acid And aliphatic monocarboxylic acids such as octenoic acid, decenoic acid, dodecenoic acid, tetradecenoic acid, hexadecenoic acid, oleic acid, vaccenic acid, linoleic acid, and linolenic acid.
In the present invention, from the viewpoint of efficiently blending the component (B) by reducing the molecular weight as much as possible, and from the viewpoint of initial perfume, among these, lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid Are preferred, and lauric acid, stearic acid, and oleic acid are more preferred.

[(B2-2) component]
The component (b2-2) is an aliphatic dicarboxylic acid having 3 to 20 carbon atoms.
By using an aliphatic dicarboxylic acid having a carbon number within the above range, in the liquid softener composition, the ester bond portion of the component (B) is less likely to come into contact with water, and the progress of hydrolysis is suppressed. The storage stability of the composition is improved. Thereby, the change of the liquid color of the product in a liquid softening agent composition can be suppressed.
The number of carbon atoms of the aliphatic dicarboxylic acid is 3 or more, preferably 6 or more, more preferably 8 or more, still more preferably 9 or more, and still more preferably 10 or more, from the viewpoint of improving the storage stability of the liquid softener composition. From the viewpoint of efficiently blending the component (B) by reducing the molecular weight as much as possible and from the viewpoint of initial perfume, it is 20 or less, preferably 16 or less, more preferably 14 or less, and even more preferably 12 or less. .
Specific examples of the aliphatic dicarboxylic acid include aliphatic dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. It is done.
In the present invention, from the viewpoint of efficiently blending the component (B) by reducing the molecular weight as much as possible and from the viewpoint of initial perfume, among these, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedi Acids are preferred, adipic acid and sebacic acid are more preferred, and sebacic acid is even more preferred.

  (B) As a component, the fragrance | flavor precursor which consists of an ester compound of (b1) component and (b2-1) component is preferable.

[Method for producing component (B)]
Component (B) can be produced, for example, by the following methods (i) to (iv).
(I) A method for producing the fragrance compound by directly esterifying the aliphatic monocarboxylic acid or aliphatic dicarboxylic acid (ii) methanol or the like with respect to the aliphatic monocarboxylic acid or aliphatic dicarboxylic acid (Iii) reacting the perfume compound with an acid halide of the aliphatic monocarboxylic acid or aliphatic dicarboxylic acid. (Iv) A method of producing by reacting the fragrance compound with the aliphatic monocarboxylic acid or an aliphatic dicarboxylic acid anhydride Among these, from the viewpoint of production efficiency, the above (iii) Produced by reacting a perfume compound with the aliphatic monocarboxylic acid or aliphatic dicarboxylic acid halide That process is preferred.

(Acid halide)
Examples of the acid halide of the aliphatic monocarboxylic acid or aliphatic dicarboxylic acid include various kinds of the aliphatic monocarboxylic acid or aliphatic dicarboxylic acid and thionyl chloride, phosphorus trichloride, phosphorus pentachloride and phosphorus tribromide. It can be obtained by reaction with a halogenating reagent.
Among these, from the viewpoint of reactivity and the availability of reagents, acid halides obtained by reaction of aliphatic monocarboxylic acids or aliphatic dicarboxylic acids with phosphorus trichloride are preferred. Preferred are the acid chlorides of the group monocarboxylic acids.

(Amount of fragrance compound charged)
(B) The amount of the fragrance compound charged when the component is produced is an aliphatic monocarboxylic acid from the viewpoint of promptly advancing the reaction and reducing the amount of unreacted aliphatic monocarboxylic acid or aliphatic dicarboxylic acid. Or 0.9 mol or more, more preferably 0.95 mol or more, still more preferably 0.98 mol or more, based on 1 mol of the acid halide of the aliphatic dicarboxylic acid, and the amount of the unreacted fragrance compound. From the viewpoint of reducing, it is preferably 1.1 mol or less, more preferably 1.05 mol or less, and still more preferably 1.02 mol or less.

(solvent)
(B) There is no restriction | limiting in particular as a solvent used for manufacture of component, For example, halogenated hydrocarbons, such as chloroform and a dichloromethane, ethyl acetate, aliphatic esters, such as isopropyl acetate, benzene, toluene, xylene, ethylbenzene, etc. Examples include aromatic hydrocarbons, cyclopentane, cyclohexane, methylcyclohexane, decalin, and alicyclic hydrocarbons such as tetralin, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane.
Among these, from the viewpoint of solubility of the fragrance compound, the aliphatic monocarboxylic acid and the aliphatic dicarboxylic acid, one or more selected from halogenated hydrocarbons, aliphatic esters, and aromatic hydrocarbons are preferable, One or more selected from dichloromethane, ethyl acetate, and toluene are more preferable. These solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

(Reaction temperature)
The reaction temperature for producing the component (B) is preferably not higher than the boiling points of all the compounds of the fragrance compound, the aliphatic monocarboxylic acid or the aliphatic dicarboxylic acid from the viewpoint of performing the reaction without losing the raw materials. The specific reaction temperature is preferably −20 ° C. or higher, more preferably −18 ° C. or higher, still more preferably −15 ° C. or higher, and still more preferably −12 ° C. or higher, from the viewpoint of improving the reaction rate. Moreover, from a viewpoint of controlling reaction, Preferably it is 50 degrees C or less, More preferably, it is 40 degrees C or less, More preferably, it is 30 degrees C or less, More preferably, it is 20 degrees C or less.
In the present invention, it is preferable to perform stirring at a predetermined temperature and time from the viewpoint of sufficiently proceeding the reaction after the reaction in the temperature range. The temperature at the time of stirring is preferably 10 ° C or higher, more preferably 15 ° C or higher, still more preferably 20 ° C or higher, and preferably 90 ° C or lower, more preferably 80 ° C or lower, still more preferably 70 ° C or lower. More preferably, it is 60 ° C. or less, and further more preferably 50 ° C. or less.
Stirring is preferably performed for 0.5 hours or longer, more preferably 0.8 hours or longer, and preferably 4 hours or shorter, more preferably 3 hours or shorter, and even more preferably 1.5 hours or shorter.

(Reaction pressure)
Component (B) can be produced under atmospheric pressure or reduced pressure, and is preferably produced under atmospheric pressure from the viewpoint that it can be produced with simple equipment.
The specific pressure at the time of manufacturing (B) component becomes like this. Preferably it is 80 kPa or more, More preferably, it is 90 kPa or more, More preferably, it is 95 kPa or more, and Preferably it is 101 kPa or less.
In addition, the production of the component (B) is preferably performed in the presence of an inert gas from the viewpoint of suppressing side reactions and from the viewpoint of suppressing water from being mixed into the reaction system. Examples of the inert gas include nitrogen, helium, argon and the like. Among these, nitrogen is preferable from the viewpoint of manufacturing at a reduced cost.

(Basic substance)
In the manufacturing method of the said (B) component, it is preferable to use a basic substance from a viewpoint of performing reaction efficiently.
Examples of the basic substance include aliphatic amines such as triethylamine and tributylamine, aromatic amines such as pyridine and picoline, and DBU (diazabicycloundecene). Among these, aliphatic amines are preferable and triethylamine is more preferable from the viewpoints of availability and handling.
The amount of the basic compound used is preferably 1 mol or more, more preferably 1.01 mol or more, still more preferably 1.02 with respect to 1 mol of the aliphatic monocarboxylic acid or aliphatic dicarboxylic acid halide. Mol or more, more preferably 1.04 mol or more, and preferably 1.2 mol or less, more preferably 1.15 mol or less, still more preferably 1.1 mol or less, from the balance of the amount used and cost. More preferably, it is 1.06 mol or less.

<Content of (A) component and (B) component>
In the liquid softener composition of the present invention, the content of the component (A) is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass from the viewpoint of obtaining a sufficient softening effect. From the viewpoint of storage stability, it is preferably 20% by mass or less, more preferably 16% by mass or less, still more preferably 14% by mass or less, still more preferably 12% by mass or less, and still more preferably 10%. It is below mass%.

  In the liquid softener composition of the present invention, the content of the fragrance precursor as the component (B) is preferably 0.001% by mass or more, more preferably 0.005, from the viewpoint of improving the scent sustainability. It is at least 0.01% by mass, more preferably at least 0.01% by mass, and preferably at most 1.0% by mass, more preferably at most 0.8% by mass, even more preferably at most 0.7% by mass.

  The liquid softening agent composition of the present invention contains 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.

<PH at 30 ° C. of liquid softener composition>
The pH at 30 ° C. of the liquid softener composition of the present invention is 2.5 or more and 5.0 or less. From the viewpoint of the fragrance and residual fragrance of the fiber product after treatment with the liquid softener composition, and storage stability. From the viewpoint of safety, it is preferably 2.5 or more, more preferably 2.7 or more, still more preferably 2.9 or more, and preferably 4.5 or less, more preferably 4.0 or less, even more preferably 3 .5 or less.

  The pH is measured at 30 ° C. according to “JIS K 3362; 2008, item 8.3. The pH can be adjusted with a pH adjusting agent such as an alkali agent or an acid agent described later.

<Viscosity of liquid softener composition at 30 ° C.>
The viscosity at 30 ° C. of the liquid softener composition of the present invention is preferably 5 mPa · s or more, more preferably 8 mPa · s or more, further preferably 10 mPa · s or more, and preferably from the viewpoint of ease of use. It is 150 mPa · s or less, more preferably 130 mPa · s or less, and still more preferably 110 mPa · s or less. The viscosity of the liquid softener composition was measured using a B-type viscometer. 1-No. Using one of the three rotors, the indicated value is 1 minute after the start of measurement at 60 r / min. The liquid softener composition is measured by adjusting the temperature to 30 ± 1 ° C. When the measurement area of the viscometer is obtained with two rotors and the converted viscosity is different, the data with the smaller rotor number is adopted.

The liquid softener composition of the present invention preferably further contains the following components.
<(C) component: perfume compound>
The liquid softening agent composition of this invention may contain a fragrance | flavor compound as (C) component.
The fragrance compound of component (C) is a fragrance compound other than the fragrance compound used in the fragrance compound forming a bond as the fragrance precursor of component (B) and the sustained-release fragrance or capsule fragrance of component (N) described later. Means a compound.
Therefore, even if the fragrance compound is the same as the fragrance compound used as the raw material of the component (B), the fragrance compound that does not form a bond as the fragrance precursor of the component (B) is treated as the component (C). That is, the fragrance compound of the component (C) is a fragrance compound dispersed in the liquid softening agent composition, and these fragrance compounds are sometimes referred to as outer fragrances.

There is no restriction | limiting in particular in the fragrance | flavor compound which can be used as (C) component, You may use the same fragrance | flavor compound as the fragrance | flavor compound used as a raw material of (B) component.
Examples of the fragrance compound that can be used as the component (C) include the fragrance compounds described in “Basic knowledge of fragrance and fragrance, edited by Motoki Nakajima, published by Sangyo Tosho Co., Ltd., April 20, 2005” In addition to the fragrance compounds known to be incorporated into softeners through patent documents and the like, a fragrance ingredient or a fragrance composition prepared by a fragrance manufacturer can be used.
For example, β-ionone (3.7), γ-undecalactone (3.8), γ-nonalactone (2.8), γ-methylionone (4.0), ambroxan (5.3), isoE Super (4.7), ethyl vanillin (1.8), ethylene brushylate (4.6), eugenol (3.0), cachemelan (manufactured by IFF) (4.0), coumarin (1.5), Geraniol (2.4), o, t-butylcyclohexyl acetate (4.1), citronellyl acetate (4.2), dimethylbenzylcarbyl acetate (2.8), sandalmysol core (3.9), dihydrojasmon Acid methyl (2.4), dihydromyrcenol (3.0), dimethyltetrahydrobenzaldehyde (2.9), jabanol (manufactured by dibodan) (4.7), nerolin yarayara (3.2) Havanolide (Filmenich) (6.2), Frutate (Kao Corporation) (3.4), Peonyl (Divodan) (4.0), Hexylcinnamic aldehyde (4.9), Heliotropin (1. 1), methyl β-naphthyl ketone (2.8), methyl anthranilate (2.0), raspberry ketone (1.1), limonene (4.4), and lyial (3.9). . The numerical value in () is a logP value.

In addition, the liquid softening agent composition of this invention may contain the diluent and retention agent of a fragrance | flavor compound. Examples of the diluent and the retaining agent include dipropylene glycol, isopropyl palmitate, diethyl phthalate, pendyl benzoate, liquid paraffin, isoparaffin, and oil.
When the diluent and the retention agent are used, the amount of the diluent and the retention agent with respect to the total of the component (C), the diluent and the retention agent is preferably 0% by mass or more and 20% by mass or less.

  By using the component (C) in combination with the component (B), it is possible to design a fragrance with a higher degree of freedom than before. Accordingly, when the liquid softener composition of the present invention combined with the component (C) is treated on a fiber product, for example, a fresh and rich scent can be imparted.

  When the liquid softening agent composition of the present invention contains the component (C), the content thereof is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass. From the viewpoint of storage stability and balance with other fragrance additives, it is preferably 2.0% by mass or less, more preferably 1.8% by mass or less, and even more preferably 1.5% by mass or less. is there. In addition, (C) component in a liquid softening agent composition can adjust the content according to a product.

In the case where the liquid softener composition of the present invention contains the component (C), the total content of the component (B) and the component (C) is from the viewpoint of sufficiently perfume the fiber product. Preferably it is 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more, and preferably 2 from the viewpoint of storage stability and balance with other fragrance additives. 0.5% by mass or less, more preferably 2% by mass or less, and still more preferably 1.5% by mass or less.
In addition, the mass of (B) component in the said total content is calculated by the mass of the fragrance | flavor compound which comprises the fragrance | flavor precursor of (B) component.

<(D) component: Cationic surfactant other than (A) component>
In the present invention, a cationic surfactant other than the component (A) may be contained as the component (D).
The component (D) is preferably an amine compound or a quaternary ammonium salt compound having one or more hydrocarbon groups having 8 to 22 carbon atoms other than cyclic.
The amine compound may be an unreacted amine compound that has not been quaternized and remains during the preparation of the component (A).
Further, from the viewpoint of giving excellent flexibility and suppressing the unsaturated fatty acid odor of the component (A), the component (D) is a quaternary ammonium compound represented by the general formula (1), and constitutes an acyl group. A quaternary ammonium salt compound obtained in the same manner is preferable except that the fatty acid composition is different. Specifically, it is a quaternary ammonium salt compound represented by the following general formula (D1), and when the acyl group is regarded as a fatty acid, the proportion of unsaturated fatty acids is all that constitutes the acyl group. The quaternary ammonium salt compound which is 50 mass% or less of a fatty acid, and also 40 mass% or less is preferable. The lower limit of the proportion of unsaturated fatty acids in the quaternary ammonium salt compound may be 10% by mass or more of the total fatty acids constituting the acyl group.

[Wherein, R ^1d , R ^2d and R ^3d are each independently a residue obtained by removing OH from a fatty acid having 16 to 22 carbon atoms (referred to as an acyl group) or a hydrogen atom, provided that R ^1d , R ^2d , and R ^3d are acyl groups, R ^4d is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an anion. ]

The fatty acid constituting the acyl group of R ^1d , R ^2d , and R ^3d is obtained by saponifying a fat selected from beef tallow, palm oil, sunflower oil, soybean oil, rapeseed oil, safflower oil, cottonseed oil, corn oil, and olive oil. The fatty acid composition obtained from beef tallow, palm oil and sunflower oil is particularly preferable from the viewpoint of softness performance. 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.

As specific examples of the other component (D), one or two of the groups bonded to the nitrogen atom that enhance the storage stability of the liquid softener composition is an alkyl group or an alkenyl group having 10 to 22 carbon atoms. A tertiary amine compound which is an alkyl group having 1 to 4 carbon atoms which may have a hydroxy group, a benzyl group, preferably a methyl group, and its acid salt, and the tertiary amine compound, Quaternized products are mentioned. Among these, from the viewpoint of imparting a bactericidal effect to the liquid softener composition, a cationic surfactant having one alkyl group or alkenyl group having 10 to 22 carbon atoms and one benzyl group is preferable. .
As the alkylating agent used for the quaternization of the compound, the compounds described in the component (A) can be used.

Examples of the component (D) include one or more cationic surfactants selected from the following (I) to (III).
(I) Di-long-chain alkyl or alkenyldimethylammonium salt having an alkyl group or alkenyl group having 10 to 22 carbon atoms (II) Mono-long-chain alkyl or alkenyltrimethyl having an alkyl group or alkenyl group having 10 to 22 carbon atoms Ammonium salt (III) Mono-long chain alkyldimethylbenzylammonium salt having 10 to 22 carbon atoms of alkyl group or alkenyl group, specifically, didecyldimethylammonium chloride salt, lauryltrimethylammonium chloride salt, myristyltrimethylammonium chloride salt, And lauryldimethylbenzylammonium chloride salt.

When the liquid softening agent composition of this invention contains (D) component, the content becomes like this. Preferably it is 0.5 mass% or more, More preferably, it is 1 mass% or more, More preferably, it is 2 mass% or more. From the viewpoint of storage stability, it is preferably 20% by mass or less, more preferably 18% by mass or less, still more preferably 16% by mass or less, and still more preferably 14% by mass or less.
Furthermore, the liquid softening agent composition of the present invention comprises (A) component and (D) component in total, preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 18% by mass or less. To do.

  Moreover, the liquid softening agent composition of this invention WHEREIN: When using (D) component together, Furthermore, when using together the quaternary ammonium salt compound shown by the said general formula (D1), (A) with respect to (D) component The ratio of components, that is, (A) / (D) is preferably 0.05 or more, more preferably 0.06 or more, still more preferably 0.1 or more, still more preferably 0.5 or more, and by mass ratio, Preferably it is 20 or less, More preferably, it is 15 or less, More preferably, it is 10 or less, More preferably, it is 5 or less.

<(E) component: nonionic surfactant>
The liquid softening agent composition of the present invention may contain a nonionic surfactant as the component (E). However, the (F) component described later is excluded from the (E) component.

(E) As a component, the nonionic surfactant which has a C8-C20 alkyl group or an alkenyl group, and an oxyalkylene group is preferable, and the nonionic surfactant represented by the following general formula (E1) An agent is more preferable.
^R1e- A-[( ^R2eO ) _x- ^R3e ] _y (E1)
[Wherein R ^1e is an alkyl group or an alkenyl group having 8 or more, preferably 10 or more carbon atoms, and preferably 18 or less, and R ^2e is an alkylene group having 2 or 3 carbon atoms. , Preferably an ethylene group, R ^3e is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, x is 2 or more, preferably 5 or more, more preferably 10 or more, and 100 or less, Preferably, the number is 80 or less, more preferably 60 or less, A is —O—, —COO—, —CON <or —N <, and y is 1 when A is —O— or —COO—. Yes, y is 2 when A is -CON <or -N <. ]

Specific examples of the compound of the general formula (E1) include compounds represented by the following formulas (E1-1) to (E1-3).
R ^1e —O— (C ₂ H ₄ O) _k —H (E1-1)
[In formula, R ^{< 1e>} is synonymous with said R ^<1e> . k is a number of 8 or more, preferably 10 or more, and 100 or less, preferably 60 or less. ]
_{^{R 1e -O - [(C 2}} H 4 O) s / (C 3 H 6 O) t] -H (E1-2)
[In formula, R ^{< 1e>} is synonymous with said R ^<1e> . s and t are each independently 2 or more, preferably 5 or more, and a number of 40 or less, and (C ₂ H ₄ O) and (C ₃ H ₆ O) are random or block adducts. Also good. “/” Is a symbol indicating that the order of bonding of (C ₂ H ₄ O) and (C ₃ H ₆ O) is not important. ]

(In the formula, R ^1e and R ^3e have the above-mentioned meanings. 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 5 or more and 60 or less. The number is preferably 40 or less.)

In this invention, it is preferable to use the nonionic surfactant represented by general formula (E1-1) as (E) component.
Since the component (E) can reduce the viscosity of the liquid softener composition, it can facilitate the production from mixing to filling of each component of the liquid softener composition. The stability of the component (B) and the component (C) in the product can be improved.

  When the liquid softener composition of the present invention contains the component (E), the content is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and the liquid softener composition From the viewpoint of suppressing the thickening of the product after long-term storage, it is preferably 8% by mass or less, more preferably 5% by mass or less.

<(F) component: ester of polyhydric alcohol and fatty acid>
The liquid softening agent composition of the present invention may contain an ester of a polyhydric alcohol and a fatty acid as the component (F) from the viewpoint of improving storage stability.
The ester of a polyhydric alcohol and a fatty acid is preferably an ester compound of a polyhydric alcohol having 3 to 6 carbon atoms and having 3 to 6 carbon atoms and a fatty acid having 12 to 22 carbon atoms.
More specifically, the carbon number is preferably 3 or more, more preferably 4 or more, and preferably 6 or less, and preferably 3 or more, more preferably 4 or more, and Preferably a polyhydric alcohol having a valence of 6 or less, and a fatty acid having a carbon number of preferably 12 or more, more preferably 14 or more, still more preferably 16 or more, and preferably 22 or less, more preferably 20 or less. It is an ester compound.

As the polyhydric alcohol constituting the component (F), 1 selected from glycerin, trimethylolethane, trimethylolpropane, 1,3,5-pentatriol, erythritol, arabitol, pentaerythritol, sorbitan, sorbitol, xylitol and mannitol. One or more species are preferred, and one or more species selected from pentaerythritol and sorbitan are more preferred.
As the fatty acid constituting the component (F), saturated fatty acids such as lauric acid, myristic acid, stearic acid, and palmitic acid, unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, and linolenic acid, palm oil fatty acid, And one or more selected from fatty acids derived from vegetable oils, such as fatty acids derived from vegetable oils, beef tallow fatty acids and hardened beef tallow fatty acids, and one selected from saturated fatty acids, fatty acids derived from vegetable oils, and fatty acids derived from animal oils. The above is more preferable, and at least one selected from stearic acid, hardened palm oil fatty acid, and hardened beef tallow fatty acid is more preferable.

  As the component (F) in the present invention, an ester compound of pentaerythritol and a fatty acid having 16 to 22 carbon atoms (hereinafter, also referred to as “pentaerythritol fatty acid ester”), sorbitan and a fatty acid having 16 to 22 carbon atoms, 1 type or more chosen from these ester compounds (henceforth "sorbitan fatty acid ester") is preferable.

  When the liquid softening agent composition of this invention contains (F) component, the content becomes like this. Preferably it is 0.1 mass% or more, More preferably, it is 0.3 mass% or more, More preferably, it is 0.5 mass%. More preferably, it is 0.7% by mass or more, and preferably 5.0% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less.

<(G) component: amphoteric surfactant>
The liquid softening agent composition of this invention can contain an amphoteric surfactant as (G) component.
(G) There will be no restriction | limiting in particular as long as it can mix | blend with a liquid softening agent composition generally, For example, alkyl (C12-C22) amidopropyl carbobetaine, alkyl (carbon number) 12 to 22) amidopropylsulfobetaine, alkyl (C12 to 22) carbobetaine, alkyl (C12 to 22) sulfobetaine, alkyl (C10 to 18) dimethylamine oxide, and the like. .

  When the liquid softener composition of the present invention contains the component (G), the content is preferably 0.01 mass from the viewpoint of reducing the viscosity of the liquid softener composition and improving the bactericidal properties. % Or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and preferably 2.0% by mass or less from the viewpoint of suppressing storage stability and a decrease in flexibility effect. More preferably, it is 1.5 mass% or less, More preferably, it is 1.0 mass% or less.

<(H) component: inorganic salt>
The liquid softening agent composition of the present invention can contain an inorganic salt as the component (H) from the viewpoint of improving storage stability.
The inorganic salt is preferably at least one selected from sodium chloride, calcium chloride, and magnesium chloride from the viewpoint of improving storage stability.
When the liquid softener composition of the present invention contains the component (H), the content is preferably 0.01% by mass or more, more preferably from the viewpoint of improving the storage stability of the liquid softener composition. 0.05% by mass or more, more preferably 0.1% by mass or more, and from the viewpoint of preventing aggregation of component (B), preferably 2.0% by mass or less, more preferably 1.0% by mass or less. It is.

<(I) component: silicone compound>
The liquid softener composition of the present invention may contain a silicone compound as a component (I) and further a water-insoluble silicone compound. In the present specification, “water-insoluble” of the component (I) means that the amount of the silicone compound dissolved in 1 L of ion-exchanged water at 20 ° C. is 1 g or less.
Specific examples of the component (I) include dimethylpolysiloxane, quaternary ammonium-modified dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amide-modified dimethylpolysiloxane, epoxy-modified dimethylpolysiloxane, carboxy-modified dimethylpolysiloxane, and polyoxyalkylene-modified. Examples thereof include silicone compounds such as dimethylpolysiloxane and fluorine-modified dimethylpolysiloxane.

The component (I) is selected from dimethylpolysiloxane, amino-modified dimethylpolysiloxane, amide-modified dimethylpolysiloxane, and polyoxyalkylene (polyoxyethylene and / or polyoxypropylene, preferably polyoxyethylene) -modified dimethylpolysiloxane. One or more selected from the above are preferred. The weight average molecular weight of these silicone compounds 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. These viscosity at 25 ° C. of the silicone compound 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.
In addition, the weight average molecular weight in (I) component is the value which measured polystyrene as the standard substance by the gel permeation chromatography method.

  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.

  When the liquid softener composition of the present invention contains (I) component, the mass ratio of (A) component to (I) component [(A) component / (I) component] is preferably 1/10 or more, More preferably, it is 1/5 or more, more preferably 1/3 or more, and preferably 60/1 or less, more preferably 50/1 or less.

  When the liquid softener composition of the present invention contains the component (I), the content is preferably 0.1% by mass or more, more preferably 0, from the viewpoint of giving a refreshing feeling as a finished feeling of the textile product. From the viewpoint of dispersibility, it is preferably 5% by mass or less.

<(J) component: acid agent>
The liquid softening agent composition of the present invention can contain an acid agent as the component (J) from the viewpoint of adjusting the pH of the liquid softening agent composition.
Examples of the acid agent include inorganic acids and organic acids, and specific examples of inorganic acids 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, a monovalent or polyvalent sulfonic acid having 1 to 20 carbon atoms, and an alkyl sulfuric acid having 1 to 3 carbon atoms. Is mentioned. More specifically, methyl sulfuric acid, ethyl sulfuric acid, p-toluenesulfonic acid, (o-, m-, p-) xylenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, glycolic acid, ethylenediaminetetraacetic acid, citric acid , Benzoic acid, and salicylic acid.
Among these, monovalent or polyvalent carboxylic acids having 1 to 10 carbon atoms are preferable, and citric acid is more preferable.
When the liquid softener composition of the present invention contains an acid agent, the content can be appropriately adjusted depending on the type and amount of the component (A), and the pH is in the above range, and the storage stability The degree which does not impair the property is preferable.

<(K) component: fatty acid>
The liquid softener composition of the present invention may contain a fatty acid as the component (K) in addition to the fatty acid as the component (J) from the viewpoint of improving the softening effect.
The fatty acid may be contained as an unreacted product during the synthesis of the component (A) or a decomposition product of the component (A).
Specific examples of fatty acids are preferably saturated or unsaturated fatty acids 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. More preferred are fatty acids selected from palmitic acid, stearic acid, oleic acid and linoleic acid.

<(L) component: Water-soluble organic solvent>
The liquid softening agent composition of the present invention can contain a water-soluble organic solvent as the component (L) from the viewpoint of storage stability and viscosity.
As a water-soluble organic solvent, the general water-soluble organic solvent used for a liquid softening agent composition is mentioned. The “water-soluble organic solvent” in component (L) refers to an organic solvent that dissolves 20 g or more in 100 g of deionized water at 20 ° C.
Specific examples of the water-soluble organic solvent include propylene glycol, ethylene glycol, glycerin, diethylene glycol, monoethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, isopropanol, and ethanol. Among these, ethylene glycol and ethanol are preferable.

When the liquid softening agent composition of the present invention is sufficiently stabilized by other components and has a low viscosity, the water-soluble organic solvent as the component (L) may not be contained.
When the liquid softening agent composition of this invention contains (L) component, the content becomes like this. Preferably it is 15 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less.

<(M) component: chelating agent>
In the liquid softener composition of the present invention, it is preferable to use a chelating agent as the component (M) from the viewpoint of suppressing the hue change during long-term storage of the liquid softener composition and the discoloration and fragrance alteration of the dye. The component (M) in the present invention also has a function as the acid agent.
Specific examples of the chelating agent include ethane-1-hydroxy-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminedisuccinic acid, L-glutamic acid-N, N-bis Examples include acetic acid, N-2-hydroxyethyliminodiacetic acid, citric acid, succinic acid, and salts thereof.
As a salt, an alkali metal salt and an ammonium salt are preferable, and a sodium salt and a potassium salt are more preferable.
When the liquid softening agent composition of the present invention contains the component (M), the content is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, and preferably 2% by mass. % Or less, more preferably 1.5% by mass or less, and still more preferably 1.0% by mass or less. In addition, when the component applicable to (M) component is used as an acid agent of (J) component, the amount shall be handled as the amount of (M) component.

<(N) component: sustained release flavor or capsule flavor>
In addition to the component (C), the liquid softener composition of the present invention includes a silicate compound described in JP-A No. 2014-125665 as a sustained-release fragrance and JP-A No. 2015-200047 as a capsule fragrance. The microcapsule perfume can be used. When the component (N) is used in the liquid softening agent composition of the present invention, it is used in accordance with the characteristics of each fragrance component.

<(O) component: other components>
In the liquid softener composition of the present invention, an antioxidant such as BTH can be used from the viewpoint of suppressing deterioration of the substrate, and from the viewpoint of preventing coloring during aesthetics and long-term storage, the liquid softener Dyes and pigments generally used in the composition can also be used. Furthermore, antibacterial and antifungal agents marketed under the trade name of Proxel can also be used.

  The liquid softening agent composition of the present invention is suitable for textile products, and examples of the textile products include clothing, fabrics, bedding, towels and the like.

  The components used in the examples are shown below.

<(A) component>
(A-1): Quaternary ammonium salt compound produced in Synthesis Example a-1 below [Synthesis Example a-1: Production of (a-1)]
Triethanolamine and a fatty acid represented by RCOOH (the composition is as described later) are esterified with a reaction molar ratio (fatty acid / triethanolamine) of 1.87 / 1, and represented by the general formula (1). An esterification reaction product containing an amine compound which is a precursor of the compound obtained was obtained.
The esterification reaction product contained 1% by mass of unreacted fatty acid. After the quaternization reaction was performed with dimethyl sulfate so that the methyl group was 0.96 equivalent to the amine of the amine compound in the esterification reaction product, ethanol was added.

As a result of analyzing the composition ratio of each component of the obtained reaction product by HPLC and using tetraoctylammonium bromide as an internal standard substance, the obtained reaction product was component (A) (a- 1) Contains 66% by mass of component, 15% by mass of ethanol, 17% by mass of unreacted amine salt (as methyl sulfate), 1% by mass of unreacted fatty acid, a trace amount of triethanolamine quaternized product and other trace components, Among them, in general formula (1), R ¹ is an acyl group, R ² and R ³ are hydrogen atoms, R ⁴ is a methyl group, and X ⁻ is methyl sulfate [hereinafter (a1-1 ) In the general formula (1), R ¹ and R ² are acyl groups, R ³ is a hydrogen atom, and R ⁴ is a methyl group. compound is methyl sulfate ^- there are, X Product [hereinafter sometimes referred to as (a2-1)] is 58% by mass in component (a-1), and in general formula (1), R ¹ , R ² and R ³ are acyl groups, and R ⁴ is methyl. The compound, which is a group and X ⁻ is methylsulfuric acid (hereinafter may be referred to as (a3-1)), was 20% by mass in the component (a-1). The quaternization rate was 80% by mass.

In addition, the composition of RCOOH used for reaction for manufacturing (a-1) is shown below.
Oleic acid: 80% by mass
Linoleic acid: 10% by mass
Linolenic acid: 2% by mass
Stearic acid: 2% by mass
Palmitic acid: 6% by mass
The composition was analyzed for the fatty acid used as a raw material by gas chromatography, and the area% of each fatty acid was regarded as mass%.
In addition, the numerical value of Table 2 is converted into (a-1) component density | concentration.

<(B) component>
(B-1): Ester of lauric acid and ethyl vanillin produced in Synthesis Example b-1 below [Synthesis Example b-1: Production of ester of lauric acid and ethyl vanillin]
Under a nitrogen atmosphere, 8.95 g (0.041 mol) of lauric acid chloride and 40 mL of dichloromethane were placed in a 300 mL four-necked flask and cooled to 0 ° C. On the other hand, 6.80 g (0.041 mol) of ethyl vanillin, 4.35 g (0.043 mol) of triethylamine, and 40 mL of dichloromethane were placed in a 100 mL dropping funnel. The reaction temperature was dropped from the dropping funnel over 40 minutes so that the reaction temperature was maintained at -5 ° C to 0 ° C. After completion of dropping, the mixture was stirred at room temperature (25 ° C.) for 2 hours. 10 mL of saturated aqueous ammonium chloride solution was added to the flask to stop the reaction. 150 mL of diethyl ether was added, the produced white solid was removed by filtration, and the filtrate was transferred to a separatory funnel. 100 mL of ion-exchanged water was added to the separatory funnel, and extraction from the aqueous layer was performed 3 times with 50 mL of diethyl ether. The extracted solution was collected, washed with saturated brine, and the solution was dried over sodium sulfate. After removing the solvent under reduced pressure, 14.20 g (99% yield) of a pale yellow solid lauric acid and ethyl vanillin ester was obtained.

The measurement results of NMR and IR are shown below.
NMR (1H, 400MHz)
0.88 (t, J = 7 Hz, 3H), 1.20-1.50 (m, 19H), 1.78 (quant., J = 7 Hz, 2H), 2.59 (t, J = 7 Hz, 2H), 4.13 (t, J = 7 Hz, 2H), 7.20 (d, J = 8 Hz, 1H), 7.46 (d, J = 8 Hz, 2H), 9.93 (s, 1H)
IR (KBr): 2918, 2850, 1763, 1693, 1273, 1115, 742 cm ⁻¹

(B-2): ester of lauric acid and ethyl maltol produced in Synthesis Example b-2 below [Synthesis Example b-2: production of ester of lauric acid and ethyl maltol]
Under a nitrogen atmosphere, 10.00 g (0.046 mol) of lauric acid chloride and 45 mL of dichloromethane were placed in a 300 mL four-necked flask and cooled to 0 ° C. On the other hand, 6.41 g (0.046 mol) of ethyl maltol, 4.86 g (0.048 mol) of triethylamine and 45 mL of dichloromethane were put into a 100 mL dropping funnel. The reaction temperature was dropped from the dropping funnel over 30 minutes so that the reaction temperature was maintained at -5 ° C to 0 ° C. After completion of dropping, the mixture was stirred at room temperature (25 ° C.) for 1 hour. 10 mL of saturated aqueous ammonium chloride solution was added to the flask to stop the reaction. 150 mL of diethyl ether was added, the produced white solid was removed by filtration, and the filtrate was transferred to a separatory funnel. 100 mL of ion-exchanged water was added to the separatory funnel, and extraction from the aqueous layer was performed 3 times with 50 mL of diethyl ether. The extracted solution was collected, washed with saturated brine, and the solution was dried over sodium sulfate. After removing the solvent under reduced pressure, 14.74 g (yield 100%) of a pale yellow solid ester of lauric acid and ethyl maltol was obtained.

The measurement results of NMR and IR are shown below.
NMR (1H, 400MHz)
0.88 (t, J = 7 Hz, 3H), 1.20 to 1.45 (m, 21H), 1.75 (quant., J = 7 Hz, 2H), 2.59 (m, 4H), 6 .39 (d, J = 6 Hz, 1H), 7.69 (d, J = 6 Hz, 1H)
IR (KBr): 2923, 2854, 1768, 1658, 1160, 1133, 1106, 825 cm ⁻¹

<(C) component>
(C-1): Perfumes listed in Table 1

<(D) component>
(D-1): Quaternary ammonium salt compound produced in Synthesis Example d-1 below [Synthesis Example d-1: Production of (d-1)]
As the component (D), a quaternary ammonium salt compound represented by the general formula (D1), which is different from the component (A) in the fatty acid composition constituting the acyl group, was prepared. That is, a fatty acid represented by triethanolamine and RCOOH (composition is as described later) is subjected to an esterification reaction at a reaction molar ratio (fatty acid / triethanolamine) of 1.65 / 1, and represented by the general formula (D1). An esterification reaction product containing an amine compound was obtained.
The esterification reaction product contained 5% by mass of unreacted fatty acid. After the quaternization reaction was performed with dimethyl sulfate so that the methyl group was 0.96 equivalent to the amine of the amine compound in the esterification reaction product, ethanol was added. As described above, among the quaternary ammonium salt compounds represented by the general formula (D1) as the component (D), the quaternary ammonium salt compound having a different fatty acid composition of the acyl group and the component (A) [hereinafter (d-1) )]] Was prepared.
As a result of analyzing the composition ratio of each component of the obtained reaction product by HPLC method and using tetraoctyl ammonium bromide as an internal standard substance, the obtained reaction product is represented by the general formula (D1) ( A) The component (d-1), which is a compound having a different fatty acid composition from the acyl group, is 75% by mass, ethanol 10% by mass, unreacted amine (as methyl sulfate) 12% by mass, unreacted fatty acid 2%, trace amount In the general formula (D1) among the components (d-1), R ^1d is an acyl group, R ^2d and R ^3d are hydrogen atoms, and R ^4d there a methyl group, X ^- is compound is methyl sulfate [hereinafter may be referred to (d1-1)] is (d-1) component 28 weight%, in the general formula ^{(D1), R 1d} and R ^2d is an acyl group R ^3d is a hydrogen atom, R ^4d is a methyl group, and X ⁻ is methyl sulfate [hereinafter may be referred to as (d2-1)] in 56% by mass in the component (d-1). In general formula (D1), R ^1d , R ^2d and R ^3d are acyl groups, R ^4d is a methyl group, and X ⁻ is methyl sulfate [hereinafter referred to as (d3-1) in some cases]. ] Was 16 mass% in the component (d-1). The quaternization rate was 80% by mass.

In addition, the composition of RCOOH used for reaction for manufacturing (d-1) is shown below.
Palmitic acid: 45% by mass
Stearic acid: 25% by mass
Oleic acid: 27% by mass
Linoleic acid: 3% by mass
The composition was analyzed for the fatty acid used as a raw material by gas chromatography, and the area% of each fatty acid was regarded as mass%.
In addition, the numerical value of Table 2 is converted into (d-1) component density | concentration.

(D-2): Amine compound (triethanolamine methylsulfate) contained in (a-1) and / or (d-1)

<(E) component>
(E-1): A compound obtained by adding an average of 29 moles of ethylene oxide to lauryl alcohol, that is, in formula (E1-1), R ^1e is a linear alkyl group having 12 carbon atoms and bonded to an oxygen atom. A nonionic surfactant in which the carbon atom of R ^1e is a primary carbon atom and k is 29

<(H) component>
(H-1) Component: Calcium chloride <(M) component>
(M-1) Component: Trisodium methylglycine diacetate

<(N) component>
(N-1) component: Si (O-Geranyl) ₄
In addition, “Gerany” in the component (n-1) represents a group obtained by removing one hydroxyl group from geraniol (primary allyl alcoholic fragrance, log P2.4).
(N-2) component: Si (O-Rasp) (O-Folrosia) ₃
Note that “Rasp” in the component (n-2) represents a group obtained by removing one phenolic hydroxyl group from raspberry ketone (phenolic fragrance, log P1.1), and “Folrosia” represents forrosia (4-isopropylcyclohexanol). A group obtained by removing one hydroxyl group from a secondary alcoholic fragrance, log P2.7).

About the said (n-1) component and the said (n-2) component, it synthesize | combined by the following synthesis example n-1 and the synthesis example n-2.
(Synthesis Example n-1: Synthesis of Si (O-Geranyl) ₄ )
In a 200 mL four-necked flask, put 27.08 g (0.13 mol) of tetraethoxysilane, 72.30 g (0.47 mol) of geraniol and 0.485 mL of 2.8 mass% sodium methoxide methanol solution, and add ethanol under a nitrogen stream. It stirred at 110-120 degreeC for 2 hours, making it distill.
After 2 hours, the pressure in the tank was gradually lowered to 8 kPa, and the mixture was further stirred at 117 to 120 ° C. for 4 hours while distilling ethanol. Four hours later, after cooling and releasing the reduced pressure, filtration was performed to obtain 76.92 g of a yellow oily substance containing a geraniol silicate ester perfume precursor.

(Synthesis Example n-2: Synthesis of Si (O-Rasp) (O-Folrosia) ₃ )
In a 500 mL four-necked flask, 83.32 g (0.40 mol) of tetraethoxysilane, 59.11 g (0.44 mol) of raspberry ketone, 153.062 g (1.08 mol) of forurodia and 5.275 mass% sodium ethoxide ethanol solution 0.50 g was added and stirred at 150 ° C. for about 2 hours while distilling ethanol under a nitrogen stream.
After 2 hours, the pressure in the tank was gradually lowered to 4 kPa, and the mixture was further stirred at 150 ° C. for 15 hours while distilling ethanol. Thereafter, cooling and decompression were released, followed by filtration to obtain 202.63 g of a yellow oily substance containing a silicate ester compound having a molar ratio of raspberry ketone to forlodia of 1: 3.

<(O) component>
(O-1) Component: Proxel BDN (manufactured by Arch Chemical Japan)
<PH adjuster>
In order to adjust the pH of the liquid softener composition, sodium hydroxide or (J) component citric acid and hydrochloric acid were appropriately used as necessary.

[Examples 1-7 and Comparative Examples 1-3]
(1) Manufacture of liquid softening agent composition The liquid softening agent composition was prepared by mixing each component so that it might become a mixing | blending composition shown in Table 2. FIG. Specifically, it is as follows. In addition, the mass% of the composition in a table | surface is mass% of an effective part.

  In a 300 mL beaker, an amount of ion-exchanged water corresponding to 80% by mass of the amount necessary for the liquid softener composition to be 200 g, (E) component, (M) component, (O) component, And a pH adjuster were added, and the temperature of ion-exchanged water was adjusted to 60 ± 2 ° C. using a water bath. (E) The liquid mixture was obtained by stirring using a stirring blade as needed so that a component might melt | dissolve uniformly in ion-exchange water. The stirring blade is a stirring blade arranged so that the long side is in the direction of 90 degrees with respect to the rotation center axis of the stirring rod having a diameter of 5 mm. / Short side = 3 cm / 1.5 cm, and blades installed at an angle of 45 degrees with respect to the rotating surface were used.

The mixed solution adjusted to a temperature of 60 ± 2 ° C. was stirred (300 r / m) with the stirring blade. The (D) component heated and dissolved at 65 ° C. together with the (A) component and the (B) component was added to this over 3 minutes, and after completion of the addition, the mixture was stirred for 15 minutes.
Next, it cooled until the temperature of the liquid mixture became 30 +/- 2 degreeC using a 5 degreeC water bath. (C) component, (N) component, and (H) component were thrown into this in order, and it stirred for 5 minutes. Furthermore, ion-exchange water was added so that it might become mass (200g), and it stirred for 5 minutes, and obtained the liquid softening agent composition.

  The visible light transmittance of the obtained liquid softening agent composition was measured. Specifically, a glass cell having an optical path length of 10 mm was used as a measurement cell, ion-exchanged water was added to a control cell, and measurement was performed using an ultraviolet-visible spectrophotometer (UV-2500PC manufactured by Shimadzu Corporation). The visible light transmittance (wavelength 660 nm) of the liquid softening compositions obtained in Examples and Comparative Examples were all less than 10%, and were emulsion-type liquid softening compositions. The results of measuring the viscosity of the liquid softener composition by the above method are shown in Table 2.

(2) Evaluation Using a commercially available weak alkaline detergent (Kao Corporation, Attack), 17 underwear made by Gunze Co., Ltd. were repeatedly washed 5 times with a fully automatic washing machine NW-6CY made by Hitachi, Ltd. The excess chemical was removed by drying in the room (detergent concentration 0.0667% by mass, tap water 47 L, water temperature 20 ° C., washing 10 minutes, rinse twice, dehydration 6 minutes).

One piece of underwear that 4L of tap water was poured into an electric bucket N-BK2-A manufactured by Panasonic Corporation, the liquid softener composition was dispersed so as to be 10 g / underwear 1.5 kg, and further washed by the above method. And stirred for 5 minutes. Thereafter, the underwear finished with the liquid softening agent composition was dehydrated for 3 minutes in a dehydration tank of a two-tank washing machine manufactured by Hitachi, Ltd. and then dried for 24 hours. This operation was separately performed four times for each liquid softener composition, and four pieces of underwear finished with the liquid softener composition were prepared.
In addition, the underwear processed with the liquid softening agent composition of the Example had sufficient softness | flexibility.

One of the prepared underwear was folded and stored in a room at 20 ° C./60% RH for 7 days.
After storage, the remaining scent was evaluated by three specialized panelists who wear underwear for 8 hours and evaluate the scent afterwards.
The evaluation was performed according to the following criteria, and the evaluation result was the one with the most results among the three evaluations. In the case where the evaluation of three people was separated from 1 point, 2 points, and 3 points, 2 points were assigned. Evaluation of fragrance was performed in a room at 20 ° C./60% RH.
<Evaluation criteria>
3: Rich and fresh fragrance is firm.
2: Slightly rich and fresh scent.
1: There is almost no rich and fresh scent.

  As is clear from the above results, the liquid softener composition of the present invention can impart excellent scent sustainability when a textile product is treated.

Claims (12)

The liquid softening agent composition containing the following (A) component, (B) component, and water, and pH at 30 degreeC is 2.5 or more and 5.0 or less.
<(A) component>
A quaternary ammonium salt compound represented by the following general formula (1), wherein when the acyl group is regarded as a fatty acid, the ratio of oleic acid, linoleic acid and linolenic acid constitutes the acyl group. Quaternary ammonium salt compound which is 60% by mass or more and 100% by mass or less of fatty acid

[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 (referred to as an acyl group) or a hydrogen atom, provided that R ¹ , R ² , and R ³ are acyl groups, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an anion. ]
<(B) component>
A fragrance precursor comprising an ester of a fragrance compound having a phenol structure or a hydroxy-4-pyrone structure and an aliphatic monocarboxylic acid having 8 to 18 carbon atoms or an aliphatic dicarboxylic acid having 3 to 20 carbon atoms.   The liquid softening agent composition of Claim 1 whose ratio of the oleic acid which comprises the acyl group of (A) component is 50 mass% or more of the total fatty acid which comprises the acyl group.   (A) The liquid softening agent composition of Claim 1 or 2 which contains a palmitic acid and a stearic acid as a fatty acid which comprises the acyl group of a component.   The liquid softening agent composition in any one of Claims 1-3 whose fragrance | flavor compound which comprises (B) component is 1 or more types chosen from a maltol, an ethyl maltol, vanillin, an ethyl vanillin, and a raspberry ketone.   The liquid according to any one of claims 1 to 4, wherein the aliphatic monocarboxylic acid constituting the component (B) is at least one selected from lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid. Softener composition.   The liquid softening agent composition according to any one of claims 1 to 5, comprising (A) component at 1% by mass to 20% by mass and (B) component at 0.001% by mass to 1.0% by mass. .   Furthermore, the liquid softening agent composition in any one of Claims 1-6 containing a fragrance | flavor compound as (C) component.   (C) The liquid softening agent composition of Claim 7 which contains 0.1 mass% or more and 2.0 mass% or less of components.   The liquid softening agent composition in any one of Claims 1-8 which contains cationic surfactants other than (A) component as (D) component. When the component (D) is a quaternary ammonium salt compound represented by the following general formula (D1) and the acyl group is regarded as a fatty acid, the proportion of the unsaturated fatty acid constitutes the acyl group The liquid softening agent composition of Claim 9 which is a quaternary ammonium salt compound which is 50 mass% or less of all the fatty acids.

[Wherein, R ^1d , R ^2d and R ^3d are each independently a residue obtained by removing OH from a fatty acid having 16 to 22 carbon atoms (referred to as an acyl group) or a hydrogen atom, provided that R ^1d , R ^2d , and R ^3d are acyl groups, R ^4d is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an anion. ]   The liquid softening agent composition of Claim 9 or 10 which contains 0.5 mass% or more and 20 mass% or less of (D) component.   Furthermore, the liquid softening agent composition in any one of Claims 1-11 which contains 0.5 mass% or more and 8 mass% or less of nonionic surfactant as (E) component.