JP6320905B2 - Liquid softener composition - Google Patents

Description

  The present invention relates to a liquid softener composition.

  In the past, softeners for clothing used quaternary ammonium salts or tertiary amine compounds having two long-chain alkyl groups having about 14 to 24 carbon atoms as the main base. In recent years, long-chain alkyl groups and long-chain alkenyl groups (hereinafter referred to as “long-chain alkyl groups” in the present invention are long-chain alkenyl groups) for the purpose of being excellent in biodegradability and reducing the environmental impact. A flexible base material having a structure derived from a fatty acid having an ester bond or an amide bond in between is developed and used. In particular, an ester-type quaternary ammonium salt obtained by quaternizing an ester compound of triethanolamine and a long-chain fatty acid with an alkylating agent such as methyl chloride or dimethylsulfuric acid has become a universal base material at the world level.

  On the other hand, researches on liquid softener compositions based on nonionic surfactants are also being conducted. Patent Document 1 and Patent Document 2 disclose a technique of a liquid softening agent composition having a nonionic surfactant as a main base. In addition, a technique in which such a nonionic surfactant and the above-described quaternary ammonium salt or tertiary amine compound are used in combination is also known. Patent Document 3 discloses a technique of a softener containing an ester group-containing quaternary ammonium softener and a fatty acid monoglyceride. Patent Document 4 describes a liquid softener composition containing a dimethyl diester quaternary ammonium type softener and a mono long-chain alkyl quaternary ammonium salt and a fatty acid ester of a polyhydric alcohol for storage stability. Patent Document 5 describes a softener composition using a conventional di-long alkyl type quaternary ammonium salt and pentaerythritol fatty acid ester. Patent Document 6 discloses a soft finish containing a quaternary ammonium salt having three or more fatty acid ester groups, a polyoxyethylene alkyl ether type nonionic surfactant, and an ester compound of a trivalent to hexavalent polyhydric alcohol and a fatty acid. An agent composition is described. Patent Document 7 discloses a liquid softener composition containing a cationic surfactant selected from a specific general formula and a polyhydric alcohol nonionic surfactant.

  Softeners are originally used as finishing agents that bring about changes in texture, mainly softness, with respect to textile products, but in order to increase commercial value, not only flexibility but also imparting aroma to fiber products. The number of softeners for the purpose has increased, and there are many products that push the perfume performance over the entire surface. As a means to increase the fragrance of textile products, a method of increasing the blending amount of the fragrance can be considered, but it is difficult to increase the blending amount because the compound that can be used as the fragrance is high, even if it is increased temporarily There is a problem of persistence after perfume. Patent Document 8 discloses a polyhydric alcohol which may have a silicate compound and a polyoxyethylene group using a fragrance component having a hydroxy group, which is known to be used as a fragrance, for the durability of the fragrance effect. A textile treatment agent containing a fatty acid ester is described.

  In addition, attempts have been made to blend fragrances into microcapsules for the purpose of sustaining fragrance and remaining fragrance. A fragrance microcapsule (hereinafter sometimes referred to as a microcapsule fragrance) is a particulate material in which a core material fragrance is wrapped with a wall material, and its role is to protect the core material fragrance and provide physical strength to the capsule. When the is added, the capsule wall is broken to release the fragrance of the core material. Patent Document 9 describes an encapsulated fragrance containing a fragrance composition having a flash point of 50 to 130 ° C. as a core substance. Patent Document 10 describes a microcapsule containing a volatile component such as a highly volatile fragrance and an additive having a higher melting point and compatibility than that.

JP 2012-127021 A Special table 2004-522866 gazette Special table 2001-525020 gazette JP-A-8-81881 JP-A-2-47370 JP 10-77575 A JP 2003-213568 A JP 2010-144308 A JP 2006-249326 A International Publication No. 2007/038570

  As described above, fatty acid ester type quaternary ammonium salts as flexible substrates are flexible substrates used on a global scale because of their good degradability. However, these ester-type quaternary ammonium salts have a problem that they are inferior in flexibility compared to the case of using a conventional dilong-chain alkyldishort-chain alkyl type quaternary ammonium salt.

  Furthermore, as described above, in recent years, there has been a demand for perfumeability to fiber products using a softening agent, and it is known to use fine particles in which a perfume is microencapsulated. Microcapsule fragrances recognize the generation of scents due to the use of physical stimuli such as sliding and impacting on the attached fiber products, destroying the shells of the microcapsules and making them more fragrant. It is something that can be done. On the other hand, textile products after treatment cannot be expected to have a significant scent when left standing, and there is an unexpected scent due to the movement of the wearer. Yes.

  The present invention provides a liquid softener composition containing a quaternary ammonium salt having a fatty acid ester structure and exhibiting excellent flexibility.

  Furthermore, the present invention provides a liquid softener composition that, when using a microcapsule fragrance, can fragrance the scent in the microcapsule fragrance even under conditions that do not give physical irritation to the treated object. To do.

The present invention relates to a liquid softening agent composition containing 5% by mass or more and 20% by mass or less of the following component (A), 0.5% by mass or more and 10% by mass or less of the component (B), and water.
<(A) component>
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,
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 hydrogen atoms at the same time, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an organic or inorganic anion. ]
<(B) component>
A component comprising a plurality of ester compounds of pentaerythritol and a fatty acid having 16 to 22 carbon atoms,
The proportion of the fatty acid monoester structure is 40% 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 45% by mass or more and 90% by mass or less in the total amount of the ester compound

ADVANTAGE OF THE INVENTION According to this invention, the liquid softening agent composition which shows the outstanding softness | flexibility even if it uses fatty acid ester structure type quaternary ammonium salt is provided.
Further, according to the present invention, when a microcapsule fragrance is used in the liquid softener composition of the fatty acid ester structure type quaternary ammonium salt, the scent in the microcapsule fragrance is physically applied to the processed object. Provided is a liquid softener composition that can be scented even under conditions that do not cause mechanical irritation.

  As a result of repeated studies, the present inventors have found that when a mixture of fatty acid ester structure type quaternary ammonium salts having different degrees of esterification of component (A) is used as a flexible substrate, esterification of component (B) It has been found that excellent flexibility can be enhanced by using fatty acid ester compounds of pentaerythritol having different degrees at a specific ratio. Furthermore, when a microcapsule fragrance is used as a fragrance, It has been found that it is possible to aroma even when no physical stimulus is given.

<(A) component>
The component (A) of the present invention is a component composed of a plurality of quaternary ammonium salts represented by the following general formula (1),
The ratio of the compound (a1) [hereinafter referred to as component (a1)] in which R ¹ in general formula (1) is an acyl group and R ² and R ³ are hydrogen atoms is represented by general formula (1). 10% by mass or more and 45% by mass or less in the total amount of quaternary ammonium salt
The ratio of 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 represented by the general formula (1). In the total amount of quaternary ammonium salt, 25% by mass or more and 70% by mass or less,
A quaternary ammonium salt in which the ratio of the compound (a3) [hereinafter referred to as component (a3)] in which R ¹ , R ² and R ^{3 in the} general formula (1) are acyl groups is represented by the general formula (1) In a total amount of 5 mass% or more, 40 mass% or less,
It is a component that is.

^{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 hydrogen atoms at the same time, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an organic or inorganic anion. ]

In the quaternary ammonium salt represented by the general formula (1), (A) R ¹ , R ² and R ^{3 in the} general formula (1) are not simultaneously hydrogen atoms, that is, R ¹ , R ² and R ^3. At least one of the above is the acyl group. Therefore, the quaternary ammonium salt represented by the general formula (1) is any one of the component (a1), the component (a2), and the component (a3). Moreover, (A) component is comprised by the said (a1) component, (a2) component, and (a3) component.
In the present invention, the total amount of the quaternary ammonium salt represented by the general formula (1) is the total content of the component (a1), the component (a2), and the component (a3).
The proportions of the component (a1), component (a2), and component (a3) in the component (A) of the present invention are not only the flexibility imparted to the textile product but also the storage stability when the component (B) is used in combination. Also affects.

The proportion of the component (a1) in the component (A) 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.
The proportion of the component (a2) in the component (A) 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.
The proportion of the component (a3) in the component (A) 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.
The proportion of the component (a1), component (a2), or component (a3) in component (A) is the sum of the contents of component (a1), component (a2), and component (a3). It is a ratio.

  The component (a2) and the component (a3) are effective components for the softening effect. However, when the component (B) is contained, the storage stability of the liquid softening agent composition is affected. 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). (A3) The difference from the content (mass%) of the component 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).
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 ⁻ represents a halogen ion, preferably a chloro ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, a fatty acid ion having 12 to 18 carbon atoms, or a carbon atom having 1 to 3 carbon atoms. An anion selected from benzenesulfonate ions optionally substituted with 1 to 3 alkyl groups is preferred, an alkyl sulfate ion having 1 to 3 carbon atoms is more preferred, a methyl sulfate ion or Ethyl sulfate ion is more preferred.

  The component (A) 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 method), or a fatty acid lower alkyl ester (lower alkyl is a methyl group, ethyl group, propyl group) An esterification reaction product obtained by a method of transesterifying ethanolamine (referred to as a transesterification method) can be obtained by quaternizing with an alkylating agent. 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 1.3: 1 or more, Preferably, a mixture of triethanolamine fatty acid esters reacted at a ratio of 1.5: 1 or more and 2.0: 1 or less, preferably 1.9: 1 or less is subjected to quaternization reaction.

  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. Particularly, those having a fatty acid composition obtained from beef tallow, palm oil and sunflower oil are preferable from the viewpoint of flexibility. 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 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 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) 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). It is a graded product. Unreacted fatty acids may also be included. When a reaction product containing the component (A) 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.

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.
For example, as HPLC conditions, column: Inertsil NH2 5 μm (4.6 × 250 mm)
Mobile phase: 0.05% (mass / volume) -trifluoroacetic acid / hexane solution: methanol: 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 55 minutes to 60 minutes
Temperature: Room temperature (25 ° C)
Injection: 20 μL
Detection: CAD
Can be measured.

<(B) component>
The component (B) of the present invention is
A component comprising a plurality of ester compounds of pentaerythritol and a fatty acid having 16 to 22 carbon atoms,
The proportion of the fatty acid monoester structure is 40% 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 45% by mass or more and 90% by mass or less in the total amount of the ester compound.

  By using the component (B), the flexibility of the component (A) can be further increased. Furthermore, when using the microcapsule which contains the fragrance | flavor of (C) component mentioned later for the softening agent composition which uses (A) component as the main base material, it is the object after a process by using (B) component. Even when there is no physical contact with the object, the odor from the component (C) can be extracted. Usually, the fragrance of the microcapsule fragrance itself is weak and strongly fragrant when the capsule is broken by physical contact. When used for textile processing, an operation such as rubbing is required in order to aroma the fragrance in the microcapsule.

  The fatty acid monoester structure and the fatty acid tetraester structure affect the phase stability such as the storage stability of the composition.

In addition, the ester compound of pentaerythritol and the fatty acid having 16 to 22 carbon atoms constituting the component (B) includes four compounds having different degrees of esterification.
Among the ester compounds constituting the component (B), the fatty acid monoester structure is a compound in which one of the four hydroxyl groups of pentaerythritol 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).
Among the ester compounds constituting the component (B), the fatty acid diester structure is a compound in which two of the four hydroxyl groups of pentaerythritol are fatty acid and ester. This compound is sometimes referred to as a fatty acid diester structure under the restriction of component (B).
Among the ester compounds constituting the component (B), the fatty acid triester structure is a compound in which three of the four hydroxyl groups of pentaerythritol are an ester with a fatty acid. This compound may be referred to as a fatty acid triester structure under the restriction of component (B).
Among the ester compounds constituting the component (B), the fatty acid tetraester structure is a compound in which all four hydroxyl groups of pentaerythritol are converted to fatty acids and esters. This compound is sometimes referred to as a fatty acid tetraester structure under the restriction of component (B).

  The fatty acid is preferably 16 or more and 18 or less. Specific examples of fatty acids include stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, palm oil fatty acid, hardened palm oil fatty acid, beef tallow fatty acid, and hardened 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 5% by mass or more, more preferably 10% by mass or more, and more preferably 12% by mass or more from the viewpoint of imparting flexibility, thereby improving flexibility. In view of the above, it is 40% by mass or less, preferably 35% by mass or less, more preferably 29% by mass or less.

The total ratio of the fatty acid diester structure and the fatty acid triester structure in the component (B) is 45% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, from the viewpoint of improving flexibility. From the viewpoint of the stability of the composition, it is 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less.
In the component (B), the proportion of the fatty acid diester structure is preferably 30% by mass or more, more preferably 35% by mass or more, and preferably 60% by mass or less, more preferably after satisfying the above-mentioned total proportion. Is 50 mass% or less.
Moreover, after satisfy | filling the said total ratio, the ratio of a fatty-acid triester structure in (B) component becomes like this. Preferably it is 10 mass% or more, More preferably, it is 15 mass% or more, Preferably, it is 40 mass% or less. More preferably, it is 35 mass% or less.

  In addition, (B) component may contain a fatty-acid tetraester structure among pentaerythritol fatty acid ester. The proportion of the fatty acid tetraester structure in the component (B) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 20% by mass or less, from the viewpoint of the stability of the composition. More preferably, it is 15 mass% or less, More preferably, it is 13 mass% or less, More preferably, it is 10 mass% or less.

As an example of the component (B),
A component comprising a plurality of ester compounds of pentaerythritol and a fatty acid having 16 to 22 carbon atoms,
The proportion of the fatty acid monoester structure is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 12% by mass or more, and 40% by mass or less, preferably 35% by mass in the total amount of the ester compound. Or less, more preferably less than 30% by mass, more preferably 29% by mass or less,
The proportion of the fatty acid diester structure is preferably 30% by mass or more, more preferably 35% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less, in the total amount of the ester compound.
The proportion of the fatty acid triester structure is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less, in the total amount of the ester compound.
The proportion of the fatty acid tetraester structure is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount of the ester compound. Preferably it is 13 mass% or less, more preferably 10 mass% or less,
The total ratio of the fatty acid diester structure and the fatty acid triester structure is 45% by mass or more, preferably 50% by mass or more, more preferably 60% by mass or more, and 90% by mass or less in the total amount of the ester compound. , Preferably 85% by mass or less, more preferably 80% by mass or less,
The component which is is mentioned.

  Regarding the ratio of the ester compound in the component (B), the ratio of each ester structure from the monoester structure to the tetraester structure shall be consistent with the total ratio of the diester structure and triester structure.

  As a method for obtaining the ester mixture as the component (B) of the present invention, for example, Example 1 of JP-A-5-140037, Example 1 of JP-A-5-140038, etc. can be referred to. .

The ratio of pentaerythritol fatty acid esters with different degrees of esterification can be measured by gel permeation chromatogram. For example, a method using a high-speed GPC device HCL-8220GPC (manufactured by Tosoh Corporation) may be mentioned. The measurement conditions when using the measurement apparatus are exemplified below.
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

  The component (B) of the present invention can be produced by an esterification reaction of pentaerythritol and a fatty acid, or a transesterification reaction of pentaerythritol and a fatty acid lower alkyl ester (lower alkyl is a methyl group, an ethyl group, or a propyl group). Preferably, in order to obtain a mixture satisfying the condition of component (B), fatty acid or fatty acid lower alkyl ester is preferably 0.8 mol or more, more preferably 1.0 mol or more, relative to 1 mol of pentaerythritol. More preferably 1.2 mol or more, and preferably 2.2 mol or less, more preferably 2.0 mol or less, more preferably 1.8 mol or less in an esterification reaction or transesterification reaction. preferable. 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 250 ° 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 250 ° 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.

  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.

  In the case of dehydration esterification reaction, the progress of the reaction is confirmed by measuring the acid value (AV) and saponification value (SV) by the method described in JISK0070-1992, preferably AV is 10 mgKOH / g or less, Preferably, the esterification reaction is terminated when it becomes 6 mgKOH / g or less, particularly when it becomes 6 mgKOH / g or less. In the case of transesterification, it can be confirmed by gas chromatography or liquid chromatography. The conditions for these chromatography vary depending on the type of polyhydric alcohol or fatty acid, and the optimum conditions are appropriately determined under known conditions. You can choose.

  After completion of the reaction, after deactivating the catalyst, such as neutralization and adsorption removal, unreacted pentaerythritol and fatty acids are distilled off under reduced pressure, unreacted substances are solidified and precipitated at low temperature, and filtered. Can be adopted.

[Component (C)]
The liquid softener composition of the present invention further contains, as component (C), a microcapsule containing a fragrance containing 90% by mass or more of a fragrance compound having a log P value of 2.0 or more and 6.0 or less. Is preferred.
The microcapsule of component (C) is obtained by encapsulating a predetermined fragrance and an arbitrary fragrance diluent or solvent. For example, fragrance | flavor is enclosed by a well-known method using resin for the outer shell (wall material) of a microcapsule. Component (C) is a microcapsule having a core-shell structure, and the core substance is a component containing a fragrance containing a fragrance compound having a log P value of 2.0 or more and 6.0 or less and 90% by mass or more, It may be a microcapsule in which the shell material is a polymer compound.

  (C) The preparation method of the microcapsule of a component is not restrict | limited in particular, A well-known microencapsulation method is employable. Specifically, chemical production methods (interfacial polymerization method, in situ polymerization method, orifice method), physicochemical methods (coacervation method), mechanical / physical methods (air suspension coating method, spray drying method, High-speed air-flow impact method). Examples of the outer shell of the microcapsule include various polymer compounds such as polyurethane, polyamide, melamine resin, urea resin, alginate, gelatin, gum arabic, and starch. It is preferable that the outer shell of the microcapsule (C) is composed of one or more selected from polyurethane, polyamide, melamine resin, urea resin, alginate, polyacrylic resin, gelatin and gum arabic, and further melamine More preferably, a resin (sometimes referred to as a melamine-formaldehyde resin) is included.

  More specifically, the manufacturing method of the microcapsule of component (C) includes “manufacturing + using microcapsules” (Kojima, Jun et al., Industrial Research Committee, published in 2005), JP 2008-63575 A, JP The methods described in Japanese Patent Application Laid-Open No. 2006-249326, Japanese Patent Application Laid-Open No. 11-216354, Japanese Patent Application Laid-Open No. 5-222672, and the like can be employed.

  As a preferred method for producing the microcapsule of the component (C) of the present invention, an emulsifier such as an ethylene-maleic anhydride copolymer, a fragrance, and an optional diluent or solvent are dispersed in water to obtain an emulsion. A method of obtaining a microcapsule slurry by adding a wall material such as melamine-formaldehyde resin to the emulsion and stirring the mixture is mentioned.

  A wall material / emulsifier mixture is prepared in advance by mixing a monomer that forms a wall material with an emulsifier such as isobutylene-maleic anhydride copolymer and acrylic acid-acrylamide copolymer in water. Examples include a method of emulsifying a wall material / emulsifier mixture, a fragrance, and an arbitrary diluent or solvent, adding formaldehyde to the emulsion, and stirring to obtain a microcapsule slurry.

  The fragrance used in the present invention is an organic compound that is known to be used as a fragrance, and is “actual knowledge of fragrance and fragrance” (by Nakajima Motoki, Sangyo Tosho Co., Ltd., June 1995). 21)) can be appropriately combined in accordance with the fragrance tone and use. Moreover, the blending amount of the fragrance component and fragrance composition described in the patent documents of softeners, glues, styling agents, and other finishing agents, which are known as finishing agents, as long as the effects of the present invention are not impaired. It can be used after considering.

  Among these, the fragrance contained in the capsule of component (C) [hereinafter referred to as fragrance (C1)] is a fragrance compound having a log P value of 2.0 or more and 6.0 or less [hereinafter referred to as fragrance compound (c1)]. 90% by mass or more. A fragrance | flavor (C1) is a composition containing the several fragrance | flavor compound normally containing a fragrance | flavor compound (c1). Further, the fragrance compound (c1) has a log P value of 2.0 or more, preferably 2.3 or more, more preferably 2.5 or more, and 6.0 or less, preferably from the viewpoint of easy production of capsules. Is 5.5 or less, more preferably 5.0 or less.

  As the fragrance compound (c1), octanal (3.0), nonanal (3.0), decanal (4.0), rilal (2.2), lyial (3.9), hexylcinnamic aldehyde (4.9) ), Amylcinnamic aldehyde (4.3), p, t-butylhydrocinnamic aldehyde (3.6), dimethyltetrahydrobenzaldehyde (2.9), hexyl acetate (4.9), tricyclodecenyl acetate (2.4), citronellyl acetate (4.2), geranyl acetate (3.7), linalyl acetate (3.5), terpinyl acetate (3.6), o, t-butylcyclohexyl acetate (4.1) P, t-butyl cyclohexyl acetate (4.1), allyl cyclohexyl propionate (2.9), tricyclodecenyl propionate (3.9), caproic acid (3.2), amyl salicylate (4.6), hexyl salicylate (5.1), benzyl salicylate (4.2), cyclohexyl salicylate (4.5), cis-3-hexenyl salicylate (4.6) , Methyl dihydrojasmonate (2.4), α-ionone (3.7), β-ionone (3.7), γ-methylionone (4.0), α-damascone (3.6), β-damascone (3.6), [delta] -damascone (3.6), [gamma] -nonalactone (2.8), [gamma] -decalactone (3.3), [gamma] -undecalactone (3.8), neroline yarayara (3.2) , Cyclamenaldehyde (3.5), limonene (4.4), tetrahydrolinalool (3.5), terpineol (2.6), geraniol (2.4), citronellol (3.3), linalool (2.6) Tetrahydrolinalol (3.5), eugenol (3.0), dihydromyrcenol (3.0), phenylhexanol (3.5), methyl anthranilate (2.0), methyl β-naphthyl ketone, (2.8), iso-E super (4.7), cedryl methyl ether (5.1), sandal mysol core (manufactured by Kao Corporation) (3.9), jabanol (manufactured by Givaudan) (4. 7), ambroxane (5.3), 1,8-cineole (2.9), geranyl nitrile (3.9), citronellyl nitrile (4.4), 11-oxa-16-hexadecanolide (Musk R- 1, one or more fragrance compounds selected from dibodan (4.5), ethylene brush rate (4.6), ethylene dodecanedioate (4.1), and cachemelan (4.0). In addition, as a fragrance | flavor whose log P value is higher than 6.0, the fragrance | flavor which also encloses a cyclopentadecanolide (6.3), a cyclohexadecanolide (6.8), and an amblet lidide (6.4). Can be used as Here, the numbers in () are logP values.

  In the present invention, the log P value is a coefficient indicating the affinity of an organic compound for water and 1-octanol. 1-octanol / water partition coefficient P is a distribution equilibrium when a trace amount of compound is dissolved as a solute in a two-liquid solvent of 1-octanol and water, and is a ratio of the equilibrium concentration of the compound in each solvent. It is common to show them in the form of their logarithm logP relative to the base 10. Log P values of many compounds have been reported, and many values are listed in databases available from Daylight Chemical Information Systems, Inc. (Daylight CIS), etc., and can be referred to. When there is no measured log P value, it can be calculated by a program “CLOGP” or the like available from Daylight CIS. This program outputs the value of “calculated logP (ClogP)” calculated by the fragment approach of Hansch, Leo together with the measured logP value, if any.

  The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bond (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammens, JBTaylor and CA Ramsden, Eds., P.295, Pergamon Press, 1990). This ClogP value can be used in place of the actual logP value in selecting a compound. In the present invention, if there is a measured value of logP, the ClogP value calculated by the program CLOGP v4.01 is used.

  In the inclusion (core substance) of the microcapsule (C), the ratio of the fragrance (C1) is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 99% by mass or less, more preferably Is 98 mass% or less. In addition to the fragrance (C1), the microcapsule (C) may contain a diluent, a solvent, and a solidifying agent. Examples of the diluent or solvent include ethylene glycol, propylene glycol, dipropylene glycol, and glycerin. Mention may be made of fatty alcohols, fatty acids, lower alcohols of fatty acids or glycerol esters. The amount of the diluent, solvent, and solidifying agent encapsulated in the microcapsule is preferably 10% by mass or less in the inclusion (core substance) of the microcapsule.

  The primary average particle size of the (C) component microcapsules is preferably 1 μm or more, and preferably 100 μm or less, more preferably 50 μm or less, and more preferably 20 μm or less. The average particle diameter of the microcapsules of the present invention is a median diameter determined by a laser diffraction / scattering particle size distribution analyzer LA-910 manufactured by HORIBA. In addition, (C) component may be partially aggregated to such an extent that storage stability is not impaired. Further, the liquid softener composition of the present invention comprises the microcapsules encapsulating a fragrance other than the fragrance (C1), the microcapsules not encapsulating the fragrance, the capsule shell fragment, the effects of the present invention, the texture of the textile product, It may be contained as long as it does not affect the beauty.

<Liquid softener composition>
In the liquid softener composition of the present invention, the component (A) is 5% by mass or more, preferably 7% by mass or more, more preferably 9% by mass or more, and 20% by mass or less, preferably 18% by mass or less, more preferably Contain 15% by mass or less.
In the liquid softener composition of the present invention, the component (B) is 0.5% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and 10% by mass or less, preferably 8% by mass or less. More preferably, the content is 5% by mass or less.
In the liquid softener composition of the present invention, the component (C) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and preferably 2%. 0.0 mass% or less, more preferably 1.0 mass% or less, more preferably 0.5 mass% or less.
In addition, the liquid softener composition of the present invention preferably has a mass ratio of the component (A) / the component (B) of 40/60 or more in order to obtain more excellent flexibility and stability of the composition. Preferably, it is 50/50 or more, and from the viewpoint of the softening effect, it is preferably 95/5 or less, more preferably 93/7 or less, and more preferably 90/10 or less.

  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 pH of the liquid softener composition of the present invention at 30 ° C. is preferably 2.5 or more, and is preferably 4.5 or less, more preferably 4.0 or less. This range is preferable in terms of both the fragrance and the residual fragrance and the storage stability of the fiber product after the treatment.
The pH is measured at 30 ° C. according to item 8.3 of JIS K 3362; 2008.
The pH is adjusted with an alkali agent and an acid agent, and an organic acid such as citric acid and succinic acid described later may be used as the acid agent.

The viscosity at 30 ° C. of the liquid softener composition of the present invention is preferably 5 mPa · s or more, more preferably 10 mPa · s or more, and preferably 200 mPa · s or less, more preferably, from the viewpoint of ease of use. 150 mPa · s.
Viscosity was measured using a B-type viscometer. 1-No. This is the indicated value one minute after the start of measurement at 60 r / min using a rotor that matches the viscosity of the measurement object among the three rotors. The liquid softener composition is measured by adjusting the temperature to 30 ± 1 ° C.

[Other ingredients]
The liquid softener composition of the present invention preferably contains the following components.
<(D) Water-soluble organic solvent>
The softener composition of the present invention preferably contains a water-soluble organic solvent as the component (D) from the viewpoint of the stability and viscosity of the composition. (D) As a component, the water-soluble organic solvent known to mix | blend with a softening agent is mentioned. Regarding the component (D), “water-soluble” means that 20 g or more is dissolved in 100 g of 20 ° C. deionized water. Specific examples include propylene glycol, ethylene glycol, glycerin, diethylene glycol, monoethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, isopropanol, ethanol, and the like. A water-soluble organic solvent selected from ethylene glycol and ethanol is 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 softening composition of the present invention contains the component (D) preferably 1.0% by mass or more and preferably 10% by mass or less.

<(E) Inorganic salt>
In the liquid softening agent composition of the present invention, an inorganic salt can be blended as the component (E) as necessary for the purpose of improving storage stability. As the inorganic salt, a water-soluble inorganic salt is preferable, and specifically, a water-soluble inorganic salt selected from sodium chloride, calcium chloride, and magnesium chloride is preferable from the viewpoint of storage stability. Regarding the component (E), “water-soluble” means that 20 g or more is dissolved in 100 g of 20 ° C. deionized water. Inorganic salts contribute to the liquid stability of the softener itself.
The liquid softener composition of the present invention comprises (E) component, preferably 0.01% by mass or more, and preferably 2.0% by mass or less, more preferably 1.0% by mass or less.

<(F) acid agent>
In the liquid softening agent composition of the present invention, the pH of the stock solution is adjusted to 2.5 or more and 4.0 or less at 30 ° C. in order to suppress decomposition due to hydrolysis of the quaternary ammonium compound of component (A). It is preferable to do. Therefore, it is preferable that the liquid softening agent composition of this invention mix | blends an acid agent as (F) component.

  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. Specific examples of the organic acid 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, methyl sulfuric acid, ethyl sulfuric acid, p-toluenesulfonic acid, (o-, m-, p-) xylenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, glycolic acid, methylglycine diacetic acid, ethylenediamine 4 Examples include acetic acid, citric acid, benzoic acid, and salicylic acid. Preferably, it is at least one selected from methylglycine diacetic acid, ethylenediaminetetraacetic acid, and citric acid.

  An acid agent is mix | blended in the range from which pH becomes the said range, and is restrict | limited to the grade which does not impair stability. (F) The compounding quantity of a component is suitably adjusted with the kind and quantity of (A) component. In the case of an organic acid, even if it is blended with an organic acid salt, an acid agent is used if a part of the acid has an acid structure due to pH.

<(G) Other surfactant>
You may mix | blend surfactant other than (A) component and (B) component as a (G) component in the liquid softening agent composition of this invention in the range which does not impair the effect of this invention.

(G) As a component, 1 or more types of surfactant chosen from a cationic surfactant and a nonionic surfactant is mentioned.
The cationic surfactant is preferably one or more selected from the following (I) to (III), more preferably one or more selected from (II).
(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 having an alkyl group or alkenyl group having 10 to 22 carbon atoms Alkyl or alkenyltrimethylammonium salt (III): mono-long-chain alkyl or alkenyldimethylbenzylammonium salt wherein the alkyl group or alkenyl group has 10 to 22 carbon atoms

Examples of the nonionic surfactant include one or more selected from the following (IV) and (V).
(IV): Nonionic surfactant represented by the following general formula (G1) R ^1g —O — [(C ₂ H ₄ O) _s (C ₃ H ₆ O) _t ] —H (G1)
[Wherein, R ^1g is 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 or block adducts. ]
(V): Nonionic surfactant represented by the following general formula (G2)

[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 component (G), a nonionic surfactant is preferable, and a nonionic surfactant represented by the general formula (G1) is more preferable.

<(H) Fatty acid>
In the liquid softener composition of the present invention, it is preferable to blend a fatty acid as the component (H) for the purpose 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 include 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. Preferably, a fatty acid selected from palmitic acid, stearic acid, oleic acid, and linoleic acid is more preferable.

<(I) Fragrance>
The liquid softening agent composition of this invention can contain the fragrance | flavor which is not included in the microcapsule which is (C) component as (I) component. The perfume of component (I) is present dissolved or dispersed in the liquid portion of the liquid softener composition.

As the fragrance | flavor of (I) component, the various natural or synthetic | combination fragrance | flavor generally used for the flexible composition is mentioned. For example,
(I ₁ ) Ethers such as fatty acid ethers, aromatic ethers (excluding phenol ethers),
(I ₂ ) Oxides such as fatty acid oxides, terpene oxides,
(I ₃ ) acetal,
(I ₄ ) Ketal,
(I ₅ ) phenol,
(I ₆ ) phenol ether,
(I ₇ ) acids such as fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, aromatic carboxylic acids,
Synthetic fragrances such as (I ₈ ) acid amide, nitromusk, nitrile, amine, pyridine, quinoline, pyrrole, indole and other nitrogen-containing compounds. 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 | combination fragrance | flavor is mentioned. As the component (I), one or two of these can be mixed and used.

  As the component (I), for example, the fragrance component described in “Perfumeand Flavor Chemicals” written by Motoichi Into in 1969 Chemical Industry Daily, “Synthetic Fragrance Chemistry and Product Knowledge”, 1969 MONTCLAIR, NTE published by STEFFEN ARCTANDER I can do it.

  Further, as the fragrance of the component (I), a fragrance component having a hydroxy group can be used in combination as a silicate ester (for example, described in JP-A-2009-256818) for the purpose of sustaining fragrance and remaining fragrance.

[Additional optional ingredients]
As further optional components, the following components may be mentioned.
The liquid softener composition of the present invention may contain a well-known antioxidant such as BHT in order to suppress deterioration of the substrate, and is already included in the component (A), the component (C) or the fragrance component. It may be blended with the base material. By blending, odor generation due to decomposition can be suppressed.

  In the liquid softener composition of the present invention, a dye or pigment known to be blended in the softener can be blended from the viewpoint of wiping out concerns due to aesthetics and coloring during long-term storage.

  In addition, the liquid softening agent composition of the present invention can be blended with an antibacterial / antifungal agent marketed under the name of proxel or caisson as long as the stability is not impaired.

  In addition, the liquid softener composition of the present invention contains methylglycine diacetic acid (also known as MGDA), ethylenediaminetetraacetic acid (which is known as EDTA) for the purpose of preventing hue change and fragrance alteration during long-term storage. Can also contain chelating agents such as citric acid and their salts, with MGDA being preferred for biodegradability. A small amount of 0.1% by mass or less in the composition is sufficiently effective. The chelating agent may function as the acid agent and may also serve the purpose of pH adjustment.

  In addition, the liquid softening agent composition of the present invention may contain dimethylpolysiloxane or various modified silicones that are generally known to be added to softening agents in order to improve the texture and feel of the textile product.

In addition to the embodiments described above, the present invention discloses the following textile product treating agent composition and textile product treating method.
<1> A liquid softener composition containing 5% by mass or more and 20% by mass or less of the following component (A), 0.5% by mass or more and 10% by mass or less of the component (B), and water.
<(A) component>
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,
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 hydrogen atoms at the same time, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an organic or inorganic anion. ]
<(B) component>
A component comprising a plurality of ester compounds of pentaerythritol and a fatty acid having 16 to 22 carbon atoms,
The proportion of the fatty acid monoester structure is 40% 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 45% by mass or more and 90% by mass or less in the total amount of the ester compound

<2> The component (C) further includes a microcapsule containing a fragrance containing 90% by mass or more of a fragrance compound having a log P value of 2.0 or more and 6.0 or less. Liquid softener composition.

<3> The liquid softening agent composition according to <2>, wherein the microcapsule has an outer shell containing a melamine resin.

<4> The mass ratio of component (A) / component (B) is preferably 40/60 or more, preferably 50/50 or more, and preferably 95/5 or less, preferably 93/7 or less. The liquid softener composition according to any one of <1> to <3>, which is preferably 90/10 or less.

<5> Component (C) is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and preferably 2.0% by mass or less, more preferably Is a liquid softener composition according to any one of the above <2> or <3>, which contains 1.0% by mass or less, more preferably 0.5% by mass or less.

<6> Of the pentaerythritol fatty acid ester of the component (B), the proportion of the fatty acid tetraester structure in the component (B) is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10%. The liquid softening agent composition according to any one of <1> to <5>, which is not more than mass%.

<7> In component (B),
The proportion of the fatty acid monoester structure is preferably 5% by mass or more, more preferably 10% by mass or more, more preferably 12% by mass or more, and preferably 35% by mass or less, more preferably 29% by mass or less,
The proportion of the fatty acid diester structure is preferably 30% by mass or more, more preferably 35% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less,
The proportion of the fatty acid triester structure is preferably 10% by mass or more, more preferably 15% by mass or more, and preferably 40% by mass or less, more preferably 35% by mass or less,
The proportion of fatty acid tetraester structure is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, more preferably 10% by mass or less. is there,
The liquid softening agent composition according to any one of <1> to <6>.

<8> Further, as component (D), a water-soluble solvent, preferably 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 selected from the above, more preferably one or more water-soluble solvents selected from ethylene glycol and ethanol are contained in an amount of 1.0% by mass or more and 10% by mass or less, in any one of the above items <1> to <7> The liquid softener composition as described.

<9> Further, as component (E), an inorganic salt, preferably a water-soluble inorganic salt, more preferably 0.01% by mass or more of one or more water-soluble inorganic salts selected from sodium chloride, calcium chloride, and magnesium chloride. The liquid softening agent composition according to any one of <1> to <8>, wherein 2.0% by mass or less is blended.

<10> Further, as component (F), an acid agent, preferably an inorganic acid selected from hydrochloric acid and sulfuric acid, or methyl sulfuric acid, ethyl sulfuric acid, p-toluenesulfonic acid, (o-, m-, p-) xylenesulfonic acid , Benzenesulfonic acid, dodecylbenzenesulfonic acid, glycolic acid, methylglycine diacetic acid, ethylenediaminetetraacetic acid, citric acid, benzoic acid and salicylic acid, more preferably methylglycine diacetic acid, ethylenediaminetetraacetic acid and citric acid The liquid softening agent composition in any one of said <1>-<9> formed by mix | blending 1 or more types of organic acids chosen from these.

<11> Further, as the component (G), a surfactant other than the components (A) and (B), preferably a nonionic surfactant represented by the following general formula (G1), <1 >-<10> The liquid softening agent composition in any one of.
_{^{R 1g -O - [(C 2}} H 4 O) s (C 3 H 6 O) t] -H (G1)
[Wherein, R ^1g is 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 or block adducts. ]

<12> Furthermore, the liquid softening agent composition in any one of said <1>-<11> containing the fragrance | flavor which is not included in the microcapsule which is (C) component as (I) component.

<Synthesis Example 1-1> Synthesis of (a-1) A fatty acid having an acid value of 206.9 mgKOH / g using palm oil as a raw material and triethanolamine were reacted at a reaction molar ratio of 1.65 / 1 (fatty acid / triethanol. Amine) was subjected to a dehydration condensation reaction 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)). The alkanoyl group of this mixture is a residue of fatty acid derived from palm oil, and the term “alkanoyl” herein includes a residue derived from an unsaturated fatty acid in addition to a saturated fatty acid, such as alkenoyl. Shall be included. The preparation procedure and reaction conditions were carried out according to Synthesis Example 2 of JP 2010-209493 A.
In the quaternary ammonium salt of the component (A) contained in (a-1), the proportion of the component (a1) is 30 mass%, the proportion of the component (a2) is 55 mass%, and the proportion of the component (a3) is 15 mass%. %Met. (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. Here, the ratio of the component (a1), the component (a2) and the component (a3), and the analysis of the other components were measured using HPLC under the following conditions.
<HPLC conditions>
Column: Inertsil NH2 5μm (4.6 × 250mm)
Mobile phase: 0.05% TFA (trifluoroacetic acid) -hexane solution: methanol: THF (tetrahydrofuran) = 85: 10: 5
Flow rate: 0.8 mL (0-10 minutes)-1.2 mL (11-55 minutes)-0.8 mL (55.1-60 minutes)
Temperature: Room temperature (25 ° C)
Injection: 20μL
Detection: CAD

<Synthesis Example 1-2> Synthesis of (a-2) Except that the reaction molar ratio was changed to 1.50 / 1 (fatty acid / triethanolamine), (a-2) was prepared in the same manner as in Synthesis Example 1-1. The proportions of component (a1), component (a2) and component (a3) were determined by the above method.
In the quaternary ammonium salt of the component (A) contained in (a-2), the proportion of the component (a1) is 36 mass%, the proportion of the component (a2) is 54 mass%, and the proportion of the component (a3) is 10 mass%. %Met.

<Synthesis Example 2-1> Synthesis of (b-1) 180 g of pentaerythritol, 562 g of stearic acid (1.5 mol of fatty acid with respect to 1 mol of pentaerythritol), 0.27 g of NaOH were charged into a four-necked flask, and nitrogen gas The reaction was carried out at 235 ° C. for 5 hours while removing water generated by the reaction. After confirming that the acid value of the reaction product was 1 mgKOH / g or less and cooling to 70 ° C., the precipitated unreacted pentaerythritol was filtered under pressure at the same temperature to synthesize the component (b-1). The obtained (b-1) is a mixture of pentaerythritol fatty acid esters, and the proportion of each ester compound is 29% by mass of fatty acid monoester structure, 43% by mass of fatty acid diester structure, and 23% by mass of fatty acid triester structure. %, Fatty acid tetraester structure 5% by mass. The ratio of the fatty acid monoester structure, the fatty acid diester structure, the fatty acid triester structure, and the fatty acid tetraester structure was measured using a high-speed GPC apparatus HCL-8220GPC (manufactured by Tosoh Corporation).

<Synthesis Example 2-2; (b-2) Synthesis of Component>
Synthesis was performed in the same manner as in Synthesis Example 2-1, except that 180 g of pentaerythritol and 658 g of stearic acid (fatty acid (1.75 mol) with respect to 1 mol of pentaerythritol) were used in Synthesis Example 2-1. (B-2) is a mixture of pentaerythritol fatty acid esters, and the proportion of each ester compound is 21% by mass of fatty acid monoester, 41% by mass of fatty acid diester, and fatty acid triester. They were 30 mass% and fatty acid tetraester 8 mass%.

<Synthesis Example 3> Synthesis of (b'-1) Synthesis was performed in the same manner as in Synthesis Example 2 except that 180 g of pentaerythritol and 263 g of stearic acid (0.7 mol of fatty acid per 1 mol of pentaerythritol) were used. (B′-1) component was obtained. The obtained (b′-1) is a mixture of pentaerythritol fatty acid esters, and the ratio of each ester compound is as follows: fatty acid monoester structure 62% by mass, fatty acid diester structure 31% by mass, fatty acid triester structure 6 The content was 1% by mass and the fatty acid tetraester structure.

<Synthesis Example 4> Production of (c-1) Diisobutylene-maleic anhydride copolymer (Demol EP, solid content 25%, Kao Corporation) was neutralized with hydrochloric acid and further diluted with ion-exchanged water. As a result, an aqueous solution having a solid content of 3% and a pH of 4.3 was obtained. Next, 36 g of the fragrance (c1-1) having the composition shown in Table 1 was added to 100 g of the diisobutylene-maleic anhydride copolymer aqueous solution, and the mixture was emulsified using a homomixer, and the temperature was raised to 50 ° C. Next, an aqueous solution in which 12 g of partially methylolated melamine resin (trade name Cymel385, solid content 80%, manufactured by Cytec Industries Inc) and 35 g of ion-exchanged water were mixed was dropped. This was kept at 50 ° C. for 2 hours, further kept at 70 ° C. for 1 hour, and further kept at 80 ° C. for 3 hours to complete the encapsulation. Then, by cooling, (c-1) was obtained as a microcapsule slurry having an average particle size of 7 μm and an effective content of 30% by mass. In (c-1), the ratio of the fragrance (C1) in the inclusion (core substance) of the microcapsule was 80% by mass.

  Here, a fragrance | flavor (c1-1) is a thing of the following Table 1.

<Synthesis Example 5> Production of (c-2) 240 g of ion exchange water was added to a 1 L four-necked flask. Two dropping funnels are connected to the four-necked flask, and 98.8 g of acrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) and 20.0 g of acrylamide are mixed in one dropping funnel (monomer solution). In another dropping funnel, 3.75 g of V-50 (manufactured by Wako Pure Chemical Industries, Ltd., 2,2-azobis (2-methylpropioamidine) dihydrochloride) was added with 75 g of ion-exchanged water. A solution diluted with (initiator solution) was added. The apparatus was degassed by repeating the operation of reducing the pressure to 210 kPa and returning to normal pressure with nitrogen three times. After the inside of the flask was heated to 70 ° C., the monomer solution was added dropwise at 3.7 g / min and the initiator solution was added at 1.3 g / min. After the addition, the reaction solution was cooled after aging for 2 hours. The polymer was reprecipitated by adding 300 g of the reaction solution dropwise to 800 g of acetone. The obtained polymer was dried at 80 ° C. under a reduced pressure of 60 kPa for 48 hours to obtain 52 g of an acrylic acid-acrylamide copolymer. The weight average molecular weight was 170,000.

  2.4 g of acrylic acid-acrylamide copolymer obtained by the above method was diluted with 84 g of ion-exchanged water, and adjusted to pH 4 with an aqueous sodium hydroxide solution. 3 g of partially methylolated melamine resin (trade name Cymel385) was added thereto and stirred for 30 minutes. Next, 76 g of the fragrance (c1-1) having the composition shown in Table 1 used in Synthesis Example 4 was added and emulsified using a homomixer, and the temperature was raised to 50 ° C. and held for 1 hour. On the other hand, an aqueous solution obtained by mixing 1 g of acrylic acid-acrylamide copolymer and 48 g of ion-exchanged water was adjusted to pH 4.8 with sodium hydroxide, and 10 g of partially methylolated melamine resin (trade name Cymel385) and 1.5 g of sodium sulfate were added. In addition, after stirring for 30 minutes, this was added to the emulsion. After maintaining at 70 ° C. for 14 hours, the mixture was cooled to obtain (c-2) as a microcapsule slurry having an average particle size of 7 μm and an effective content of 30% by mass. In (c-2), the ratio of the fragrance (C1) in the inclusion (core substance) of the microcapsule was 80% by mass.

Of the components used in Examples and Comparative Examples, those indicated by symbols in the table are shown below.
<(A) component>
(A-1): Reaction product containing a quaternary ammonium salt mixture produced in Synthesis Example 1-1. The numerical value of (a-1) shown in Table 2 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 1-2. The numerical value of (a-2) shown in Table 2 is the content concentration in the form of (a-2). The (A) component density | concentration in (a-2) is 80 mass%.

<(B) component>
(B-1): Reaction product containing pentaerythritol fatty acid ester mixture produced in Synthesis Example 2-1 (b-2): Reaction containing pentaerythritol fatty acid ester mixture produced in Synthesis Example 2-2 Product

<(B ′) component>
(B′-1): reaction product produced in Synthesis Example 3 and containing a pentaerythritol fatty acid ester mixture

<(C) component>
(C-1) Microcapsule fragrance produced in Synthesis Example 4 (c-2) Microcapsule fragrance produced in Synthesis Example 5

<(G) component>
(G-1): Polyoxyethylene lauryl ether (average number of moles of oxyethylene group added is 30 moles)

Examples 1-11 and Comparative Examples 1-3
Liquid softener compositions having the compositions shown in Table 2 were prepared by the following method. About the obtained liquid softening agent composition, the softness | flexibility provision effect and the fragrance | flavor effect were evaluated in the following way. The results are also shown in Table 2.

<Preparation of liquid softener composition>
In a 300 mL glass beaker (inner diameter: 7 cm, height: 11 cm), an amount of ion-exchanged water (65 ° C.) and component (D) corresponding to 95% of the amount required to achieve a final weight of 300 g of the liquid softener composition. A water-soluble organic solvent, an acid agent as component (F), a surfactant as component (G), preferably a nonionic surfactant, are added and heated in a water bath so that the temperature of the content is 65 ° C. or higher. did. Next, a stirring blade (turbine type stirring blade, three blades, blade length 2 cm) attached to a three-one motor (manufactured by Shinto Kagaku Co., Ltd., TYPE HEIDON 1200G) was installed at a height of 1 cm from the bottom of the glass beaker. A quaternary ammonium compound of the fatty acid ester structure type that is the component (A) and the pentaerythritol fatty acid that is the component (B) or (B ′), which are previously melted and mixed at 65 ° C. with stirring at a rotational speed of 350 r / min. After the ester and the microcapsule fragrance particles as the component (C) were added, the mixture was stirred at 65 ° C. for 10 minutes at 350 r / min, and then the water-soluble inorganic salt as the component (E) was added and stirred for 10 minutes. Next, the solution was stirred and cooled at a rotational speed of 350 r / min until the contents reached 30 ° C. in a water bath containing ice water. After the temperature of the contents has dropped to 30 ° C., an amount of ion-exchanged water necessary for the concentration of each component to reach the value shown in Table 2 is added, and the mixture is stirred for 10 minutes at 30 ° C. and a rotation speed of 200 r / min. A liquid softener composition was obtained.

<Flexibility evaluation method>
(1) Pretreatment of evaluation towel In advance, 24 non-ionic surfactants (ethylene oxide adduct of lauryl alcohol (average added mole number 8)), 24 cotton towels (Takei towel, TW-220) The washing process of Hitachi automatic washing machine NW-6CY was repeated 5 times (non-ionic surfactant use amount 4.5 g, standard course, water volume 45 L, water temperature 20 ° C., washing time 10 minutes, rinsing 2 times). Thereafter, it was dried for 1 day under the conditions of 20 ° C. and 43% RH.

(2) Softening treatment of evaluation towel 4.5L of city water adjusted to 20 ° C is poured into National Electric bucket washing machine (MiniMini, model number: NA-35) and pretreated by the method of (1) above. Two pieces of cotton towel were put in and stirred for 1 minute. After stirring, the liquid softener composition shown in Table 2 was added in an amount of 10 g per 1.5 kg of cotton towel, and stirred for 5 minutes. Then, it dehydrated for 3 minutes in the dehydration layer, and dried for 1 day under the conditions of 20 ° C. and 43% RH.

(3) Evaluation of flexibility The softness of the cotton towel treated and dried in Comparative Example 1 was compared with the softness of the cotton towel treated and dried in Comparative Example 1 by 10 panelists. The softness values in Table 2 represent the average value of 10 panelists. In this evaluation, the average score is preferably 1.5 or more.
Evaluation criteria:
0: Not softer than Comparative Example 1: 1: Softness equivalent to Comparative Example 1: 2: Softer than Comparative Example 1

<Evaluation of fragrance of treated fiber product>
After the softening treatment by the method (2) of the “flexibility evaluation method”, the dried cotton towel was allowed to stand for 10 minutes in a state of being folded in four. After standing, the cotton towel was opened from the four-folded state to the two-folded state, and the strength of the scent of the opened part was compared with that of the cotton towel treated and dried in Comparative Example 1. The evaluation was performed by 10 panelists, and after each paneler evaluation, the sample was allowed to stand for 10 minutes in a four-fold state, and then sensory evaluation was performed in a two-fold state. The numerical value of the fragrance intensity in Table 2 shows the average value of 10 panelists. In this evaluation, the average score is preferably 1.1 or more.
Evaluation criteria:
0: Fragrance weaker than Comparative Example 1: 1: Fragrance strength equivalent to Comparative Example 1: 2: Fragrance stronger than Comparative Example 1

Claims (6)

The liquid softening agent composition containing 5 mass% or more and 20 mass% or less of the following (A) component, 0.5 mass% or more and 10 mass% or less of (B) component, and water.
<(A) component>
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,
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 hydrogen atoms at the same time, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and X ⁻ is an organic or inorganic anion. ]
<(B) component>
A component comprising a plurality of ester compounds of pentaerythritol and a fatty acid having 16 to 22 carbon atoms,
The proportion of the fatty acid monoester structure is 40% 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 45% by mass or more and 90% by mass or less in the total amount of the ester compound   Furthermore, the liquid softening agent composition of Claim 1 which contains the microcapsule which included the fragrance | flavor which contains 90 mass% or more of fragrance | flavor compounds whose logP value is 2.0 or more and 6.0 or less as (C) component. object.   The liquid softening agent composition according to claim 2, wherein the microcapsule has an outer shell containing a melamine resin.   The liquid softening agent composition of any one of Claims 1-3 whose mass ratio of (A) component / (B) component is 40/60 or more and 95/5 or less.   Furthermore, the liquid softening agent composition in any one of Claims 1-4 which contains surfactant other than (A) component and (B) component as (G) component. The liquid softening agent composition of Claim 5 which contains the nonionic surfactant shown by the following general formula (G1) as (G) component.
_{^{R 1g -O - [(C 2}} H 4 O) s (C 3 H 6 O) t] -H (G1)
[Wherein, R1g represents an alkyl group or an alkenyl group having 8 to 18 carbon atoms. s and t are average addition mole numbers, s is a number of 2-50, and t is a number of 0-5. (C ₂ H ₄ O) and (C ₃ H ₆ O) may be random or block adducts. ]