WO2019176430A1

WO2019176430A1 - Liquid softener composition

Info

Publication number: WO2019176430A1
Application number: PCT/JP2019/005186
Authority: WO
Inventors: 竹内賢二; 木下隼人
Original assignee: 花王株式会社
Priority date: 2018-03-15
Filing date: 2019-02-14
Publication date: 2019-09-19
Also published as: JP6716181B2; JP2019163579A

Abstract

The present invention is a liquid softener composition which comprises (A) 3-20 mass% tertiary amine or compound obtained by neutralizing or quaternizing the amine, the amine or compound containing an ester group and having one or more C_9-23 hydrocarbon groups in the molecule, (B) an ester of a C_12-22 fatty acid with a C_3-22 aliphatic alcohol, (C) 0.1-8 mass% quaternary ammonium compound represented by general formula (c1), and water, wherein the (A)/(B) mass ratio is 2-200.

Description

Liquid softener composition

The present invention relates to a liquid softener composition.

BACKGROUND ART In recent years, a soft base having an intramolecular ester group has been used as a main base of a softener for the purpose of rapidly decomposing even when discharged into the environment and reducing the burden on the environment. Ester-based soft bases are excellent in environmental degradability, while ester groups are easily hydrolyzed in water, affecting the quality such as softness and storage stability of liquid softener compositions that use the soft base. Is concerned about giving.

On the other hand, it has been clarified that microorganisms generated by raw drying such as room drying produce an unpleasant odor, and the countermeasure is desired.

JP 63-6168 discloses a softener composition containing an ester group in the molecule and containing a rapid biodegradable quaternary ammonium softener. It is disclosed that the hydrolyzability of the ester group of the softening base is suppressed by adjusting the pH of the softening agent composition. JP 2012-82538 A includes a soft base having an ester group in the molecule, a higher alcohol alkylene oxide addition nonionic surfactant having a relatively large number of added alkylene oxides, and a fatty acid ester. Furthermore, it is disclosed that the hydrolyzability of the ester group of the flexible base is suppressed by defining the mass ratio of the two. Japanese Patent Application Laid-Open No. 2012-233281 discloses that a soft base having an ester group in the molecule contains a specific fatty acid ester and a specific perfume, thereby suppressing hydrolysis of the ester group of the soft base. Is disclosed.

Also, JP-T-2004-522010 discloses a detergent composition for suppressing a dry odor containing a carbonyl compound having a specific structure. Japanese Patent Application Laid-Open Nos. 2007-112984, 2001-336065, and 2001-200166 describe a flexible base that uses an antibacterial agent in combination with a flexible base having a fatty acid ester structure of a quaternary ammonium salt. An agent composition is described.

SUMMARY OF THE INVENTION In addition to the problem that the liquid softener composition is stored in a hot and humid environment, the base is hydrolyzed, the viscosity is easily changed, and the usability is reduced. It has been found that there may be a problem that the inherent antibacterial effect is reduced.

The present invention is an antibacterial liquid softening agent composition for suppressing odor caused by drying in the room and a return odor during use, in which a decrease in antibacterial effect due to storage is suppressed, and a viscosity suitable for handling even after storage. Provided is a liquid softener composition capable of maintaining

The present invention provides (A) a tertiary amine or a neutralized product or quaternized product thereof (hereinafter referred to as (A) containing an ester group and having one or more hydrocarbon groups of 9 to 23 carbon atoms in the molecule. ) Component] is 3% by mass or more and 20% by mass or less,
(B) an ester of a fatty acid having 12 to 22 carbon atoms and an aliphatic alcohol having 3 to 22 carbon atoms [hereinafter referred to as component (B)],
(C) A quaternary ammonium compound represented by the following general formula (c1) [hereinafter referred to as the component (C)] is contained in an amount of 0.1% by mass to 8% by mass, and water.
(A) component / (B) component mass ratio is 2 or more and 200 or less,
The present invention relates to a liquid softener composition.

(In the formula, R ^1c is a hydrocarbon group having 8 to 16 carbon atoms, R ^2c and R ^3c are each an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and R ^4c is An alkylene group having 1 to 3 carbon atoms or a hydroxyalkylene group.)

According to the liquid softener composition of the present invention, it is possible not only to maintain a softness-imparting effect on textile products but also to maintain viscosity and antibacterial properties suitable for handling even after storage.

MODE FOR CARRYING OUT THE INVENTION <Liquid Softener Composition>
[(A) component]
The component (A) contains an ester group, a tertiary amine having at least one hydrocarbon group having 9 to 23 carbon atoms in the molecule, a neutralized product of the tertiary amine, and the tertiary One or more compounds selected from quaternized amines.
The hydrocarbon group contained in the component (A) preferably has 11 or more carbon atoms, more preferably 13 or more carbon atoms, and preferably 21 or less carbon atoms.

As the component (A), (A1) a tertiary amine compound represented by the following general formula (a1) and its acid salt (hereinafter referred to as the (A1) component), and (A2) the following general formula (a1) One or more compounds selected from the quaternized products of the tertiary amine compounds represented below (hereinafter referred to as the component (A2)) can be mentioned.
[R ^1a —C (═O) —O— (C _p H _2p O) _r —C _q H _2q ] _m N (R ^2a ) _3-m (a1)
[Wherein, R ^1a is a hydrocarbon group having 11 to 23 carbon atoms, and R ^2a is a hydrocarbon group having 1 to 3 carbon atoms and a HO— (C _p H _2p O) _r —C _q H _2q group. Wherein m is a number from 1 to 3, p and q are 2 or 3, and r is a number from 0 to 5. When there are a plurality of R ^1a , R ^2a , HO— (C _p H _2p O) _r —C _q H _2q groups, p, q, and r in the same molecule, they may be the same or different. ]

The (A) component can be exemplified as a compound selected from the (A1) component and the (A2) component or a mixture containing them.

R ^1a is preferably a hydrocarbon group having 13 to 21 carbon atoms from the viewpoint of softening the fiber product.
Specific examples of the hydrocarbon group of R ^1a are a group selected from an alkyl group having 11 or more, 13 or more, and 21 or less and an alkenyl group having 11 or more, 13 or more, and 21 or less carbon. . From the viewpoint of ease of production of the liquid softening agent composition, R ^1a is preferably a group selected from an alkyl group having 11 to 23 carbon atoms and an alkenyl group having 11 to 23 carbon atoms. More preferably, R ^1a is a group selected from an alkyl group having 13 to 21 carbon atoms and an alkenyl group having 13 to 21 carbon atoms.

The unsaturated group contained in the alkenyl group has a cis form and a trans form. Regarding R ^1a , specific examples of the ratio of cis isomer to trans isomer include cis isomer / trans isomer = 30/70 or more and 99/1 or less. From the viewpoint of availability of the alkenyl group, 50/50 or more and 97/3 or less are preferable. In the present invention, the ratio of the cis form to the trans form can be calculated by the integral ratio of ¹ H-NMR.

p and q are numbers of 2 or 3, respectively. (A) From the viewpoint of ease of production of the component, q is preferably a number of 2.
r is preferably a number of 0 or more and 2 or less, more preferably 0, from the viewpoint of softening of the fiber product.

The tertiary amine compound represented by the general formula (a1) as the component (A1) may be partially or entirely present in the form of an acid salt depending on the pH of the liquid softening agent composition.
Examples of the acid when present in the acid salt of the tertiary amine compound 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, methylsulfuric acid, ethylsulfuric acid, p-toluenesulfonic acid, (o-, m-, p-) xylenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, glycolic acid, citric acid, benzoic acid, salicylic acid Is mentioned.

The production method for obtaining the amine compound represented by the general formula (a1) as the component (A1) is not particularly limited. For example, an esterification reaction between an alkanolamine compound represented by the following general formula (a2) and a fatty acid, or It can be obtained by a transesterification reaction with a fatty acid ester.
(HO—C _q H _2q ) _{m ′} N (R ^{2a ′} ) _{3-m ′} (a2)
[Wherein, R ^{2a ′} is a hydrocarbon group having 1 to 3 carbon atoms, preferably a methyl group, and m ′ is a number of 1 to 3, preferably 2 or 3, more preferably 3 And q represents the same meaning as in the general formula (a1). ]
Preferred specific compounds of the general formula (a2) are triethanolamine or diethanolmethylamine.

As an example of the esterification reaction, for example, the method described on pages 8 to 9 of JP-T-2000-510171 can be applied.

As an example of the transesterification reaction, for example, the method described in [0013] to [0016] of JP-A-7-138211 can be applied.

The quaternized product of the compound represented by the general formula (a1) as the component (A2) can be obtained by a quaternization reaction using the amine compound represented by the general formula (a1) and an alkylating agent. . Examples of the alkylating agent include methyl chloride, dimethyl sulfate, diethyl sulfate and the like. As examples of the quaternization reaction, for example, the method described in [0017] to [0023] of JP-A-7-138211, or the production method described in JP-A-11-106366 can be applied. .

The component (A) may be a single compound or a mixture of two or more compounds. When the component (A) is a mixture of two or more compounds, a mixture having a number average number of m in the general formula (a1) of 1.2 or more and 2.5 or less can be used. From the viewpoint of softening the fiber product, the number average number of m is preferably 1.3 or more, more preferably 1.4 or more, and preferably 2.0 or less, more preferably 1.9 or less. .

In the present invention, the component (A) preferably includes the component (A1) and the component (A2). When the component (A) includes the component (A1) and the component (A2), the mass ratio of the component (A1) to the component (A2) is preferably (A1) component / (A2) component = 1/99 or more. / 97 or more is more preferable, 5/95 or more is more preferable, 50/50 or less is preferable, 40/60 or less is more preferable, and 35/65 or less is more preferable. In preparing the composition, a mixture containing the components (A1) and (A2) can be used as the component (A).

[Component (B)]
As the component (B), an ester composed of a fatty acid having 12 to 22 carbon atoms and an aliphatic alcohol having 3 to 22 carbon atoms is used. The fatty acid is preferably a saturated or unsaturated fatty acid having 12 to 18 carbon atoms. The aliphatic alcohol is preferably a branched chain alcohol having 3 to 18 carbon atoms. The aliphatic alcohol is preferably a primary alcohol.

Specific examples of the component (B) include 2-ethylhexyl laurate, lauryl laurate, 2-octyldodecyl laurate, 2-ethylhexyl myristate, myristyl myristate, 2-octyl dodecyl myristate, isopropyl palmitate, palmitic acid Examples thereof include 2-ethylhexyl, palmityl palmitate, 2-octyldodecyl palmitate, 2-ethylhexyl stearate, stearyl stearate, 2-octyldodecyl stearate and the like. The component (B) is preferably one or more fatty acid esters selected from isopropyl palmitate, 2-octyldodecyl myristate, 2-ethylhexyl stearate, and stearyl stearate. The component (B) is more preferably one or more fatty acid esters selected from isopropyl palmitate, 2-octyldodecyl myristate, and 2-ethylhexyl stearate.

[Component (C)]
The component (C) is a quaternary ammonium compound represented by the general formula (c1). Component (C) is known as a bactericidal agent, but in the present invention, an increase in viscosity after long-term storage of the liquid softener composition can be suppressed by using it together with component (B).
In formula (c1), R ^1c is a hydrocarbon group having 8 to 16 carbon atoms. The hydrocarbon group for R ^1c is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group. R ^1c has 8 or more carbon atoms, preferably 10 or more, more preferably 12 or more, and 16 or less, preferably 14 or less. R ^1c preferably has 12 to 16 carbon atoms. R ^1c is more preferably an alkyl group having 12 to 14 carbon atoms, more preferably one or more alkyl groups selected from an alkyl group having 12 carbon atoms and an alkyl group having 14 carbon atoms, and linear alkyl having 12 carbon atoms. Even more preferable are one or more linear alkyl groups selected from a group and a linear alkyl group having 14 carbon atoms.
In Formula (1), R ^2c and R ^3c are each an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms, preferably a methyl group. R ^4c is an alkylene group having 1 to 3 carbon atoms or a hydroxyalkylene group having 1 to 3 carbon atoms, preferably a methylene group.

The component (C) may be a mixture of compounds having different carbon numbers for R ^1c .
Within the component (C), the total proportion of the compounds compounds and R ^1c R ^1c is a hydrocarbon group having 12 carbon atoms is a hydrocarbon group of 14 carbon atoms, preferably 80 wt% or more, more preferably 85 % By mass or more, more preferably 90% by mass or more, and preferably 99% by mass or less, more preferably 98% by mass or less, and still more preferably 97% by mass or less.
In the component (C), the ratio of the compound in which R ^1c is a hydrocarbon group having 12 carbon atoms is preferably 40% by mass or more, more preferably 45% by mass or more, still more preferably 50% by mass or more, and Preferably it is 85 mass% or less, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less.

[Contents of (A) component, (B) component and (C) component]
Content of (A) component in the liquid softening agent composition of this invention is 3 mass% or more and 20 mass% or less. The content of the component (A) in the liquid softener composition of the present invention is preferably 5% by mass or more, more preferably 8% by mass or more, from the viewpoint that the amount used per wash can be reduced. Preferably it is 18 mass% or less, More preferably, it is 15 mass% or less.

The content of the component (B) in the liquid softening agent composition of the present invention is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, more preferably 0.2% by mass or more, And preferably it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less.

The content of the component (C) in the liquid softener composition of the present invention is 0.1% by mass or more and 8% by mass or less. The content of the component (C) in the liquid softener composition of the present invention is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and preferably 5% by mass or less, more Preferably it is 3 mass% or less.

In the liquid softener composition of the present invention, from the viewpoint of maintaining an appropriate viscosity of the component (A) and the antibacterial effect, the mass ratio of the component (A) to the component (B) is (A) component / (B ) Component is 2 or more and 200 or less. The mass ratio of component (A) / component (B) is preferably 3 or more, more preferably 5 or more, and is preferably 100 or less, more preferably 80 or less, more preferably 50 or less, more preferably 40. Hereinafter, it is still more preferably 30 or less.

[Optional ingredients]
The liquid softener composition of the present invention includes, as optional components, a surfactant other than the component (A) (hereinafter referred to as the component (D)), a chelating agent (hereinafter referred to as the component (E)), a fragrance composition (hereinafter referred to as the component). And (F) component] and a water-soluble organic solvent (hereinafter referred to as (G) component).
The liquid softener composition of the present invention includes, as optional components, an inorganic electrolyte, an oil agent other than the component (B), an antioxidant, a dye, an antiseptic, a silicone compound, a polymer compound (a polymer compound other than a silicone compound), (A) The pH adjuster for adjusting to pH suitable for stabilization of a component can be contained.

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

(D1) As a nonionic surfactant of a component, 1 or more types chosen from the following (D11) and (D12) are mentioned.
(D11): Nonionic surfactant represented by the following general formula (d1) R ^1d —O — [(C ₂ H ₄ O) _s (C ₃ H ₆ O) _t ] —H (d1)
[Wherein, R ^1d represents an alkyl group or an alkenyl group having 8 or more, preferably 10 or more, and 18 or less, preferably 16 or less carbon atoms. s and t are the average number of added moles, respectively, 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 The number is preferably 3 or less. (C ₂ H ₄ O) and (C ₃ H ₆ O) may be either a random polymer or a block polymer. ]
(D12): Nonionic surfactant represented by the following general formula (d2)

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

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

The liquid softener composition of the present invention preferably contains the component (D1) as the component (D), and may contain the nonionic surfactant (D11) represented by the general formula (d1). More preferred.

When the liquid softening agent composition of the present invention contains the component (D), the content of the component (D) in the composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and 10 mass% or less is preferable and 8 mass% or less is more preferable. In the concentration limitation of the component (D), the content of the nonionic surfactant (D11) represented by the general formula (d1) is preferably 0.5% by mass or more in the liquid softener composition of the present invention. Furthermore, 1 mass% or more is more preferable, and 8 mass% or less is preferable.

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

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

Examples of the component (E) include ethane-1-hydroxy-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminedisuccinic acid, L-glutamic acid-N, N— One or more selected from diacetic acid, N-2-hydroxyethyliminodiacetic acid, citric acid, succinic acid and their salts are preferred, and further selected from ethylenediaminetetraacetic acid, methylglycine diacetic acid, citric acid and their salts One or more selected from the above are more preferred, and methylglycine diacetate is even more preferred. These chelating agents may play a role as pH adjusting agents described later.

When the liquid softening agent composition of the present invention contains the component (E), the content of the component (E) in the composition is preferably 0.005% by mass or more in terms of acid type, 01 mass% or more is more preferable, 5 mass% or less is preferable, and 1 mass% or less is more preferable.

[(F) Fragrance composition]
The liquid softening agent composition of the present invention preferably contains a perfume composition not only for perfume of the composition itself but also for the purpose of perfume to textiles.
The fragrance composition used in the present invention is used to give consumers a high preference for the softener composition. Preference is not only the effect of giving a pleasant feeling such as exhilaration, sedation, exhilaration, but also the effect of deodorizing unpleasant odors such as sweat odor, cigarette odor, fresh odor, cooling action, heat action, hypnosis It may also include functional effects such as action, aphrodisiac action, antidepressant action, antibacterial action, and diet action. Examples of the fragrance component include the fragrance described in “Basic knowledge of fragrance and fragrance, edited by Motoki Nakajima, published by Sangyo Tosho Co., Ltd., April 20, 2005,” published in JP 10-507793. Perfume can be used.

From the viewpoint of the quality and strength of the fragrance and the stability in the softener system, the fragrance component is appropriately selected and used. Hereinafter, the compounds that can be blended in the present invention and that are used as a perfume component are classified into the categories shown in the perfume field and are as follows. Examples of terpene compound-based fragrance components include limonene, p-cymene, α-pinene, β-pinene, and β-caryophyllene. Examples of alcohol compound-based fragrance components include cis-3-hexenol, trans-2-hexenol, and methyltrimethylcyclohexane. Pentenylbutenol, dihydromyrcenol, l-menthol, phenylethyl alcohol, citronellol, geraniol, nerol, linalool, terpineol, tetrahydrolinalol, tetrahydrogeraniol, dimethylbenzylcarbinol, β-phenylethyl alcohol, benzyl alcohol, cinnamic alcohol , Anis alcohol, farnesol, nerolidol, dimethylphenylethyl carbinol, o, t-butylcyclohexanol, p, t-butylcyclohex Nord, Sandalmysol core (2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol) (manufactured by Kao Corporation), Bagdanol (IFF) And ester fragrance components such as benzyl acetate, dimethylbenzylcarbvinyl acetate, linalyl acetate, neryl acetate, o, t-butylcyclohexyl acetate, and p, t-butylcyclohexyl acetate. Citronellyl acetate, geranyl acetate, tetrahydrogeranyl acetate, terpenyl acetate, isobornyl acetate, l-menthyl acetate, tricyclodecenyl acetate, 2-phenylethyl acetate, 3-phenylpropyl acetate, styrylyl acetate, cis-3-hexenyl acetate , Trans-2-hexenyl acetate, hexyl acetate, syn acetate Namyl, isobutyl propionate, 2-phenylethyl propionate, citronellyl propionate, benzyl propionate, tricyclodecenyl propionate, geranyl propionate, allyl propionate, geranyl butyrate, citronellyl butyrate, isoamyl butyrate, amyl butyrate, butyric acid Allyl, phenoxyethyl isobutyrate, geranyl isobutyrate, geranyl isovalerate, ethyl caproate, allyl caproate, ethyl enanthate, allyl enanthate, ethyl octoate, methyl anthranilate, cis-3-hexenyl benzoate, benzoic acid Benzyl, amyl salicylate, isoamyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, hexyl salicylate, 2-phenylethyl salicylate, methyl dihydrojasmonate, coumarin, γ Octalactone, γ-undecalactone, γ-decalactone, γ-nonalactone, δ-nonalactone, δ-decalactone, δ-undecalactone, δ-dodecalactone, cyclopentadecanolide, cyclopentadecenolide (havalolide, Filmmenich), cyclohexadecanolide, ambretolide, 11-oxa-16-hexadecanolide (Musk R-1, manufactured by Dibodan), 10-oxa-16-hexadecanolide (oxalide, manufactured by Takasago International Corporation), 12-oxahexadecanolide, ethylene brushate, ethylenedodecanedioate (Musk C-14), and aldehyde compound-based fragrance ingredients such as octanal, nonanal, decanal, undecanal, 10-undecenal, dodecanal, citral, Citronella , Anisaldehyde, phenylacetaldehyde, mylacaldehyde, lilyal, lyral, dimethyltetrahydrobenzaldehyde, amylcinnamic aldehyde, hexylcinnamic aldehyde, cyclamenaldehyde, vanillin, ethyl vanillin, heliotropin, helional, and ketone compounds , Florarozone, l-carvone, menthone, cis jasmon, geranylacetone, and damascons, damacenones, α-dynascon, ionones, methylionones, β-methylnaphthyl ketone, iso-E super, raspberry ketone, maltol, Ethyl maltol, cachemelan (manufactured by IFF), 5-cyclohexedenon-1-one (Musk TM-II) are known as perfumes. As ether compound perfume ingredients, anethole, eugenol, methyl eugenol, methyl isoeugenol, diphenyl oxide, 1,8-cineol, cedryl methyl ether, ambroxan (3α, 6,6,9α-tetramethyldodecahydronaphtho [2 , 1-b] furan), ethoxymethylcyclododecyl ether (boasambrenforte, manufactured by Kao Corporation), nitrogen-containing compound-based fragrance ingredients such as geranyl nitrile, citronellil nitrile, indole, acetyl cedrene, methyl anthranilate N-methyl anthranilate methyl, auranthiol, peony (manufactured by Dibodan) and the like can be used.

Of these, the ester compound-based fragrance component also has an effect on inhibiting hydrolysis of the component (A), and is preferably contained in an amount of 30% by mass or more in the fragrance composition of the component (F), and contained in an amount of 40% by mass or more. More preferably.

In the fragrance composition of the component (F), a fragrance may be microencapsulated and blended for the purpose of sustaining fragrance and remaining fragrance. The fragrance microcapsule is a spherical substance that is made by wrapping the fragrance of the core material with a wall material. Its role is to protect the fragrance of the core material, and when the capsule is subjected to physical force, the capsule wall breaks and the core It releases the fragrance of the substance. As the microencapsulated fragrance, a generally known fragrance can be used.

In addition, for the purpose of sustaining the fragrance and remaining fragrance, an ester of silicic acid and an alcohol used as a fragrance (hereinafter referred to as “alcoholic fragrance”), for example, a general formula (Japanese Patent Application Laid-Open No. 2009-256818) ( The compound represented by 1) can be used. Examples of alcoholic fragrances include alcohols i) to iii) below.

i) an aliphatic alcohol having a log P of 1 to 5, specifically, cis-3-hexenol (1.4), geraniol (2.8), nerol (2.8), 2,6-dimethyl-2 -Heptanol (3.0), menthol (3.2), citronellol (3.3), rosinol (3.3), 9-decenol (3.5), tetrahydrolinalool (3.5), tetrahydrogeraniol (3 .7), 4-methyl-3-decen-5-ol (3.7), tetrahydrogeraniol (3.7) and the like. Here, the values in () are logP values (the same applies to the following ii) and iii).

ii) An aromatic alcohol having a log P of 1 to 5, specifically, anis alcohol (1.0), raspberry ketone (1.1), phenylethyl alcohol (1.2), eugenol (2.4), isoeugenol (2.6), dimethylbenzyl carbinol (3.0), phenylethylmethylethyl carbinol (3.0), 3-methyl-5-phenylpentanol (3.2), thymol (3.4), etc. Is mentioned.

iii) a saturated or unsaturated cyclic alcohol having a log P of 1 to 5, specifically, p-tert-butylcyclohexanol (3.1), o-tert-butylcyclohexanol (3.1), l- Menthol (3.2), 4-isopropylcyclohexylmethanol (3.3), 1- (4-isopropylcyclohexyl) ethanol (3.6), santalol (3.9), 2-methyl-4- (2, 2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol (3.9), vetiverol (4.2) and the like.

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 a 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. The 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. If 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 Hansch, Leo fragment approach 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, JB Taylor 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 an actual measured value of logP, it is used, and if not, the ClogP value calculated by the program CLOGP 実測 v4.01 is used.

When the component (F) is used, the content in the composition can be appropriately determined in consideration of the kind of odor and the nature of the fragrance component.

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

[Other optional ingredients]
The liquid softening agent composition of the present invention may contain an inorganic electrolyte. The inorganic electrolyte is preferably one that dissolves 5 g or more in 100 g of water at 20 ° C.
The inorganic electrolyte is preferably used to adjust the softener composition to a viscosity suitable for use. Examples thereof include inorganic salts in which the cation is an ion of a substance selected from alkali metals and alkaline earth metals, and the anion is an ion of a substance selected from halogen compounds and sulfates. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium and calcium. Examples of the halogen compound include chloride, bromide, and iodide.
Specific examples of the inorganic electrolyte include one or more inorganic electrolytes selected from sodium chloride, sodium sulfate, calcium chloride, calcium sulfate, magnesium chloride, and magnesium sulfate.

In the liquid softener composition of the present invention, sufficient stability can be obtained even when the inorganic electrolyte is not substantially contained.

The liquid softener composition of the present invention can contain an oil agent other than the component (B). The oil agent is used for imparting further excellent softness performance to the fiber product, and also has an effect for inhibiting hydrolysis of the component (A). Examples thereof include hydrocarbons having 14 or more carbon atoms and aliphatic alcohols, preferably octadecane, liquid paraffin, stearyl alcohol and the like. Moreover, the esterified product of a polyhydric alcohol and a fatty acid is mentioned, Preferably, glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitan fatty acid ester, etc. are mentioned. From the viewpoint of improving the softness performance, the fatty acid is preferably palmitic acid, stearic acid, or a mixture thereof.

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

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

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

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

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

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

In the present invention, a polymer compound, that is, a polymer compound (a polymer compound other than a silicone compound) having a structural unit obtained by polymerizing a polymerizable monomer can be contained. The polymer compound is used for adjusting the viscosity of the softening agent composition and capturing residual detergent components during the finishing of the softening agent. Specific examples include cationic polymers. The cationic polymer is not particularly limited, but dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, diethylaminoethyl methacrylate, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, diethylaminopropyl acrylamide, or diethylaminopropyl Examples include acid neutralized products obtained by polymerizing methacrylamide as a monomer and neutralizing them with an acid, or quaternary ammonium salts quaternized with a quaternizing agent.

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

The liquid softener composition of the present invention has a viscosity at 30 ° C. of preferably 250 mPa · s or less, more preferably 200 mPa · s or less, more preferably 150 mPa · s or less. The lower limit of the viscosity is preferably 20 mPa · s or more, more preferably 50 mPa · s or more, and further preferably 70 mPa · s or more. This viscosity is measured using a B-type viscometer (model number: TVB-10 manufactured by Toki Sangyo Co., Ltd., No. 2 rotor, 60 r / min), and the liquid softener composition is stirred. The value 1 minute after the start is adopted. For example, even when the liquid softener composition is distributed as a commercial product, even when time has elapsed since the preparation of the composition, it is determined that the viscosity of the present invention is satisfied if the viscosity is in the above range. Moreover, this viscosity may be the initial viscosity evaluated in the below-mentioned Example.

The liquid softening agent composition of the present invention can maintain a viscosity suitable for handling even after storage. The liquid softener composition of the present invention has a viscosity after storage by the following method of preferably 500 mPa · s or less, more preferably 250 mPa · s or less, and more preferably 150 mPa · s or less.
<Viscosity after storage>
A container (glass wide-mouth standard bottle No. 6) filled with 30 g of the liquid softening agent composition is stored stationary at 50 ± 2 ° C. for 10 weeks, and then the container is allowed to stand at 25 ± 2 ° C. for 24 hours. While still in the container, the viscosity of the liquid softener composition was measured using a B-type viscometer (model number: TVB-10 manufactured by Toki Sangyo Co., Ltd., No. 2 rotor, 60 r / min). To measure. As the viscosity, a value one minute after the start of stirring of the liquid softener composition is adopted.

The pH of the liquid softening composition of the present invention is 25 ° C., preferably 2 or more, and preferably 7 or less, more preferably 5 or less, from the viewpoint of hydrolytic stability of the component (A). Preferably it is 4 or less. The pH is measured at 25 ° C. according to 8.3 of JIS K 3362; 2008.

Examples of the pH adjuster used for adjusting the pH of the liquid softener composition of the present invention include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, lactic acid, glycolic acid, oxalic acid, succinic acid, Organics such as citric acid, maleic acid, fumaric acid, propionic acid, malonic acid, glutaric acid, adipic acid, malic acid, crotonic acid, benzoic acid, paratoluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, polyacrylic acid, etc. Examples thereof include acids, inorganic bases such as sodium hydroxide, potassium hydroxide, triethanolamine, and organic bases. The pH adjuster is preferably used so that the pH of the liquid softening agent composition falls within the above-described range.

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

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

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

Examples of the present invention are illustrated below. The matters described in the liquid softener composition of the present invention can be appropriately applied to these embodiments.
<1>
(A) Tertiary amine or neutralized product or quaternized product thereof (hereinafter referred to as “component (A)”) containing an ester group and having at least one hydrocarbon group having 9 to 23 carbon atoms in the molecule. 3 mass% or more and 20 mass% or less,
(B) an ester of a fatty acid having 12 to 22 carbon atoms and an aliphatic alcohol having 3 to 22 carbon atoms [hereinafter referred to as component (B)],
(C) A quaternary ammonium compound represented by the following general formula (c1) [hereinafter referred to as the component (C)] is contained in an amount of 0.1% by mass to 8% by mass, and water.
(A) component / (B) component mass ratio is 2 or more and 200 or less,
Liquid softener composition.

<2>
The component (A) is (A1) a tertiary amine compound represented by the following general formula (a1) and its acid salt (hereinafter referred to as the (A1) component), and (A2) represented by the following general formula (a1). <1> The liquid softener composition according to <1>, which is one or more compounds selected from quaternized products of tertiary amine compounds [hereinafter referred to as component (A2)].
[R ^1a —C (═O) —O— (C _p H _2p O) _r —C _q H _2q ] _m N (R ^2a ) _3-m (a1)
[Wherein, R ^1a is a hydrocarbon group having 11 to 23 carbon atoms, and R ^2a is a hydrocarbon group having 1 to 3 carbon atoms and a HO— (C _p H _2p O) _r —C _q H _2q group. Wherein m is a number from 1 to 3, p and q are 2 or 3, and r is a number from 0 to 5. When there are a plurality of R ^1a , R ^2a , HO— (C _p H _2p O) r—C _q H _2q groups, p, q, and r in the same molecule, they may be the same or different. ]

<3>
(A) A liquid softening agent composition as described in <2> in which a component contains (A1) component and (A2) component.

<4>
The component (A) includes the component (A1) and the component (A2), and the mass ratio of the component (A1) to the component (A2) is (A1) component / (A2) component = 1/99 or more, and further 3/97 The liquid softener composition according to <2> or <3>, which is 5/95 or more, 50/50 or less, 40/60 or less, or 35/65 or less.

<5>
In general formula (a1), the hydrocarbon group represented by R ^1a is selected from an alkyl group having 11 or more carbon atoms, further 13 or more carbon atoms, and an alkenyl group having 11 or more carbon atoms and further 13 or more carbon atoms and 21 or less carbon atoms. The liquid softener composition according to any one of <2> to <4>, wherein

<6>
The hydrocarbon group of component (A) contains an alkenyl group, and the molar ratio of the cis isomer to the trans isomer in the alkenyl group is cis / trans = 30/70 or more, more preferably 50/50 or more, and 99 / The liquid softening agent composition according to any one of <1> to <5>, which is 1 or less, further 97/3 or less.

<7>
The liquid softener composition according to any one of <1> to <6>, wherein the fatty acid constituting the component (B) is a saturated or unsaturated fatty acid having 12 to 18 carbon atoms.

<8>
(B) The liquid softener composition according to any one of <1> to <7>, wherein the aliphatic alcohol constituting the component is a branched chain alcohol having 3 to 18 carbon atoms.

<9>
The liquid softener composition according to any one of <1> to <8>, wherein the aliphatic alcohol constituting the component (B) is a primary alcohol.

<10>
(B) component is 2-ethylhexyl laurate, lauryl laurate, 2-octyldodecyl laurate, 2-ethylhexyl myristate, myristyl myristate, 2-octyldodecyl myristate, isopropyl palmitate, 2-ethylhexyl palmitate, One or more fatty acid esters selected from palmitic acid palmitate, 2-octyldodecyl palmitate, 2-ethylhexyl stearate, stearyl stearate, and 2-octyldodecyl stearate, preferably isopropyl palmitate, myristate 2 One or more fatty acid esters selected from octyldodecyl, 2-ethylhexyl stearate, and stearyl stearate, more preferably isopropyl palmitate, myristic acid - octyldodecyl, and one or more fatty acid ester selected from stearic acid 2-ethylhexyl, <1> to the liquid softener composition according to any one of <9>.

<11>
The liquid softener composition according to any one of <1> to <10>, wherein in formula (c1) of component (C), R ^1c is an alkyl group having 12 to 16 carbon atoms.

<12>
(C) The liquid softener composition according to any one of <1> to <11>, wherein R ^2c and R ^{3c in} the general formula (c1) of the component are each a methyl group.

<13>
The content of the component (A) in the liquid softening agent composition is preferably 5% by mass or more, more preferably 8% by mass or more, and preferably 28% by mass or less, more preferably 25% by mass or less. <1>-<12> The liquid softener composition according to any one of <1> to <12>.

<14>
The content of the component (B) in the liquid softening agent composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and preferably Is a liquid softener composition according to any one of <1> to <13>, which is 15% by mass or less, more preferably 10% by mass or less, and more preferably 5% by mass or less.

<15>
The content of the component (C) in the liquid softening agent composition is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and preferably 5% by mass or less, more preferably 2% by mass. The liquid softener composition according to any one of <1> to <14>, which is not more than mass%.

<16>
The mass ratio of component (A) / component (B) is preferably 3 or more, more preferably 5 or more, and is preferably 100 or less, more preferably 80 or less, more preferably 50 or less, more preferably 40. The liquid softener composition according to any one of <1> to <15>, which is still more preferably 30 or less.

<17>
(A) Surfactant other than component [hereinafter referred to as (D) component], chelating agent (hereinafter referred to as (E) component), perfume composition (hereinafter referred to as (F) component), and water-soluble organic solvent [ The liquid softener composition according to any one of <1> to <16>, which contains at least one component selected from the following (G) component].

<18>
The component (D) is one or more selected from nonionic surfactants (hereinafter referred to as the component (D1)) and cationic surfactants other than the component (A) (D2) (hereinafter referred to as the component (D2)). The liquid softening agent composition according to <17>, which is a surfactant.

<19>
The content of the component (D) in the liquid softening agent composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less. The liquid softener composition according to <17> or <18>.

<20>
The liquid softener composition according to any one of <17> to <19>, further comprising a chelating agent as component (E).

<21>
(E) component is ethane-1-hydroxy-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, methylglycine diacetic acid, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, L-glutamic acid-N, N-diacetic acid, One or more selected from N-2-hydroxyethyliminodiacetic acid, citric acid, succinic acid and salts thereof, and further one or more selected from ethylenediaminetetraacetic acid, methylglycine diacetic acid, citric acid and salts thereof The liquid softener composition according to <20>, further comprising at least one selected from methylglycine diacetic acid and a salt thereof.

<22>
The content of the component (E) in the liquid softener composition is preferably 0.005% by mass or more, more preferably 0.01% by mass or more, and preferably 5% by mass or less in terms of acid type. The liquid softener composition according to <20> or <21>, more preferably 1% by mass or less.

<23>
<17> to <22>, further comprising a fragrance composition of component (F), wherein the content of the ester compound fragrance component in the fragrance composition is 30% by mass or more, and further 40% by mass or more. A liquid softener composition as described in 1. above.

<24>
The liquid flexibility according to any one of <1> to <23>, wherein the pH is 25 ° C., preferably 2 or more, and preferably 7 or less, more preferably 5 or less, more preferably 4 or less. Agent composition.

<25>
The liquid softener composition according to any one of <1> to <24>, which is used for textile products.

<26>
The liquid softener composition according to any one of <1> to <24>, wherein the viscosity at 30 ° C. is 250 mPa · s or less, preferably 200 mPa · s or less, more preferably 150 mPa · s or less.

<27>
The liquid softness according to any one of <1> to <24>, wherein the viscosity after storage by the following method is preferably 500 mPa · s or less, more preferably 250 mPa · s or less, more preferably 150 mPa · s or less. Agent composition.
<Viscosity after storage>
A container (glass wide-mouth standard bottle No. 6) filled with 30 g of the liquid softening agent composition is stored stationary at 50 ± 2 ° C. for 10 weeks, and then the container is allowed to stand at 25 ± 2 ° C. for 24 hours. While still in the container, the viscosity of the liquid softener composition was measured using a B-type viscometer (model number: TVB-10 manufactured by Toki Sangyo Co., Ltd., No. 2 rotor, 60 r / min). To measure. As the viscosity, a value one minute after the start of stirring of the liquid softener composition is adopted.

<28>
Use of the composition according to any one of <1> to <27> as a liquid softener composition.

Examples Components used in Examples and Comparative Examples are shown below.
[Component (A)]
(A-1): Quaternary ammonium salt mixture obtained in Synthesis Example 1 below <Synthesis Example 1: Synthesis of (a-1)>
A fatty acid mixture having the following composition and triethanolamine are subjected to a dehydration condensation reaction at a reaction molar ratio of 1.65 / 1 (fatty acid / triethanolamine) to give N, N-dialkanoyloxyethyl-N-hydroxy. A condensate containing ethylamine as a main component was obtained.
Next, the amine value of this condensate was measured, and quaternization was carried out in an ethanol solvent in which 0.96 equivalent of dimethyl sulfate was used for the condensate and the water content was reduced to the minimum, and N, N— A quaternary ammonium salt mixture containing dialkanoyloxyethyl-N-hydroxyethyl-N-methylammonium methyl sulfate as a main component and containing 10% by mass of ethanol was obtained (hereinafter referred to as (a-1)). The preparation procedure and reaction conditions were carried out according to Synthesis Example 2 of JP 2010-209493 A.

The composition of the fatty acid mixture used in the reaction for producing (a-1) is shown below.
Palmitic acid: 45% by mass
Stearic acid: 25% by mass
Fatty acid having 18 carbon atoms and one unsaturated group: 27% by mass
Fatty acid with 18 carbon atoms and two unsaturated groups: 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%. The mass ratio of the cis / trans isomer of the unsaturated group is 85/15 (integral ratio according to ¹ H-NMR).

The composition ratio of each component in the obtained quaternary ammonium salt mixture was analyzed by the HPLC method under the following conditions, and quantified using tetraoctylammonium bromide as an internal standard substance. As a result, (a-1) was (A1) ) Component tertiary amine compound, component (A2) quaternized product, and unreacted fatty acid. Since 2% by mass of fatty acid was contained in the mixture, the total of components (A1) and (A2) in the mixture was 85% by mass-2% by mass = 83% by mass. Further, the mass ratio of the component (A1) / the component (A2) in the mixture is 14/86, and the acyl group R ^1a -C (= in the general formula (a1) of the component (A1) and the component (A2) O) was composed of fatty acids each having an unsaturated fatty acid / saturated fatty acid mass ratio of 0.43.

<HPLC conditions>
Column: Inertsil NH2 5 μm (4.6 × 250 mm) Room temperature (25 ° C.)
Mobile phase: 0.05% TFA (trifluoroacetic acid) in hexane: methanol: THF (tetrahydrofuran) = 85: 10: 5
Flow rate: 0.8 mL (0-10 minutes) -1.2 mL (10-55 minutes) -0.8 mL (55-60 minutes)
Injection: 20 μL
Detection: CAD

In preparation of the liquid softener composition, (a-1) is blended as a mixture containing the component (A1), the component (A2), fatty acid, ethanol and other trace components. The mass% of 1) indicates mass% based on the amounts of the components (A1) and (A2), and the amounts of the other components were added to the balance of ion-exchanged water.

[(B) component]
(B-1): Isopropyl palmitate (b-2): 2-octyldodecyl myristate (b-3): 2-ethylhexyl stearate

[Component (C)]
(C-1): benzalkonium chloride [alkyl (C _12-16 ) benzyldimethylammonium chloride (Sanisol B-50 (Kao Corporation))

[Component (D)]
(D-1): Nonionic surfactant (polyoxyethylene lauryl ether having an average addition mole number of oxyethylene groups of 21 moles)

[(E) component]
(E-1): Methyl glycine diacetate 3Na (Trilon M Liquid (registered trademark), BASF Japan Ltd.) (Used so that the effective amount of methyl glycine diacetate 3Na is the value shown in Table 2)

[(F) component]
(F-1): Perfume composition f1 shown in Table 1
(F-2): Perfume composition f2 shown in Table 1

[Other ingredients]
Preservative: 1,2-benzisothiazolin-3-one (Proxel BDN (registered trademark) (manufactured by Arch Chemical Japan))

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

<Evaluation method>
(1) Viscosity 30 g of the liquid softening agent composition shown in Table 2 was filled in a container (glass wide-mouth standard bottle No. 6), and the temperature of the composition was adjusted to 30 ° C. Using a B-type viscometer (model number: TVB-10 manufactured by Toki Sangyo Co., Ltd., No. 2 rotor, 60 r / min), the viscosity measurement of the liquid softener composition was started at the above temperature. The later value was read (the unit of viscosity is “mPa · s”). This was the initial viscosity. Further, 30 g of the liquid softening agent composition shown in Table 2 was filled in a storage container (glass wide-mouth standard bottle No. 6). The storage container filled with the liquid softening agent composition was stored at 50 ± 2 ° C. for 10 weeks. Next, the viscosity of the liquid softener composition that was allowed to stand at 25 ± 2 ° C. for 24 hours was measured in the same manner. This was taken as the viscosity after storage. The results are shown in Table 2. In this evaluation, the initial viscosity is preferably 250 mPa · s or less. The viscosity after storage is preferably 500 mPa · s or less.

(2) Storage stability The storage stability of the liquid softening agent composition was evaluated by the residual ratio of component (A) after storage under the following predetermined conditions.
[Method for preserving liquid softener composition]
A storage container (glass wide-mouth standard bottle No. 6) was filled with 30 g of the liquid softener composition shown in Table 2. The storage container filled with the liquid softening agent composition was stored at 50 ± 2 ° C. for 10 weeks. Next, a sample that was allowed to stand for 24 hours in a room at 25 ± 2 ° C. was used as an evaluation sample.

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

Component (A) contains quaternized products of monoester, diester, triester, and triethanolamine. Since each ester is hydrolyzed, purely from the reference sample. Only the triester form can be measured for the hydrolysis rate, and the residual rate was examined. The tribody component amount in the reference sample was taken as 100%, and the proportion of the tribody remaining amount in the evaluation sample was taken as the residual ratio. In terms of commercial value, a bird body remaining ratio after storage of 70% or more is considered acceptable. The results are shown in Table 2.

(3) Flexibility (I) Pre-treatment method of evaluation towel Using a commercially available powder detergent (manufactured by Kao Corporation, “Attack” produced in November 2017), a commercially available cotton towel (manufactured by Takei towel, “TW” -220 ") A series of washing steps were repeated 5 times using a Panasonic full-automatic washing machine NA-F60PB3 (attack usage amount 40.5 g, water amount 51 L, water temperature 20 ° C., washing time 10 minutes, rinsing 2 Times, dehydration 9 minutes). Then, it dried on 20 degreeC and 45% RH conditions.

(II) Method for softening the evaluation towel 4 L of water at 20 ° C. was poured into an electric bucket N-BK2-A manufactured by Panasonic Corporation, and two cotton towels pretreated by the method (I) were added. Stir for minutes. After stirring, the liquid softener composition after being stored at 50 ° C./10 weeks under the condition (2) was added in an amount of 10 ml per 1.5 kg of cotton towel, and treated for 5 minutes while stirring. After the treatment, it was dehydrated for 2 minutes in a dewatering tank of a two-layer washing machine and dried under conditions of 20 ° C. and 45% RH.

(III) Evaluation of flexibility Ten panelists evaluated the softness with a cotton towel treated and dried with the liquid softener composition having the composition shown in Table 2. Evaluation was based on the softness of the cotton towel treated and dried in Comparative Example 4.
The softness values in Table 2 represent the average value of 10 panelists. In this evaluation, it is preferable that the softness has an average score of 1.5 or more. The results are shown in Table 2.
Flexibility criteria:
0: Not softer than Comparative Example 1: Softness equivalent to Comparative Example 4: 2: Softer than Comparative Example 4

(4) Antibacterial (odor evaluation)
(I) Underwear for odor evaluation Used used underwear (T-shirts) collected from ordinary households and used for half a year to one year was used. The collected used underwear (T-shirt) was cut into a right body and a left body.

(II) Odor Evaluation Underwear Treatment Method 4 L of water at 20 ° C. was poured into an electric bucket N-BK2-A manufactured by Panasonic Corporation, and the left body of (I) was added and stirred for 1 minute. After stirring, the liquid softening agent composition stored at 50 ° C./10 weeks under the condition (1) was added in an amount of 10 ml per 1.5 kg of underwear, and treated for 5 minutes while stirring. After treatment, dehydrate for 2 minutes in the dehydration tank of a two-layer washing machine, wrap the underwear immediately after dehydration with a wrap film, seal it in a zipper-type plastic bag, and store it in a thermostatic bath at 30 ° C for 5 hours. Generated. The right body was treated in the same way as the left body without a liquid softener composition.

(III) Evaluation of odor Ten panelists evaluated the odor of used underwear after treatment. The right body (without the liquid softener composition) and the left body (with the liquid softener composition) collected from the same underwear were paired and the odors were evaluated. The odor values in Table 2 represent the average value of 10 panelists. In this evaluation, the average odor score is preferably 1.0 or less. The results are shown in Table 2.
Almost no smell ... 0
I feel a slight smell but I don't mind ... 1
I smell ... 2
It smells remarkably ... 3

Claims

(A) Tertiary amine or neutralized product or quaternized product thereof (hereinafter referred to as “component (A)”) containing an ester group and having at least one hydrocarbon group having 9 to 23 carbon atoms in the molecule. 3 mass% or more and 20 mass% or less,
(B) an ester of a fatty acid having 12 to 22 carbon atoms and an aliphatic alcohol having 3 to 22 carbon atoms [hereinafter referred to as component (B)],
(C) A quaternary ammonium compound represented by the following general formula (c1) contains 0.1% by mass to 8% by mass, and water,
(A) component / (B) component mass ratio is 2 or more and 200 or less,
Liquid softener composition.

(In the formula, R 1c is a hydrocarbon group having 8 to 16 carbon atoms, R 2c and R 3c are each an alkyl group or a hydroxyalkyl group having 1 to 3 carbon atoms, and R 4c is An alkylene group having 1 to 3 carbon atoms or a hydroxyalkylene group.)
The component (A) is (A1) a tertiary amine compound represented by the following general formula (a1) and its acid salt, and (A2) a tertiary amine compound 4 represented by the following general formula (a1). The liquid softening agent composition of Claim 1 which is 1 or more types of compounds chosen from a graded material.
[R 1a —C (═O) —O— (C p H 2p O) r —C q H 2q ] m N (R 2a ) 3-m (a1)
[Wherein, R 1a is a hydrocarbon group having 11 to 23 carbon atoms, and R 2a is a hydrocarbon group having 1 to 3 carbon atoms and a HO— (C p H 2p O) r —C q H 2q group. Wherein m is a number from 1 to 3, p and q are 2 or 3, and r is a number from 0 to 5. When there are a plurality of R 1a , R 2a , HO— (C p H 2p O) r—C q H 2q groups, p, q, and r in the same molecule, they may be the same or different. ]
Furthermore, the liquid softening agent composition of Claim 1 or 2 containing a chelating agent.
The liquid softening agent composition according to any one of claims 1 to 3, further comprising a fragrance composition, wherein the content of the ester compound fragrance component in the fragrance composition is 30% by mass or more.