WO2017164321A1

WO2017164321A1 - Liquid fabric softener composition

Info

Publication number: WO2017164321A1
Application number: PCT/JP2017/011769
Authority: WO
Inventors: 恵美子橋本; 沙枝石川; 耕平森田; 志緒梨中村
Original assignee: ライオン株式会社
Priority date: 2016-03-23
Filing date: 2017-03-23
Publication date: 2017-09-28
Also published as: KR102323638B1; JP6626754B2; JP2017172067A; KR20180119571A; MY197982A

Abstract

The present invention provides a liquid fabric softener composition which contains: (A) one or more compounds selected from the group consisting of an amine compound having at least one hydrocarbon group having 10 to 26 carbon atoms in each molecule, which hydrocarbon group may be interrupted by an ester group (-COO-) and/or an amide group (-NHCO-), a neutralized product thereof, and a quaternized product thereof, (B) 0.1 to 10 mass% of an amino-modified silicone, (C) a perfume composition containing, relative to the total mass of the liquid fabric softener composition, at least 0.1 mass% of Iso E Super, and also containing citronellol, and (D) an antibacterial agent.

Description

Liquid softener composition

The present invention relates to a liquid softener composition. Specifically, the present invention relates to a liquid softener composition in which gelation is suppressed and / or odor generation after storage is suppressed.

Conventionally, a fiber treatment agent combining a cationic activator and an aminosilicone has been proposed for imparting a texture of clothing (giving flexibility, imparting smoothness, appealing for wrinkle prevention) (Japanese Patent Application Laid-Open No. 2008-150756). JP 2008-297675 A, JP 2009-12012 A).
In order to increase the stability of the fiber treatment agent comprising the cationic surfactant and amino-modified silicone, a glycol ether compound is applied (Japanese Patent Laid-Open No. 2008-150756), propylene oxide, ethylene oxide group There is a technique for applying a specific nonion imparted with sucrose (Japanese Patent Laid-Open No. 2012-7265) or a technique for applying trehalose to improve stability during high-temperature storage (Japanese Patent Laid-Open No. 2014-118640).

In addition, as a texture imparting effect after storage, there is a technique (non-patent document No. 2012-7265) using a nonion in which ethylene oxide and propylene oxide groups are added at a specific ratio, and as a technique for suppressing deterioration of aroma after storage. Have a technology of blending urea (International Publication No. 2014/003180) and a technology of blending a specific perfume and an antioxidant (Japanese Patent Laid-Open No. 2012-56392).

However, in the prior art, when the product is placed outdoors, for example, gel (film) formation when exposed to ultraviolet light, gel formation in freezing and restoration, or when the product is stored outdoors or after long-term storage It is not possible to sufficiently suppress the generation of odors. In addition, the degree of gel formation of a softening agent composition changes with fragrance | flavor compositions, and the softening agent composition by which gelatinization was suppressed is desired.

As a result of intensive studies to solve the above-mentioned problems, the present inventors can suppress gel formation and odor generation by blending an amino-modified silicone, a fragrance composition containing a predetermined fragrance component, and an antibacterial agent. The present inventors have found that a softener composition having an excellent imparting effect can be provided, and have completed the present invention.
The present invention has been completed based on such novel findings.

In one embodiment of the present invention, a liquid softener composition containing the following components (A) to (D) is provided.
(A) An amine compound having one or more hydrocarbon groups having 10 to 26 carbon atoms in the molecule which may be separated by an ester group (—COO—) and / or an amide group (—NHCO—), and neutralization thereof And one or more compounds selected from the group consisting of compounds and quaternized compounds thereof,
(B) Amino-modified silicone 0.1-10% by mass,
(C) A perfume composition containing 0.1% by mass or more of ISOE super based on the total mass of the liquid softening agent composition and containing citronellol, and (D) an antibacterial agent.

According to one embodiment of the present invention, the component (C) further includes one or more perfume ingredients selected from the group consisting of coumarin, hexylcinnamic aldehyde, and habanolide.

According to one embodiment of the present invention, a softener composition in which gelation is suppressed can be provided.
According to one embodiment of the present invention, a softener composition in which odor generation after storage is suppressed can be provided.
According to one embodiment of the present invention, it is possible to provide a softener composition in which gelation is suppressed and generation of odor after storage is suppressed.
According to one embodiment of the present invention, it is possible to provide a softening agent composition that is suppressed in gelation and / or in which odor generation after storage is suppressed and that has an excellent texture imparting effect.

[(A) component]
The component (A) contained in the softener composition of the present invention includes a hydrocarbon group having 10 to 26 carbon atoms which may be separated by an ester group (—COO—) and / or an amide group (—NHCO—). It is one or more compounds selected from the group consisting of one or more amine compounds in the molecule, neutralized products thereof, and quaternized products thereof, and functions as a cationic surfactant. The component (A) is mainly blended together with the component (B) to give a softening agent composition a texture-imparting effect (particularly, an effect of imparting softness to clothing such as underwear).
The carbon number of the predetermined hydrocarbon group is 10 to 26, preferably 12 to 24, particularly preferably 14 to 20.
This hydrocarbon group may be separated by one or more groups selected from the group consisting of ester groups and amide groups. Of the ester groups and amide groups, ester groups are particularly preferred. The number of groups to be divided is one per hydrocarbon group. In addition, the carbon atom which a parting group has shall be counted to carbon number of a hydrocarbon group.
The hydrocarbon group may be saturated or unsaturated, and may be linear and branched.

The neutralized product of an amine compound is a compound obtained by neutralizing an amine compound with an acid. Examples of the acid used for neutralization include hydrochloric acid, sulfuric acid, methyl sulfuric acid, and paratoluenesulfonic acid. The neutralized product is preferably in the form of an amine salt.
The neutralized product is produced by dispersing an amine compound that has been neutralized with an acid in advance, adding a liquid or solid amine compound into an aqueous acid solution, or simultaneously adding an amine compound and an acid into water, etc. Can be performed.
The quaternized amine compound is a compound obtained by treating an amine compound having 3 hydrocarbon groups bonded to a nitrogen atom (tertiary amine) with a quaternizing agent. is there. Examples of the quaternizing agent include methyl chloride and dimethyl sulfate.

Examples of the component (A) include amine compounds represented by any one of the following general formulas (AI) to (A-VII), neutralized products thereof, or quaternized products thereof.

In each of the above formulas (AI) to (A-VII), R ¹ may be the same or different from a hydrocarbon group having 15 to 17 carbon atoms (in other words, from a fatty acid having 16 to 18 carbon atoms). Residue derived by removing the carboxyl group). The hydrocarbon group may be an alkyl group or an alkenyl group. Examples of fatty acids from which R ¹ is derived include saturated fatty acids, unsaturated fatty acids, linear fatty acids and branched fatty acids. In the case of an unsaturated fatty acid, a cis isomer and a trans isomer are present, and the mass ratio is preferably cis isomer / trans isomer = 25/75 to 100/0, and preferably 40/60 to 80/20. Is particularly preferred.
Preferred fatty acids for inducing R ¹ include stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, linolenic acid, arachidic acid, gatoleic acid, eicosenoic acid, partially hydrogenated palm oil fatty acid (iodine value 10 To 60), partially hydrogenated beef tallow fatty acid (iodine value 10 to 60), and the like. More preferably, it is a mixture of stearic acid, palmitic acid, oleic acid, elaidic acid, linoleic acid and linolenic acid, and the mass ratio of saturated fatty acid / unsaturated fatty acid is 95/5 to 50/50, cis isomer / trans isomer Is 40/60 to 80/20, iodine value is 10 to 50, and the fatty acid content of 18 carbon atoms is 80% by mass or more based on the total mass of the mixture, and the total amount of linoleic acid and linolenic acid is the total amount of the mixture The mixture is 2% by mass or less based on the mass.

(A) When using the composition containing the compound represented by general formula (AI) and the compound represented by general formula (A-II) as a component, the said composition is said fatty acid mixture or The methyl esterified product can be synthesized by a condensation reaction of methyldiethanolamine. At that time, from the viewpoint of improving the dispersion stability in the liquid softening agent composition, the compound is synthesized so that the mass ratio of each compound is (A-II) / (AI) = 99/1 to 50/50. It is preferable to do.
When using a composition containing a quaternized product of the compound represented by the general formula (AI) and a quaternized product of the compound represented by the general formula (A-II), methyl chloride or the like is used as the quaternizing agent. Although dimethyl sulfate can be used, methyl chloride is preferred because it has a low molecular weight and can reduce the amount required for quaternization. At that time, from the viewpoint of improving the dispersion stability in the liquid softening agent composition, the quaternized product in which the mass ratio of each quaternized product is (A-II) / quaternary product in (AI) = 99 / It is preferable to synthesize so as to be 1 to 50/50.
In the above quaternization reaction, unreacted substances (that is, the compound represented by (AI) and the compound represented by (A-II)) remain. At that time, from the viewpoint of stability against hydrolysis of the ester group contained in the quaternized product, the quaternized product (quaternized product of (AI) + quaternized product of (A-II)) and unreacted product ( It is preferable to synthesize so that the mass ratio of (compound represented by (AI) + compound represented by (A-II)) is quaternized product / unreacted product = 99/1 to 70/30. .

As the component (A), a composition comprising a compound represented by the general formula (A-III), a compound represented by the general formula (A-IV), and a compound represented by the general formula (A-V) When using a product, the composition can be synthesized by subjecting the fatty acid composition or its methyl esterified product to a condensation reaction with triethanolamine. At that time, from the viewpoint of improving the dispersion stability in the liquid softening agent composition, the mass ratio of each compound is [(A-IV) + (A-V)] / (A-III) = 99/1 to It is preferable to synthesize so as to be 50/50.
A quaternized product of the compound represented by the general formula (A-III), a quaternized product of the compound represented by the general formula (A-IV), and a quaternized product of the compound represented by the general formula (A-V). In the case of using a composition containing dimethylsulfate, methyl chloride, dimethyl sulfate, or the like can be used as the quaternizing agent, but dimethyl sulfate is preferred from the viewpoint of the reactivity of the quaternization reaction. At that time, from the viewpoint of improving the dispersion stability in the liquid softening agent composition, the mass ratio of each quaternized product is [(A-IV) + (A-V)] / (A-III) = 99 / It is preferable to synthesize so as to be 1 to 50/50.
In the quaternization reaction, an unreacted product (that is, a compound represented by the general formula (A-III), a compound represented by the general formula (A-IV), and a general formula (A-V) The compound represented) remains. At that time, from the viewpoint of stability against hydrolysis of the ester group contained in the quaternized product, the quaternized product (quaternized product of (A-III) + quaternized product of (A-IV) + (A-V) Quaternized product) and unreacted material (compound represented by (A-III) + compound represented by (A-IV) + compound represented by (A-V)) are quaternized. It is preferable to synthesize so that / unreacted material = 99/1 to 70/30.

(A) When using the composition containing the compound represented by general formula (A-VI) and the compound represented by general formula (A-VII) as a component, the said composition is the said fatty acid composition, N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine (Adduct of N-methylethanolamine and acrylonitrile according to the method described in J. Org. Chem., 26, 3409 (1960)) Can be synthesized by a condensation reaction. From the viewpoint of improving the texture-imparting effect, the compounds are preferably synthesized such that the mass ratio of each compound is (A-VII) / (A-VI) = 99/1 to 50/50.
When a composition containing a quaternized product of the compound represented by the general formula (A-VI) and a quaternized product of the compound represented by the general formula (A-VII) is used, methyl chloride is used as a quaternizing agent. Can be used. At that time, from the viewpoint of improving the texture-imparting effect, the mass ratio of each quaternized product is (A-VII) quaternized product (A-VI) quaternized product = 99/1 to 50/50. It is preferable to synthesize.
In the quaternization reaction, unreacted substances (that is, the compound represented by (A-VI) and the compound represented by (A-VII)) remain. At that time, from the viewpoint of stability against hydrolysis of the ester group contained in the quaternized product, the quaternized product (quaternized product of (A-VI) + quaternized product of (A-VII)) and unreacted product ( It is preferable to synthesize so that the mass ratio of the compound represented by (A-VI) + the compound represented by (A-VII) is quaternized product / unreacted product = 99/1 to 70/30. .

In the above, the quaternized product of the compound represented by the general formula (A-III), the quaternized product of the compound represented by the general formula (A-IV), and the general formula (A-V). More preferred is a composition containing a quaternized product of the above compound.
In this case, from the viewpoint of further enhancing the function as a softener, the content of each quaternized product in the composition is such that the quaternized product of the compound represented by (A-III) is based on the total mass of the composition. 5 to 98% by mass, 1 to 60% by mass of the quaternized product of the compound represented by (A-IV), 0.1 to 40% by mass of the quaternized product of the compound represented by (A-V) Preferably there is. More preferably, the quaternized product of the compound represented by (A-III) is 10 to 55% by mass with respect to the total mass of the composition, and the quaternized product of the compound represented by (A-IV) is 30%. The quaternized product of the compound represented by (A-V) is 5 to 35% by mass.
The component (A) is easily available in the market or can be synthesized by a known method.
(A) A component may be used individually by 1 type and may be used as a mixture (composition) which consists of 2 or more types. When used as a mixture (composition), the content of the amine compound having 2 or 3 hydrocarbon groups bonded to nitrogen atoms is 50% by mass or more based on the total mass of the mixture (composition). Since the function as a softening agent can be improved more, it is preferable.
The amount of component (A) is not particularly limited, but is 10 to 30% by mass, preferably 10 to 20% by mass, based on the total mass of the softener composition. (A) The handling property fall by the liquid viscosity of a softening agent composition becoming it high that the compounding quantity of a component is 30 mass% or less can be suppressed. When the blending amount of the component (A) is 10% by mass or more, a sufficient texture imparting effect can be obtained.

[Component (B)]
Component (B) contained in the softener composition of the present invention is an amino-modified silicone. The component (B) is mainly blended together with the component (A) in order to give the softener composition a texture-imparting effect (particularly, an effect of imparting smoothness to clothing such as underwear).
Amino-modified silicone is a compound formed by introducing amino groups into both ends or side chains of a dimethyl silicone skeleton.
Preferred amino-modified silicones have the following general formula (B):

Wherein R is independently selected from the group consisting of —H, —OH, —CH ₃ and —Si (CH ₃ ) ₃ , and X is — (CH ₂ ) _a —NH ₂ , or , — (CH ₂ ) _a —NH (CH ₂ ) _b NH ₂ (a is an integer from 0 to 3, b is an integer from 1 to 3), n is from 1 to 10,000, and m is 1 to 1000.)
And a compound formed by introducing an amino group into the side chain X.
The amino-modified silicone as the component (B) has a kinematic viscosity at 25 ° C. of preferably 100 to 20000 mm ² / s, more preferably 500 to 10,000 mm ² / s. When the kinematic viscosity at 25 ° C. is in the range of 100 to 20000 mm ² / s, a high texture-imparting effect is obtained, and the manufacturability and handleability of the softener composition are facilitated. The kinematic viscosity can be measured with an Ostwald viscometer.
The amino-modified silicone as the component (B) has an amine equivalent of preferably 400 to 8000 g / mol, more preferably 500 to 5000 g / mol, and still more preferably 1200 to 4000 g / mol. When the amine equivalent is in the range of 400 to 8000 g / mol, a sufficient blending effect can be obtained. The amine equivalent can be determined by dividing the weight average molecular weight of the amino-modified silicone by the number of nitrogen atoms contained in the amino-modified silicone. The number of nitrogen atoms can be determined by elemental analysis.

The amino-modified silicone as component (B) may be in the form of an oil (silicone oil), or in the form of an emulsion (silicone emulsion) emulsified by using a nonionic surfactant or a cationic surfactant as an emulsifier. There may be. It is preferably in the form of a silicone emulsion.
(B) A commercially available thing can be used for a component. Examples of silicone oils are those sold under the trade names: SF-8417, BY16-849, BY16-892, FZ-3785, or BY16-890 from Toray Dow Corning Co., Ltd., or from Shin-Etsu Chemical Co., Ltd. Product names: KF-864, KF-860, KF-880, KF-8004, KF-8005, KF-8002, KF-867 or those sold under KF-869, KF-861, KF-8610, etc. can give.
(B) A component may be used individually by 1 type and may be used as a mixture which consists of 2 or more types.
The blending amount of the component (B) is 0.1 to 10% by mass, preferably 0.5 to 5.0% by mass, more preferably 0.5 to 2.% by mass with respect to the total mass of the softener composition. 0% by mass. When the blending amount of the component (B) is 0.1% by mass or more, the blending effect of the component (B) can be sufficiently exhibited. When the blending amount of the component (B) is 10% by mass or less, a significant increase in viscosity stability can be suppressed, and an increase in manufacturing cost can be suppressed.
About the compounding ratio of (B) component and (A) component, it is preferable that it is rich in (A) component from a viewpoint of the texture provision effect. The mass ratio ((A) / (B)) between the component (A) and the component (B) is more preferably 2/1 to 50/1, and further preferably 2/1 to 10/1. .

[Component (C)]
The component (C) contained in the softener composition of the present invention is a fragrance composition, containing 0.1% by mass or more of isoether based on the total mass of the softener composition of the present invention, and citronellol. A fragrance composition containing
(C) 10 mass% or more is preferable, and, as for the content rate of the ISOE super in a component, 15 mass% or more is more preferable. (C) As for the content rate of the citronellol in a component, 3 mass% or more is preferable. Moreover, it is preferable that citronellol is mix | blended 0.02 mass% or more based on the total mass of the softening agent composition of this invention. The component (C) suppresses gelation when it is frozen and restored, and also increases the ability to suppress odor generation when exposed to sunlight. In addition, it is thought that the same effect is acquired even if it mix | blends with a softener composition separately from a fragrance | flavor composition, and ISOE super and citronellol. In the present application, the component (C) is, in terms of form, a fragrance composition containing isoea super and citronellol, but isoea super and citronellol are blended into the softener composition separately from the fragrance composition. Also good.
The component (C) preferably further contains at least one fragrance component selected from the group consisting of coumarin, hexylcinnamic aldehyde and havanolide, and more preferably contains all of coumarin, hexylcinnamic aldehyde and havanolide. preferable.
(C) component can contain another fragrance | flavor component further. The perfume ingredients are not particularly limited, but a list of perfume ingredients used can be found in various documents such as “Perfume and Flavor Chemicals”, Vol. Iand II, Steffen Arctander, Allured Pub. Co. (1994) and "Synthetic fragrance chemistry and commercial knowledge", Motoichi Into, Chemical Industry Daily (1996) and "Perfume and Flavor Materials of Natural Origin", Stephen Arctander, Allred Pub. Co. (1994) and "Encyclopedia of Scents", edited by Japan Fragrance Association, Asakura Shoten (1989) and "Performer Material Performance V.3.3", Boelens Aroma Chemical Information Service (1996) and "Flower oil". , Danute Lajaujis Anonis, Allured Pub. Co. (1993).

For example, specific examples of fragrance ingredients include aldehydes, phenols, alcohols, ethers, esters, hydrocarbons, ketones, lactones, musks, fragrances having a terpene skeleton, natural fragrances, animal fragrances, etc. There are the following.
The aldehyde is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include undecylenaldehyde, lauryl aldehyde, aldehyde C-12MNA, miracaldehyde, α-amylcinnamic aldehyde, cyclamenaldehyde, citral, Citronellal, ethyl vanillin, heliotropin, anisaldehyde, α-hexylcinnamic aldehyde, octanal, ligustral, lyial, lilar, triplar, vanillin, helional and the like.
There is no restriction | limiting in particular as phenols, According to the objective, it can select suitably, For example, eugenol, isoeugenol, etc. are mentioned.
The alcohol is not particularly limited and may be appropriately selected depending on the intended purpose.For example, citronellol, dihydromyrcenol, dihydrolinalool, geraniol, linalool, nerol, sandalol, santarex, terpineol, tetra Hydrolinalol, menthol, borneol, 1-decanal, vacudanol, phenylethyl alcohol and the like can be mentioned.
There is no restriction | limiting in particular as ethers, According to the objective, it can select suitably, For example, cedula bar, glycalva, methyl eugenol, methyl isoeugenol, rose oxide etc. are mentioned.
The esters are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cis-3-hexenyl acetate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, and p-cresyl. Acetate, pt-butylcyclohexyl acetate, amyl acetate, methyl dihydrojasmonate, amyl salicylate, benzyl salicylate, benzyl benzoate, benzyl acetate, cedryl acetate, citronellyl acetate, decahydro-β-naphthyl acetate, dimethylbenzyl cal Vinyl acetate, Erica propionate, ethyl acetoacetate, Erica acetate, geranyl acetate, geranyl formate, hedion, linalyl acetate, β-phenylethyl acetate, he Examples include xyl salicylate, styrylyl acetate, terpinyl acetate, butyleveryl acetate, ot-butylcyclohexyl acetate, manzanate, and allyl heptanoate.
Hydrocarbons are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include limonene (particularly d-limonene), α-pinene, β-pinene, myrcene, camphene, and terpinolene. It is done.
The ketones are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include α-ionone, β-ionone, methyl-β-naphthyl ketone, α-damascon, β-damascon, δ-damascon, Examples include damasenone, cis-jasmon, methyl ionone, allyl ionone, cashamelan, dihydrojasmon, isoea super, belt fix, isolone diforanone, coabon, carvone, rosephenone, raspberry ketone, dinascon and maltol.
The lactone is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include γ-decalactone, γ-undecalactone, γ-nonalactone, γ-dodecalactone, coumarin, and ambroxan. It is done.
The musk is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include cyclopentadecanolide, ethylene brushate, galaxolide, musk ketone, tonalid, tonalide, and nitromusk.
The fragrance having a terpene skeleton is not particularly limited and may be appropriately selected depending on the intended purpose. For example, geraniol (zelaniol), nerol, linalool, citral, citronellol, menthol, mint, citronellal, myrcene, α-pinene , Β-pinene, limonene, terpineol, carvone, ionone (for example, β-ionone), camphene, borneol and the like.
The natural fragrance is not particularly limited and can be appropriately selected depending on the purpose.For example, orange oil, lemon oil, lime oil, petitgren oil, yuzu oil, neroli oil, bergamot oil, lavender oil, lavandin oil, Abies oil, anise oil, bay oil, bored rose oil, ylang ylang oil, citronella oil, geranium oil, peppermint oil, peppermint oil, spearmint oil, eucalyptus oil, lemongrass oil, patchouli oil, jasmine oil, rose oil, cedar oil, Examples include essential oils such as vetiver oil, galvanum oil, oak moss oil, pine oil, camphor oil, sandalwood oil, melamine oil, turpentine oil, clove oil, clove leaf oil, cassia oil, nutmeg oil, cananga oil, and thyme oil. .
There is no restriction | limiting in particular as animal fragrance | flavor, According to the objective, it can select suitably, For example, a fragrance | flavor, a ghost cat fragrance, a sea bream incense, a dragon fragrance, etc. are mentioned.
Among these fragrance components, when one or more components such as rose oxide, damasenone, and δ-damascon are blended, the suppression of gelation when frozen and restored can be promoted.

You may mix | blend the solvent generally used for a liquid softening agent composition with a fragrance | flavor composition. Examples of the fragrance solvent include acetin (triacetin), MMB acetate (3-methoxy-3-methylbutyl acetate), sucrose diacetate hexaisobutyrate, ethylene glycol dibutyrate, hexylene glycol, dibutyl sebacate, and deltile extra ( Isopropyl myristate), methyl carbitol (diethylene glycol monomethyl ether), carbitol (diethylene glycol monoethyl ether), TEG (triethylene glycol), benzyl benzoate (BB), propylene glycol, diethyl phthalate, tripropylene glycol, aborin ( Dimethyl phthalate), deltyl prime (isopropyl palmitate), dipropylene glycol (DPG), farnesene, dioctyl adipate Tributyrin (glyceryl tributanoate), hydrolite-5 (1,2-pentanediol), propylene glycol diacetate, cetyl acetate (hexadecyl acetate), ethyl abiate, avaline (methyl abietate), citroflex A-2 (Acetyl triethyl citrate), citroflex A-4 (tributyl acetyl citrate), citroflex no. 2 (triethyl citrate), Citroflex No. 4 (tributyl citrate), durafix (methyl dihydroabietate), MITD (isotridecyl myristate), polylimonene (limonene polymer), 1,3-butylene glycol and the like.
The amount of the solvent is, for example, 0.1 to 30% by mass, preferably 1 to 20% by mass, based on the total mass of the fragrance composition.

The perfume composition may be blended with an antioxidant generally used in liquid softener compositions, specifically, 3,5-di-tert-butyl-4-hydroxytoluene (BHT). , T-butyl-p-hydroxyanisole (BHA), p-methoxyphenol, β-naphthol, phenyl-α-naphthylamine, tetramethyldiaminodiphenylmethane, γ-oryzanol, vitamin E (α-tocopherol, β-tocopherol, γ- Tocopherol, δ-tocopherol), 2,2'-ethylidenebis (4,6-di-t-butylphenol), tris (tetramethylhydroxypiperidinol) 1/3 citrate, bis (2,2,6 , 6-tetramethyl-4-piperidyl) sebacate, quercetin and 4,4'-bis (α, α-dimethylbenzyl) Phenyl amine. Preferred is 3,5-di-tert-butyl-4-hydroxytoluene (BHT).
The blending amount of the antioxidant is, for example, 0.001 to 10% by mass, preferably 0.01 to 5% by mass with respect to the total mass of the fragrance composition.
The total amount of component (C) is not particularly limited, but is preferably 0.1 to 5.0% by mass, more preferably 0.5 to 3.0%, based on the total mass of the softener composition. % By mass.

[(D) component]
(D) component contained in the softening agent composition of this invention is an antibacterial agent.
Examples of the component (D) include isothiazolone organic sulfur compounds, benzisothiazolone organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, and the like.
Examples of isothiazolone-based organic sulfur compounds include 5-chloro-2-methyl-4-isothiazoline-3-one, 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, 2-phenyl-3-isothiazolone 5-trimethylene-4-isothiazolin-3-one, 2-methyl-4,5-dichloroisothiazolone, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, 5-chloro-2-methyl- Examples include 3-isothiazolone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof. Among them, 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one and 2-methyl-4,5 -Trimethylene-4-isothiazolin-3-one is preferred, and a mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one is more preferred. A mixture of 77% by weight and the latter about 23% by weight is particularly preferred. A mixture of 2-methyl-4-isothiazolin-3-one and 2-methyl-4,5-trimethylene-4-isothiazolin-3-one is also preferred, with the former being about 50% by weight and the latter being about 50% by weight. The mixture of is particularly preferred.
Examples of the benzisothiazolone organic sulfur compound include 1,2-benzisothiazolin-3-one, dithio-2,2-bis (benzmethylamide) as a related compound, or a mixture thereof. Of these, 1,2-benzisothiazolin-3-one is particularly preferable.
The amount of component (D) is not particularly limited, but is preferably 0.0001 to 1% by mass with respect to the total mass of the softener composition. When the blending amount of the component (D) is not less than the above lower limit value, an effect of adding an antibacterial agent is easily obtained, and when it is not more than the above upper limit value, a decrease in storage stability can be sufficiently suppressed.

[Optional ingredients]
The liquid softening agent composition of the present invention may contain the following components in addition to the components (A) to (D) as necessary, as long as the effects of the present invention are not impaired. For example, inorganic salts, nonionic surfactants, dyes and / or pigments, water, ultraviolet absorbers, antibacterial agents and the like can be blended.

<Inorganic salt>
The inorganic salt is effective as a viscosity control agent for the softener composition.
As the inorganic salt, a water-soluble inorganic salt is preferable. In the present specification, a compound that dissolves 10 g or more in 100 g of deionized water at 20 ° C. is defined as a water-soluble inorganic salt.
Preferred inorganic salts include inorganic salts selected from alkali metal chlorides and alkaline earth metal chlorides. Furthermore, at least one inorganic salt selected from the group consisting of sodium chloride, potassium chloride, calcium chloride and magnesium chloride is preferred from the viewpoint of the storage stability of the composition. From the viewpoint of viscosity adjustment, one or more inorganic salts selected from the group consisting of calcium chloride and magnesium chloride are more preferable.
The blending amount of the inorganic salt in the softening agent composition of the present invention is preferably 0.01 to 1.0% by mass as a range that can provide a viscosity that can be used without any problem.

<Nonionic surfactant>
The nonionic surfactant is mainly used for the purpose of improving the emulsion dispersion stability of the oil-soluble component in the emulsion when the softener composition is an emulsion. When a nonionic surfactant is blended, it is easy to ensure stability (freezing and restoring stability) when frozen and restored in terms of commercial value.
Examples of nonionic surfactants include those derived from higher alcohols, higher amines or higher fatty acids. Examples of such nonionic surfactants include polyoxyethylene alkyl ethers having an alkyl group or an alkenyl group having 10 to 22 carbon atoms and an average addition mole number of ethylene oxide of 10 to 100 moles; Alkyl (alkyl having 1 to 3 carbon atoms) ester; polyoxyethylene alkylamine having an average addition mole number of ethylene oxide of 10 to 100 moles; alkyl polyglucoside having an alkyl group or alkenyl group having 8 to 18 carbon atoms; Examples include hydrogenated castor oil having an average added mole number of 10 to 100 moles. Of these, polyoxyethylene alkyl ethers having an alkyl group having 10 to 18 carbon atoms and an average addition mole number of ethylene oxide of 20 to 80 moles are preferred.
The content of the nonionic surfactant in the softening agent composition of the present invention can be determined according to the desired function. For example, 0.01 to 10% by mass is preferable in the liquid agent, and 0.1 to 8% by mass. Is more preferable, and 0.5 to 5% by mass is even more preferable. If content of nonionic surfactant is more than the said lower limit, the emulsification dispersion stability of the oil-soluble component in an emulsion and the freeze restoration stability of an emulsion can be improved more. If content of nonionic surfactant is below the said upper limit, the raise of the viscosity of a liquid agent will be suppressed and usability can be improved.

<Dye and / or pigment>
The dye and / or pigment can be blended for the purpose of improving the appearance of the softener composition. Preferably, it is one or more of red and yellow water-soluble dyes selected from acidic dyes, and specific examples include acid yellow and acid red.
Specific examples of the dyes that can be added are described in the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, published on July 20, 1970, Maruzen Co., Ltd.).
From the viewpoint of the storage stability of the softener composition of the present invention and the dyeing property to fibers, an acidic dye having at least one functional group selected from a hydroxyl group, a sulfonic acid group, an amino group, and an amide group in the molecule is provided. The blending amount is preferably 1 to 50 ppm, more preferably 1 to 30 ppm, based on the entire composition.

<Water>
The softener composition of the present invention is preferably an aqueous composition and preferably contains water.
As water, any of tap water, ion exchange water, pure water, distilled water, and the like can be used. Of these, ion-exchanged water is preferred.
Water is preferably blended in the softener composition of the present invention in an amount of 50% by mass or more, more preferably 60% by mass or more. When the water content is equal to or higher than the lower limit, handling properties are good.

<Ultraviolet absorber>
In the softening agent composition of the present invention, an ultraviolet absorber can be blended. An ultraviolet absorber is a chemical | medical agent with the effect which protects an ultraviolet-ray, it is a component which absorbs an ultraviolet-ray, converts into infrared rays, visible light, etc., and discharge | releases.
Examples of the ultraviolet absorber include aminobenzoic acid derivatives such as p-aminobenzoic acid, ethyl p-aminobenzoate, glyceryl p-aminobenzoate, and amyl p-dimethylaminobenzoate; ethylene glycol salicylate, dipropylene glycol salicylate , Salicylic acid derivatives such as octyl salicylate, myristyl salicylate; methyl diisopropylcinnamate, ethyl p-methoxycinnamate, isopropyl p-methoxycinnamate, 2-ethylhexyl p-methoxycinnamate, p-methoxycinnamic acid Cinnamic acid derivatives such as butyl; benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and 2,2′-dihydroxy-4-methoxybenzophenone; urocanic acid, Ouro Examples thereof include azole compounds such as ethyl kanate; 4-t-butyl-4′-methoxybenzoylmethane and the like.

<Other antibacterial agents>
In the softener composition of the present invention, in addition to the component (D), the following antibacterial agents can be blended. The antibacterial agent is a component having an effect of suppressing the growth of bacteria on the fiber and further suppressing the generation of an unpleasant odor derived from the degradation product of the microorganism.
Antibacterial agents include, for example, cationic fungicides such as quaternary ammonium salts (benzalkonium chloride, didecyldimethylammonium chloride), diclosan, triclosan, bis- (2-pyridylthio-1-oxide) zinc, polyhexa Examples include methylene biguanidine hydrochloride, 8-oxyquinoline, polylysine and the like.

<Others>
In addition to the above compounds, in the softener composition of the present invention, as an antioxidant, a reducing agent, an emulsion such as polystyrene emulsion, an opaque agent, and a function improver for improving the stability of aroma and color tone, Odor base, anti-shrink agent, anti-wrinkle agent, shape retainer, drape retainer, ironability improver, oxygen bleach inhibitor, whitening agent, whitening agent, fabric softening clay, antistatic agent, polyvinyl Fluorescent whitening of dye transfer inhibitors such as pyrrolidone, polymer dispersants, stain removers, scum dispersants, 4,4-bis (2-sulfostyryl) biphenyl disodium (Cino Pearl CBS-X manufactured by Ciba Specialty Chemicals) Agent, dye fixing agent, anti-fading agent such as 1,4-bis (3-aminopropyl) piperazine, stain remover, fiber surface modifier as cellulase, amylase, protear Silk protein powders, surface modified products, emulsified dispersions, specifically K-50, K, and the like that can impart silk texture and functions such as enzymes such as lipase and keratinase, foam suppressors, moisture absorption and release -30, K-10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk solution (upper hair), Silken G Solvel S (Ichimaru Falcos), alkylene terephthalate and / or A nonionic polymer compound composed of an alkylene isophthalate unit and a polyoxyalkylene unit, for example, an antifouling agent such as FR627 manufactured by Kyoyo Chemical Industry, SRC-1 manufactured by Clariant Japan, and the like can be blended.

[PH]
The pH of the softener composition of the present invention is not particularly limited, but the pH at 25 ° C. is within the range of 1 to 6 from the viewpoint of suppressing hydrolysis of the component (A) accompanying storage aging. Preferably, it is in the range of 2-4.
When adjusting pH, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, p-toluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethane diphosphonic acid, phytin PH adjusting agents such as acids, short-chain amine compounds such as ethylenediaminetetraacetic acid and dimethylamine, alkali metal hydroxides such as sodium hydroxide, alkali metal carbonates and alkali metal silicates can be used.

[viscosity]
The viscosity of the softener composition of the present invention is not particularly limited, but is preferably less than 1000 mPa · s (B-type viscometer, manufactured by TOKIMEC, 25 ° C., the same applies hereinafter). Considering the increase in viscosity due to storage aging, the viscosity immediately after production is more preferably less than 800 mPa · s, and further preferably less than 500 mPa · s. When it is in such a range, the usability such as handling property at the time of loading into the washing machine is good.

[Production method]
The softener composition of the present invention can be produced by a known method, for example, a method similar to the conventional method for producing a liquid softener composition using a cationic surfactant as a main agent.
For example, an emulsion obtained by mixing an oil phase containing (A) component, (B) component and (C) component and an aqueous phase containing (D) component under temperature conditions equal to or higher than the melting point of (A) component. And then, if necessary, can be produced by adding and mixing other components to the obtained emulsion. (B) You may add a component, after mixing an oil phase and an aqueous phase and obtaining an emulsion.

[Use / How to use]
Although the use of the liquid softening agent composition of this invention is not specifically limited, Desirable texture and fragrance can be provided also to any of natural fiber products, such as cotton, and chemical fiber products, such as polyester.
Specifically, when the softening treatment is performed, it is preferable to use such an amount that the concentration of the component (A) + the component (B) is 15 ppm to 100 ppm with respect to the total amount of water used. Incidentally, even if the number of times of rinsing is one time or multiple times, it can be used in the same manner, and the texture and scent that are the characteristics of the softener can be imparted to the clothing.

[container]
The main body container used for enclosing the softener composition of the present invention preferably includes at least a container main body bottle and a cap, and more preferably includes three members: a container main body bottle, a nozzle cap, and a measuring cap. It is provided. One or more kinds of other members may be contained.
(Weighing cap)
Representative examples of the material of the measuring cap that can be used in the softener composition of the present invention include materials such as high density polyethylene, low density polyethylene, polyethylene terephthalate, polypropylene, polycarbonate, and acrylic resin, and the internal volume is 10-80 mL is desirable. The cross-sectional shape of the measuring cap is generally circular, but may be a polygon such as a quadrangle, hexagon, or octagon. Further, if necessary, the inner surface or the outer surface can be engraved or printed for capacity display, or knurled for slip prevention. Further, pigments, antistatic agents, ultraviolet absorbers, slipping agents and the like can also be included. In particular, when a pigment and an ultraviolet absorber are contained, the composition is prevented from becoming a gel when the container is placed under ultraviolet light.
(Nozzle cap)
The nozzle cap that can be used in the softener composition of the present invention is a cap body assembled to the mouthpiece of the main body, and a partition wall is provided in the cylindrical assembly cylinder to vertically separate the contents. It has a spout for pouring out, and the liquid discharge speed can be adjusted by the diameter of the spout. Furthermore, even when trying to return the contents from the outside of the container, those having good recoverability of the liquid into the container main body are used due to the shape of the partition wall. Alternatively, the partition wall may have one or more air holes other than the spout. In addition to the nozzle cap, in order to prevent liquid dripping from the main body, a cap stopper having a funnel mechanism assembled to the main body tube can be used. The material of the member used here is selected from materials such as high density polyethylene, low density polyethylene, polyethylene terephthalate, polypropylene, polycarbonate, and acrylic resin. Further, pigments, antistatic agents, ultraviolet absorbers, slipping agents and the like can also be included.
(Container body bottle)
As a container main body bottle which accommodates the softening agent composition of this invention, the thing of materials, such as a high density polyethylene, a low density polyethylene, a polyethylene terephthalate, a polypropylene, a polycarbonate, an acrylic resin, is suitable. The cross-sectional shape of the main body may be any of a circular shape, an elliptical shape, etc., but those having an internal volume of about 200 to 1000 mL are used. A handle, a label, etc. can be given and usability can also be improved. Further, pigments, antistatic agents, ultraviolet absorbers, slipping agents and the like can also be included.

(Refill)
As the refill container that can be used for encapsulating the softener composition of the present invention, the following can be suitably used.
A bag-like container having a film structure, which is a storage bag in which the innermost layer of the film is made of low-density polyethylene. As the film constituting the container body of the refill container, a multilayer film is suitable, and as the material constituting the multilayer film, in addition to the property stability and aroma stability of the contents, the strength and economics of the storage bag From the viewpoint of container usability, stretched nylon, linear low density polyethylene, stretched polypropylene, ethylene vinyl alcohol copolymer, polyethylene terephthalate and the like can be mentioned. As the multilayer film, two or more kinds of films may be used, and the same film may be laminated in two or more layers. Among these, in particular, it is desirable to use stretched nylon, stretched polypropylene, polyethylene terephthalate or the like in combination with linear low density polyethylene so that the innermost layer is linear low density polyethylene. When manufacturing a storage bag using the said multilayer film, it can be based on the method of laminating the film used for each layer, and heat-sealing, However, It is not limited to a specific shaping | molding method.
The storage bag that can store the softener composition of the present invention preferably has a thickness in the range of 20 to 400 μm. As the refill pack that can be used in the present invention, for example, those having a width of about 70 to 200 mm, a height of about 100 to 400 mm, and a depth of about 20 to 100 mm are preferably used. The multilayer film may contain additives such as coloring ink, stabilizer, plasticizer, antioxidant, antistatic agent, ultraviolet absorber, lubricant, and dispersant. Furthermore, the refill which has vapor-deposited aluminum is preferable in terms of viscosity stability of the composition, suppression of gelation, and aroma stability.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. In the examples, the component blending amounts are all expressed by mass% (in terms of pure content, unless otherwise specified).

[(A) component]
The following A-1 and A-2 were synthesized and used.
A-1: Compound (A-III), Compound (A-IV) and Compound (AV) ((A-III) to (AV) wherein R ¹ is an alkyl having 15 or 17 carbon atoms. A mixture or a alkenyl group (unsaturated cis / trans = 75/25 (mass ratio)) quaternized with dimethyl sulfate (molecular weight 798.6). In accordance with the procedure described in Example 4 of JP-A-2003-12471, the compound was synthesized by the following synthesis method.
<Synthesis Method of A-1>
782 g (2.68) of a mixture of fatty acid lower alkyl esters containing 45% by mass of methyl stearate, 35% by mass of methyl oleate and 20% by mass of methyl palmitate (a mixture of Lion Corporation, Pastel M180, Pastel M181, Pastel M16) Mol), 250 g (1.68 mol) of triethanolamine, 0.52 g of magnesium oxide, and 2.06 g of 25% aqueous sodium hydroxide solution (transesterification catalyst; catalyst for the total mass of the fatty acid lower alkyl ester and triethanolamine) The amount used: 0.10% by mass) was charged into a 2 L five-necked flask equipped with a stirrer, a partial condenser, a cooler, a thermometer, and a nitrogen inlet tube. After nitrogen substitution, nitrogen was allowed to flow at a flow rate of 0.52 L / min. The temperature was raised to 190 ° C. at a rate of 1.5 ° C./min and reacted for 5 hours. After confirming that the amount of unreacted methyl ester was 1% by mass or less, the reaction was stopped. The fatty acid salt derived from the catalyst was removed by filtration from the obtained product to obtain an intermediate alkanolamine ester. The molecular weight of the obtained alkanolamine ester was 582.
300 g (0.515 mol) of the obtained alkanolamine ester (molecular weight 582) was charged into a 1 L four-necked flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Then, it heated at 60 degreeC and 63.7 g (0.505 mol) of dimethyl sulfuric acid was dripped over 1 hour. The temperature was adjusted so that there was no sudden temperature rise due to heat of reaction, and reached 90 ° C. at the end of the addition of dimethyl sulfate. The mixture was kept at 90 ° C. and stirred for 1.5 hours. After completion of the reaction, the reaction solution was cooled while dropping about 69 g of ethanol to obtain an ethanol solution containing A-1. All operations were performed under nitrogen flow.

A-2: Compound (A-III), Compound (A-IV), and Compound (AV) ((A-III) to (AV), wherein R ¹ is an alkyl having 15 or 17 carbon atoms. A mixture (molecular weight 802.6), which is a quaternary group of alkenyl group and cis isomer / trans isomer of unsaturated part = 75/25 (mass ratio) with dimethyl sulfate. In accordance with the procedure described in Example 4 of JP-A-2003-12471, the compound was synthesized by the following synthesis method.
<Method for synthesizing A-2>
782 g (2.68) of a mixture of fatty acid lower alkyl esters containing 30% by mass of methyl stearate, 40% by mass of methyl oleate and 30% by mass of methyl palmitate (Lion Corporation, pastel M180, pastel M181, pastel M16) Mol), 250 g (1.68 mol) of triethanolamine, 0.52 g of magnesium oxide, and 2.06 g of 25% aqueous sodium hydroxide solution (transesterification catalyst; catalyst for the total mass of the fatty acid lower alkyl ester and triethanolamine) The amount used: 0.10% by mass) was charged into a 2 L five-necked flask equipped with a stirrer, a partial condenser, a cooler, a thermometer, and a nitrogen inlet tube. After nitrogen substitution, nitrogen was allowed to flow at a flow rate of 0.52 L / min. The temperature was raised to 190 ° C. at a rate of 1.5 ° C./min and reacted for 5 hours. After confirming that the amount of unreacted methyl ester was 1% by mass or less, the reaction was stopped. The fatty acid salt derived from the catalyst was removed by filtration from the obtained product to obtain an intermediate alkanolamine ester. It was 558 when the obtained alkanolamine ester amine value was measured and molecular weight was calculated | required.
300 g (0.538 mol) of the obtained alkanolamine ester (molecular weight 558) was charged into a 1 L four-necked flask equipped with a thermometer, a dropping funnel and a condenser, and purged with nitrogen. Then, it heated at 60 degreeC and 66.5 g (0.527 mol) of dimethyl sulfuric acid was dripped over 1 hour. The temperature was adjusted so that there was no sudden temperature rise due to heat of reaction, and reached 90 ° C. at the end of the addition of dimethyl sulfate. The mixture was kept at 90 ° C. and stirred for 1.5 hours. After completion of the reaction, cooling was performed while dropping about 65 g of ethanol to obtain an ethanol solution containing A-2. All operations were performed under nitrogen flow.

[Component (B)]
The following B-1 to B-4 were used.
B-1: Side chain-modified type amino-modified silicone oil obtained from Shin-Etsu Chemical Co., Ltd. under the trade name: KF-864. (Kinematic viscosity at 25 ° C. 1700 mm ² / s, amine equivalent 3800 g / mol)
B-2: Side chain modified type amino modified silicone oil obtained from Shin-Etsu Chemical Co., Ltd. under the trade name: KF-880. (Kinematic viscosity at 25 ° C. 650 mm ² / s, amine equivalent 1800 g / mol)
B-3: Side chain modified type amino modified silicone oil obtained from Shin-Etsu Chemical Co., Ltd. under the trade name: KF-8005. (Kinematic viscosity at 25 ° C. 1200 mm ² / s, amine equivalent 11000 g / mol)
B-4 (Comparative Example): The polyether-modified silicone described as (B-2) used in Example 2 of JP-A-2005-187987.

[Component (C)]
C-1 to C-6 shown in Table 1 below were used.

The numerical values in the table are blending amounts (mass%) based on the total mass of the fragrance composition.
The numerical value in parentheses in the table is a blending amount (% by mass) based on the total mass of the softener composition.

[(D) component]
The following D-1 to D-4 were used.
D-1: 1,2-benzisothiazolin-3-one (BIT) (trade name: Proxel BDN: Lonza)
D-2: 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (MIT) / 2-methyl-4-isothiazolin-3-one (MTI) = 1/1 (trade name: Proxel MW: Lonza )
D-3: 2-methyl-4,5-trimethylene-4-isothiazolin-3-one (MIT) (trade name: NEOLONE M-10 (MIT): Dow Chemical)
D-4: 5-chloro-2-methyl-4-isothiazolin-3-one / 2-methyl-4-isothiazolin-3-one (trade name: Caisson CG-ICP: Dow Chemical)

[Other ingredients (common ingredients)]
・ Nonionic surfactant: (trade name: TA600-75: Lion) 1.8%
・ Antioxidant: BHT 0.01%
・ Calcium chloride 0.6%
-Ion-exchange water balance The above-mentioned numerical value is mass% to the total mass of a softener composition.

[container]
A container made of each part made of the following materials was used.
E-1: PP bottle, PE nozzle cap, PE / Pigment / Measurement cap with UV absorber added (Absorbance 360nm, 0%)
E-2: PP bottle, PE nozzle cap, PE / measuring cap with pigment (absorbance 360nm, 15%)

[Method for Preparing Liquid Softener Composition]
Using a glass container having an inner diameter of 100 mm and a height of 150 mm and a stirrer (Agitator SJ type, manufactured by Shimadzu Corporation), the blending amounts of the respective components were adjusted as in Examples and Comparative Examples described in Table 3 below. A liquid softener composition was prepared by the procedure.
First, (A) component, (C) component which melt | dissolved BHT previously, and nonionic surfactant were mixed and stirred, and the oil phase mixture was obtained. On the other hand, the component (D) was dissolved in ion-exchange water for balance to obtain an aqueous phase mixture. Next, the oil phase mixture heated above the melting point of component (A) is placed in a glass container and stirred, and the aqueous phase mixture heated above the melting point of component (A) is added in two portions. And stirred. Here, the division ratio of the aqueous phase mixed grains is 30:70 (mass ratio), and the stirring is performed at a rotational speed of 1500 rpm for 3 minutes after the first aqueous phase mixture addition and for 2 minutes after the second aqueous phase mixture addition. It was. Thereafter, calcium chloride and component (B) are added, and if necessary, hydrochloric acid (reagent 2 mol / L, Kanto Chemical) or sodium hydroxide (reagent 1 mol / L, Kanto Chemical) is added in an appropriate amount to adjust the pH to 2.5. Then, ion-exchanged water was added so that the total mass became 1000 g to obtain the desired softener compositions (Examples 1 to 12 and Comparative Examples 1 to 5).

[Evaluation methods]
Using the liquid softener composition prepared as described above, the following procedures are used to create a “texture of preserved product”, “liquid appearance after freeze restoration”, “liquid appearance during UV irradiation”, “preservative power of preserved product ( Antibacterial agent residual ratio) ”and“ odor of preserved products ”were evaluated. In Table 3, they are represented as “feel”, “freezing and restoring”, “UV irradiation”, “residual rate”, and “odor”, respectively.

1. Texture of preserved product (1) Pre-treatment method of evaluation cloth Commercially available cotton shirt (BVD) was washed with a commercially available detergent “Blue Diamond” (Lion Corporation). ) Was used 3 times (standard amount of detergent used: 30 times the bath ratio; 45 ° C. tap water; 10 minutes of washing and 10 minutes of water rinsing twice).
(2) Treatment with a softener in the rinsing process during washing Course / setting with 1.5 kg of pre-washed commercial cotton shirt (BVD) using a vertical fully automatic washing machine (Toshiba TW-80V) (Detergent used: “Top NANOX” (manufactured by Lion), washing 15 minutes, rinsing once, dehydration 5 minutes). Therefore, the liquid softener compositions prepared above were charged from the automatic charging port in the first rinsing. The amount of detergent used was 10 mL, and the amount of liquid softener composition used was 10 mL.
(3) Evaluation of texture The texture of the garment treated with the softener composition was evaluated using the smooth and soft feel of the treated article after the treatment as an index. Specifically, sensory evaluation and paired comparison were performed according to the following evaluation criteria for the good texture brought to the cotton shirt by the treatment with each softener composition. It was conducted by 5 expert panelists.
<Evaluation criteria>
As a control, a cotton skin shirt softly processed by the same method as in (2) above using “Saffron floral aroma of fragrance and deodorant” manufactured by Lion Corporation was used.
3: It feels much better than the control 2: It feels slightly better than the control 1: Equivalent to the control 0: It doesn't feel better than the control Take the average of the scores of the five panelists and get an average score of 2.0 or more It was determined that the touch after storage was acceptable.

2. Liquid appearance after freeze-restoration 80 mL of each liquid softener composition prepared above was sealed in a glass container containing 100 mL, stored in a freezer at −15 ° C. for 24 hours, and then returned to 25 ° C. for each composition. The appearance of was evaluated. Evaluation was performed according to the following evaluation criteria.
<Evaluation criteria>
3: There is no gel-like solid.
2: A gel-like solid is slightly attached to the wall surface.
1: The gel-like solid substance has adhered to the wall surface.
An average of N2 was taken, and an evaluation of 2.0 or more was determined to be acceptable in terms of commercial value as a softener.

3. Liquid appearance at the time of UV irradiation Each of the liquid softener compositions prepared above was sealed in a container provided with 600 mL, and irradiated with UV at 30 MJ. Each composition after irradiation was passed through a 100-mesh sieve, and the amount of the gelled product was evaluated according to the following evaluation criteria.
<Evaluation criteria>
3: There is no film-like solid.
2: A film-like solid is slightly seen.
1: A film-like solid is seen.
0: A film-like solid is considerably observed.
Taking an average at N = 2, an evaluation of 2.0 or more was determined to be acceptable in terms of commercial value as a softener.

4). Antiseptic power of stored products (antibacterial agent remaining rate)
The prepared liquid softener composition (80 mL) was sealed in a glass container containing 100 mL, stored in a constant temperature bath at 40 ° C. for 60 days, and then the amount of the antibacterial agent in each composition was quantified by liquid chromatography. The residual rate from the initial stage was calculated. Those having a residual rate of 50% or more were determined to be acceptable.

5. Odor of Preserved Goods 80 mL of each liquid softener composition prepared above was sealed in a glass container containing 100 mL and stored outdoors for 60 days, and then the odor of each composition was evaluated according to the following evaluation criteria.
<Evaluation criteria>
3 points: There is no odor degradation compared to products stored at 5 ° C.
2 points: Slight odor degradation compared to products stored at 5 ° C.
1 point: There is odor degradation compared to products stored at 5 ° C.
Two or more points were considered acceptable in terms of commercial value.

The numerical value in a composition table | surface represents the mass%.

Claims

Liquid softener composition containing the following components (A) to (D):
(A) An amine compound having one or more hydrocarbon groups having 10 to 26 carbon atoms in the molecule which may be separated by an ester group (—COO—) and / or an amide group (—NHCO—), and neutralization thereof And one or more compounds selected from the group consisting of compounds and quaternized compounds thereof,
(B) Amino-modified silicone 0.1-10% by mass,
(C) A perfume composition containing 0.1% by mass or more of ISOE super based on the total mass of the liquid softening agent composition and containing citronellol, and (D) an antibacterial agent.
The liquid softener composition according to claim 1, wherein the component (C) further comprises one or more fragrance components selected from the group consisting of coumarin, hexylcinnamic aldehyde, and habanolide.