JP2017025443A - Liquid softener composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid softener composition using a free flavor (flavor which is not encapsulated) high in hydrophobicity and capable of suppressing deterioration of peeling paint while enhancing dispersibility of an encapsulated flavor.SOLUTION: There is provided a liquid softener composition containing following (A) to (D) components: (A) at least one kind of compound selected from a group consisting of an amine compound having 1-3 hydrocarbon group(s) with 10-26 carbon atoms in a molecule which may be segmented by an ester group and/or an amide group, a salt thereof and a quaternary compound thereof, (B) an encapsulated flavor, (C) a flavor composition which is not encapsulated and contains a flavor component having ClogP value of 5 or more of 25 mass% or more based on total mass of the flavor composition, and (D) a water soluble polymer compound.SELECTED DRAWING: None

Description

  The present invention relates to a liquid softener composition. Specifically, the present invention relates to a liquid softener composition that is excellent in dispersibility of encapsulated fragrances and that suppresses deterioration of paint peeling due to the blended components.

  In recent years, an increasing number of consumers use a softening agent for the purpose of imparting a scent, and it is required that a good scent lasts long. In order to make the fragrance last long, the amount of the fragrance used is increased, or the use of an encapsulated fragrance in which the fragrance is included is performed. One of the important issues in using an encapsulated fragrance is the dispersibility of the encapsulated fragrance in a softening agent. In order to improve the dispersibility of the encapsulated fragrance, a method using a specific mono-long-chain alkylamine or a salt thereof, a semipolar surfactant, or a polyoxyethylene alkylamine or a salt thereof (Patent Document 1), or a nonion A method for increasing the blending amount (Patent Document 2) is known.

International Publication No. 2014/204012 JP 2012-167389 A

  However, when the liquid softening agent is brought into contact with the painted flooring or the like for a long time (for example, when the liquid softening agent is left spilled), the painting such as the flooring may be peeled off, and an improvement has been desired. As a result of investigations by the present inventors, in particular, the components described in Patent Document 1 or 2 (mono-long chain alkylamine or salt thereof, semipolar surfactant, polyoxyethylene alkylamine or salt thereof, or nonionic surfactant) It was found that the softening agent having a composition with a large amount of) and the softening agent containing a highly hydrophobic fragrance component having a ClogP value of 5 or more worsen the paint peeling.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a water-soluble polymer so that a free perfume (a perfume not encapsulated in a capsule) has a high hydrophobicity, and a capsule While improving dispersibility of the fragrance | flavor, it discovered that the deterioration of paint peeling could be suppressed, and came to complete this 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) Selected from the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms which may be separated by an ester group and / or an amide group, a salt thereof and a quaternized product thereof At least one compound (B) encapsulated fragrance (C) is a fragrance composition not encapsulated in capsules, and 25 masses of fragrance components having a ClogP value of 5 or more with respect to the total mass of the fragrance composition Perfume composition containing at least%, and (D) water-soluble polymer compound

  According to one embodiment of the present invention, the component (D) is selected from the group consisting of a nonionic glucan, polyethyleneimine or a derivative thereof, and a cationic (meth) acrylic polymer.

According to one embodiment of the present invention, a liquid softener composition excellent in dispersibility of encapsulated fragrance can be provided.
According to one embodiment of the present invention, it is possible to provide a liquid softener composition excellent in dispersibility and scent sustainability of encapsulated fragrance.
According to one embodiment of the present invention, it is possible to provide a liquid softener composition that is excellent in dispersibility of encapsulated fragrance and that suppresses deterioration of paint peeling due to the blended components.
According to one embodiment of the present invention, it is possible to provide a liquid softener composition that is excellent in dispersibility and scent sustainability of encapsulated fragrances and that suppresses the deterioration of paint peeling due to the blended components.
According to one embodiment of the present invention, there is provided a liquid softener composition that uses a highly hydrophobic free perfume and improves the dispersibility of the encapsulated perfume while suppressing deterioration of paint peeling. be able to.
According to one embodiment of the present invention, a liquid softener that uses a highly hydrophobic free perfume and suppresses the deterioration of paint peeling while improving the dispersibility of the encapsulated perfume and the sustainability of the scent. A composition can be provided.

[(A) component]
The component (A) contained in the softener composition of the present invention is a hydrocarbon group having 10 to 26 carbon atoms (hereinafter referred to as “long chain carbonization”) which may be separated by an ester group and / or an amide group. It is at least one compound selected from the group consisting of an amine compound having 1 to 3 hydrogen groups in the molecule, a salt thereof and a quaternized product thereof. (A) A component is mix | blended in order to improve the dispersibility of encapsulated fragrance | flavor ((B) component) while providing a softness | flexibility to textiles etc.
The carbon number of the long chain hydrocarbon group is 10 to 26, preferably 17 to 26, and more preferably 19 to 24. When the number of carbon atoms is 10 or more, flexibility is good, and when it is 26 or less, handling properties are good. The long chain hydrocarbon group may be saturated or unsaturated. When the long chain hydrocarbon group is unsaturated, the position of the double bond may be anywhere, but when there is one double bond, the position of the double bond is the long chain carbonization. It is preferably at the center of the hydrogen group or around the center.
The long chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group containing a ring in the structure, and is preferably a chain hydrocarbon group. The chain hydrocarbon group may be linear or branched. As the chain hydrocarbon group, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

The long chain hydrocarbon group may be separated by an ester group (—COO—) and / or an amide group (—NHCO—). That is, the long-chain hydrocarbon group has at least one kind of splitting group selected from the group consisting of an ester group and an amide group in the carbon chain, and the carbon chain is split by the splitting group. May be. Having the splitting group is preferable from the viewpoint of improving biodegradability.
When it has this dividing group, the number of the dividing groups which one long-chain hydrocarbon group has may be one, or may be two or more. That is, the long chain hydrocarbon group may be divided at one place by a dividing group, or may be divided at two or more places. When having two or more splitting groups, each splitting group may be the same or different.
In addition, when it has a splitting group in a carbon chain, the carbon atom which a splitting group shall count to carbon number of a long-chain hydrocarbon group. The long-chain hydrocarbon group is usually an unhydrogenated fatty acid derived from beef tallow, which is used industrially, a fatty acid obtained by hydrogenation or partial hydrogenation of an unsaturated part, palm-derived palm oil, oil palm-derived It is introduced by using a hydrogenated fatty acid or fatty acid ester, or a fatty acid or fatty acid ester obtained by hydrogenation or partial hydrogenation of an unsaturated portion.
The amine compound as the component (A) contained in the softener composition of the present invention is preferably a secondary amine compound or a tertiary amine compound, and more preferably a tertiary amine compound.

〔式中、Ｒ¹〜Ｒ³はそれぞれ独立に、炭素数１０〜２６の炭化水素基、−ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴（Ｙは水素原子又はＣＨ₃であり、Ｒ⁴は炭素数７〜２１の炭化水素基である。）若しくは−（ＣＨ₂）_nＮＨＣＯＲ⁵（ｎは２又は３であり、Ｒ⁵は炭素数７〜２１の炭化水素基である。）、水素原子、炭素数１〜４のアルキル基、−ＣＨ₂ＣＨ（Ｙ）ＯＨ、又は−（ＣＨ₂）_nＮＨ₂であり、Ｒ¹〜Ｒ³のうちの少なくとも１つは、炭素数１０〜２６の炭化水素基、−ＣＨ₂ＣＨ（Ｙ）ＯＣＯＲ⁴又は−（ＣＨ₂）_nＮＨＣＯＲ⁵である。〕 More specifically, examples of the amine compound as the component (A) contained in the softener composition of the present invention include compounds represented by the following general formula (A1).

[Wherein, R ^{1 to} R ³ are each independently a hydrocarbon group having 10 to 26 carbon atoms, —CH ₂ CH (Y) OCOR ⁴ (Y is a hydrogen atom or CH ₃ , and R ⁴ is 7 carbon atoms. . ~ 21 is a hydrocarbon group) or _{-. (CH 2) n NHCOR} 5 (n is 2 or 3, R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms), a hydrogen atom, the number of carbon atoms 1 to 4 alkyl group, —CH ₂ CH (Y) OH, or — (CH ₂ ) _n NH ₂ , and at least one of R ^{1 to} R ³ is a hydrocarbon group having 10 to 26 carbon atoms. _{, -CH 2 CH (Y) OCOR} 4 or - (CH _{2) n} NHCOR ^5. ]

In formula (A1), the carbon number of the hydrocarbon group having 10 to 26 carbon atoms in R ^{1 to} R ³ is preferably 17 to 26, and more preferably 19 to 24. The hydrocarbon group may be saturated or unsaturated. The hydrocarbon group is preferably an alkyl group or an alkenyl group.
In —CH ₂ CH (Y) OCOR ⁴ , Y is a hydrogen atom or CH ₃ , and a hydrogen atom is particularly preferable. R ⁴ is a hydrocarbon group having 7 to 21 carbon atoms, preferably a hydrocarbon group having 15 to 19 carbon atoms. When R ⁴ is more present in the compounds represented by formula (A1), may be R ⁴ of said plurality of mutually identical, may be different.

Hydrocarbon group R ⁴ is a residue obtained by removing a carboxy group from a fatty acid having 8 to 22 carbon atoms (R ⁴ COOH) (fatty acid residues), R ⁴ Nomoto become fatty (R ⁴ COOH) is Saturated fatty acids or unsaturated fatty acids may be used, and straight-chain fatty acids or branched fatty acids may be used. Of these, saturated or unsaturated linear fatty acids are preferred. In order to impart good water absorption to the soft-treated garment, the saturated / unsaturated ratio (mass ratio) of the fatty acid serving as R ⁴ is preferably 90/10 to 0/100, and 80/20 to 0 / 100 is more preferable.
When R ⁴ is an unsaturated fatty acid residue, a cis isomer and a trans isomer are present, and the mass ratio of the cis isomer / trans isomer is preferably 40/60 to 100/0, and 70/30 to 90/10. Particularly preferred.

Specific examples of fatty acids used as R ⁴ include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), partial Examples include hydrogenated beef tallow fatty acid (iodine value of 10 to 60). Among them, a fatty acid prepared by combining two or more selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid in predetermined amounts to satisfy the following conditions (a) to (c) It is preferable to use a composition.
(A) The ratio (mass ratio) of saturated fatty acid / unsaturated fatty acid is 90/10 to 0/100, more preferably 80/20 to 0/100. (B) The ratio (mass ratio) of cis isomer / trans isomer is 40/60 to 100/0, more preferably 70/30 to 90/10. (C) The fatty acid having 18 carbon atoms is 60 mass% or more, preferably 80 mass% or more, the fatty acid having 20 carbon atoms is less than 2 mass%, and the fatty acid having 21 to 22 carbon atoms is less than 1 mass%. .

In — (CH ₂ ) _n NHCOR ⁵ , n is 2 or 3, and 3 is particularly preferable. R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms, preferably 15 to 19 carbon atoms. When R ⁵ is more present in the compounds represented by formula (A1), may be R ⁵ of said plurality of mutually identical, may be different. Examples of R ⁵ include the same as R ⁴ .

At least one of R ^{1 to} R ³ is a long-chain hydrocarbon group (a hydrocarbon group having 10 to 26 carbon atoms, —CH ₂ CH (Y) OCOR ⁴ , or — (CH ₂ ) _n NHCOR ⁵ ). Two are preferably long-chain hydrocarbon groups. When one or two of R ^{1 to} R ³ are long-chain hydrocarbon groups, the remaining two or one is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, —CH ₂ CH (Y) OH or — (CH ₂ ) _n NH ₂ , preferably an alkyl group having 1 to 4 carbon atoms, —CH ₂ CH (Y) OH, or — (CH ₂ ) _n NH ₂ . Among these, as a C1-C4 alkyl group, a methyl group or an ethyl group is preferable, and a methyl group is especially preferable. Y in —CH ₂ CH (Y) OH is the same as Y in —CH ₂ CH (Y) OCOR ⁴ . _{N in} — (CH ₂ ) _n NH ₂ is the same as n in — (CH ₂ ) _n NHCOR ⁵ .

〔式中、Ｒ⁷及びＲ⁸はそれぞれ独立に、炭素数１０〜２６の炭化水素基である。Ｒ⁹及びＲ¹⁰はそれぞれ独立に、炭素数７〜２１の炭化水素基である。〕 Preferable examples of the compound represented by the general formula (A1) include compounds represented by the following general formulas (A1-1) to (A1-8).

[Wherein, R ⁷ and R ⁸ are each independently a hydrocarbon group having 10 to 26 carbon atoms. R ⁹ and R ¹⁰ are each independently a hydrocarbon group having 7 to 21 carbon atoms. ]

Examples of the hydrocarbon group for R ⁷ and R ⁸ include the same hydrocarbon groups as those having 10 to 26 carbon atoms for R ^{1 to} R ³ .
Examples of the hydrocarbon group having 7 to 21 carbon atoms in R ⁹ and R ¹⁰ include those similar to the hydrocarbon group having 7 to 21 carbon atoms in R ⁴ . When R ⁹ is more present in the formula, R ⁹ of the plurality of may be the same as each other, it may be different.
The component (A) in the softener composition of the present invention may be a salt of an amine compound.

The salt of an amine compound is obtained by neutralizing an amine compound with an acid. The acid used for neutralization of the amine compound may be an organic acid or an inorganic acid, and examples thereof include hydrochloric acid, sulfuric acid, and methyl sulfuric acid. Neutralization of the amine compound can be performed by a known method.
A quaternized product of an amine compound is obtained by reacting the amine compound with a quaternizing agent. Examples of the quaternizing agent used for the quaternization of the amine compound include alkyl halides such as methyl chloride and dialkyl sulfates such as dimethyl sulfate. When these quaternizing agents are reacted with an amine compound, the alkyl group of the quaternizing agent is introduced into the nitrogen atom of the amine compound, and a salt of a quaternary ammonium ion and a halogen ion or a monoalkyl sulfate ion is formed. . The alkyl group introduced by the quaternizing agent is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The quaternization of the amine compound can be performed by a known method.

The component (A) contained in the softener composition of the present invention is preferably at least one selected from the group consisting of the compound represented by the general formula (A1), a salt thereof, and a quaternized product thereof. At least one selected from the group consisting of formulas (A1-1) to (A1-8), a salt thereof, and a quaternized product thereof is more preferable, and (A1-4) to (A1-6), a salt thereof and the salt thereof More preferred is at least one selected from the group consisting of graded products.
As the compound represented by the formula (A1), a salt thereof, and a quaternized product thereof, commercially available products may be used, or those produced by a known method may be used.

For example, a compound represented by the general formula (A1-2) (hereinafter “compound (A1-2)”) and a compound represented by the general formula (A1-3) (hereinafter “compound (A1-3)”) are: The fatty acid composition, or a fatty acid methyl ester composition obtained by replacing the fatty acid in the fatty acid composition with a methyl ester of the fatty acid, and methyldiethanolamine can be synthesized. At that time, from the viewpoint of improving flexibility, the abundance ratio represented by “compound (A1-2) / compound (A1-3)” is synthesized such that the mass ratio is 99/1 to 50/50. It is preferable to do.
Furthermore, when the quaternized product is used, it is more preferable to use dimethyl sulfate as a quaternizing agent. At that time, from the viewpoint of flexibility, the abundance ratio represented by “a quaternized compound (A1-2) / a quaternized compound (A1-3)” is 99/1 to 50/50 in mass ratio. It is preferable to synthesize.

Compound represented by general formula (A1-4) (hereinafter “compound (A1-4)”), compound represented by general formula (A1-5) (hereinafter “compound (A1-5)”), general formula The compound represented by (A1-6) (hereinafter “compound (A1-6)”) can be synthesized by a condensation reaction of the fatty acid composition or fatty acid methyl ester composition and triethanolamine. In that case, the content ratio of each component with respect to the total mass of the compounds (A1-4), (A1-5), and (A1-6) is 1 to 60 masses of the compound (A1-4) from the viewpoint of flexibility. %, Compound (A1-5) is preferably 5-98% by mass, compound (A1-6) is preferably 0.1-40% by mass, compound (A1-4) is 30-60% by mass, compound ( It is more preferable that A1-5) is 10 to 55% by mass and the compound (A1-6) is 5 to 35% by mass.
In addition, when using the quaternized product, it is more preferable to use dimethyl sulfate as a quaternizing agent in that the quaternization reaction proceeds sufficiently. The abundance ratio of each quaternized compound (A1-4), (A1-5), and (A1-6) is a mass ratio from the viewpoint of flexibility, and the quaternized compound (A1-4) is 1 to 4. 60% by mass, the quaternized compound (A1-5) is preferably 5 to 98% by mass, and the quaternized compound (A1-6) is preferably 0.1 to 40% by mass, and the compound (A1-4) ) Is 30 to 60% by mass, the quaternized compound (A1-5) is 10 to 55% by mass, and the quaternized compound (A1-6) is 5 to 35% by mass. preferable. In addition, when the compounds (A1-4), (A1-5), and (A1-6) are quaternized, esteramine that is not quaternized generally remains after the quaternization reaction. At that time, the ratio of “quaternized product / non-quaternized ester amine” is preferably in the range of a mass ratio of 70/30 to 99/1.

  The compound represented by general formula (A1-7) (hereinafter “compound (A1-7)”) and the compound represented by general formula (A1-8) (hereinafter “compound (A1-8)”) are as described above. From an adduct of a fatty acid composition, N-methylethanolamine and acrylonitrile, J. Org. Org. Chem. , 26, 3409 (1960), by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized by a known method. In that case, it is preferable to synthesize | combine so that the abundance ratio represented by "compound (A1-7) / compound (A1-8)" may be 99 / 1-50 / 50 by mass ratio. When the quaternized product is used, it is preferable to use methyl chloride as a quaternizing agent, which is represented by “a quaternized compound (A1-7) / a quaternized compound (A1-8)”. It is preferable to synthesize the abundance ratio such that the mass ratio is 99/1 to 50/50.

  In the softener composition of the present invention, the amount of component (A) is not particularly limited, but is preferably 5 to 30% by weight, more preferably 8 to 20% by weight, based on the total weight of the softener composition. More preferably, it is 10-16 mass%. When the blending amount of the component (A) is 5% by mass or more, better flexibility imparting effect and dispersion stability of the encapsulated fragrance can be obtained. (A) The storage stability of a liquid softening agent composition is more favorable in the compounding quantity of a component being 30 mass% or less.

[Component (B)]
The encapsulated fragrance of the component (B) contained in the softener composition of the present invention improves the fragrance of the fiber product treated with the liquid softener composition, increases the fragrance persistence, or the fiber product. It is blended to give a fragrance effect due to friction during use.
The encapsulated fragrance is composed of a core substance and a wall substance covering the core substance.

The core material includes a fragrance composition.
As the fragrance composition, those used in the field of the liquid softener composition can be used without particular limitation, and can be appropriately selected according to the purpose. For example, essential oils and absolutes commonly used in clothing softeners and clothing detergents, and hydrocarbons, alcohols, aldehydes, ketones, ethers, acetals, ketals and nitriles Synthetic perfume ingredients and the like.
Examples of preferable fragrance ingredients to be blended in the fragrance composition are described in JP 2010-52028 A, for example, Agrumex, Aldron, Ambrettolide, Ambroxan, benzyl cinnamate, benzyl salicylate, Boisambrene, cedrol, acetic acid Cedryl, Celestolide / Crysolide, Cetalox, citronellyl etoxalate, Fixal, Fixolide, Galaxolide, Guaiacwood Acetate, cis-3-hexenyl salicylate, hexylcinnaldehyde, hexyl salicylate, IsoE Super, linalyl benzoate, linalyl cinnamate, phenyl Linalyl acetate, Javanol, methyl cedryl ketone, Moskene, Musk, Musk Ketone, Musk Tibetine, Musk Xylol, Myraldyl Acetate, nerolidyl acetate, Novalide, Okoumal, paracresyl caprylate, paracresyl phenyl acetate, Phantalid, phenylethyl cinnamate, salicylic acid Phenylethyl, Rose Crystals Rosone, Sandela, tetradecanonitrile, Thibetolide, Traseolide, Trimofix O, 2-methylpyrazine, acetaldehyde phenylethylpropyl acetal, acetophenone, alcohol C6 (in the following, the notation Cn represents n carbon atoms and one hydroxyl function Alcohol C8, aldehyde C6 (in the following, the notation Cn includes all isomers having n carbon atoms and one aldehyde function), aldehyde C7, aldehyde C8, aldehyde C9, nonenylic aldehyde, allyl amyl glycolate, allyl caproate, amyl butyrate, aldehyde anisique, benzaldehyde, benzyl acetate, benzylacetone, benzyl alcohol, benzyl butyrate, benzyl formate, iso Benzyl valerate, benzyl methyl ether, benzyl propionate, Bergamyl Acetate, butyl acetate, camphor, 3-methyl-5-propyl-2-cyclohexenone, cinnamic aldehyde, cis-3-hexenol, cis-3-hexenyl acetate, Cis-3-hexenyl formate, cis-3-hexenyl isobutyrate, cis-3-hexenyl propionate, cis-3-hexenyl tiglate, citronellal, citronellol, citronellonitrile, 2-hydroxy-3-methyl-2-cyclopentene -1-one, cuminaldehyde, cyclal C, acetic acid (cyclohexyloxy) -2-propenyl ester, damacenone, alpha-damascone, beta-damascone, decahydrobeta-naphthyl formate, diethyl malonate, dihydrojasmon, dihydrolinalo , Dihydromyrcenol, dihydroterpineol, dimethyl anthranilate, dimethylbenzyl carbinol, dimethyl benzyl carvinyl acetate, dimethyl octenone, dimetol, dimyrcetol, estragal, ethyl acetate, ethyl acetoacetate, ethyl benzoate, Ethyl heptanoate, ethyl linalool, ethyl salicylate, ethyl 2-methyl butyrate, eucalyptol, eugenol, fenkylacetate, fenkyl alcohol, 4-phenyl-2,4,6-trimethyl 1,3-dioxane, methyl 2-octanoate, 4-isopropylcyclohexanol, 2-sec-butylcyclohexanone, styryl allyl acetate, geranyl nitrile, hexyl acetate, alpha-ionone, isoamyl acetate, isobutyl acetate, iso-cyclosito Lahr, dihydroisojasmon, iso-menton, iso-pentylate, iso-pulegol, cis jasmon, levorotatory carvone, phenylacetaldehyde glyceryl acetal, carbinic acid 3-hexenylmethyl ether, 1-methyl-cyclohexa-1, 3-diene, linalool, linalool oxide, 2-ethylethyl pentanoate, 2,6-dimethyl-5-heptenal, menthol, menthone, methyl acetophenone, methyl amyl ketone, methyl benzoate, alpha-methylcinnaldehyde, methyl heptenone, Methyl hexyl ketone, methyl paracresol, methyl phenyl acetate, methyl salicylate, neral, nerol, 4-tert-pentyl-cyclohexanone, para-cresol, para-cresi acetate , Para-t-butylcyclohexanone, para-toluylaldehyde, phenylacetaldehyde, phenylethyl acetate, phenylethyl alcohol, phenylethyl butyrate, phenylethyl formate, phenylethyl isobutyrate, phenylethyl propionate, phenylpropyl acetate, phenylpropylaldehyde Tetrahydro-2,4-dimethyl-4-pentyl-furan, 4-methyl-2- (2-methyl-1-propenyl) tetrahydropyran, 5-methyl-3-heptanone oxime, stilallyl propionate, styrene, 4 -Methylphenylacetaldehyde, terpineol, terpinolene, tetrahydro-linalool, tetrahydro-myrsenol, trans-2-hexenal, verzyl acetate, viridine and the like.
In the fragrance composition, one kind of fragrance component may be blended, or two or more kinds of fragrance ingredients may be blended.
In addition, the fragrance | flavor composition of (B) component and the fragrance | flavor composition of the following (C) component may be the same, and may differ. When a highly volatile fragrance component is used as the component (B) and a fragrance component with low volatility is used as the component (C), the scent sustaining effect can be further enhanced.

As the wall material, those generally used as a fragrance encapsulating material in the field of liquid softener compositions can be used without any particular limitation. For example, the wall material is composed of a polymer material, specifically, natural polymers such as gelatin and agar, oily film forming materials such as fats and waxes, polyacrylic acid, polyvinyl, polymethacrylic acid, Examples include melamine-based and urethane-based synthetic polymer substances, and the like can be used alone or in combination of two or more.
From the viewpoint of fragrance when the encapsulated fragrance is destroyed, the wall material is preferably an aminoplast polymer, polyacrylic acid-based or polymethacrylic acid-based polymer composed of melamine-formaldehyde resin or urea-formaldehyde resin. . Aminoplast polymers as described in JP 2010-520928 A are particularly preferred. Specifically, a terpolymer comprising a polyamine-derived moiety / aromatic polyphenol-derived moiety / methylene unit, an alkylene having dimethoxymethylene and dimethoxymethylene and an alkyleneoxy moiety is preferred.

The component (B) is easily available on the market or can be synthesized by a known method.
As the component (B), one type of encapsulated fragrance may be used alone, or a mixture of two or more types may be used.
The blending amount of the component (B) (the blending amount as the amount of the fragrance in the component (B)) is not particularly limited as long as it can achieve the blending purpose, but the fragrance is based on the total mass of the liquid softener composition. The amount is preferably 0.01 to 3% by mass, more preferably 0.05 to 2% by mass, and still more preferably 0.1 to 1% by mass. When the blending amount of the component (B) is 0.01% by mass or more, the aroma is strong and better scent sustainability can be obtained. (B) When the compounding quantity of a component is 3 mass% or less, the deterioration of paint peeling is suppressed more.

[Component (C)]
The liquid softener composition of the present invention is not encapsulated as a component (C) separately from the fragrance composition contained as the core material of the component (B) in order to impart aroma to the fiber product. A fragrance composition (free fragrance composition) is further included.
(C) component mix | blended with the liquid softening agent composition of this invention should be suitably selected according to the objective from the fragrance | flavor composition containing 1 or more types of fragrance | flavor components generally used for a liquid softening agent composition. However, it contains 25% by mass or more of a fragrance component having a ClogP value of 5 or more with respect to the total mass of the fragrance composition as the component (C).
Specific examples of the perfume component are not particularly limited and may be appropriately selected depending on the intended purpose. For example, aldehydes, phenols, alcohols, ethers, esters, hydrocarbons, ketones, lactones , Musks, fragrances having a terpene skeleton, natural fragrances, animal fragrances, and the like.
Specific examples of each fragrance are as follows.
The aldehyde is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 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, 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, cedolyl acetate, citronellyl acetate, decahydro-β-naphthyl acetate, dimethylbenzyl cal Vinyl acetate, ericapropionate, ethyl acetoacetate, erica acetate, geranyl acetate, geranyl formate, hedion, linalyl acetate, β-phenylethyl acetate, Examples include xyl salicylate, styrylyl acetate, terpinyl acetate, vetiberyl acetate, ot-butylcyclohexyl acetate, manzanate, and allyl heptanoate.
There is no restriction | limiting in particular as hydrocarbons, According to the objective, it can select suitably, For example, limonene (especially d-limonene), alpha-pinene, beta-pinene, myrcene, camphene, terpinolene, etc. are mentioned. It is done.
The ketones are not particularly limited and may be appropriately selected depending on the intended purpose. For example, α-ionone, β-ionone, methyl-β-naphthyl ketone, α-damascone, β-damascone, δ-damascone, 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 (eg 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 moth incense, etc. are mentioned.

Component (C) is a fragrance component having a ClogP value of 5 or more, preferably 25 mass% or more, preferably 30 mass% or more, more preferably 35 mass%, relative to the total mass of the fragrance composition as component (C). More preferably, the content is 40% by mass or more. When the blending amount of the fragrance component having a ClogP value of 5 or more in the component (C) is 25% by mass or more, better fragrance persistence can be obtained.
The type of the perfume component having a ClogP value of 5 or more is not particularly limited, but preferred examples include ambroxan (5.3), tonalide (6.3), hexyl salicylate (5.1), and galaxolide (6.1). ), Muscon (6.0), Exaltolide (6.2), IsoEsuper (5.2), Belt Fix (acetyl cedrene) (5.0), Cedryl methyl ether (5.1) and the like. (The number in parenthesis represents the ClogP value). Of these, more preferred are ambroxan, galaxolide, iso-Esuper and tonalide.
The ClogP value is a value representing a 1-octanol / water partition coefficient P representing a ratio of equilibrium concentrations in 1-octanol and in water in the form of logarithmic logP with respect to the base 10 for a chemical substance. The ClogP value can be determined by decomposing the chemical structure of a compound into its constituent elements by f-value method (hydrophobic fragment constant method) and integrating the hydrophobic fragment constants and f values possessed by each fragment (for example, Clog 3 Reference Manual Daylight Software 4.34, Albert Leo, David Weininger, Version 1, March 1994).
In general, since the fragrance is more hydrophobic as the ClogP value is larger, the fragrance composition containing more fragrance components having a smaller ClogP value is more hydrophilic than the fragrance composition containing more fragrance components having a larger ClogP value. You can say that.

The perfume composition may be blended with a liquid softener composition, for example, a solvent commonly used in textile finishes or softener compositions. 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, deltil 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 compounding quantity of a solvent is 0.1-30 mass% with respect to the total mass of a fragrance | flavor composition, Preferably it is 1-20 mass%.

The perfume composition may be blended with liquid softener compositions, for example, antioxidants commonly used in textile finishes or softener compositions. As antioxidants for fragrances, 3,5-di-tert-butyl-4-hydroxytoluene (BHT), t-butyl-p-hydroxyanisole (BHA), p-methoxyphenol, β-naphthol, phenyl-α -Naphtylamine, 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, 4,4′-bis (α, α -Dimethylbenzyl) diphenylamine and the like. Preferred is 3,5-di-tert-butyl-4-hydroxytoluene (BHT).
The compounding quantity of antioxidant is 0.001-10 mass% with respect to the total mass of a fragrance | flavor composition, Preferably it is 0.01-5 mass%.

  (C) Although the compounding quantity of a component is not specifically limited as long as it is the quantity which can achieve a compounding objective, 0.01-5 mass% with respect to the total mass of a liquid softening agent composition, Preferably 0.3-5 mass %, More preferably 0.8 to 3% by mass. When the blending amount of the component (C) is 0.01% by mass or more, the aroma is strong and a better scent sustaining effect can be obtained. When the blending amount of component (C) is 5% by mass or less, deterioration of paint peeling is further suppressed.

[(D) component]
Component (D) contained in the softener composition of the present invention is a water-soluble polymer compound. Here, “water-soluble” means that when 1 g of the target polymer compound is added to 1000 g of water at 25 ° C. and stirred, and left to stand at 25 ° C. for 24 hours, precipitation and layer separation appear on the appearance. A solution that cannot be obtained. Here, the “polymer compound” means a compound having a weight average molecular weight of 3000 to 5 million.
In the softener composition of the present invention, by blending the component (D), the dispersibility of the encapsulated fragrance in the softener composition can be improved, and deterioration of paint peeling can be suppressed. . (D) A component may be used individually by 1 type and may combine 2 or more types suitably.
Specific examples of the water-soluble polymer compound as component (D) include the following (D-1) to (D-3).

(D-1): Nonionic glucan The component (D-1) that can be contained in the softener composition of the present invention is a nonionic glucan having a weight average molecular weight in the range of 10,000 to 2,000,000. Glucan is a condensation polymer of D-glucopyranose, and includes starch, glycogen, dextrin, cellulose and the like. It is divided into α-glucan and β-glucan by the configuration at the C1 position, and 1 → 3, 1 → 4, 1 → 6 bonds are distinguished by the position of the glycosidic bond. The nonionic glucan as the component (D-1) contained in the softener composition of the present invention may be linear or branched. In addition, the nonionic glucan as the component (D-1) contained in the softening agent composition of the present invention may have a chain structure or a cyclic structure. Specifically, in the softener composition of the present invention, as the component (D-1), a polymer dextrin (Sanwa Starch Co., Ltd., trade name: Sandeck # 30), a cyclic structure, and a branched structure For example, a nonionic glucan having a cyclic structure, for example, a branched glucan having a cyclic structure (described in JP 2012-120471 A), a highly branched cyclic dextrin (trade name: cluster dextrin manufactured by Glyco Nutrition Foods Co., Ltd.), and the like can be used. (D-1) A component may be used individually by 1 type and may combine 2 or more types suitably.

The glucan as the component (D-1) contained in the softener composition of the present invention is a nonionic compound, and has cationic properties such as cationic starch and cationized cellulose in which a part of the glucan is modified. Etc. do not correspond to the component (D-1).
Nonionic glucan having a cyclic structure and a branched structure is produced by the method described in JP-A-8-134104, the method described in Takata et al., Carbohydrate Research, 295, 91-101, 1996, etc. However, the present invention is not limited to these.

The highly branched cyclic dextrin is a glucan having an inner branched cyclic structure portion and an outer branched structure portion and having a polymerization degree in the range of 50 to 10,000, where the inner branched cyclic structure portion is α-1 , 4-glucoside bond and α-1,6-glucoside bond, and the outer branched structure part is a non-cyclic structure part bonded to the inner branched cyclic structure part. is there.
The highly branched cyclic dextrin as the component (D-1) contained in the softener composition of the present invention has a weight average molecular weight of about 30,000 to 1,000,000, and has one cyclic structure in the molecule. It mainly contains dextrin having a weight average degree of polymerization of about 2500, in which a large number of glucan chains are bonded to the cyclic portion.
The inner branched cyclic structure portion of the highly branched cyclic dextrin as the component (D-1) contained in the softener composition of the present invention is composed of about 10 to 100 glucoses. The outer branch structure part which consists of many non-cyclic branched glucan chains is couple | bonded.

For example, the polymerization degree of the highly branched cyclic dextrin as the component (D-1) contained in the softener composition of the present invention is in the range of 50 to 5000.
For example, the polymerization degree of the inner branched cyclic structure portion of the highly branched cyclic dextrin as the component (D-1) contained in the softener composition of the present invention is in the range of 10-100.
For example, the degree of polymerization of the outer branched structure portion of the highly branched cyclic dextrin as the component (D-1) contained in the softener composition of the present invention is 40 or more.
For example, the degree of polymerization of each unit chain of the outer branched structure portion of the highly branched cyclic dextrin as the component (D-1) contained in the softener composition of the present invention is 10 to 20 on average.

The highly branched cyclic dextrin as the component (D-1) contained in the softener composition of the present invention is produced, for example, by using starch as a raw material and an enzyme called a branching enzyme. Starch, which is a raw material, is composed of amylose in which glucose is linearly bound by α-1,4-glucoside bonds and amylopectin having a structure that is complicatedly branched by α-1,6-glucoside bonds. It is a macromolecule with many connected structures. Branching enzyme, an enzyme used, is a glucan chain transferase widely distributed in animals, plants, and microorganisms. It acts on the seam portion of the cluster structure of amylopectin and catalyzes the reaction of cyclizing it.
More specifically, the highly branched cyclic dextrin as the component (D-1) contained in the softener composition of the present invention comprises an inner branched cyclic structure portion and an outer branched structure portion described in JP-A-8-134104. It is a glucan having a polymerization degree in the range of 50 to 10,000. In the present specification, the highly branched cyclic dextrin can be understood in consideration of the description in JP-A-8-134104.

The cyclic structure-containing branched glucan has a cyclic structure and at least one branched structure based on an α-1,6 bond and an α-1,4 bond, and at least in a sugar chain constituting the cyclic structure. It is a glucan having a structure in which one α-1,6 bond exists.
In the branched structure-containing branched glucan as the component (D-1) contained in the softener composition of the present invention, the branching frequency is, for example, 8% or more.
The branching frequency of the cyclic structure-containing branched glucan as the component (D-1) contained in the softener composition of the present invention is indicated by the ratio of α-1,6 branches. The proportion of α-1,6 branches is, for example, about 10% or more, about 11% or more, about 12% or more, about 13% or more, about 14% or more, about 15% or more, about 16% or more, about 17% or more, It can be about 20% or more. Although there is no upper limit to the proportion of α-1,6 branches, it can be, for example, about 50% or less, about 40% or less, about 30% or less, about 25% or less, about 20% or less.
Note that the branching frequency is calculated by the following formula:
Branching frequency (%) = {(number of branches) / (number of glucose units in the whole molecule)} × 100

The weight average molecular weight of the cyclic structure-containing branched glucan as the component (D-1) contained in the softener composition of the present invention is preferably about 30,000 or more, more preferably about 50,000 or more, Preferably, it is about 100,000 or more, preferably about 500,000 or less, more preferably about 300,000 or less, and particularly preferably about 200,000 or less.
The average degree of polymerization of the cyclic structure portion in the cyclic structure-containing branched glucan as the component (D-1) contained in the softener composition of the present invention is preferably about 10 or more, more preferably about 15 or more. More preferably about 20 or more, preferably about 500 or less, more preferably about 300 or less, and still more preferably about 100 or less.
The average degree of polymerization of the branched structure portion in the cyclic structure-containing branched glucan as the component (D-1) contained in the softener composition of the present invention is preferably about 40 or more, more preferably about 100 or more. More preferably about 300 or more, still more preferably about 500 or more, preferably about 4 × 10 ³ or less, more preferably about 3 × 10 ³ or less, and still more preferably about 2 × 10 ³ or less, and even more preferably about 1 × 10 ³ or less.

The cyclic structure-containing branched glucan as the component (D-1) contained in the softening agent composition of the present invention may have at least one α-1,6-glucoside bond, for example, one or more, There may be 5 or more, 10 or more, for example, about 200 or less, about 50 or less, about 30 or less, about 15 or less, about 10 or less, and the like.
As the cyclic structure-containing branched glucan as the component (D-1) contained in the softener composition of the present invention, one having one degree of polymerization may be used alone, or a mixture having various degrees of polymerization. It may be used. Preferably, the degree of polymerization of the cyclic structure-carrying branched glucan is such that the ratio of the degree of polymerization between the maximum degree of polymerization and the minimum degree of polymerization is about 100 or less, more preferably about 50 or less, even more preferably about 10 or less.
The cyclic structure-containing branched glucan as the component (D-1) contained in the softener composition of the present invention preferably has a part of the branched glucan structure forming a ring. Here, the cyclic structure portion is a cyclic structure portion formed by an α-1,4-glucoside bond and an α-1,6-glucoside bond, and the branched structure portion is bonded to the cyclic structure portion. It is an acyclic structure part. The degree of polymerization of each unit chain of the branched structure portion is preferably about 2 or more, more preferably about 4 or more, still more preferably about 6 or more, and preferably about 20 or less, more Preferably it is 18 or less, More preferably, it is 15 or less.

The average polymerization degree of the cyclic structure-containing branched glucan as the component (D-1) contained in the softener composition of the present invention is preferably about 50 or more, more preferably about 70 or more, and further preferably About 100 or more, most preferably about 150 or more, preferably about 5 × 10 ³ or less, more preferably about 4 × 10 ³ or less, and even more preferably about 3 × 10 ³ or less. And most preferably about 2 × 10 ³ or less.
The number of branches of the cyclic structure-containing branched glucan as the component (D-1) contained in the softener composition of the present invention (that is, the number of α-1,6-glucoside bonds) is preferably about 10 or more. More preferably about 15 or more, further preferably about 20 or more, preferably about 1000 or less, more preferably about 800 or less, and further preferably about 500. It is as follows.
In the branched structure-containing glucan having a cyclic structure as the component (D-1) contained in the softener composition of the present invention, the ratio of the number of α-1,4-glucoside bonds to the number of α-1,6-glucoside bonds (“Number of α-1,6-glucoside bonds”: “number of α-1,4-glucoside bonds”) is preferably 1: 3 to 1:13, more preferably 1: 4 to 1: 1. 12, more preferably 1: 5 to 1:10, and still more preferably 1: 5 to 1: 9.
The cyclic structure-retaining branched glucan as the component (D-1) contained in the softener composition of the present invention is:
i) A branching enzyme is allowed to act on a branched glucan as a substrate, and then a 4-α-glucanotransferase is allowed to act;
ii) causing 4-α-glucanotransferase to act on the substrate branched glucan and then allowing the branching enzyme to act; or
iii) It is produced by simultaneously acting a branching enzyme and 4-α-glucanotransferase on a branched glucan as a substrate.
More specifically, the cyclic structure-containing branched glucan as the component (D-1) contained in the softener composition of the present invention is described in JP2012-120471A. In the present specification, the cyclic structure-carrying branched glucan can be understood with reference to the description in JP2012-120471A.

In the softener composition of the present invention, the blending amount of the component (D-1) is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.8%, based on the total mass of the softener composition. It is 05-3 mass%, More preferably, it is 0.2-2 mass%. When the blending amount of component (D-1) is 0.01% by mass or more, the dispersibility of the encapsulated fragrance can be further improved, and deterioration of paint peeling can be further suppressed. (D-1) The usability of a liquid softening agent composition becomes it more favorable that the compounding quantity of a component is 5 mass% or less.
Instead of the nonionic glucan (D-1) component contained in the softener composition of the present invention, α-cyclodextrin (n = 6), β-cyclodextrin (n = 7), γ-cyclodextrin Even when a general cyclodextrin having 6 to 8 glucoses such as (n = 8) bonded thereto is blended in the softener composition, the dispersion stability of the encapsulated fragrance equivalent to the softener composition of the present invention is excellent. The effect of suppressing the deterioration of paint removal and paint peeling cannot be obtained.

(D-2): Polyethyleneimine or a derivative thereof The component (D-2) that can be included in the softener composition of the present invention is polyethyleneimine or a derivative thereof. Examples of the polyethyleneimine derivatives include amide derivatives of polyethyleneimine, alkoxylated polyethyleneimine, alkylpolyethyleneimine, and quaternized polyethyleneimine. (D-2) A component may be used individually by 1 type and may combine 2 or more types suitably.
Specifically, in the softener composition of the present invention, as component (D-2), Lupasol SK (manufactured by BASF) which is an amide derivative of polyethyleneimine, Lupasol PS (manufactured by BASF) which is polyethyleneimine, and the like are used. Can be.
Moreover, the weight average molecular weight of (D-2) component becomes like this. Preferably it is 3000-3 million, More preferably, it is 10,000-2 million, More preferably, it is 100,000-2 million. When the weight average molecular weight of the component (D-2) is 3000 or more, the dispersion stabilizing effect of the encapsulated fragrance can be satisfactorily obtained, and when the weight average molecular weight of the component (D-2) is 3 million or less, liquid Usability of the softener composition becomes better.
In the softener composition of the present invention, the blending amount of the component (D-2) is not particularly limited, but is preferably 0.01 to 8% by mass, more preferably 0.8%, based on the total mass of the softener composition. It is 1-5 mass%, More preferably, it is 0.5-3 mass%. When the blending amount of component (D-2) is 0.01% by mass or more, the dispersibility of the encapsulated fragrance can be further improved, and deterioration of paint peeling can be further suppressed. When the blending amount of the component (D-2) is 8% by mass or less, the usability of the liquid softener composition becomes better.

(D-3): Cationic (meth) acrylic polymer The component (D-3) that can be included in the softener composition of the present invention has a cationic (meth) acrylic polymer, that is, a cationic functional group. It is a (meth) acrylic polymer. Examples of the cationic functional group in the component (D-3) include a primary amino group, a secondary amino group, a tertiary amino group, and a quaternary ammonium group. Among them, a tertiary amino group and a quaternary ammonium group are exemplified. Groups are preferred.
Examples of the monomer constituting the component (D-3) include (meth) acrylamide, N- (hydroxymethyl) acrylamide, N- (2-hydroxyethyl) acrylamide, N- (methoxymethyl) acrylamide, and the following formula Examples thereof include a compound represented by (d-1), a compound represented by the following formula (d-2), a dialkyl diallylammonium salt, and the like.

〔式中、Ｒ²¹は水素原子又はメチル基を示し、Ｙは酸素原子又は−ＮＨ−を示し、Ｒ²²は水酸基で置換されていてもよい炭素数１〜８の直鎖状又は分岐鎖状のアルキレン基を示し、Ｒ²³及びＲ²⁴はそれぞれ独立に、炭素数１〜１２の直鎖状、分岐鎖状又は環状のアルキル基を示す。〕

[Wherein, R ²¹ represents a hydrogen atom or a methyl group, Y represents an oxygen atom or —NH—, and R ²² represents a linear or branched chain having 1 to 8 carbon atoms which may be substituted with a hydroxyl group. R ²³ and R ²⁴ each independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. ]

Examples of the compound represented by the formula (d-1) include dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylamino (Meth) acrylate dialkylaminoalkyl compounds such as ethyl (meth) acrylate; dimethylaminoethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, dimethylaminobutyl (meth) acrylamide, dialkyl such as diethylaminoethyl (meth) acrylamide Examples include aminoalkyl (meth) acrylamide compounds.

〔式中、Ｒ²¹、Ｙ及びＲ²²はそれぞれ前記式（ｄ−１）における定義と同じであり、Ｒ²⁵〜Ｒ²⁷はそれぞれ独立に、炭素数１〜１２の直鎖状、分岐鎖状又は環状のアルキル基を示し、Ｚはハロゲンイオン、ＯＨ、１／２ＨＳＯ₄ ^2-、１／３ＰＯ₄ ^3-、ＨＣＯ₂ ^-又はＣＨ₃ＣＯ₂ ^-を示す。〕

[Wherein, R ²¹ , Y and R ²² are the same as defined in the formula (d-1), and R ^{25 to} R ²⁷ are each independently a linear or branched chain having 1 to 12 carbon atoms. Or Z represents a halogen ion, OH, 1 / 2HSO ₄ ²⁻ , 1 / 3PO ₄ ³⁻ , HCO ₂ ^— or CH ₃ CO ₂ ^— . ]

Examples of the compound represented by the formula (d-2) include (meth) acrylic acid dimethylaminoethylmethyl chloride, (meth) acrylic acid dimethylaminoethylethyl chloride, (meth) acrylic acid dimethylaminoallylethylethyl chloride, (Meth) acrylic acid dimethylaminoethyl ethyl sulfate, (meth) acrylic acid dimethylaminoethyl methyl phosphoric acid, (meth) acrylic acid dimethylaminoethyl ethyl phosphoric acid, (meth) acrylic acid diethylaminoethyl methyl chloride, (meth) acrylic acid Diethylaminoethylethyl chloride, diethylaminoethylethylsulfate (meth) acrylate, diethylaminoethylmethylphosphate (meth) acrylate, diethylaminoethylethylphosphate (meth) acrylate, dimethylaminopropyl ( T) Acrylamide methyl chloride, dimethylaminopropyl (meth) acrylamide ethyl chloride, dimethylaminopropyl (meth) acrylamide ethyl sulfate, dimethylaminopropyl (meth) acrylamide methyl phosphate, dimethylaminopropyl (meth) acrylamide ethyl phosphate, etc. It is done.
Among these, (meth) acrylic acid dimethylaminopropyl chloride and dimethylaminopropyl (meth) acrylamide chloride are preferable.

〔式中、Ｒ²⁸およびＲ²⁹はそれぞれ独立に炭素数１〜３のアルキル基を示し、Ｘａはハロゲン原子を示す。〕 Examples of the dialkyl diallylammonium salt include a compound represented by the following formula (d-3).

[Wherein, R ²⁸ and R ²⁹ each independently represents an alkyl group having 1 to 3 carbon atoms, and Xa represents a halogen atom. ]

In the formula, the alkyl group in R ²⁸ and R ²⁹ is most preferably a methyl group.
Examples of the halogen atom for Xa include a chlorine atom and a bromine atom, with a chlorine atom being preferred.
When the dialkyl diallylammonium salt is polymerized, a repeating unit having a 5-membered or 6-membered ring structure is usually formed by cyclopolymerization.

Specifically, in the softener composition of the present invention, Rheovis FRC (manufactured by BASF), Rheovis CDE (manufactured by BASF) and the like can be used as the component (D-3). (D-3) A component may be used individually by 1 type and may combine 2 or more types suitably.
In the softener composition of the present invention, the blending amount of the component (D-3) is not particularly limited, but is preferably 0.05 to 1% by mass, more preferably 0.8%, based on the total mass of the softener composition. It is 1-0.8 mass%, More preferably, it is 0.2-0.5 mass%. When the blending amount of component (D-3) is 0.05% by mass or more, the dispersibility of the encapsulated fragrance can be further improved, and deterioration of paint peeling can be further suppressed. (D-3) The usability of a liquid softening agent composition becomes it more favorable that the compounding quantity of a component is 1 mass% or less.

In the softener composition of the present invention, the blending amount of the entire component (D) is not particularly limited, but is preferably 0.01 to 8% by mass, more preferably 0.02% with respect to the total mass of the softener composition. ˜3 mass%.
In the softener composition of the present invention, the ratio of the total mass of the fragrance component having a ClogP value of 5 or more in the (C) component to the total mass of the entire (D) component is not particularly limited, but is preferably 2.5 or less, 1 or less is more preferable, and 0.6 or less is most preferable. When this blending ratio is 2.5 or less, deterioration of paint peeling can be further suppressed.

[(E) component]
The softener composition of the present invention may further contain a nonionic surfactant as the component (E). By blending the component (E) in the softener composition of the present invention, the storage stability (particularly freeze-recoverability) of the liquid softener composition can be further improved, and in the composition of the encapsulated fragrance Can be further improved.
As the component (E), a nonionic surfactant known in the field of liquid softener compositions can be used without particular limitation. For example, an alkylene oxide adduct of alcohol or fatty acid can be used.
Each carbon chain portion of the alcohol and fatty acid may be branched or linear, and may be unsaturated. There may also be a distribution in the carbon chain. Carbon number of a carbon chain becomes like this. Preferably it is 6-20, More preferably, it is 8-18. When the carbon chain is a straight chain, the carbon number is preferably 6 to 14, more preferably 8 to 12, and most preferably 10 to 12. When the carbon chain is a branched chain, the carbon number is preferably 6 to 18, more preferably 9 to 18, and most preferably 13.
As the raw material of the nonionic surfactant, Exxal Mobil Exaral, BASF LUTENSOL series, Kyowa Hakko Kogyo Oxocol, Hoechst AG Genapol series, Shell DOBANOL series, and the like can be used. When the nonionic surfactant is an alkylene oxide adduct of alcohol, both primary alcohol and secondary alcohol can be used. The alcohol having 13 carbon atoms is produced, for example, using dodecene as a raw material, but the starting material may be butylene or propylene.
When the carbon chain contains an unsaturated group, those having 18 carbon atoms are particularly preferred. The stereoisomer structure of the unsaturated group may be a cis isomer, a trans isomer, or a mixture of both, and the ratio of the cis isomer / trans isomer is particularly 25/75 to 100/0 (mass ratio). It is preferable that

The alkylene oxide is preferably ethylene oxide (EO), but may be one in which propylene oxide (PO) or butylene oxide (BO) is added together with EO. The average added mole number of EO is preferably 10 to 100 mol, more preferably 20 to 80 mol, and particularly preferably 20 to 70 mol. Moreover, 1-5 are suitable as an average addition mole number of PO or BO added with EO, More preferably, it is 1-3 mol. At this time, PO or BO may be added after adding EO, or EO may be added after adding PO or BO.
Specific examples of the component (E) include nonyl alcohol average EO9PO1 adduct, primary isononyl alcohol average EO40 mol adduct, primary isodecyl alcohol average EO20 mol adduct, lauryl alcohol average EO20 mol adduct, primary Examples include an average EO 60 mol adduct of isohexadecyl alcohol, an average EO 60 mol adduct of primary isotridecyl alcohol, an average EO 50 mol adduct of tridecyl alcohol, and an average EO 20 mol adduct of lauric acid. Examples of commercially available products that can be used include Emulex series manufactured by Japan Emulsion, Emalmin series manufactured by Sanyo Kasei, TDA series manufactured by Lion Chemical, Softanol series manufactured by Nippon Shokubai, and LUTESOL series manufactured by BASF.

In the softener composition of the present invention, the blending amount of the component (E) is not particularly limited as long as it is an amount capable of achieving the blending purpose, but is preferably more than 0% by weight to 5% with respect to the total weight of the softening agent composition. It is 1 mass% or less, More preferably, it is 1-3 mass%, More preferably, it is 1.5-3 mass%. When the blending amount of the component (E) is more than 0% by mass, the freeze-restoring property is further improved, and when it is 5% by mass or less, the deterioration of paint peeling can be further suppressed.
In the softener composition of the present invention, the mass ratio of the component (E) to the component (D) is not particularly limited, but is preferably 20 or less, more preferably 10 or less, and most preferably 5 or less. When this mass ratio is 20 or less, deterioration of paint peeling can be further suppressed.

[Optional ingredients]
The liquid softening agent composition of the present invention may contain the following components in addition to the above components (A) to (E) as necessary, as long as the effects of the present invention are not impaired. For example, water, amphoteric surfactants, water-soluble solvents, sugar compounds, dyes and / or pigments, preservatives, ultraviolet absorbers, antibacterial agents, silicone compounds, and the like can be blended.

（式中、
Ｒ^1'は炭素数９〜２３の直鎖又は分岐鎖のアルキル基又はアルケニル基であり、
Wはエステル基又はアミド基であり、
rは１〜４の整数であり、
Ｒ^2'は炭素数１〜３のアルキル基又はヒドロキシアルキル基であり、
Ｒ^3'は−（ＣＨ₂）_s−Ｔ又は−ＣＨ₂ＣＨ（ＯＨ）ＣＨ₂−Ｔ（式中、sは０〜４であり、Ｔは−ＣＯＯ^-、−ＳＯ₃ ^-、−ＯＳＯ₃ ^-又は−Ｏ^-である）であり、
Ｒ^4'はＲ^1'−Ｓ−（ＣＨ₂）_r−、Ｒ^2'又はＲ^3'である）。 <Water>
The liquid softener composition of the present invention is preferably an aqueous composition containing 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.
Although the compounding quantity of water is not specifically limited, Preferably it is 50 mass% or more with respect to the total mass of a liquid softening agent composition, More preferably, it is 60 mass% or more. When the blending amount is 50% by mass or more, the handling property becomes better.
<Amphoteric surfactant>
Amphoteric surfactants can be formulated to further improve the stability of the liquid softening agent composition, in particular to further improve the freeze recovery properties.
Examples of amphoteric surfactants include betaine, N-alkyl amino acids, N-alkenyl amino acids, and salts thereof.
Examples of betaines include alkylbetaines, carbobetaines, amide betaines, sulfobetaines, amide sulfobetaines, imidazolinium betaines, and phosphobetaines.
In the N-alkylamino acid or N-alkenylamino acid, an alkyl group or an alkenyl group is bonded to a nitrogen atom, and one or two “—R—COOH” (wherein R represents a divalent hydrocarbon group, Preferably it is an alkylene group, and it is especially preferable that it is C1-C2). In a compound in which one “—R—COOH” is bonded, a hydrogen atom is further bonded to the nitrogen atom. One “—R—COOH” is called a mono form, and two are called a di form. As the amphoteric surfactant, any of these mono- and di-forms can be used. In each of the N-alkyl amino acid and the N-alkenyl amino acid, the alkyl group and the alkenyl group may be linear or branched.
The amphoteric surfactant is preferably sulfobetaine or amidosulfobetaine, more preferably sulfobetaine represented by the following general formula (IV) or a mixture thereof.

(Where
R ^{1 ′} is a linear or branched alkyl group or alkenyl group having 9 to 23 carbon atoms,
W is an ester group or an amide group,
r is an integer of 1 to 4,
R ^{2 ′} is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group,
R ^{3 ′} is — (CH ₂ ) _s —T or —CH ₂ CH (OH) CH ₂ —T (wherein s is 0 to 4, T is —COO ⁻ , —SO ₃ ⁻ , —OSO ₃ ^- a a a) ^- or -O
R ^{4 ′} is R ^{1 ′} —S— (CH ₂ ) _r —, R ^{2 ′} or R ^{3 ′} ).

In general formula (IV), R ^{1 ′} preferably has 11 to 17 carbon atoms. R ^{1 ′} is a fatty acid residue, and specific examples thereof include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, palmitooleic acid, elaidic acid, linoleic acid, and eicoic acid.
W is preferably an ester group.
Specific examples of R ^{2 ′} include a methyl group, an ethyl group, a hydroxyethyl group, a hydroxypropyl group, and the like.
S in R ^{3 ′} is preferably 2 to 3.

（各式中、Ｒ^1'の定義は、一般式（ＩＶ）のＲ^1'と同じである） Specific examples of the sulfobetaine represented by the general formula (IV) include sulfobetaines represented by the following general formulas (V) to (VII). Among these, the compounds represented by (V) and (VI) are more preferable.

(In each the formula, R 1 ^'definition of, R ¹ of the general formula ^(IV)' is the same as)

In the general formula (VI), R ^{1 ′} may be the same or different.
The iodine value of the fatty acid composition from which R ^{1 ′} is based is preferably 0 to 100, more preferably 0 to 70, and still more preferably 20 to 45.

Amphoteric surfactants are readily available on the market or can be synthesized by known methods.
As the amphoteric surfactant, one type may be used alone, or a mixture of two or more types may be used. For example, a mixture composed of a plurality of types of sulfobetaines represented by the general formula (IV) or a mixture composed of any combination of sulfobetaines represented by the general formulas (V) to (VII) can be used.
In the mixture consisting of a plurality of types of sulfobetaines represented by the general formula (IV), the geometric isomerism based on the alkenyl group constituting each sulfobetaine is 25 to 95%, preferably 40 to 90%. If it exists, the viscosity of a liquid softening agent composition can be made moderate.

  The compounding amount of the amphoteric surfactant is not particularly limited as long as it is an amount that can achieve the compounding purpose, but is preferably 0.01 to 3% by mass, more preferably 0.05 to the total mass of the liquid softener composition. It is -2 mass%, More preferably, it is 0.1-1 mass%. When the blending amount is 0.01% by mass or more, better freeze-recoverability can be obtained, and when it is 3% by mass or less, better storage stability can be obtained at high temperatures.

<Water-soluble solvent>
The water-soluble solvent can be added to further improve the stability of the liquid softening agent composition, in particular, to further improve the freeze recovery property.
The water-soluble solvent is preferably one or more selected from the group consisting of alcohols having 1 to 4 carbon atoms, glycol ether solvents, and polyhydric alcohols. Specifically, it is selected from ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and a water-soluble solvent represented by the following general formula (X). It is preferable to mix a solvent component.
R ⁶ —O— (C ₂ H ₄ O) _y — (C ₃ H ₆ O) _Z —H (X)
(In the formula, R ⁶ is an alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms, y and z are average addition mole numbers, and y is 1 to 10, preferably 2 to 2. And z is 0-5, preferably 0-2.)
Of those mentioned above, ethanol, ethylene glycol, butyl carbitol, propylene glycol, dipropylene glycol monomethyl ether and diethylene glycol monobutyl ether are preferred.
Although the compounding quantity of a water-soluble solvent is not specifically limited, Preferably it is 0-30 mass% with respect to the total mass of a liquid softening agent composition, More preferably, it is 0.01-25 mass%, More preferably, it is 0.1-20. % By mass.

<Sugar-based compounds>
The sugar-based compound can be formulated for further improving the stability of the liquid softening agent composition, in particular, further improving the freeze-restoration property.
As the sugar compounds, those having a sugar skeleton repeating unit (polymerization degree) of 1 to 40 are preferable, 1 to 20 are more preferable, and 1 to 5 (that is, a monosaccharide and an oligo having a polymerization degree of more than 1 and 5 or less). Sugar) is particularly preferred. Preferred sugar compounds include monosaccharides, disaccharides, oligosaccharides and sugar alcohols.
Specific examples of sugars include glucose, fructose, galactose, arabinose, ribose, maltose, isomaltose, cellobiose, lactose, sucrose, trehalose, talose, maltotriose, isomaltotriose, and partial hydrolysis of natural polysaccharides. Examples include oligosaccharides obtained and compounds (sugar derivatives) in which substituents are introduced into these sugars. Examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkoxy group, a hydroxyalkyl group, an amine group, a quaternary ammonium group, a carboxyl group, and the like. Is mentioned. As a substituent, a C1-C18 alkyl group, an alkenyl group, or an alkoxy group is preferable, a C1-C12 alkyl group, an alkenyl group, or an alkoxy group is more preferable, and a C1-C6 alkyl group is further Preferably, an alkyl group having 1 to 3 carbon atoms is most preferable.
The sugar is selected from monosaccharides and oligosaccharides having a polymerization degree of 1 to 5, and compounds in which at least one hydroxyl group hydrogen atom is substituted with an alkyl group in the monosaccharide and oligosaccharide having a polymerization degree of 1 to 5. One or more are preferred. Among the above, trehalose is preferable from the viewpoint of freeze-recoverability.
Examples of the sugar alcohol include erythritol, threitol, pentitol, hexitol, dulcitol, sorbitol, mannitol, boremitol, perseitol, xylitol, maltitol, lactitol and the like.
One type of sugar compound may be used alone, or a mixture of two or more types may be used.
The blending amount of the sugar compound is not particularly limited as long as it can achieve the blending purpose, but is 0.01 to 10% by mass, preferably 0.05 to 7% by mass, based on the total mass of the liquid softening agent composition. More preferably, it is 0.1-5 mass%.

<Dye and / or pigment>
Dyes and pigments can each be formulated to improve the appearance of the liquid softener composition.
For both the dye and the pigment, known components in the field of the liquid softener composition can be used without particular limitation. 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.). JP-A-6-123081, JP-A-6-123082, JP-A-7-18573, JP-A-8-27669, JP-A-9-250085, JP-A-10-77576, The dyes described in JP-A-11-43865, JP-A-2001-181972, JP-A-2001-348784, and the like can also be used.
Preferably, it is one or more of red, blue, yellow or purple water-soluble dyes selected from acid dyes, direct dyes, basic dyes, reactive dyes, and mordant / acid mordant dyes.
From the viewpoint of the storage stability of the liquid softener composition and the dyeing property to the fiber, an acid dye or a direct 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 Or a reactive dye is preferable.
About each of dye and a pigment, you may use individually by 1 type and may use it as a mixture which consists of 2 or more types. Moreover, you may use together a dye and a pigment.
The blending amounts of the dye and the pigment are not particularly limited as long as they can achieve the blending purpose, but are preferably 1 to 50 ppm, more preferably 1 to 30 ppm with respect to the total mass of the liquid softening agent composition.

<Preservative>
An antiseptic | preservative can mainly be mix | blended in order to strengthen the antiseptic | preservative power and bactericidal power of a liquid softening agent composition, and to preserve | save preservative during long-term storage.
As the preservative, known components in the field of the liquid softener composition can be used without particular limitation. Specific examples include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitro-1,3-propanediol, and the like.
Examples of isothiazolone 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. 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolin-3-one, and mixtures thereof. Of these, 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one are preferred, and 5-chloro-2-methyl-4-isothiazolin-3-one and 2 A mixture of -methyl-4-isothiazolin-3-one is more preferable, and a mixture of about 77% by mass of the former and about 23% by mass of the latter and a diluted solution thereof (for example, isothiazolone solution) are particularly preferable.
Examples of benzisothiazolone-based organic sulfur compounds include 1,2-benzisothiazoline-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and dithio-2,2-bis ( Benzmethylamide) and mixtures thereof. Among these, 1,2-benzisothiazolin-3-one is particularly preferable.
Examples of the benzoic acid include benzoic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, and benzyl paraoxybenzoate.
Although the compounding quantity of an antiseptic | preservative is not specifically limited as long as it is the quantity which can achieve a compounding objective, Preferably it is 0.0001-1 mass% with respect to the total mass of a liquid softener composition. When the amount is 0.0001% by mass or more, a preservative compounding effect is sufficiently obtained, and when the amount is 1% by mass or less, the high storage stability of the liquid softener composition can be sufficiently maintained.

<Ultraviolet absorber>
UV absorbers can be formulated to protect the liquid softener composition from UV radiation.
The ultraviolet absorber is a component that exhibits an ultraviolet protective effect by absorbing ultraviolet rays, converting them into infrared rays, visible rays, and the like and releasing them.
As an ultraviolet absorber, a well-known component in the liquid softening agent composition field | area can be especially used without a restriction | limiting. Specific examples include, for example, 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 and myristyl salicylate; methyl diisopropylcinnamate, ethyl p-methoxycinnamate, isopropyl p-methoxycinnamate, p-methoxycinnamate-2-ethylhexyl and p-methoxycinnamate Cinnamic acid derivatives such as butyl cinnamate; benzophenone derivatives such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and 2,2′-dihydroxy-4-methoxybenzophenone; Urocanic acid, Azole compounds such as ethyl urocanate; 4-t-butyl-4′-methoxybenzoylmethane and the like.
Although the compounding quantity of a ultraviolet absorber is not specifically limited as long as it is the quantity which can achieve a compounding objective, Preferably it is 0.001-5 mass% with respect to the total mass of a liquid softening agent composition.

<Antimicrobial agent>
Antimicrobial agents can be formulated to increase the shelf life of the liquid softener composition.
As the antibacterial agent, known components in the field of the liquid softener composition can be used without particular limitation. Specific examples include, for example, diclosan, triclosan, benzalkonium chloride, bis- (2-pyridylthio-1-oxide) zinc, 8-oxyquinoline, biguanide compounds (for example, polyhexamethylene biguanide), chlorohexidine hydrochloride, And polylysine. Among these, benzalkonium chloride, biguanide compounds, and chlorohexidine hydrochloride are preferable.
The blending amount of the antibacterial agent is not particularly limited as long as it can achieve the blending purpose, but is preferably 0.001 to 5% by mass with respect to the total mass of the liquid softening agent composition.

<Silicone compound>
A silicone compound may be mix | blended in order to improve the sustainability (fragrance) and softness of a fragrance more.
There is no restriction | limiting in particular in the kind of silicone compound which can be mix | blended with the liquid softening agent composition of this invention, According to the objective, it can select suitably. The molecular structure of the silicone compound may be linear, branched, or cross-linked. The silicone compound may be a modified silicone compound, and the modified silicone compound may be modified with one organic functional group or modified with two or more organic functional groups. It may be.
The silicone compound can be used in the state of oil, and can also be used in the state of an emulsion dispersed by any emulsifier.
Specific examples of the silicone compound include, 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. Examples thereof include modified silicone and amino-modified silicone.
Among these, polyether-modified silicone, amino-modified silicone, dimethyl silicone and the like are preferable from the viewpoint of versatility and deodorizing and deodorizing effect, and polyether-modified silicone and amino are particularly preferable from the viewpoint of effect and handling during production. Modified silicone is preferred.

  Specific examples of the polyether-modified silicone include, for example, a copolymer of alkylsiloxane and polyoxyalkylene. In addition, as carbon number of the alkyl group of the said alkylsiloxane, 1-3 are preferable, and as carbon number of the alkylene group of the said polyoxyalkylene, 2-5 are preferable. Among these, the polyether-modified silicone is preferably a copolymer of dimethylsiloxane and polyoxyalkylene (polyoxyethylene, polyoxypropylene, a random or block copolymer of ethylene oxide and propylene oxide, etc.). Specific examples of such a polyether-modified silicone include, for example, a compound represented by the following general formula (I), a compound represented by the following general formula (II), and the like.

  In the general formula (I), M, N, a, and b represent the average degree of polymerization, and R represents hydrogen or an alkyl group. Here, M is preferably 10 to 10,000, and more preferably 100 to 300. N is preferably 1 to 1,000, and more preferably 1 to 100. Furthermore, it is preferable that M> N. a is preferably 2 to 100, and more preferably 2 to 50. b is preferably 0 to 50, and more preferably 0 to 10. R is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.

  The polyether-modified silicone represented by the general formula (I) generally has an organohydrogenpolysiloxane having a Si-H group and a carbon-carbon double bond such as polyoxyalkylene allyl ether at the terminal. It can be produced by addition reaction of polyoxyalkylene alkyl ether with a platinum catalyst. Therefore, the polyether-modified silicone may contain a slight amount of unreacted polyoxyalkylene alkyl ether or organohydrogenpolysiloxane having a Si—H group. Since the organohydrogenpolysiloxane having a Si—H group has high reactivity, the abundance in the polyether-modified silicone is preferably 30 ppm or less (as the amount of Si—H).

  In the general formula (II), A, B, h, and i are average polymerization degrees, R represents an alkyl group, and R ′ represents hydrogen or an alkyl group. Here, A is preferably 5 to 10,000, and B is preferably 2 to 10,000. h is preferably 2 to 100, and i is preferably 0 to 50. R is preferably an alkyl group having 1 to 5 carbon atoms. R ′ is preferably hydrogen or an alkyl group having 1 to 4 carbon atoms.

  The linear polysiloxane-polyoxyalkylene block copolymer represented by the general formula (II) has a polyoxyalkylene compound having a reactive terminal group and a terminal group that reacts with the reactive terminal group of the compound. It can be produced by reacting with dihydrocarbylsiloxane. Such polyether-modified silicone has a longer side chain polyoxyalkylene chain, and the higher the degree of polymerization of the polysiloxane chain, the higher the viscosity. Therefore, it is easy to improve workability during production and blend into aqueous compositions. Therefore, it is preferable to use it in the form of a premix with a water-soluble organic solvent. Examples of the water-soluble organic solvent include ethanol, dipropylene glycol, butyl carbitol and the like.

  More specifically, examples of the polyether-modified silicone include SH3772M, SH3775M, FZ-2166, FZ-2120, L-720, SH8700, L-7002, and L-, manufactured by Toray Dow Corning Co., Ltd. 7001, SF8410, FZ-2164, FZ-2203, FZ-2208, manufactured by Shin-Etsu Chemical Co., Ltd., KF352A, KF615A, X-22-6191, X-22-4515, KF-6012, KF-6004, etc. Examples include TSF4440, TSF4441, TSF4445, TSF4450, TSF4446, TSF4452, and TSF4460 manufactured by Momentive Performance Materials Japan GK.

The amino-modified silicone is a silicone oil in which an amino group is introduced into the terminal or side chain of the dimethyl silicone skeleton, and a substituent such as a hydroxyl group, an alkyl group, or a phenyl group may be substituted in addition to the amino group. Moreover, the form of oil may be sufficient, and the form of the amino modified silicone emulsion which emulsified the nonionic surfactant or the cationic surfactant as an emulsifier may be sufficient.
A preferred amino-modified silicone oil or base oil in the case of an emulsion is represented by the following general formula (III).

In formula (III), R _{1 ′} and R _{6 ′} may be the same as or different from each other and each represents a methyl group, a hydroxyl group, or hydrogen. R _{2 ′} represents any _one of — (CH ₂ ) _n —A ₁ and — (CH ₂ ) _n —NHCO— (CH ₂ ) _m —A ₁ . A ₁ represents any _one of —N (R _{3 ′} ) (R _{4 ′} ) and —N ⁺ (R _{3 ′} ) (R _{4 ′} ) (R _{5 ′} ) · X ⁻ . R _{3 ′ to} R _{5 ′} may be the same as or different from each other, and are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a phenyl group, and — (CH ₂ ) _n —NH ₂ . Represents either. X ⁻ represents any one of fluorine ion, chlorine ion, bromine ion, iodine ion, methyl sulfate ion, and ethyl sulfate ion. The values of m and n may be the same as or different from each other, and represent an integer of 0 to 12. The values of p and q represent the degree of polymerization of the polysiloxane and may be the same or different from each other. p is 0 to 20000, preferably 10 to 10000, q is 1 to 500, preferably 1-100 are represented.

For amino-modified silicone oil used in the softener composition of the present invention preferably has a kinematic viscosity at 25 ° C. is 50~20000mm ² / s, more preferably 100~10000mm ² / s. When the kinematic viscosity is in this range, a high texture imparting effect is exhibited, manufacturability is good, and the composition is easy to handle, which is preferable.
Commercially available amino-modified silicones can be used. For example, amino-modified silicone oils sold by Toray Dow Corning Co., Ltd. as SF-8417, BY16-892, BY16-890. From Shin-Etsu Chemical Co., Ltd., KF-864, KF-860, KF-8004, KF-8002, KF-8005, KF-867, KF-861, KF-880, KF-867S and the like can be mentioned.
The amino-modified silicone emulsion type is sold by Toray Dow Corning Co., Ltd. as SM8904, BY22-079, FZ-4671, FZ-4672, and sold by the Shin-Etsu Chemical Co., Ltd. in the Polon series. Examples include Polon MF-14, Polon MF-29, Polon MF-14D, Polon MF-44, Polon MF-14EC, Polon MF-52.

The kinematic viscosity of the dimethyl silicone is not particularly limited but is preferably 1~100,000,000mm ² / s, more preferably ^{10~10,000,000mm 2 / s, 100~1,000,000mm 2 /} s Is more preferable. Further, it may be an oil or an emulsion.
Although it does not specifically limit as a compounding quantity of the silicone compound contained in the softening agent composition of this invention, Preferably it is 0.01-10 mass%, More preferably, it is 0.05-8 mass%, More preferably, it is 0.1. ˜5 mass%. When the silicone compound is blended in an amount of 0.01% by mass or more, the fragrance of the scent increases, but the effect does not tend to increase even if it is blended in an amount of 10% by mass or more.

  In addition to the aforementioned optional components, antioxidants and reducing agents for improving the stability of the fragrance and color tone of the liquid softener composition, emulsion agents (polystyrene emulsion, etc.), opaque agents, anti-shrink agents, and laundry Anti-wrinkle agent, shape retention agent, drape retention agent, ironability improver, oxygen bleach inhibitor, whitening agent, whitening agent, fabric softening clay, antistatic agent, dye transfer inhibitor (such as polyvinylpyrrolidone), high Molecular dispersant, stain remover, scum dispersant, fluorescent brightener (4,4-bis (2-sulfostyryl) biphenyl disodium (such as Chino Pearl CBS-X manufactured by Ciba Specialty Chemicals), dye fixing agent, anti-fading Agents (1,4-bis (3-aminopropyl) piperazine, etc.), stain removers, fiber surface modifiers (cellulase, amylase, protease, lipase, keratinase, etc.) Enzymes), foam suppressors, moisture-absorbing / releasing components such as silk texture and function (silk protein powders, surface modification products thereof, emulsified dispersions, specifically K-50, K-30, K- 10, A-705, S-702, L-710, FP series (Idemitsu Petrochemical), hydrolyzed silk fluid (upper hair), Silken G Solvel S (Ichimaru Falcos)) and antifouling agents (alkylene terephthalate and / or Alternatively, a nonionic polymer compound composed of an alkylene isophthalate unit and a polyoxyalkylene unit (for example, FR627 manufactured by Kyodo Chemical Industry Co., Ltd., SRC-1 manufactured by Clariant Japan) and the like can be appropriately blended.

[PH of composition]
The pH of the liquid softener composition is not particularly limited, but the pH at 25 ° C. is 1 to 6 from the viewpoint of improving the dispersibility of the encapsulated fragrance and suppressing the hydrolysis of the component (A) accompanying storage aging. Is preferably in the range of 2 to 4, more preferably in the range of 2 to 3, and still more preferably in the range of 2 to 3.
For pH adjustment, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, p-toluenesulfonic acid, citric acid, malic acid, succinic acid, lactic acid, glycolic acid, hydroxyethanediphosphonic acid, phytic acid, ethylenediaminetetraacetic acid, A short-chain amine compound such as dimethylamine, an alkali metal hydroxide such as sodium hydroxide, an alkali metal carbonate, or a pH adjuster such as an alkali metal silicate can be used.

[Viscosity of composition]
Although the viscosity of a liquid softening agent composition is not specifically limited unless the usability is impaired, It is preferable that it is less than 1000 mPa * s.
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 less than 800 mPa · s, the usability such as the handling property at the time of charging into the washing machine is good. From the viewpoint of usability, the lower limit of the viscosity is not particularly limited.
In addition, inorganic or organic water-soluble salts can be used for the purpose of controlling the viscosity of the liquid softening agent composition of the present invention. Specifically, calcium chloride, magnesium chloride, sodium chloride, sodium p-toluenesulfonate, sodium citrate and the like can be used, among which calcium chloride, magnesium chloride and sodium citrate are preferable. These water-soluble salts can be blended in an amount that does not impair the dispersibility of the encapsulated fragrance. Is 0 to 0.3 mass%, more preferably 0 to 0.1 mass%. The water-soluble salt may be blended in any step of manufacturing the liquid softening agent composition.
The viscosity of the liquid softening agent composition in the present invention refers to a value measured at 25 ° C. using a B-type viscometer (for example, an analog viscometer T manufactured by Brookfield).

[Method for producing composition]
The method for preparing the liquid softener composition of the present invention is not particularly limited. It can be produced by a known method for preparing a liquid softener composition, for example, a method similar to a conventional method for preparing a softener composition using a cationic surfactant as a main agent.
For example, the (A) component, the (C) component, optionally the oil phase containing the (E) component, and the aqueous phase containing the (D) component are mixed under a temperature condition equal to or higher than the melting point of the (A) component. It can manufacture by preparing an emulsion and then adding and mixing (B) component to the obtained emulsion.
The oil phase is prepared by mixing component (A), component (C), optionally (E), and optionally other optional components at a temperature equal to or higher than the melting point of component (A). be able to.
A water phase can be prepared by mixing (D) component, water, and another arbitrary component as needed.
The blending time of the component (B) is not particularly limited, but it is preferable to add (post-addition) to the emulsion obtained after mixing the oil phase and the water phase. When added afterwards, the release of the core material due to the collapse of the capsule wall of the encapsulated fragrance due to the shearing force applied during the preparation of the emulsion can be suppressed.
The blending time of the component (D) is not particularly limited, but it can be added (post-added) to the emulsion obtained after mixing the oil phase and the water phase without being previously mixed with the water phase.
(E) Although the mixing | blending time of a component is not restrict | limited in particular, It is preferable to add one part to an oil phase and to add the remainder to the emulsion obtained after mixing with the said oil phase and a water phase.

[How to use the composition]
There is no restriction | limiting in particular in the usage method of the liquid softening agent composition of this invention, It can use by the method similar to a general softening agent composition. For example, a method of softening a washing object by dissolving the liquid softener composition of the present invention in rinse water at the stage of rinsing or water in a container such as a tub with the liquid softener composition of the present invention. There is a method in which the product is dissolved, and further, an article to be cleaned is put in and immersed.
The fiber product that can be treated with the softener composition of the present invention is not particularly limited, and examples thereof include clothing, curtains, sofas, carpets, towels, handkerchiefs, sheets, and macula covers. The material may also be natural fibers such as cotton, silk, and wool, or chemical fibers such as polyester.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. 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 to A-4 were used.
A-1: cationic surfactant (compound described in Example 4 of JP2003-12471)
A-1 is a compound represented by the general formulas (A1-4), (A1-5) and (A1-6) (in each formula, R ⁹ is an alkyl group or alkenyl group having 15 to 17 carbon atoms). ) Is quaternized with dimethyl sulfate.
A-2: Cationic surfactant (made by Tonan Gosei Co., Ltd., trade name: HITEX RO16E)
A-3: cationic surfactant (manufactured by Stepan, trade name: Stepantex SE-88)
A-4: Dodecyltrimethylammonium chloride (manufactured by Tokyo Chemical Industry)

[Component (B)]
The following B-1 to B-2 were used.
・ B-1: GREEN BREEZE CAPS (GIVAUDAN)
・ B-2: RAINBOW CAPS (GIVAUDAN)
Each of B-1 and B-2 is an encapsulated fragrance having a fragrance composition as a core substance and a melamine-formaldehyde resin as a capsule wall.

[Component (C)]
C-1 to C-4 shown in Table 1 below were used.

[(D) component]
The following D-1 to D-5 were used.
-D-1: Highly branched cyclic dextrin (Product name: Cluster dextrin, Weight average molecular weight: 400,000)
D-2: Polymer dextrin (Sanwa Starch Co., Ltd., trade name: Sandeck # 30, weight average molecular weight: 100,000)
D-3 (comparison): β cyclodextrin (manufactured by Tokyo Chemical Industry Co., Ltd., weight average molecular weight: 1135)
D-4: Cationic (meth) acrylic polymer (BASF product name: Rheovis FRC)
D-5: Polyethyleneimine (BASF product name: Lupasol PS, weight average molecular weight: 750,000)

[(E) component]
The following E-1 to E-2 were used.
E-1: 60 mol of polyoxyethylene isotridecyl ether EO (added ethylene oxide to BASF Rutensol TO3 (EO 60 mol indicates that the average number of added moles of ethylene oxide is 60))
E-2: Polyoxyethylene lauryl ether EO 20 mol (manufactured by Nippon Emulsion Co., Ltd. (EO 20 mol indicates that the average number of added moles of ethylene oxide is 20))

[Common components: (G)]
Antiseptic: isothiazolone solution (trade name: Caisson CG-ICP, manufactured by Dow Chemical Company)
0.01%
Viscosity control agent: Calcium chloride (Product name: Granular calcium chloride, manufactured by Tokuyama Corporation) 0.03%
Water-soluble solvent: 95% synthetic ethanol (made by Junsei Chemical) 2%
The notation of the amount of each component is mass% of each component with respect to the total mass of the prepared liquid softening agent composition.

[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 are adjusted as shown in Table 2 below. Was prepared.
First, component (A) (components A-1 to A-3), component (C), component (E), and a water-soluble solvent were mixed and stirred to obtain an oil phase mixture. On the other hand, an isothiazolone liquid which is a common component was dissolved in ion-exchange water for balance to obtain an aqueous phase mixture. Here, the mass of ion-exchange water for balance corresponds to the balance obtained by subtracting the total amount of the oil phase mixture and the common component isothiazolone liquid from 980 g.
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 mixture was 30:70 (mass ratio), and the stirring was performed at a rotational speed of 1,000 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, (B) component, (D) component, remainder of (E) component, A-4 component, common component calcium chloride is added, and hydrochloric acid (reagent 1 mol / L, Kanto Chemical) is added as necessary. Alternatively, sodium hydroxide (reagent 1 mol / L, Kanto Chemical) is added in an appropriate amount to adjust the pH to 2.5, and ion-exchanged water is added so that the total mass becomes 1,000 g. Compositions (Examples 1 to 20 and Comparative Examples 1 to 9) were obtained.

[Evaluation method]
About the liquid softening agent composition prepared as described above, evaluation of “persistence of fragrance”, “dispersibility of component (B)”, and “paint peeling” was performed according to the following procedure.
<1. Treatment of cotton towel with liquid softener composition>
(Pretreatment of evaluation cloth)
For the commercial cotton towel (manufactured by Toshinsha Co., Ltd.), as a pretreatment, the following pretreatment was carried out using a two-layer washing machine (Toshiba VH-30S) with a commercial detergent "Top Platinum Clear" (manufactured by Lion Corporation). 3 times.
Pretreatment: Standard amount of detergent used, 30 times bath ratio, 45 ° C. tap water, washing 10 minutes → water rinsing 10 minutes twice.

(Processing in the rinsing process when washing)
Wash 1.0 kg of cotton towel (manufactured by Toshin Co., Ltd.) pretreated as above with a commercial detergent “Top Platinum Clear” (manufactured by Lion) using a two-tank washing machine (Toshiba VH-30S). (Standard use amount, standard course, bath ratio 30 times, use of tap water at 25 ° C.), and then the first rinse was performed for 3 minutes. The first rinse was followed by a second rinse for 3 minutes. At the start of this second rinse, the liquid softener composition prepared as described above was added and a softening treatment for 3 minutes (finishing agent 6.67 mL, bath ratio 20 times, using tap water at 25 ° C.) was performed. It was. Dehydration was performed for 1 minute between the washing and rinsing steps.
After the treatment, a cotton towel was taken out from the two-tank washing machine and dried for 8 hours under the irradiation of sunlight at an average temperature of 25 ° C. and 30 Langley, and used as a treatment cloth for evaluation.

<2. Evaluation of scent sustainability>
The treatment cloth for evaluation treated as described above was dried and then subjected to sensory evaluation on the fragrance intensity after storage for 1 day under 20 ° C. and 40% RH conditions according to the following 6-step odor intensity display method. Based on the average score of 8 professional panelists, fragrance persistence was determined according to the following criteria. In terms of product value, ○ or more was considered acceptable. The results are shown in Table 2 below.
<6-level odor intensity display method>
0: Odorless 1: A scent that can be finally detected 2: A scent that can understand what scent 3: A scent that can be easily detected 4: A strong scent 5: A strong scent <Criteria>
◎◎◎: 3.0 points or more ◎◎: 2.5 points or more and less than 3.0 points ◎: 2.0 points or more and less than 2.5 points ○: 1.5 points or more and less than 2.0 points △: 1. 0 point or more and less than 1.5 point ×: less than 1.0 point

<3. (B) Dispersibility evaluation of component>
The liquid softening agent composition prepared as described above was put into a light-weight PS glass bottle (PS-No. 11, manufactured by Tanuma Glass Industrial Co., Ltd.) and sealed, and the dispersibility of the component (B) was evaluated by a five-step evaluation method shown below. Evaluation was performed. Similarly, the sealed sample was stored for 3 months at 25 ° C., and visually evaluated by 8 professional panelists based on the following criteria. The results were expressed as the average value of 8 people. From the viewpoint of commercial value, it is preferably ◯ or more. The results are shown in Table 2 below.
<Evaluation criteria>
4: Recognized as equivalent to the sample before storage.
3: Slight floating is recognized.
2: Although floating is recognized, it re-disperses easily by light shaking.
1: Floating is observed, and there is adhesion to the glass bottle. Re-dispersion is difficult with light shaking.
<Criteria>
◎◎◎: 3.5 points or more ◎◎: 3.0 points or more and less than 3.5 points ◎: 2.5 points or more and less than 3.0 points ○: 2.0 points or more and less than 2.5 points △: 1. 5 points or more and less than 2.0 points ×: less than 1.5 points

<4. Paint peeling evaluation>
(Preparation of evaluation plate)
Apply a commercially available aqueous varnish “Aqueous Niss Transparent Clear” (manufactured by Washin Paint Co., Ltd.) to the wooden board “Agathis board” (manufactured by Holtz Market) using a brush and dry at 20 ° C. and 40% RH for 3 hours. This operation was repeated three times to obtain an evaluation plate.
(Evaluation of paint peeling)
500 μl of the liquid softening agent composition prepared as described above was dropped on the surface of the aqueous varnish coated on the wooden board produced by the above method, and dried at 20 ° C. and 45% RH for 12 hours. Thereafter, the dried liquid softener composition was well wiped off with a cotton towel wetted with water and squeezed firmly. The state of the wooden board after wiping was evaluated by visual observation and touch according to the following evaluation criteria, and the degree of paint peeling was determined from the average score of 8 professional panelists according to the following criteria. In terms of product value, ○ or more was considered acceptable. The results are shown in Table 2 below.
<Evaluation criteria>
5: A change is not recognized at all like the state before liquid softening agent composition dripping.
4: A slight amount of paint peeling is observed.
3: Slight peeling of paint is observed.
2: Paint peeling is recognized.
1: Considerable peeling of paint is observed.
0: The surface of the wood board before the aqueous bismuth coating is completely exposed.
<Criteria>
◎◎◎: 4.0 points or more ◎◎: 3.5 points or more and less than 4.0 points ◎: 3.0 points or more and less than 3.5 points ○: 2.0 points or more and less than 3.0 points Δ: 1. 0 point or more and less than 2.0 point ×: less than 1.0 point

組成表中の数字は質量％を表す。尚、（Ｂ）成分の数値は、液体柔軟剤組成物の総質量に対する、芯物質として含まれる香料成分としての配合量（質量％）であり、（Ｃ）成分の数値は、液体柔軟剤組成物の総質量に対する、（Ｃ）成分自体（香料組成物）の配合量（質量％）である。

The numbers in the composition table represent mass%. In addition, the numerical value of (B) component is the compounding quantity (mass%) as a fragrance | flavor component contained as a core substance with respect to the total mass of a liquid softening agent composition, and the numerical value of (C) component is a liquid softening agent composition. It is the compounding quantity (mass%) of (C) component itself (fragrance | flavor composition) with respect to the total mass of a thing.

Claims (2)

The following components (A) to (D):
(A) Selected from the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms which may be separated by an ester group and / or an amide group, a salt thereof and a quaternized product thereof At least one compound,
(B) encapsulated fragrance,
(C) A fragrance composition not encapsulated in a capsule, the fragrance composition containing 25% by mass or more of a fragrance component having a ClogP value of 5 or more with respect to the total mass of the fragrance composition, and (D) a water-soluble composition Liquid softener composition containing a functional polymer compound.   The liquid softener composition according to claim 1, wherein the component (D) is selected from the group consisting of a nonionic glucan, polyethyleneimine or a derivative thereof, and a cationic (meth) acrylic polymer.