KR20220116140A - liquid softener composition - Google Patents

Abstract

The present invention provides a liquid softener having excellent deodorizing effect, usability and freeze restoration properties. Specifically, the present invention provides the following components (A) to (D): (A) an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be divided into an ester group and/or an amide group; Compounds selected from the group consisting of salts and quaternaries thereof, (B) water-soluble salts of divalent metals, (C) aminocarboxylic acid compounds having a specific structure, ricinoleic acid, and salts thereof A compound and (D) nonionic surfactant are included, and mass ratio ([B+C]/A) with respect to (A) component of (B)component and (C)component sum total is 0.01-0.5, and (B) Mass ratio ([B+C]/D) with respect to (D)component of component and (C)component sum total is 0.1-4, The liquid softening agent composition characterized by the above-mentioned is provided.

Description

liquid softener composition

The present invention relates to a liquid emollient composition.

In recent years, the market scale of the softening agent in Japan tends to expand, and the share of the softening agent which has a deodorizing function among them is increasing year by year. On the other hand, most of the current deodorization techniques rely on masking by fragrance, and there are concerns about problems, such as smell harassment.

Then, the deodorization technique which does not depend on a fragrance is calculated|required. As the specific example, the technique of mix|blending a water-soluble inorganic zinc compound (zinc chloride etc.) and water-soluble zinc hydroxycarboxylic acid (zinc citrate etc.) with a liquid softening agent is known (patent document 1).

Moreover, although it is not a softening agent, the deodorant which used together the water-soluble salt of a divalent metal (zinc sulfate etc.) and a chelating agent (methylglycine diacetic acid etc.) is known (patent document 2).

In addition, in order to improve the color stability of a softening agent, the technique of mix|blending methylglycine diacetic acid is known (patent document 3).

International Publication No. 2009/075284 International Publication No. 2012/090989 Japanese Patent Laid-Open No. 2015-200049

However, as a result of this inventor examining the technique of patent documents 1-2, the subject was found. About the technique of patent document 1, the subject that a sufficient deodorizing effect was not acquired only by mixing|blending a zinc compound, and the subject that a remarkably fall or raise of the softening agent viscosity occurred depending on the kind of zinc compound, and the subject that usability fell were discovered. . About the technique of patent document 2, when the water-soluble salt of a divalent metal and a chelating agent were mix|blended with a softening agent, the subject that usability fell was discovered.

As a result of earnestly examining the said subject, the present inventors have (A) a specific type of cationic surfactant, (B) a water-soluble salt of a divalent metal, (C) a specific type of aminocarboxylic acid compound or ricinoleic acid, ( D) It has been found that, when a nonionic surfactant is blended in a specific ratio, a liquid softening agent excellent in deodorizing effect (especially, deodorizing effect on indoor drying smell), usability, and freeze recovery property is obtained. The present invention has been made based on this knowledge.

That is, the present invention relates to the following [1] to [6].

[1] As a liquid softening agent composition, the following (A)-(D) components:

(A) a compound selected from the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in its molecule, which may be divided by an ester group and/or an amide group, a salt thereof, and a quaternary product thereof;

(B) water-soluble salts of divalent metals;

(C) a compound selected from the group consisting of aminocarboxylic acid compounds represented by formulas (I) to (IV), ricinoleic acid, and salts thereof;

(During the meal,

A ^I is a linear or branched alkyl group having 8 to 22 carbon atoms, a sulfo group, an amino group, a hydroxyl group, a hydrogen atom, or COOM ^I ;

M ^I may be the same or different from each other, and is selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group, and an alkanolamine;

m ^I and n ^I are each an integer of 0 to 2.)

(During the meal,

X ^II-1 to X II ^-4 may be the same or different, and are selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group, and an alkanolamine;

Q ^II is a hydrogen atom or a straight-chain or branched alkyl group having 8 to 22 carbon atoms,

R ^II is a hydrogen atom or a hydroxyl group,

n ^II is 0 or 1.)

(During the meal,

R ^III is a straight-chain or branched alkyl or alkenyl group having 8 to 22 carbon atoms,

A ^III is H, a methyl group or (CH ₂ )m ^III -COOX ^III ,

m ^III is 1-3,

X ^III is H, alkali metal, alkaline earth metal, alkanolamine or NH ₄ ,

n ^III is 1-3.)

(During the meal,

X ^IV is a hydrogen atom, an alkali metal or an alkaline earth metal,

n ^IV is 1 or 2.), and

(D) nonionic surfactant

including,

Mass ratio ([B+C]/A) with respect to (A) component of (B) component and (C)component sum total is 0.01-0.5, and

(B) Mass ratio ([B+C]/D) with respect to (D)component of a component and (C)component sum total is 0.1-4, The liquid softening agent composition characterized by the above-mentioned.

[2] The liquid softening agent composition according to the above [1], wherein the component (B) is a water-soluble zinc salt or a water-soluble copper salt.

[3] (C) The liquid softening agent composition as described in said [1] or [2] whose component is the compound represented by Formula (I), its salt, or ricinoleic acid or its salt.

[4] The liquid according to any one of the above [1] to [3], wherein the mass ratio ([B+C]/A) of the component (B) and the component (C) to the component (A) is 0.25 to 0.45. emollient composition.

[5] The liquid according to any one of [1] to [4], wherein the mass ratio ([B+C]/D) of the sum of the component (B) and the component (C) to the component (D) is 1-2 emollient composition.

[6] The liquid according to any one of [1] to [5], wherein the component (D) is polyoxyethylene alkyl ether having an alkyl group having 10 to 18 carbon atoms and having an average added mole number of ethylene oxide of 20 to 80 moles. emollient composition.

As will be shown in Examples to be described later, the liquid softener composition of the present invention has excellent deodorizing effect, usability, and freeze recovery properties. Therefore, the present invention is useful as a softening agent having added value not found in conventional products.

[(A) component: cationic surfactant]

The component (A) is "a compound selected from the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in the molecule, which may be segmented by an ester group and/or an amide group, a salt thereof, and a quaternary product thereof" It is a cationic surfactant.

(A) Component is mix|blended in order to provide a softness|flexibility provision effect to a liquid softening agent composition.

Carbon number of a C10-C26 hydrocarbon group (Hereinafter, it may call a "long chain hydrocarbon group" in this specification) is 10-26, 17-26 are preferable and 19-24 are more preferable. When carbon number is 10 or more, a softness|flexibility is favorable, and when it is 26 or less, handling property is favorable. The long-chain hydrocarbon group may be saturated or unsaturated. When the long-chain hydrocarbon group is unsaturated, the position of the double bond does not matter at any location, but when there is one double bond, the position of the double bond is preferably in the center of the long-chain hydrocarbon group or around the center.

The long-chain hydrocarbon group may be a chain hydrocarbon group or a hydrocarbon group containing a ring in its structure, and is preferably a chain hydrocarbon group. The chain hydrocarbon group may be either 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 segmented by an ester group (-COO-) and/or an amide group (-NHCO-). That is, the long-chain hydrocarbon group may have at least one branching group selected from the group consisting of an ester group and an amide group in its carbon chain, and the carbon chain may be branched by the branching group. Having the above-mentioned dividing group is preferable from the viewpoint of improving biodegradability.

When it has the said branching group, the number of the branching groups which one long-chain hydrocarbon group has may be one or two or more may be sufficient as it. That is, one place of a long-chain hydrocarbon group may be segmented by a dividing group, and two or more places may be segmented. In the case of having two or more dividers, each dividing unit may be the same or different.

In the case of having a branching group in the carbon group, the number of carbon atoms included in the branching group is counted as the number of carbon atoms in the long-chain hydrocarbon group.

The long-chain hydrocarbon group is usually an unhydrogenated fatty acid derived from tallow used industrially, a fatty acid obtained by hydrogenating or partially hydrogenating an unsaturated part, an unhydrogenated fatty acid or fatty acid ester derived from plants such as palm palm and oil palm, or It is introduced by using a fatty acid or fatty acid ester obtained by hydrogenating or partially hydrogenating an unsaturated part.

(A) As an amine compound which is a component, a secondary amine compound or a tertiary amine compound is preferable, and a tertiary amine compound is more preferable.

(A) As an amine compound which is a component, the compound represented by the following general formula (A1) is mentioned more specifically.

[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 a hydrocarbon group having 7 to 21 carbon atoms) ) or -(CH ₂ ) _n NHCOR ⁵ (n is 2 or 3, and R ⁵ is a hydrocarbon group having 7 to 21 carbon atoms), a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, —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 to be.]

In general formula (A1), 17-26 are preferable and, as for carbon number of the C10 ^- C26 hydrocarbon group in R1 ^- R3, 19-24 are more preferable. The hydrocarbon group may be saturated or unsaturated. As said hydrocarbon group, an alkyl group or an alkenyl group is preferable.

Among -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 two or more R ⁴ is present in the compound represented by the general formula (A1), the plurality of R ⁴ may be the same as or different from each other.

The hydrocarbon group of R ⁴ is a residue (fatty acid residue) excluding a carboxy group from a fatty acid having 8 to 22 carbon atoms (R ⁴ COOH), and the fatty acid (R ⁴ COOH) underlying R ⁴ may be a saturated fatty acid or an unsaturated fatty acid, Moreover, a straight-chain fatty acid or a branched fatty acid may be sufficient. Among them, saturated or unsaturated straight-chain fatty acids are preferable. In order to impart good absorbency to the cast garment, the saturated/unsaturated ratio (mass ratio) of the fatty acid serving as the basis for R ⁴ is preferably 90/10 to 0/100, and more preferably 80/20 to 0/100. do.

When R ⁴ is an unsaturated fatty acid residue, a cis-isomer and a trans-isomer exist. The mass ratio of the cis-isomer/trans-isomer is preferably 40/60 to 100/0, particularly preferably 70/30 to 90/10.

As the fatty acid underlying R ⁴ , specifically, stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine number of 10 to 60), partially hydrogenated Added tallow fatty acid (iodine number 10-60), etc. are mentioned. Among them, two or more selected from stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic acid were combined in a predetermined amount to satisfy the following conditions (a) to (c). Preference is given to using fatty acid compositions.

(a) The ratio (mass ratio) of saturated fatty acid/unsaturated fatty acid is 90/10 - 0/100, More preferably, it is 80/20 - 0/100. (b) The ratio (mass ratio) of the cis-isomer/trans-isomer is 40/60-100/0, More preferably, it is 70/30-90/10. (c) A fatty acid having 18 carbon atoms is 60 mass% or more, preferably 80 mass% or more, a fatty acid having 20 carbon atoms is less than 2 mass%, and a fatty acid having 21 to 22 carbon atoms is less than 1 mass%.

Among -(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 two or more R ⁵ is present in the compound represented by the general formula (A1), the plurality of R ⁵ may be the same as or different from each other. Examples of R ⁵ include the same as those of R ⁴ .

Of R1 to R ³ , at least one 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 ), and two of them are long-chain hydrocarbon groups desirable. Among R1 to R ³ , when one or two is a long-chain hydrocarbon group, 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 .

Preferred 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 for R ¹ to R ³ with 10 to 26 carbon atoms.

Examples of the hydrocarbon group having 7 to 21 carbon atoms in R ⁹ and R ¹⁰ include the same hydrocarbon group as the hydrocarbon group having 7 to 21 carbon atoms in R ⁴ . When a plurality of R ⁹ is present in the formula, the plurality of R ⁹ may be the same as or different from each other.

(A) The salt of an amine compound or a quaternary thing may be sufficient as a component.

A salt of an amine compound is obtained by neutralizing the amine compound with an acid. An organic acid or an inorganic acid may be sufficient as an acid used for neutralization of an amine compound, For example, hydrochloric acid, sulfuric acid, methylsulfuric acid, etc. are mentioned. Neutralization of the amine compound can be performed by a known method.

The quaternization product of an amine compound is obtained by making the said amine compound react with a quaternization agent. As a quaternization agent used for quaternization of an amine compound, alkyl halides, such as methyl chloride, dialkyl sulfuric acid, such as dimethyl sulfuric acid, etc. are mentioned, for example. When these quaternizing agents are reacted with an amine compound, an 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. Quaternization of an amine compound can be performed by a well-known method.

(A) As a component, at least 1 sort(s) chosen from the group which consists of a compound represented by the said General formula (A1), its salt, and its quaternary is preferable, and said General formula (A1-1) - (A1-8) , at least one selected from the group consisting of salts and quaternaries thereof is more preferable, and (A1-4) to (A1-6) (in each formula, R ⁹ is an alkyl group having 15 to 17 carbon atoms or an alkenyl group. ), at least one selected from the group consisting of salts and quaternaries thereof is particularly preferable.

A commercially available thing may be used for the compound represented by General formula (A1), its salt, and its quaternary thing, and what was manufactured by a well-known method may be used for it.

For example, the compound represented by the general formula (A1-2) (hereinafter “Compound (A1-2)”) and the compound represented by the general formula (A1-3) (hereinafter “Compound (A1-3)”) are , the fatty acid composition or a fatty acid methyl ester composition in which the fatty acid in the fatty acid composition is substituted with a methyl ester of the fatty acid can be synthesized by a condensation reaction of methyldiethanolamine. In that case, it is preferable to synthesize|combine so that the abundance ratio represented by "compound (A1-2)/compound (A1-3)" may become 99/1-50/50 by mass ratio from a viewpoint of making a softness|flexibility favorable.

Moreover, when using this quaternization material, it is more preferable to use dimethyl sulfuric acid as a quaternization agent. At that time, from the viewpoint of flexibility, synthesis is performed so that the abundance ratio expressed as "quaternary product of compound (A1-2)/quaternary product of compound (A1-3)" is 99/1 to 50/50 by mass ratio. it is preferable

The compound represented by the general formula (A1-4) (hereinafter “Compound (A1-4)”), the compound represented by the general formula (A1-5) (hereinafter “Compound (A1-5)”), the general formula (A1) The compound represented by -6) (hereinafter "compound (A1-6)") can be synthesized by a condensation reaction of the fatty acid composition or fatty acid methyl ester composition with triethanolamine. In that case, the content ratio of each component with respect to the total mass of compounds (A1-4), (A1-5) and (A1-6) is 1-60 mass of compound (A1-4) from a viewpoint of flexibility. %, compound (A1-5) is preferably 5 to 98 mass%, compound (A1-6) is preferably 0.1 to 40 mass%, compound (A1-4) is 30 to 60 mass%, compound (A1-5) ) is 10-55 mass %, and it is more preferable that compound (A1-6) is 5-35 mass %.

Moreover, when using this quaternization material, it is more preferable to use dimethyl sulfuric acid as a quaternization agent at the point which advances a quaternization reaction sufficiently. The abundance ratio of each quaternary product of compounds (A1-4), (A1-5) and (A1-6) is a mass ratio from the viewpoint of flexibility, and the quaternary product of compound (A1-4) is 1-60 mass %, the quaternary product of compound (A1-5) is preferably 5-98 mass %, the quaternary product of compound (A1-6) is 0.1-40 mass %, and the quaternary product of compound (A1-4) is preferable It is more preferable that this 30-60 mass %, 10-55 mass % of the quaternized substance of a compound (A1-5), and 5-35 mass % of a quaternary substance of a compound (A1-6) are. In addition, when compounds (A1-4), (A1-5), and (A1-6) are quaternized, esteramines which are not generally quaternized remain after the quaternization reaction. In that case, it is preferable that the ratio of "the quaternized substance / the ester amine which is not quaternized" exists in the range of the mass ratio of 70/30-99/1.

The compound represented by the general formula (A1-7) (hereinafter “Compound (A1-7)”) and the compound represented by the general formula (A1-8) (hereinafter “Compound (A1-8)”) are the fatty acid composition and from the adduct of N-methylethanolamine with acrylonitrile, J. Org. Chem., 26, 3409 (1960), can be synthesized 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 become 99/1-50/50 by mass ratio. In addition, when using the quaternized substance, it is preferable to use methyl chloride as a quaternizing agent, and the abundance ratio expressed by "quaternized substance of compound (A1-7)/quaternized substance of compound (A1-8)" is , it is preferable to synthesize it so that the mass ratio becomes 99/1 to 50/50.

(A) A component is a well-known substance, it can obtain easily in a market, or can prepare it.

(A) A component may use a single type and may use multiple types together.

Although the content of (A) component is not specifically limited as long as the compounding objective is achieved and the compounding ratio with other components mentioned later is satisfied, For example, 4-16 mass % with respect to the total mass of a liquid softening agent composition, Preferably it is 6-14 mass %, More preferably, it is 8-12 mass %. (A) When the content of component is 4 mass % or more, a more improved softness|flexibility provision effect is acquired, and when it is 16 mass % or less, the softening agent viscosity which enables more favorable usability is obtained.

[(B) component: water-soluble salt of divalent metal]

(B) A component is mix|blended in order to provide a deodorizing effect to a liquid softening agent composition.

"Water solubility" means dissolving 10 g or more in 1 liter of water at 25°C.

(B) As a specific example of a component, a water-soluble zinc salt (zinc sulfate, zinc chloride, etc.), a water-soluble copper salt (copper sulfate, copper chloride, etc.), a water-soluble iron salt (iron sulfate, etc.), a water-soluble manganese salt (manganese chloride, etc.), etc. can be heard (B) These hydrates are also included in a component.

(B) As a component, a water-soluble zinc salt and a water-soluble copper salt are preferable from the point of deodorization performance.

As the water-soluble zinc salt, zinc sulfate and zinc chloride are preferable.

As a water-soluble copper salt, copper sulfate and its hydrate are preferable, copper sulfate hydrate is more preferable, and copper sulfate pentahydrate is still more preferable.

(B) A component is a well-known substance, it can obtain easily in a market, or can prepare it.

(B) A component may use a single type and may use multiple types together. When using two or more types together, it is preferable to contain a zinc salt.

(B) The content of the component is not particularly limited as long as it achieves the purpose of blending and satisfies the blending ratio with other ingredients described later, but it is, for example, 0.05 to 3% by mass relative to the total mass of the liquid softening agent composition, Preferably it is 0.1-3 mass %, More preferably, it is 0.5-2.5 mass %, More preferably, it is 1.5-2.5 mass %. Moreover, when (B) component is a hydrate, content as an anhydride is meant. (B) If the content of the component is 0.05 mass % or more, a more improved deodorizing effect will be acquired, and if it is 3 mass % or less, the softening agent viscosity which enables more favorable usability will be obtained.

[(C)component: aminocarboxylic acid compound, ricinoleic acid, and salts thereof]

(C) A component is mix|blended in order to provide a deodorizing effect to a liquid softening agent composition.

(C) A component is a compound represented by following formula (I) - (IV), ricinoleic acid, and these salts.

In formula (I), A ^I represents a C8-C22 linear or branched alkyl group, a sulfo group, an amino group, a hydroxyl group, a hydrogen atom, or COOM ^I. As A ^I , CH ₃ , OH, H, and COOM ^I are preferable, CH ₃ , H is more preferable, and CH ₃ is particularly preferable.

M ^I may be the same or different from each other, and each represents one selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group, and an alkanolamine. As an alkali metal, sodium and potassium are preferable. As an alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable. As M ^I , an alkali metal is preferable, and sodium is particularly preferable.

m ^I and n ^I are each an integer of 0 to 2. m ^I is preferably 0 or 1. n ^I is preferably 0 or 1. When m ^I and n ^I are both 0, A ^I is CH ₃ .

Among the compounds represented by the formula (I), suitable ones include methylglycine diacetic acid (MGDA), aspartic acid diacetic acid (ASDA), isocerine diacetic acid (ISDA), β-alanine diacetic acid (ADAA), serine diacetic acid ( SDA), glutamic acid diacetic acid (GLDA), or these salts are mentioned. Especially, MGDA or its salt is preferable.

In the formula (II), X ^II -1 to X II ^-4 may be the same or different, and each represents one selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group, and an alkanolamine. . As an alkali metal, sodium and potassium are preferable. As an alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable. As X ^II-1 to X II ^-4 , an alkali metal is preferable, and sodium is particularly preferable.

Q ^II represents a hydrogen atom or a straight-chain or branched alkyl group having 8 to 22 carbon atoms.

R ^II represents a hydrogen atom or a hydroxyl group.

n ^II represents 0 or 1.

Among the compounds represented by formula (II), suitable examples thereof include iminodisuccinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), and salts thereof, and among them, IDS or a salt thereof is more preferable.

In formula (III), R ^III represents a straight-chain or branched alkyl or alkenyl group having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms.

A ^III represents H, a methyl group, or (CH ₂ )m ^III -COOX ^III . As A ^III , (CH ₂ )m ^III -COOX ^III is preferable. m ^III represents a number in any one of 1-3.

X ^III represents H, an alkali metal, an alkaline earth metal, an alkanolamine or NH ₄ . As an alkali metal, sodium and potassium are preferable. As an alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable.

n ^III represents any one of 1 to 3.

As a specific example of the compound represented by Formula (III),

alkyl and alkenylamino acetate salts such as sodium octylaminoacetate, sodium laurylaminoacetate, sodium myristylaminoacetate, sodium palmitylaminoacetate, and sodium oleylaminoacetate;

alkyl and alkenylaminopropionates such as sodium octylaminopropionate, sodium decylaminopropionate, sodium laurylaminopropionate, sodium myristylaminopropionate, sodium palmitylaminopropionate, and sodium oleylaminopropionate;

N-alkyl and alkenylglycine salts such as sodium N-octylglycine, sodium N-decylglycine, sodium N-laurylglycine, sodium N-myristylglycine, sodium N-palmitylglycine, and sodium N-oleylglycine;

N-octyl-N-methyl-β-alanine sodium, N-decyl-N-methyl-β-alanine sodium, N-dodecyl-N-methyl-β-alanine sodium, N-myristyl-N-methyl-β -N-alkyl and alkenyl-N-methyl-β-alanine salts such as sodium alanine, sodium N-palmityl-N-methyl-β-alanine, and sodium N-oleyl-N-methyl-β-alanine;

alkyl and alkenylaminodiacetate salts such as sodium octylaminodiacetate, sodium decylaminodiacetate, sodium laurylaminodiacetate, sodium myristylaminodiacetate, sodium palmitylaminodiacetate, and sodium oleylaminodiacetate; and

Alkyl and alkenylaminodipropionates such as sodium octylaminodipropionate, sodium decylaminodipropionate, sodium laurylaminodipropionate, sodium myristylaminodipropionate, sodium palmitylaminodipropionate, sodium oleylaminodipropionate, etc. can be heard

Among these, from the viewpoint of storage stability, alkyl and alkenylaminodiacetic acid salts are preferable, and among these, decylaminodiacetic acid, laurylaminodiacetic acid, myristylaminodiacetic acid, palmitylaminodiacetic acid or salts thereof are preferable. and particularly preferably laurylaminodiacetic acid, myristylaminodiacetic acid, palmitylaminodiacetic acid, or a salt thereof.

In the formula (IV), X ^IV represents a hydrogen atom, an alkali metal or an alkaline earth metal.

n ^IV represents 1 or 2, and when n ^IV is 2, X ^IV may be the same or different. The substitution position of the (COOX ^IV )n ^IV group is not particularly limited, but the α-position is preferable.

Ricinoleic acid (12-hydroxy-9-cis-octadecenoic acid) is a compound having the following structure.

As a salt of ricinoleic acid, a sodium salt, a zinc salt, a copper salt, etc. are mentioned.

(C) As a component, the compound represented by Formula (I) or (II), its salt, and ricinoleic acid are preferable, and especially MGDA, IDS, these salts, and ricinoleic acid are preferable. From the point of deodorizing effect, MGDA, its salt, and ricinoleic acid are the most preferable. In terms of the deodorizing effect, the usability of the liquid softening agent composition, and the freeze recovery properties, MGDA is the most preferable.

(C) A component is a well-known substance, it can obtain easily in a market, or it can prepare it.

(C) A component may use a single type and may use multiple types together.

(C) Although the content of component is not specifically limited as long as the compounding objective is achieved and the compounding ratio with other components mentioned later is satisfied, For example, 0.05-3 mass % with respect to the total mass of a liquid softening agent composition, Preferably it is 0.1-3 mass %, More preferably, it is 0.5-2.5 mass %, More preferably, it is 1.5-2.5 mass %. (C) If the content of component is 0.05 mass % or more, a more improved deodorizing effect will be acquired, and if it is 3 mass % or less, the softening agent viscosity which enables more favorable usability will be obtained.

From the point of the deodorizing effect, mass ratio ((B)/(C)) of (B)component and (C)component becomes like this. Preferably it is 0.1-10, More preferably, it is 0.2-5, More preferably, it is 0.5-2. .

[(D) component: nonionic surfactant]

(D) A component is mix|blended in order to improve the usability and freeze recovery property of a liquid softening agent composition.

(D) As a component, the thing derived from a polyhydric alcohol, a higher alcohol, a higher amine, or a higher fatty acid can be used, for example.

(D) As a specific example of a component,

glycerin fatty acid ester or pentaerythritol in which a fatty acid having 10 to 22 carbon atoms is ester-bonded with glycerin or pentaerythritol;

polyoxyethylene alkyl ethers having an alkyl group or alkenyl group having 10 to 22 carbon atoms and having an average added mole number of ethylene oxide (EO) of 10 to 100 moles;

polyoxyethylene fatty acid alkyl (the alkyl having 1 to 3 carbon atoms) ester;

polyoxyethylene alkylamines having an average added mole number of ethylene oxide of 10 to 100 moles;

Alkyl polyglycosides having an alkyl group or alkenyl group having 8 to 18 carbon atoms;

and hydrogenated castor oil having an average added mole number of ethylene oxide of 10 to 100 moles.

(D) As a component, it has a C10-18 alkyl group, and the average added mole number of ethylene oxide is 20-80 mol (preferably 30-60 mol) polyoxyethylene alkyl ether is preferable.

(D) A component is a well-known substance, it can obtain easily in a market, or can prepare it.

(D) A component may use a single type and may use multiple types together.

(D) The content of the component is not particularly limited as long as it achieves the purpose of blending and satisfies the blending ratio with other ingredients described later, but it is, for example, 0.5 to 10% by mass relative to the total mass of the liquid softening agent composition, Preferably it is 1-5 mass %, More preferably, it is 1.5-4 mass %, Especially preferably, it is 1.5-3 mass %. (D) When the content of component is 0.5 mass % or more, high temperature stability is obtained in addition to more improved usability and freeze-resistance property, and when it is 10 mass % or less, the viscosity and separation stability which enable better usability and separation stability are obtained.

[Ratio of each ingredient]

In this invention, mass ratio ([B+C]/A) with respect to (A) component of (B)component and (C)component sum total ([B+C]) is 0.01-0.5, Preferably it is 0.08-0.45, More preferably, it is 0.25-0.45. When mix|blending in this ratio, the outstanding deodorizing effect will be acquired, and also the liquid softening agent composition will become difficult to separate, and usability improves. This is the result that when excessive introduction of a part of (B) component and (C) component to a vesicle composed of (A) component occurs, the vesicle particle diameter increases and the liquid softening agent composition is easily separated, resulting in the mass ratio It is thought that this is because excessive increase in the vesicle particle diameter is suppressed by blending with However, this invention is not limited by the said theory.

In this invention, mass ratio ([B+C]/D) with respect to (D)component of (B)component and (C)component sum total ([B+C]) is 0.1-4, Preferably it is 0.4-2.5, More preferably, it is 1-2. When blended in this proportion, an excellent deodorizing effect is obtained, and the freeze recovery properties and usability of the liquid softener composition are improved. This is because when some of the components (B) and (C) are introduced into the vesicle composed of the component (A), the particle size distribution and the excluded volume of the vesicle change, making the liquid softener composition easier to thicken (reducing usability) As a result, it is thought that it is because the particle size distribution of a vesicle and the excessive change of the excluded volume are suppressed by mix|blending by the said mass ratio as a result, and freeze recovery property improves by (D)component. However, this invention is not limited by the said theory.

[Optional Ingredients]

You may mix|blend the following arbitrary components with the liquid softening agent composition other than the essential component of said (A)-(D) in the range which does not impair the effect of this invention.

[(E) component: fragrance composition not encapsulated]

(E) A component is a fragrance composition (free fragrance composition) which is not contained in a capsule, different from the fragrance composition contained as a core substance in the capsule fragrance|flavor ((H)component) mentioned later.

(E) A component is mix|blended in order to improve the deodorizing effect of a liquid softening agent composition by the masking effect by the fragrance.

Although (E) component can be suitably selected according to the objective from the fragrance composition containing one or more types of fragrance components generally used for a liquid softening agent composition, ClogP value is 5 with respect to the total mass of the fragrance composition as (E) component. It is preferable to contain 25 mass % or more of the above perfume components.

Specific examples of the perfume component are not particularly limited and may be appropriately selected according to the purpose. For example, aldehydes, phenols, alcohols, ethers, esters, hydrocarbons, ketones, lactones, musk, terpene Fragrances having a skeleton, natural fragrances, animal fragrances, and the like are exemplified.

The specific example of each fragrance|flavor is as follows.

The aldehydes are not particularly limited and can be appropriately selected according to the purpose. For example, undecylenealdehyde, laurylaldehyde, aldehyde C-12MNA, miracaldehyde, α-amylcinnamaldehyde, cyclamenaldehyde, citral, Citronellal, ethylvanillin, heliotropin, anisaldehyde, α-hexylcinnamaldehyde, octanal, ligustral, lilyal, lilar, preflal, vanillin, helional, etc. are mentioned.

There is no restriction|limiting in particular as phenols, According to the objective, it can select suitably, For example, Eugenol, isoegenol, etc. are mentioned.

There is no restriction|limiting in particular as an alcohol, According to the objective, it can select suitably, For example, citronellol, dihydromyrcenol, dihydrolinalool, geraniol, linalool, nerol, sandalore, santa Rex, terpineol, tetrahydrolinalool, menthol, borneol, 1-decanal, bactanol, phenylethyl alcohol, etc. are mentioned.

There is no restriction|limiting in particular as ethers, According to the objective, it can select suitably, For example, Sedraber, Grizalva, methyleugenol, methylisoeugenol, etc. are mentioned.

There is no restriction|limiting in particular as ester, According to the objective, it can select suitably, For example, cis-3-hexenyl acetate, cis-3-hexenyl propionate, cis-3-hexenyl salicylate, p-cresyl acetate, p-t-butylcyclohexyl acetate, amyl acetate, methyl dihydrojasmonate, amyl salicylate, benzyl salicylate, benzyl benzoate, benzyl acetate, cedryl acetate, citronellyl acetate, deca Hydro-β-naphthyl acetate, dimethyl benzyl carvinyl acetate, ericapropionate, ethyl acetoacetate, erica acetate, geranyl acetate, geranyl formate, hedione, linalyl acetate, β-phenylethyl acetate, hexyl salicil Late, styralyl acetate, terpinyl acetate, betiberyl acetate, o-t-butylcyclohexyl acetate, manzanate, allyl heptanoate, etc. are mentioned.

There is no restriction|limiting in particular as hydrocarbons, According to the objective, it can select suitably, For example, limonene (particularly, d-limonene), alpha-pinene, beta-pinene, myrcene, campene, terpinolene, etc. can be heard

The ketones are not particularly limited, and can be appropriately selected according to the purpose. -Damascon, Damaxenone, Cis-Jasmon, Methylionone, Allylionone, Cashmeran, Dihydrojasmon, Iso E Super, Belt Fix, IsolongiPolanone, Corebone, Carvone, Rosephenone, raspberry ketone, dynascone, maltol, etc. are mentioned.

There is no restriction|limiting in particular as lactones, According to the objective, it can select suitably, For example, γ-decalactone, γ-undecalactone, γ-nonalactone, γ-dodecalactone, coumarin, and ambroc. mountains, and the like.

There is no restriction|limiting in particular as a musk, According to the objective, it can select suitably, For example, cyclopentadecanolide, ethylene brasylate, galaxolide, musketone, tonaride, tonylide, and nitromus screw. and the like.

There is no restriction|limiting in particular as a fragrance|flavor which has a terpene skeleton, According to the objective, it can select suitably, For example, geraniol (geraniol), nerol, linalool, citral, citronellol, menthol, mint. , citronellal, myrcene, α-pinene, β-pinene, limonene, terepineol, carvone, ionone (eg, β-ionone), camphene, bolneol, and the like.

There is no restriction|limiting in particular as a natural fragrance|flavor, It can select suitably according to the purpose, For example, orange oil, lemon oil, lime oil, petitgrain oil, citron oil, fairy tale oil, bergamot oil, lavender oil, lavandin oil, avian abies. S-U, anise oil, bay oil, boa 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, Essential oils such as cedar oil, vetiver oil, galbanam oil, oakmos oil, pine oil, camphor oil, sandalwood oil, soy sauce oil, turpentine, clove oil, clove oil, cassia oil, nutmeg oil, cananga oil, thyme oil, etc. have.

There is no restriction|limiting in particular as an animal fragrance|flavor, According to the objective, it can select suitably, For example, musk, musk, sagebrush, and ragweed incense are mentioned.

(E) component is 25 mass % or more of the fragrance component whose ClogP value is 5 or more with respect to the total mass of the fragrance composition as said (E) component, Preferably it is 30 mass % or more, More preferably, 35 mass % or more, More preferably, it is preferable to contain 40 mass % or more. (E) In a component, more favorable fragrance durability can be obtained as the compounding quantity of the fragrance|flavor component whose ClogP value is 5 or more is 25 mass % or more.

The type of perfume ingredient having a ClogP value of 5 or more is not particularly limited, but preferred examples include ambroxane (5.3), tonalide (6.3), hexyl salicylate (5.1), galaxolide (6.1), muscon (6.0), exaltolide (6.2), isoisuper (5.2), belt fix (acetylcedrene) (5.0), cedryl methyl ether (5.1), etc. (numbers in parentheses indicate ClogP values) . Among them, ambroxane, galaxolide, isoisuper, and tonalide are more preferable.

The ClogP value is a value expressed in the form of logarithmic logP with respect to the base 10 of the 1-octanol/water partition coefficient P indicating the ratio of equilibrium concentrations in 1-octanol and in water for a chemical substance. The ClogP value can be obtained by decomposing the chemical structure of a compound into its components by the f-value method (hydrophobic fragment constant method), and integrating the hydrophobic fragment constant·f value of each fragment (for example, Clog 3 Reference) See Manual DaylightSoftware 4.34, Albert Leo, David Weininger, Version 1, March 1994).

In general, since perfumes are more hydrophobic as the ClogP value increases, a perfume composition containing a large number of perfume components having a small ClogP value is more hydrophilic than a perfume composition containing a large amount of perfume components having a large ClogP value.

You may mix|blend the solvent generally used for a liquid softening agent composition, for example, the finishing agent composition for textiles, or a softening agent composition with a fragrance|flavor composition. As a solvent for perfume, acetin (triacetin), MMB acetate (3-methoxy-3-methylbutyl acetate), sucrose diacetate hexaisobutylate, ethylene glycol butyrate, hexylene glycol, dibutyl sebacate, dentyl 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, avolin (dimethyl phthalate), deltyl prime (isopropyl palmitate), dipropylene glycol (DPG), farnesene, dioctyl adipate, tributylline (glyceryl tributanoate), hydrolite -5 (1,2-pentanediol), propylene glycol diacetate, cetyl acetate (hexadecyl acetate), ethyl abietate, avaline (methyl abietate), Citroflex A-2 (acetyl triethyl citrate) ), Citroflex A-4 (tributylacetyl citrate), Citroflex No.2 (triethyl citrate), Citroflex No.4 (tributyl citrate), Dorafix (methyldihydroabier) tate), MITD (isotridecyl myristate), polylimonene (limonene polymer), and 1,3-butylene glycol.

The compounding quantity of a solvent is 0.1-30 mass % with respect to the gross mass of a fragrance|flavor composition, Preferably it is 1-20 mass %.

You may mix|blend the antioxidant generally used for a liquid softening agent composition, for example, the finishing agent composition for textiles, or a softening agent composition with a fragrance|flavor composition. As antioxidants for perfumes, 3,5-di-tert-butyl-4-hydroxytoluene (BHT), t-butyl-p-hydroxyanisole (BHA), p-methoxyphenol, β-naphthol, phenyl -α-naphthylamine, tetramethyldiaminodiphenylmethane γ-olizanol, vitamin E (α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol), 2,2'-ethylidenebis (4, 6-di-t-butylphenol), tris(tetramethylhydroxypiperidinol)/1/3 citrate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, quercetin and 4,4'-bis(α,α-dimethylbenzyl)diphenylamine. Preferably it 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 %.

(E) Although content of component is not specifically limited as long as it is the quantity which can achieve the compounding objective, 0.1-2 mass % with respect to the total mass of a liquid softening agent composition, Preferably it is 0.5-1.5 mass %. (E) The outstanding masking effect is acquired as content of a component is 0.1 mass % or more. (E) Separation stability of a liquid softening agent composition can be maintained more favorably as content of a component is 2 mass % or less.

[(F) component: highly branched cyclic dextrin]

(F) A component is mix|blended in order to provide the further improvement of stability (especially freeze recovery property) of a liquid softening agent composition, and deodorization and deodorization property to a textile product.

(F) The highly branched cyclic dextrin of the component means a glucan having an internally branched cyclic structural moiety and an externally branched cyclic structural moiety and has a weight average degree of polymerization in the range of 50 to 10,000.

A glucan having an internally branched cyclic structural moiety and an externally branched cyclic structural moiety is a substance also called highly branched cyclic dextrin or cluster dextrin.

A highly branched cyclic dextrin has a structure in which a plurality (for example, 100) of acyclic glucose chains (externally branched structural moieties) are bonded to one inner branched cyclic structure moiety.

The internally branched cyclic structural moiety refers to a cyclic structural moiety formed by an α-1,4-glucosidic bond and an α-1,6-glucosidic bond. The highly branched cyclic dextrin has an internally branched cyclic structure composed of about 10 to 100 glucose. That is, the degree of polymerization of the internally branched cyclic structure portion is in the range of 10 to 100.

The outer branching structural moiety refers to a non-cyclic structural moiety bonded to the inner branching annular structural moiety. The average degree of polymerization in the acyclic glucose chain constituting the externally branched structural moiety of the highly branched cyclic dextrin is 10 to 20. However, the degree of polymerization in one acyclic glucose chain may be 40 or more.

The weight average degree of polymerization of glucose in the highly branched cyclic dextrin is in the range of 50 to 10,000, specifically, in the range of 50 to 5000, more specifically, about 2500.

In addition, the molecular weight of the highly branched cyclic dextrin in this invention is the range of about 30,000-1 million.

Highly branched cyclic dextrin having such a structure and degree of polymerization (molecular weight) is α-cyclodextrin (degree of polymerization 6), β-cyclodextrin (degree of polymerization 7), γ-cyclodextrin, which are general cyclodextrins having a polymerization degree of 6 to 8 in glucose. (Polymerization degree 8) is a different substance.

The highly branched cyclic dextrin can be produced, for example, by using starch as a raw material to act on an enzyme called a branching enzyme.

Starch as a raw material consists of amylose in which glucose is linearly bound by α-1,4-glucosidic bonds, and amylopectin having a complexly branched structure by α-1,6-glucosidic bonds. Amylopectin is a macromolecule with many linked cluster structures.

The branch enzyme used is a glucan chain transferase widely found in animals, plants, and microorganisms. Branching enzymes act on the seams of the cluster structure of amylopectin and catalyze the reaction to cycle them.

Specific examples of highly branched cyclic dextrin include glucans having an internally branched cyclic structural moiety and an externally branched cyclic structural moiety and a polymerization degree in the range of 50 to 10000 described in Japanese Unexamined Patent Publication No. 8-134104. In the present invention, highly branched cyclic dextrin can be understood in consideration of the description of Japanese Patent Application Laid-Open No. 8-134104.

(F) A component can be manufactured as mentioned above, and it can obtain easily in a market. As a commercial item of highly branched cyclic dextrin, "Cluster Dextrin" (trademark) of Glico Eiyou Shokuhin Co., Ltd. is mentioned.

(F) A component may use a single type and may use multiple types together.

(F) Content of component is although it does not specifically limit as long as the compounding objective is attainable, Preferably it is 0.01-10 mass % with respect to the total mass of a liquid softening agent composition, More preferably, it is 0.05-5 mass %, More preferably is 0.1 to 2 mass %. When the content is 0.01% by mass or more, the blending effect (particularly, the effect of imparting deodorizing properties and deodorizing properties to fibers) can be sufficiently expressed. When the content is 10% by mass or less, the increase in the viscosity of the liquid softener composition can be suppressed, and usability such as dischargeability from a container and ease of putting into the inlet of a washing machine can be maintained favorably.

[(G) ingredient: preservative]

(G) A component is mix|blended mainly in order to maintain the antiseptic property during long-term storage.

(G) Specific examples of the component include isothiazolone-based organic sulfur compounds, benzisothiazoline-based organic sulfur compounds, benzoic acids, 2-bromo-2-nitropropane-1,3-diol, and the like. .

Examples of the isothiazolone-based organic sulfur compound include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolone, and 2-benzyl-3-isothiazolone. , 2-phenyl-3-isothiazolone, 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazolone-3- on, and mixtures thereof. Preferably, it is an aqueous mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, more preferably about 77% 5- It is an aqueous mixture of chloro-2-methyl-4-isothiazolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one (eg isothiazolone solution).

Examples of the benzisothiazoline-based organic sulfur compound include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and the like. , dithio-2,2-bis(benzmethylamide) and the like can also be used as the analog compound. These compounds can be used in any mixing ratio. Among these, 1,2-benzisothiazolin-3-one is particularly preferable.

Examples of benzoic acids include benzoic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, and benzyl paraoxybenzoate.

(G) A component is a well-known substance, it can obtain easily in a market, or can prepare it.

(G) A component may use a single type and may use multiple types together.

(G) Although content of a component is not specifically limited as long as a compounding objective can be achieved, Preferably it is 0.0001-1 mass % with respect to the gross mass of a liquid softening agent composition.

[(H)Component: Functional Capsule]

(H) Component is mix|blended in order to provide the various functions resulting from the core substance contained in the capsule to a liquid softening agent composition.

The functional capsule is composed of a core material and a wall material covering the core material.

As the core material, those generally used as a capsule encapsulation material in the field of liquid softeners may be used without particular limitation. Specific examples include perfumes, essential oils, brighteners, insect repellents, silicones, waxes, flavoring agents, vitamins, skin care agents, enzymes, probiotics, dyes, pigments, perfume precursors, cooling agents, warming agents, attractants such as pheromone, antibacterial agents, bleaching agents , a flavoring agent, a sweetener, a wax, a pharmaceutical, a fertilizer, a herbicide, and the like.

A core substance may be used individually by 1 type, and may combine 2 or more types suitably.

As the wall material, those generally used as encapsulating materials in the field of liquid softening agent compositions can be used without particular limitation. Specific examples include natural polymers such as gelatin and agar, oily film-forming substances such as oils and fats and waxes, and synthetic polymers such as polyacrylic acid, polyvinyl, polymethacrylic, melamine, and urethane. These 1 type can be used individually or 2 or more types can be used together suitably.

Specific examples of the encapsulated perfume having a perfume as the core material include BLUEFLOWERPOP "FFMHN2814" manufactured by Filmenich, GREEN BREEZE CAPS, GREENBREEZE DeoB, ORCHARD GARDEN CAPS, RAINBOW CAPS, VELVET UP, AURORACAPS, and COSMICCAPS manufactured by Divoan. and UNICAP101 and UNICAP503 manufactured by IFF Corporation.

As a specific example of the cooling capsule which uses a cooling agent as a core material, MultiSal SalCool, HydroSal FreshCool, SalS here SalCool by SALVONA Technologies, Neoage AROMA-C by Nikka Chemical Co., Ltd., etc. are mentioned.

As a specific example of the warming capsule which uses a warming agent as a core substance, Ricken resin RMC-TO by Miki Riken Co., Ltd., Hydrosal Heat by SALVONA Technologies, etc. are mentioned.

As another specific example, Miki Riken Co., Ltd. Rickenresin NFHO-W (antibacterial effect), Rickenresin RMC-HBP (insect repellent effect), RMC-PT (insect repellent effect), etc. are mentioned.

It is preferable that the average particle diameter of a functional capsule is 10-30 micrometers. The functional capsule which has the said particle diameter is excellent in the adsorption property to clothes, and can be disperse|distributed stably in a liquid softening agent composition.

(H) A component is a well-known substance, it can obtain easily in a market, or it can prepare it.

(H) A component may use a single type and may use multiple types together.

(H) Although content of a component is not specifically limited as long as a compounding objective can be achieved, Preferably it is 0.0001-1 mass % with respect to the gross mass of a liquid softening agent composition.

[water]

The liquid softening agent composition is preferably an aqueous composition containing water.

As water, tap water, ion-exchange water, pure water, distilled water, etc. can be used. Among them, ion-exchanged water is preferable.

Although the content of water is not specifically limited, Preferably it is 50 mass % or more, More preferably, it is 60 mass % or more with respect to the total mass of a liquid softening agent composition. If the content is 50% by mass or more, handling properties will be better.

[pH of liquid softener composition]

Although the pH of a liquid softening agent composition is not specifically limited, From a viewpoint of suppressing the hydrolysis of the ester group contained in the molecule|numerator of (A) component by the progress of a storage day, pH in 25 degreeC in the range of 1-6. It is preferable to adjust, and it is more preferable to adjust in the range of 2-4. Any inorganic or organic acid and alkali can be used as the pH adjuster.

[Viscosity of liquid softener composition]

Although the viscosity of a liquid softening agent composition is not specifically limited unless the usability is impaired, It is preferable that the viscosity in 25 degreeC is less than 800 mPa*s. Considering the increase in viscosity with the lapse of storage days, the viscosity at 25°C of the liquid softener composition immediately after production is more preferably less than 500 mPa·s, and still more preferably less than 300 mPa·s. When it exists in such a range, usability, such as handling property at the time of inject|throwing-in to a washing machine, is favorable.

The viscosity of the liquid softening agent composition can be measured using a B-type viscometer (manufactured by TOKIMEC).

[Manufacturing method]

A liquid softening agent composition can be manufactured by a well-known method, for example, the method similar to the manufacturing method of the conventional liquid softening agent composition using a cationic surfactant as a main ingredient.

For example, (A) component, (D) component, the oil phase containing component (E), and the aqueous phase containing component (G) are mixed under the temperature conditions more than melting|fusing point of (A) component to prepare an emulsion, , It can manufacture by adding and mixing another component to the obtained emulsion after that (B) component, (C)component, and as needed.

Moreover, (B)component, (C)component, and (D)component are not limited to the addition method of the said base material.

[How to use the liquid softener composition]

The processing method in particular of the textile product using the liquid softening agent composition is not restrict|limited, It can use similarly to the conventional liquid softening agent. For example, a method of dissolving a liquid softening agent composition in rinsing water in the rinsing step of laundry to perform treatment, or dissolving a liquid softening agent composition in water in a container such as a basin, and placing a textile product for immersion treatment have. In either case, it is diluted to an appropriate concentration and used, but the bath ratio (weight ratio of the treatment liquid to the textile product) is preferably 3 to 100 times, particularly preferably 5 to 50 times. Specifically, the concentration of the component (A) is preferably 0.01 ppm to 1000 ppm, more preferably 0.1 ppm to 300 ppm with respect to the total amount of use.

The type of textile products that can be treated with the liquid softener composition is not particularly limited, and examples thereof include clothes, curtains, sofas, carpets, towels, handkerchiefs, sheets, and pillow covers. The material may also be natural fibers, such as cotton, silk, and wool, or chemical fibers, such as polyester.

(Example)

Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.

In addition, in an Example and a comparative example, the compounding quantity of each component shows all mass % (Except when there exists a designation, conversion of pure part).

[(A) component: cationic surfactant]

The following A-1 was used.

A-1: The cationic surfactant described in the Example (Synthesis Example 1) of Unexamined-Japanese-Patent No. 2019-163559. A-1 is a compound represented by the general formulas (A1-4), (A1-5) and (A1-6) (wherein R ⁹ is an alkyl group or alkenyl group having 15 to 17 carbon atoms) with dimethyl sulfuric acid It is a composition comprising a quaternized with.

[(B) component: divalent water-soluble metal salt]

The following B-1 was used.

B-1: Zinc sulfate (Supplier: Mitsubishi Kinzoku Kogyo Co., Ltd. Trade name: Zinc sulfate heptahydrate)

[(C)component: aminocarboxylic acid compound and ricinoleic acid]

The following C-1 to C-3 were used.

C-1: methylglycine diacetic acid trisodium "MGDA" (manufactured by BASF)

C-1 is a compound in general formula (I), wherein A ^I is CH ₃ , M ^I disodium, m ^I is 0, and n ^I is 0.

C-2: ricinoleic acid (supplier: Tokyo Kasei Kogyo Co., Ltd. trade name: ricinoleic acid)

C-3: citric acid (supplier: Lion Co., Ltd. trade name: citric acid)

C-3 did not correspond to any of the aminocarboxylic acid compound and ricinoleic acid, and was used in the comparative example.

[(D) component: nonionic surfactant]

The following D-1 was used.

D-1: Polyoxyethylene isotridecyl ether EO 60 moles (equivalent to an average EO 60 mole adduct of primary isotridecyl alcohol (C13)) (Supplier: Lion Corporation. Trade name: TA600)

[(E) ingredient: fragrance not encapsulated]

Free perfume compositions E-1 to E-2 having compositions shown in the following tables were used. The value of the perfume component in the table is the content (mass %) with respect to the total mass of the perfume composition.

E-1

E-2

[(F) component: highly branched cyclic dextrin]

The following F-1 was used.

F-1: Highly branched cyclic dextrin (manufactured by Glico Eiyou Shokuhin Co., Ltd., brand name: Cluster Dextrin)

[(G) ingredient: preservative]

The following G-1 was used.

G-1: isothiazolone solution (Dow Chemical Nippon Co., Ltd. trade name: Caison CG-ICP)

[(H)Component: Functional Capsule]

The following H-1 to H-2 were used.

H-1: Encapsulated Fragrance (Supplier: Givaudan Co., Ltd. Product Name: GREENBREEZE DeoB)

H-2: Encapsulated Fragrance (Supplier: Givaudan Co., Ltd. Product Name: VELVET UP)

[Method for preparing liquid softener composition]

The liquid softening agent composition which has a composition shown in Table 1 of a postscript was prepared. In Table 1, the unit of the numerical value of each component is mass % with respect to the total mass of a liquid softening agent composition.

"(B+C)/A" in Table 1 shows mass ratio with respect to (A) component of (B)component and (C)component sum total (B+C).

"(B+C)/D" shows mass ratio with respect to (D)component of (B)component and (C)component sum total (B+C).

The liquid softening agent composition was prepared by the following procedure using a glass container (inner diameter 100 mm, height 150 mm) and a stirrer (Ajita SJ type, Shimadzu Corporation make).

First, (A) component and a part of (D)component, (E)component were mixed and stirred, and the oil phase mixture was obtained.

On the other hand, (G)component was melt|dissolved in the ion-exchange water for balance, and the aqueous phase mixture was obtained. The mass of the ion-exchanged water for balance is the balance obtained by subtracting the total amount of the oil phase mixture, (B) component, (C) component, (D) component, (F) component, and (H) component from 980 g. It was considerable.

Next, the aqueous phase mixture heated to the melting point of the component (A) or higher was placed in a glass container and stirred, while the aqueous mixture heated to the melting point or higher of the component (A) was divided into two portions and added, followed by stirring. The division ratio of the aqueous phase mixture was set to 30:70 (mass ratio), and stirring was performed at a rotational speed of 1,000 rpm for 3 minutes after the first addition of the aqueous mixture and for 2 minutes after the second addition of the aqueous mixture.

Then, (B) component, (C) component, the remainder of (D) component, (F) component, and (H) component are added, and hydrochloric acid (reagent 1 mol/L, Kanto Ka) is added as needed. Chemical) or sodium hydroxide (reagent 1 mol/L, Kanto Chemical) is added in an appropriate amount to adjust the pH to 3.0 (25°C), and ion-exchanged water is added so that the total mass becomes 1,000 g, the intended liquid softening agent composition got

[Evaluation of liquid softener composition]

The "deodorizing effect" "usability" and "freeze recovery property" of the prepared liquid softening agent composition were evaluated.

[Inhibition (deodorization) effect of indoor drying odor]

Old towels, which were concerned about the dry smell, were recovered from ordinary households and used as evaluation cloths.

The evaluation cloth was processed with the liquid softening agent composition, and after spin-drying|dehydration, it dried (indoor drying) in the room (25 degreeC, relative humidity 100%RH) for 6 hours. The smell of the evaluation cloth after indoor drying was sensory-evaluated according to the following evaluation criteria. Evaluation was performed by 6 expert panelists.

<Evaluation criteria>

0 points: No off-flavor at all.

1 point|piece: Off-flavor is felt to a barely perceptible level.

2 points|pieces: The off-flavor is felt weakly.

3 points|pieces: The off-flavor is felt a little strong.

4 points|pieces: The off-flavor is felt strongly.

5 points|pieces: The off-flavor is felt strongly.

The deodorizing effect of the liquid softening agent composition was judged according to the following criterion based on the average score (computed to the first decimal place) of six expert panelists. A result is shown in the "deodorization effect" column of Table 1. ○ or ◎ was judged as pass in terms of product value.

<Criteria for Judgment>

◎: less than 2.0 points

○: 2.0 points or more and less than 2.5 points

△: 2.5 points or more and less than 3.0 points

×: 3.0 points or more

[Usability]

400 mL of the liquid softening agent composition was filled in the container of the commercially available fiber treatment agent (the container of "Sofran Premium Deodorization" by Lion Corporation). The usability of the liquid softening agent composition after filling was evaluated according to the following evaluation criteria from the viewpoints of "viscosity increase or pourability when measuring in a measuring cap" and "easiness of refilling from a pouch to a bottle". Evaluation was performed by 5 expert panelists.

<Evaluation Criteria>

3 points|pieces: It can measure without a problem, and can refill.

2 points|pieces: Although a viscosity rise is seen, it can measure without a problem, and can refill.

1 point|piece: A remarkable viscosity rise is seen, and it is difficult to measure or it cannot measure, or it is difficult to refill, or it cannot refill.

The usability of the liquid softening agent composition was judged according to the following criterion based on the average score (computed to the first decimal place) of five expert panelists. A result is shown in the "Usability" column of Table 1. ○ or ◎ was judged as pass in terms of product value.

<Criteria for Judgment>

◎: 2.5 points or more

○: 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

[Freeze resilience]

What put 80 mL of liquid softening agent composition into a lightweight glass bottle (PS-No.11, the product made in Tanuma Glass Kogyo Co., Ltd.) and sealed tightly was made into the sample for evaluation.

The evaluation sample was subjected to an endurance test in which a cycle of holding (freezing) at -15°C for 40 hours and then holding (dissolving) at 25°C for 8 hours was repeated three times.

The liquid state in 25 degreeC of the sample for evaluation after an endurance test was visually observed, and the following evaluation criteria evaluated. Evaluation was performed by 8 expert panelists.

<Evaluation criteria>

5: There is sufficient fluidity|liquidity, and a change is hardly recognized compared with before the durability test.

4: Although a raise of a viscosity is confirmed compared with before the durability test, fluidity|liquidity is sufficient.

3: A viscosity increase is confirmed compared with before the durability test, but fluidity is confirmed.

2: Compared with before the durability test, the viscosity rises, and there is not much fluidity|liquidity.

1: Compared with before the durability test, a viscosity rises remarkably, and there is little fluidity|liquidity.

0: Compared with before the durability test, the viscosity remarkably rises, and there is no fluidity|liquidity at all.

The freeze recovery property of the liquid softener composition was judged according to the following criteria by the average score (computed to the first decimal place) of 8 expert panelists. A result is shown in the "freeze recovery property" column of Table 1. ○ or ◎ was judged as pass in terms of product value.

<Criteria for Judgment>

◎: 4.0 or higher

○: 3.0 points or more and less than 4.0 points

△: 2.0 points or more and less than 3.0 points

×: less than 2.0 points

(Industrial Applicability)

The present invention is applicable in the field of softening agents.

Claims (6)

As a liquid softening agent composition, following (A)-(D) component:
(A) a compound selected from the group consisting of an amine compound having 1 to 3 hydrocarbon groups having 10 to 26 carbon atoms in its molecule, which may be split by an ester group and/or an amide group, a salt thereof, and a quaternary product thereof;
(B) water-soluble salts of divalent metals;
(C) a compound selected from the group consisting of aminocarboxylic acid compounds represented by formulas (I) to (IV), ricinoleic acid, and salts thereof;

(During the meal,
A ^I is a linear or branched alkyl group having 8 to 22 carbon atoms, a sulfo group, an amino group, a hydroxyl group, a hydrogen atom, or COOM ^I ;
M ^I may be the same or different from each other, and is selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group, and an alkanolamine;
m ^I and n ^I are each an integer of 0 to 2.)

(During the meal,
X ^II-1 to X II ^-4 may be the same or different, and are selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group, and an alkanolamine;
Q ^II is a hydrogen atom or a straight-chain or branched alkyl group having 8 to 22 carbon atoms,
R ^II is a hydrogen atom or a hydroxyl group,
n ^II is 0 or 1.)

(During the meal,
R ^III is a straight-chain or branched alkyl or alkenyl group having 8 to 22 carbon atoms,
A ^III is H, a methyl group or (CH ₂ )m ^III -COOX ^III ,
m ^III is 1-3,
X ^III is H, alkali metal, alkaline earth metal, alkanolamine or NH ₄ ,
n ^III is 1-3.)

(During the meal,
X ^IV is a hydrogen atom, an alkali metal or an alkaline earth metal,
n ^IV is 1 or 2.), and
(D) nonionic surfactant
including,
Mass ratio ([B+C]/A) with respect to (A) component of (B)component and (C)component sum total is 0.01-0.5, and
(B) Mass ratio ([B+C]/D) with respect to (D)component of a component and (C)component sum total is 0.1-4, The liquid softening agent composition characterized by the above-mentioned. The method of claim 1,
(B) The liquid softening agent composition whose component is a water-soluble zinc salt or a water-soluble copper salt. 3. The method according to claim 1 or 2,
(C) The liquid softening agent composition whose component is the compound represented by Formula (I), its salt, or ricinoleic acid or its salt. 4. The method according to any one of claims 1 to 3,
(B) The liquid softening agent composition whose mass ratio ([B+C]/A) with respect to (A) component of a component and (C)component sum total is 0.25-0.45. 5. The method according to any one of claims 1 to 4,
(B) The liquid softening agent composition whose mass ratio ([B+C]/D) with respect to (D)component of (B)component and (C)component sum total is 1-2. 6. The method according to any one of claims 1 to 5,
(D) The liquid softening agent composition whose component has a C10-18 alkyl group, and is polyoxyethylene alkylether whose average added mole number of ethylene oxide is 20-80 mol.