JP6668125B2 - Liquid softener composition - Google Patents

Description

  The present invention relates to a liquid softener composition for imparting softness to textiles suitable for home use.

  Laundry is one of the household tasks that are indispensable to family life, and softeners are often used as finishing agents for adjusting the texture of textiles after washing. As a base material used in current softeners, cationic surfactants having an intramolecular ester group are the main softeners for the purpose of decomposing quickly even when discharged into the environment and reducing the burden on the environment. Used as an agent. It is well known that ester groups are easily hydrolyzed in water, and it is also well known that when a soft base having an ester group is hydrolyzed in a liquid softener composition, quality such as soft performance and storage stability tends to deteriorate. It is.

  Patent Literature 1 discloses a softener composition containing a rapid biodegradable quaternary ammonium softener having an ester group in the molecule. It is disclosed that by adjusting the pH of the softener composition, the hydrolysis of the ester group of the softener is suppressed. Patent Literature 2 discloses that a flexible base having an ester group in the molecule contains a higher alcohol alkylene oxide-added nonionic surfactant having a relatively large addition mole number of alkylene oxide and a fatty acid ester. It is disclosed that by defining the mass ratio of the two, the hydrolyzability of the ester group of the flexible base is suppressed. Patent Document 3 discloses that the hydrolyzability of the ester group of the flexible base is suppressed by including the specific fatty acid ester and the specific flavor in the flexible base having an ester group in the molecule. It has been disclosed.

JP-A-63-6168 JP 2012-82538 A JP 2012-233281 A

  In the softener compositions of Patent Documents 1, 2, and 3, the effect of suppressing hydrolysis of the soft base having an ester group in the molecule is not sufficient. Therefore, for example, the effect of imparting flexibility after storage was not sufficient.

  The present invention provides a liquid softener composition which can maintain a high softening effect on textile products and has a viscosity suitable for handling.

The present invention
(A) a tertiary amine or a neutralized or quaternized product thereof (hereinafter, referred to as a component (A)) having an ester group and having at least one hydrocarbon group having 9 to 23 carbon atoms in a molecule; From 10% by weight to 30% by weight,
(B) An ester compound of a fatty acid having 2 to 20 carbon atoms and a monohydric alcohol having 1 to 20 carbon atoms, wherein an ester compound having a total carbon number of 18 to 28 [hereinafter, referred to as component (B) 0.1% to 5% by mass,
(C) an oil agent other than the component (B) [hereinafter referred to as the component (C)] in an amount of from 0.1% by mass to 5% by mass;
The present invention relates to a liquid softener composition containing (D) a cationic polymer (hereinafter, referred to as a component (D)) in an amount of from 0.1% by mass to 1.5% by mass, and water.

  The liquid softener composition of the present invention can stably maintain a high softening effect on fiber products. Further, the liquid softener composition of the present invention has a viscosity suitable for handling.

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

As the component (A), (A1) a tertiary amine compound represented by the following general formula (1) and an acid salt thereof (hereinafter, referred to as a component (A1)); One or more compounds selected from the quaternized tertiary amine compounds [hereinafter, referred to as component (A2)] are exemplified.
^{_{[R 1 -C (= O) -O-}} (C p H 2p O) r -C q H 2q ] ^{_{m N (R 2) 3-}} m (1)
Wherein, ^{R 1} is a hydrocarbon group having 11 to 23 carbon atoms, ^{R 2} is a hydrocarbon group having 1 to 3 carbon atoms, and _{HO- (C p H 2p O)} r -C q H 2q group M is a number of 1 or more, 3 or less, p and q are numbers of 2 or 3, and r is a number of 0 or more and 5 or less. ^{If R 1,} R ₂ in the same _{molecule, HO- (C p H 2p O} ) r -C q H 2q group, p, q, r there are a plurality, they may be the same or different. ]

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

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

Alkenyl groups include cis and trans forms. Regarding R1, specific examples of the ratio of the cis-form to the trans-form include a cis-form / trans-form = 30/70 or more and 99/1 or less in molar ratio. From the viewpoint of availability of the alkenyl group, the ratio is preferably 50/50 or more and 97/3 or less. In the present invention, the ratio between the cis form and the trans form can be calculated from the integral ratio of ¹ H-NMR.

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

A part or all of the tertiary amine compound represented by the general formula (1) as the component (A1) may be present in the form of an acid salt depending on the pH of the liquid softener composition.
The acid when present as an acid salt of a tertiary amine compound includes an inorganic acid or an organic acid. As specific examples of the inorganic acid, hydrochloric acid and sulfuric acid can be used. Specific examples of the organic acid include a monovalent or polyvalent carboxylic acid having 1 to 10 carbon atoms or a monovalent or polyvalent sulfonic acid having 1 to 20 carbon atoms. More specifically, methyl sulfate, ethyl sulfate, p-toluenesulfonic acid, (o-, m-, p-) xylenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, formic acid, glycolic acid, citric acid, benzoic acid And salicylic acid.

The method for producing the amine compound represented by the general formula (1), which is the component (A1), is not particularly limited. For example, an esterification reaction between an alkanolamine compound represented by the following general formula (2) and a fatty acid, or It can be obtained by a transesterification reaction with a fatty acid ester.
_{(HO-C q H 2q)} m 'N (R 2') 3-m '(2)
[In the formula, R ^{2 ′} is a hydrocarbon group having 1 to 3 carbon atoms, m ′ is a number 1 to 3 and q represents the same meaning as in the general formula (1). ]

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

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

  The quaternized product of the compound represented by the general formula (1), which is the component (A2), can be obtained by a quaternization reaction using the amine compound represented by the general formula (1) and an alkylating agent. . Examples of the alkylating agent include methyl chloride, dimethyl sulfate, and diethyl sulfate. As an example of the quaternization reaction, for example, the methods described in [0017] to [0023] of JP-A-7-138211 and the production method described in JP-A-11-106366 can be applied. .

  The component (A) may be a single compound or a mixture of two or more compounds. When the component (A) is a mixture of two or more compounds, a mixture in which the number average number of m in the general formula (1) is 1.2 or more and 2.5 or less can be used. In light of softening of the textile, the number average of m is preferably equal to or greater than 1.3, more preferably equal to or greater than 1.4, and is preferably equal to or less than 2.0, and more preferably equal to or less than 1.9. It is.

  As the component (A), a mixture containing the component (A1) and the component (A2) can be used. When the component (A) is a mixture containing the component (A1) and the component (A2), the mass ratio of the component (A1) to the component (A2) is such that the component (A1) / the component (A2) = 1/99 or more. Preferably, 3/97 or more is more preferable, 5/95 or more is more preferable, and 50/50 or less is preferable, 40/60 or less is more preferable, and 35/65 or less is more preferable.

[Component (B)]
The component (B) is an ester compound of a fatty acid having 2 to 22 carbon atoms and a monohydric alcohol having 1 to 20 carbon atoms, wherein the total number of carbon atoms is 18 to 28.

  Fatty acids are linear monocarboxylic acids. Preferred are fatty acids selected from acetic acid, caprylic acid, isooctanoic acid, 2-ethylhexanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and arachidic acid. These fatty acids are more preferably combined with the aliphatic alcohol described below.

  As the monohydric alcohol, a primary alcohol is preferable. Specifically, methanol, ethanol, propanol, butanol, amyl alcohol, hexyl alcohol, octanol, nonanol, decanol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, penta alcohol Decyl alcohol, cetanol, palmitoleyl alcohol, 1-heptadecanol, stearyl alcohol, isostearyl alcohol, elaidyl alcohol, oleyl alcohol, linoleyl alcohol, elide linoleyl alcohol, linolenyl alcohol, elide linolen alcohol, Ricinoleyl alcohol, nonadecyl alcohol, arachidyl alcohol, heneicosanol, behenyl alcohol, erucyl alcohol, rig Seryl alcohol, ceryl alcohol, 1-heptacosanol and montanyl alcohol include methanol, ethanol, propanol, isopropanol, n-octanol, isooctanol, 2-ethylhexyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentane Decyl alcohol, cetanol, palmitoleyl alcohol, 1-heptadecanol, stearyl alcohol, isostearyl alcohol are preferred.

The component (B) preferably includes an ester compound selected from the following (i) and (ii). These can be used in combination of one or more.
(I) a fatty acid having 2 or more, preferably 6 or more, and 10 or less, preferably 8 or less carbon atoms and a monovalent monovalent having 12 or more, preferably 14 or more, and 20 or less, preferably 18 or less. An ester compound with an alcohol, wherein the total number of carbon atoms is 16 or more and 24 or less; (ii) a fatty acid having 10 or more, preferably 12 or more, and 22 or less, preferably 14 or less carbon atoms and 1 or more carbon atoms, And an ester compound with a monohydric alcohol having 5 or less, preferably 3 or less carbon atoms, wherein the ester compound has a total of 14 or more and 22 or less.

More specifically, the compound (i) includes a fatty acid selected from acetic acid, isooctanoic acid and 2-ethylhexanoic acid, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetanol, palmitoleyl alcohol, An ester compound with a monohydric alcohol selected from 1-heptadecanol, stearyl alcohol and isostearyl alcohol is exemplified.
More specifically, as the compound (ii), more specifically, a fatty acid selected from lauric acid, myristic acid, palmitic acid, stearic acid and arachidic acid and a monohydric alcohol selected from methanol, ethanol and isopropanol are used. Ester compounds are exemplified.

[(C) component]
The component (C) is an oil agent other than the component (B).
The oil agent used in the present invention is used to suppress an increase in viscosity after storage, and also has an effect of suppressing hydrolysis of the component (A).
Examples of the component (C) include a hydrocarbon having 14 or more carbon atoms, an aliphatic alcohol having 8 to 22 carbon atoms, and an ester compound other than the component (B). The hydrocarbon group preferably includes octadecane, liquid paraffin, and the aliphatic alcohol includes stearyl alcohol. Examples of the ester other than the component (B) include an ester compound of a polyhydric alcohol having 2 to 10 carbon atoms having 2 to 6 hydroxy groups and a fatty acid having 12 to 24 carbon atoms. It is preferable to use this ester compound in combination, because the hydrolysis of (A) is further suppressed. Preferred examples of the ester compound include glycerin fatty acid ester, pentaerythritol fatty acid ester, and sorbitan fatty acid ester. From the viewpoint of improving the flexibility performance, as the fatty acid of the ester compound, palmitic acid, stearic acid, and a mixture thereof are preferable.

[(D) component]
The component (D) is a cationic polymer.
The component (D) is preferably a cationic polymer having a structural unit derived from a polymerizable monomer having an amine or a quaternary ammonium group.
The component (D) is a compound represented by the following general formula (D1), a monomer unit derived from at least one compound selected from an acid salt and a quaternary salt thereof (hereinafter, referred to as a monomer unit (D1)). Containing cationic polymers are more preferred.

[In the general formula (D1), R ^1d and R ^2d each independently represent a hydrogen atom or a methyl group, and R ^3d represents —C (O) OM (M is a hydrogen atom or an alkali metal atom) or a hydrogen atom. Is shown. X ^{is, -C (O) O-R} 6d -, - C (O) NR 7d -R 8d - or -CH ₂ - shows a. R ^4d has the general formula (D1 ′) when X is —CH ₂ —.

In the other cases, X represents an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group having 1 to 3 carbon atoms. R ^5d represents an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group having 1 to 3 carbon atoms, or a hydrogen atom. R ^6d and R ^8d each independently represent an alkylene group having 1 to 4 carbon atoms, and R ^7d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

Among the compounds represented by the general formula (D1) from which the monomer unit (D1) is derived, compounds in which X in the general formula (D1) is —C (O) O—R ^6d — include acrylic acid (Or methacrylic acid) N, N-dimethylaminomethyl, acrylic acid (or methacrylic acid) N, N-dimethylaminoethyl, acrylic acid (or methacrylic acid) N, N-dimethylaminopropyl, acrylic acid (or methacrylic acid) N, N-dimethylaminobutyl, acrylic acid (or methacrylic acid) N, N-diethylaminomethyl, acrylic acid (or methacrylic acid) N, N-diethylaminoethyl, acrylic acid (or methacrylic acid) N, N-diethylaminopropyl, N, N-diethylaminobutyl acrylate (or methacrylic acid) and the like.

Further, among the compounds represented by the general formula (D1), compounds in which X in the general formula (D1) is —C (O) NR ^7d —R ^8d — include N, N-dimethylaminopropylacrylic acid (Or methacrylic acid) amide, N, N-dimethylaminomethylacrylic (or methacrylic) amide, N, N-dimethylaminoethylacrylic (or methacrylic) amide, N, N-dimethylaminobutylacrylic (or (Methacrylic acid) amide and the like.

When X in the general formula (D1) is —CH ₂ —, R ^4d is a group represented by the general formula (D1 ′). Such compounds include diallylamine and the like.

  As the compound represented by the general formula (D1), an acid salt or a quaternary salt thereof can be used. Examples of the acid salt include a neutralized salt of the compound represented by the general formula (D1) with an inorganic acid such as hydrochloric acid or sulfuric acid, and a neutralized salt with various organic acids. Examples of the quaternary salt include a quaternary salt obtained by quaternizing a compound represented by the general formula (D1) with an alkyl halide having 1 to 3 carbon atoms or an alkyl sulfuric acid having 1 to 3 carbon atoms. . As quaternary salts, N, N, N-trimethyl-N- (2-methacryloyloxyethyl) ammonium chloride, N, N-dimethyl-N-ethyl-N- (2-methacryloyloxyethyl) ammonium ethyl sulfate, diallyldimethyl Ammonium chloride. These compounds are marketed, for example, by MRC Unitech under the trade names QDM and MOEDES.

  Among the compounds represented by the general formula (D1), more preferred compounds are N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl acrylate, and acrylic acid One or more selected from N, N-dimethylaminomethyl.

  The component (D) according to the present invention includes a monomer unit (D1) and a monomer unit derived from a polymerizable vinyl compound copolymerizable with the compound represented by the general formula (D1) [hereinafter, referred to as a monomer unit (D2). ] May be used.

  Examples of the monomer unit (D2) include a monomer unit derived from a compound represented by the following general formula (D2).

[Wherein, R ^11d and R ^12d each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and Y represents an aryl group, —OC (O) —R ^13d , —C (O ) ^O-(shown R _14d -O) ^{n -R 15d,} or ^-C a ^(O) NR 16d ^{-R 17d.} R ^13d , R ^15d , and R ^17d each independently represent a linear, branched, or cyclic alkyl or alkenyl group having 1 to 22 carbon atoms, or an arylalkyl group having 6 to 14 carbon atoms in total. R ^14d represents an alkylene group having 2 or 3 carbon atoms, n represents a number of 0 to 50, and R ^16d represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

Y in the general formula (D2) is _{^{-C (O) O- (R 14d}} -O) n -R 15d is preferred.
In Y of _{^{-C (O) O- (R 14d}} -O) n -R 15d, R 15d is 8 or more carbon atoms, further more than 10, and, 18 or less, further 14 or less alkyl groups are preferred. R ^14d is preferably ethylene. n is a number of 0 or more, preferably 20 or less, more preferably 10 or less. n is more preferably 0.

  Specific polymerizable vinyl compounds represented by the general formula (D2) and copolymerizable with the starting material of the monomer unit (D1) include alkyl groups having 1 or more, preferably 8 or more, and 22 or less carbon atoms. Alkyl acrylate or methacrylic acid alkyl ester, which is preferably 14 or less, is preferable in that the effects of the present invention can be more enjoyed.

  Examples of the polymerizable vinyl compound (hereinafter, referred to as other polymerizable compounds) copolymerizable with the starting material of the monomer unit (D1) other than the compound of the general formula (D2) include (1) vinyl alcohol and (2) hydroxyethyl Polyhydric alcohols such as (meth) acrylates or (meth) acrylamides having a hydroxyalkyl group having 1 to 22 carbon atoms such as (meth) acrylate and hydroxypropyl (meth) acrylamide, and (3) glycerin (meth) acrylate (4) diacetone (meth) acrylamide, (5) N-vinyl cyclic amide such as N-vinylpyrrolidone, (6) N- (meth) acryloylmorpholine, (7) vinyl chloride, (8) acrylonitrile, (9) (meth) acrylic acid, maleic acid, itaconic acid, styrene Vinyl compounds having a carboxyl group such Nkarubon acid, (10) 2-acrylamido-2-methylpropane sulfonic acid, vinyl compounds having a sulfonic acid group such as styrenesulfonic acid, etc. are exemplified.

  The component (D) is (1) a compound selected from the compound represented by the general formula (D1), an acid salt thereof and a quaternary salt thereof, specifically, N, N-dimethylaminoethyl methacrylate, methacrylic acid. A cationic homopolymer of a monomer selected from N, N-dimethylaminomethyl, N, N-dimethylaminoethyl acrylate, and N, N-dimethylaminomethyl acrylate; and (2) represented by the general formula (D1) At least one compound selected from the group consisting of a compound, an acid salt and a quaternary salt thereof, specifically, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminomethyl methacrylate, N, N-acrylate acrylate. A monomer selected from dimethylaminoethyl and N, N-dimethylaminomethyl acrylate, and a compound represented by the general formula (D2), specifically an alkyl group Prime cationic copolymer obtained by copolymerization of one or more compounds selected from 8 to 14 alkyl acrylate esters and alkyl methacrylate, cationic polymers selected from the preferred.

  As the component (D), a copolymer having a monomer unit (D1) and a monomer unit (D2), among which a monomer unit derived from the compound represented by the general formula (D2) is preferable in terms of the softening effect. Such a copolymer preferably has a monomer unit (D1) / monomer unit (D2) molar ratio of 20/80 or more and 99/1 or less, more preferably 50/50 or more and 95/5 or less. Is more preferably 70/30 or more and 95/5 or less. In addition, the total of the monomer unit (D1) and the monomer unit (D2) is preferably 60 mol% or more, more preferably 80 mol% or more in all monomer units of the component (D) from the viewpoint of the effect of improving flexibility. , 100 mol% or less. The ratio of the monomer units may be the molar ratio of the polymerizable compounds of the general formula (D1) and the general formula (D2) used during the polymerization.

  The weight average molecular weight (Mw) of the component (B) is preferably 2,000 or more, more preferably 3,000 or more, still more preferably 6,000 or more, and still more preferably 12,000 or more, from the viewpoint of the softening effect. And preferably 2,000,000 or less, more preferably 1,500,000 or less, still more preferably 100,000 or less, and still more preferably 60,000 or less. The ratio Mw / Mn of Mw to Mn (number average molecular weight) is preferably 1.0 or more, more preferably 1.5 or more, and preferably 40 or less, more preferably 35.

  In addition, Mw, Mn, and Mw / Mn of the component (D) of the present invention use values measured by gel permeation chromatography (GPC). As the eluent, any of water, alcohol, chloroform, dimethylformamide, tetrahydrofuran, acetonitrile and a solution obtained by combining these solvents is used. If the polymer of the component (D) is relatively hydrophilic, polyethylene glycol is used. To be used as a standard, the molecular weight is calculated in terms of polyethylene glycol (hereinafter, also referred to as PEG). In the case of relatively hydrophobic, polystyrene is used as a standard, and thus, in terms of polystyrene (hereinafter sometimes referred to as PSt). ).

That is, when the polymer to be measured is considered to be relatively hydrophilic with a large proportion of the monomer unit (D1), use a mixed solvent of (1% acetic acid / ethanol): water = 3: 7 (mass ratio). Using a prepared 50 mmol / L solution of LiBr as a solvent, two GPC columns for polar solvent “α-M (manufactured by Tosoh Corporation)” are used in series, and the molecular weight is calculated based on the molecular weight in terms of polyethylene glycol (measurement method A). . If the polymer is considered to be relatively hydrophobic, a 1 mmol / L-CHCl ₃ solution of Farmin DM20 (manufactured by Kao Corporation) is used to prepare an organic solvent GPC column “K-804 (manufactured by Showa Denko KK). )) Are used in series, and the molecular weight is calculated based on the molecular weight in terms of polystyrene (measurement method B).
When preparing the liquid softener composition of the present invention, the cationic polymer of the component (D) may be used in the form of being dissolved or dispersed in a water-soluble organic solvent of the component (H) described later. The amount of the water-soluble organic solvent used at that time is not limited to the storage stability and viscosity physical properties of the softener composition as the final product, but may be used in the minimum necessary amount in consideration of the production method and the production equipment. preferable. The component (D) is preferably a hydrophilic cationic polymer.

[Content of components (A) to (D), etc.]
The content of the component (A) in the liquid softener composition of the present invention is from 10% by mass to 30% by mass. When used as a concentrated type, the content of the component (A) in the liquid softener composition of the present invention is preferably 12% by mass or more, more preferably 15% by mass, since the amount used per washing can be reduced. % By mass or more, and preferably 28% by mass or less, more preferably 25% by mass or less.

  The content of the component (B) in the liquid softener composition of the present invention is from 0.1% by mass to 5% by mass. From the viewpoint of flexibility after long-term storage and suppression of excessive viscosity increase, the content of the component (B) in the composition is preferably 0.5% by mass or more, and more preferably 2% by mass or less. Preferably it is 1% by mass or less.

  In the liquid softener composition of the present invention, from the viewpoint of inhibiting the hydrolysis of the component (A) and imparting an appropriate viscosity to the composition, the mass ratio of the component (A) to the component (B) is: The component (B) is preferably 2 or more and 300 or less. The mass ratio of component (A) / component (B) is more preferably 3 or more, even more preferably 5 or more, and is preferably 100 or less, more preferably 80 or less.

  The content of the component (C) in the liquid softener composition of the present invention is from 0.1% by mass to 5% by mass. From the viewpoint of flexibility after long-term storage and suppression of excessive viscosity increase, the content of the component (C) in the composition is preferably 0.3% by mass or more, and more preferably 3% by mass or less. .

  The content of the component (D) in the liquid softener composition of the present invention is from 0.1% by mass to 1.5% by mass. From the viewpoints of phase stability during storage and a sufficient flexibility effect, the content of the component (D) in the composition is preferably 0.2% by mass or more, and more preferably 1.0% by mass or less. .

(Optional components)
The liquid softener composition of the present invention includes, as optional components, a surfactant other than the component (A) [hereinafter, referred to as a component (E)], a chelating agent [hereinafter, referred to as a component (F)], an inorganic electrolyte [hereinafter, referred to as Component (G)], a water-soluble organic solvent (hereinafter, referred to as component (H)), and a fragrance composition (hereinafter, referred to as component (I)).
In addition, the liquid softener composition of the present invention is adjusted to have a pH suitable for stabilizing an antioxidant, a dye, a preservative, a silicone compound, a polymer other than the component (D), and the component (A) as optional components. PH adjuster can be included.

[(E) component: surfactant]
The liquid softener composition of the present invention preferably contains a surfactant other than the component (A) as the component (E), and includes a nonionic surfactant [hereinafter referred to as the component (E1)] and (A). )) More preferably, it contains one or more surfactants selected from the cationic surfactants (E2) [hereinafter referred to as “component (E2)”].

Examples of the nonionic surfactant of the component (E1) include one or more selected from the following (E11) and (E12).
(E11): Nonionic surfactant represented by the following general formula (3): R ^1e —O — [(C ₂ H ₄ O) _s (C ₃ H ₆ O) _t ] —H (3)
[In the formula, R ^1e is an alkyl group or alkenyl group having 8 or more, preferably 10 or more, and 18 or less, preferably 16 or less carbon atoms. s and t are the average number of moles added, s is a number of 2 or more, preferably 10 or more, and 50 or less, preferably 40 or less, t is 0 or more, preferably 1 or more, and 5 or less, preferably Is a number of 3 or less. (C ₂ H ₄ O) and (C ₃ H ₆ O) may be a random polymer or a block polymer. ]
(E12): a nonionic surfactant represented by the following general formula (4)

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

As the cationic surfactant of the component (E2), one or more selected from the following (E21) to (E23) is preferable, and one or more selected from the following (E22) is more preferable. The salt is preferably a chloride salt.
(E21): a di-long-chain alkyl or alkenyldimethylammonium salt having an alkyl group or an alkenyl group having 10 to 22 carbon atoms (E22): a mono-long-chain alkyl having an alkyl group or an alkenyl group having 10 to 22 carbon atoms or Alkenyltrimethylammonium salt (E23): a mono-long-chain alkyl or alkenylbenzyldimethylammonium salt having 10 to 22 carbon atoms in the alkyl or alkenyl group

  The softener composition of the present invention preferably contains the component (E1) as the component (E), and more preferably contains the nonionic surfactant (E11) represented by the general formula (3). preferable.

  The content of the surfactant (E) in the composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and preferably 10% by mass or less, more preferably 8% by mass or less. . In the concentration limitation of the component (E), the content of the nonionic surfactant (E11) represented by the general formula (3) is 0.1% by mass or more and 1% by mass in the softener composition of the present invention. The following is preferred.

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

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

  As the component (F), for example, ethane-1-hydroxy-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, methylglycinediacetic acid, hydroxyethyliminodiacetic acid, ethylenediaminedisuccinic acid, L-glutamic acid-N, N- One or more selected from diacetate, N-2-hydroxyethyliminodiacetic acid, citric acid, succinic acid and salts thereof, and more preferably selected from ethylenediaminetetraacetic acid, methylglycine diacetate, citric acid and salts thereof One or more types are more preferable. In the case of a salt, an alkali metal salt is preferred. These chelating agents may play a role as a pH adjuster described later. Methylglycine diacetate, ethylenediaminetetraacetic acid and salts thereof are effective in suppressing the fading of the dye, and exert their effects with a small amount. In the present invention, it is preferable to use one or more selected from methylglycine diacetate and ethylenediaminetetraacetic acid together with citric acid, and the organic acid may be an alkali metal salt.

  The content of the chelating agent (F) in the composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 1% by mass or less, assuming an acid structure. 0.5 mass% or less is more preferable. The content of methylglycine diacetate, ethylenediaminetetraacetic acid or a salt thereof is preferably 0.001% by mass or more, preferably 0.05% by mass or less as an acid structure in the composition. It is preferable that the content range of the component (F) is satisfied by containing an acid or a salt thereof.

[Component (G): inorganic electrolyte]
The liquid softener composition of the present invention preferably contains an inorganic electrolyte as the component (G). It is preferable that the inorganic electrolyte of the component (G) be soluble in 100 g of water at 20 ° C. in an amount of 5 g or more.
The inorganic electrolyte of the component (G) is preferably used for adjusting the viscosity of the softener composition to a level suitable for use. For example, examples of the component (G) include inorganic salts in which the cation is an ion of a substance selected from an alkali metal and an alkaline earth metal, and the anion is an ion of a substance selected from a halogen compound and a sulfate. Can be Accordingly, the composition of the present invention may contain a combination of a cation of a substance selected from alkali metals and alkaline earth metals and an anion of a substance selected from halides and sulfates. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium and calcium. Examples of the halogen compound include chloride, bromide, and iodide.
Specific examples of the inorganic electrolyte of the component (G) include one or more inorganic electrolytes selected from sodium chloride, sodium sulfate, calcium chloride, calcium sulfate, magnesium chloride, and magnesium sulfate.

  The content of the inorganic electrolyte (G) in the composition is 0.1% by mass or more, preferably 0.3% by mass or more, more preferably 0.6% by mass or more and 1.5% by mass or less in terms of anhydrous content. , Preferably 1.2% by mass or less. When a combination of the cation and the anion is contained, the combination is also contained at a concentration converted to an inorganic electrolyte.

[(H) water-soluble organic solvent]
The softener composition of the present invention preferably contains a water-soluble organic solvent as the component (H) from the viewpoint of stability and viscosity of the composition. As the component (H), a water-soluble organic solvent which is known to be blended with a softener is exemplified. Regarding the component (H), “water-soluble organic solvent” means that 20 g or more is dissolved in 100 g of deionized water at 20 ° C. Specific examples of the component (H) include propylene glycol, ethylene glycol, glycerin, diethylene glycol, monoethylene glycol monophenyl ether, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, isopropanol, and ethanol. . Preferably, it is at least one water-soluble organic solvent selected from ethylene glycol and ethanol. When the viscosity of the liquid softener composition is high or when it is desired to adjust the phase stability, it is preferable to use a water-soluble organic solvent. The liquid softener composition of the present invention contains the component (H) in an amount of preferably 1.0% by mass or more, and more preferably 10% by mass or less.

[(I) Fragrance composition]
The softener composition of the present invention preferably contains a fragrance composition not only for flavoring the composition itself but also for flavoring textile products.
The fragrance composition used in the present invention is used to give consumers a high preference for the softener composition. The palatability is not only an effect of giving a pleasant feeling such as a feeling of euphoria, sedation, and exhilaration, but also an effect of deodorizing an unpleasant odor such as a sweat odor, a cigarette odor, and a dry odor, a cooling effect, a heating effect, and a hypnotic effect. It can also include functional effects such as action, aphrodisiac action, antidepressant action, antibacterial action, and diet action. As the fragrance component, for example, the fragrance described in “Basic knowledge of fragrance and incense, edited by Mototaka Nakajima, published by Sangyo Tosho Co., Ltd., 4th printing on April 20, 2005”, and described in JP-T-Hei 10-507793. Perfumes can be used.

  From the viewpoint of the quality and strength of the fragrance and the stability in the softener system, the fragrance component is appropriately selected and used. Hereinafter, the compounds used as the fragrance component which can be blended in the present invention are classified as shown in the field of fragrance and listed below. Examples of the terpene compound-based flavor component include limonene, p-cymene, α-pinene, β-pinene, and β-caryophyllene. As the alcohol compound-based flavor component, cis-3-hexenol, trans-2-hexenol, and methyltrimethylcyclo. Pentenylbutenol, dihydromyrcenol, l-menthol, phenylethyl alcohol, citronellol, geraniol, nerol, linalool, terpineol, tetrahydrolinalool, tetrahydrogeraniol, dimethylbenzylcarbinol, β-phenylethyl alcohol, benzyl alcohol, cinnamic alcohol , Anise alcohol, farnesol, nerolidol, dimethylphenylethylcarbinol, o, t-butylcyclohexanol, p, t-butylcyclohexyl Nol, sandal mysole core (2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol) (manufactured by Kao Corporation), bagdanol (IFF company) And Javanol (manufactured by Divaudan Co., Ltd.). As the ester compound-based flavor component, benzyl acetate, dimethylbenzylcarbyl acetate, linalyl acetate, neryl acetate, o, t-butylcyclohexyl acetate, p, t-butylcyclohexyl acetate , Citronellyl acetate, geranyl acetate, tetrahydrogeranyl acetate, terpenyl acetate, isobornyl acetate, l-menthyl acetate, tricyclodecenyl acetate, 2-phenylethyl acetate, 3-phenylpropyl acetate, styralyl acetate, cis-3-hexenyl acetate , Trans-2-hexenyl acetate, hexyl acetate, syn acetate Namyl, isobutyl propionate, 2-phenylethyl propionate, citronellyl propionate, benzyl propionate, tricyclodecenyl propionate, geranyl propionate, allyl propionate, geranyl butyrate, citronellyl butyrate, isoamyl butyrate, amyl butyrate, butyric acid Allyl, phenoxyethyl isobutyrate, geranyl isobutyrate, geranyl isovalerate, ethyl caproate, allyl caproate, ethyl enanthate, allyl enanthate, ethyl octanoate, methyl anthranilate, cis-3-hexenyl benzoate, benzoic acid Benzyl, amyl salicylate, isoamyl salicylate, benzyl salicylate, cis-3-hexenyl salicylate, hexyl salicylate, 2-phenylethyl salicylate, methyldihydrojasmonate, coumarin, γ Octalactone, γ-undecalactone, γ-decalactone, γ-nonalactone, δ-nonalactone, δ-decalactone, δ-undecalactone, δ-dodecalactone, cyclopentadecanolide, cyclopentadecenolide (havanolide, Filmenich), cyclohexadecanolide, ambrettolide, 11-oxa-16-hexadecanolide (Musk R-1, manufactured by Givaudan), 10-oxa-16-hexadecanolide (oxalide, manufactured by Takasago International Corporation), 12-oxahexadecanolide, ethylene brassate, ethylene dodecandioate (Musk C-14), and as aldehyde compound-based flavor components, octanal, nonanal, decanal, undecanal, 10-undecenal, dodecanal, citral, Citronella , Anisaldehyde, phenylacetaldehyde, mylacaldehyde, lilial, liral, dimethyltetrahydrobenzaldehyde, amylcinnamic aldehyde, hexyl cinnamic aldehyde, cyclamenaldehyde, vanillin, ethyl vanillin, heliotropin, helional, and ketone compounds. , Flolorozone, l-carvone, menthone, cis jasmon, geranylacetone, and furthermore, damascones, damacenones, α-dynascones, ionones, methylionones, β-methylnaphthyl ketone, iso-E super, raspberry ketone, maltol, Ethyl maltol, Kashmeran (manufactured by IFF) and 5-cyclohexedesenen-1-one (Musk TM-II) are known as fragrances. As ether compound-based flavor components, anethole, eugenol, methyl eugenol, methyl isoeugenol, diphenyl oxide, 1,8-cineole, seryl methyl ether, ambroxane (3α, 6,6,9α-tetramethyldodecahydronaphtho [2 , 1-b] furan), ethoxymethylcyclododecyl ether (Boasambrenforte, manufactured by Kao Corporation), geranyl nitrile, citronellyl nitrile, indole, acetylsedrene, methyl anthranilate as a nitrogen-containing compound-based flavor component , N-methylmethyl anthranilate, aurantiol, paeonil (manufactured by Divaudan) and the like.

  Among them, the ester compound-based fragrance component also has an effect on inhibiting the hydrolysis of the component (A), and is preferably contained in the fragrance composition of the component (I) in an amount of 30% by mass or more, more preferably 40% by mass or more. Is more preferable.

  The fragrance may be microencapsulated and blended with the fragrance composition of the component (I) for the purpose of maintaining fragrance and remaining fragrance. Perfume microcapsules are spherical substances in which the fragrance of the core substance is wrapped in a wall material.The role of the microcapsules is to protect the fragrance of the core substance, and when physical force is applied to the capsule, the capsule wall is broken and the core is broken. It releases the fragrance of the substance.

  Further, for the purpose of maintaining the scent and remaining scent, an ester of silicic acid and an alcohol used as a fragrance (hereinafter referred to as “alcoholic fragrance”), for example, a general formula (JP-A-2009-256818). The compound represented by 1) can be used. Examples of the alcoholic flavor include the following alcohols i) to iii).

i) Aliphatic alcohol having logP of 1 or more and 5 or less Specifically, cis-3-hexenol (1.4), geraniol (2.8), nerol (2.8), 2,6-dimethyl-2 -Heptanol (3.0), menthol (3.2), citronellol (3.3), rosinol (3.3), 9-decenol (3.5), tetrahydrolinalool (3.5), tetrahydrogeraniol (3) .7), 4-methyl-3-decene-5-ol (3.7), tetrahydrogeraniol (3.7) and the like. Here, the values in parentheses are logP values (the same applies to ii) and iii) below).

ii) Aromatic alcohol having a log P of 1 to 5 Specifically, anise alcohol (1.0), raspberry ketone (1.1), phenylethyl alcohol (1.2), eugenol (2.4), isoeugenol (2.6), dimethylbenzylcarbinol (3.0), phenylethylmethylethylcarbinol (3.0), 3-methyl-5-phenylpentanol (3.2), thymol (3.4) and the like Is mentioned.

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

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

  The fragment approach is based on the chemical structure of the compound and takes into account the number of atoms and the type of chemical bond (cf. A. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C. Hansch, PG Sammens, JB Taylor and CA Ramsden, Eds., P.295, Pergamon Press, 1990). This ClogP value can be used instead of the actually measured logP value when selecting a compound. In the present invention, if there is an actually measured value of logP, if not, the ClogP value calculated by the program CLOGP v4.01 is used.

[Other optional components]
The softener composition of the present invention can contain an antioxidant. The antioxidant is, for example, an antioxidant having a phenol group in the molecule. An antioxidant having a phenol group in the molecule is used to suppress a change in the odor of the fragrance. When an antioxidant is used in combination with a fragrance, the change in odor can be suppressed, but the discoloration of the softener composition is promoted by coloring the antioxidant having an oxidized phenol group, thereby preventing oxidation. The compounding amount of the agent is used after sufficiently confirming the flavor component and the content thereof which are easily affected by oxidation.
From the viewpoint of availability, antioxidants having a phenol group in the molecule include 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol. And at least one antioxidant selected from butylhydroxyanisole. From the viewpoint of suppressing discoloration, one or more antioxidants selected from 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol are preferable. .
The antioxidant may be blended for storage stability of other base materials such as the component (A), and may be mixed with the softener composition of the present invention by blending the component (A). is there.

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

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

  By using the dye in combination with the chelating agent, it is possible to suppress the discoloration of the softener composition containing the fragrance or the fragrance and the antioxidant. From the viewpoint of suppressing discoloration, one or more dyes selected from a color index acid red dye and a color index acid yellow dye are preferred. The most effective chelating agents are ethylenediaminetetraacetic acid, methylglycinediacetic acid or their alkali metal salts.

  The preservative used in the present invention is used for imparting preservability to the softener composition. For example, biguanide compounds, isothiazoline compounds, and isothiazolinone compounds can be used. Specific examples include polyhexamethylene biguanide hydrochloride, 5-chloro-2-methyl-4-isothiazolin-3-one, and 1,2-benzisothiazolin-3-one, each of which is commercially available as "Proxel IB" "," Caisson CG "and" Proxel BDN "can also be used.

  The present invention may optionally include a silicone compound to add a new impression to the feel to the textile. Silicone compounds are used to impart even better flexibility to textiles. For example, dimethyl silicone, polyether-modified silicone, methylphenyl silicone, alkyl-modified silicone, higher fatty acid-modified silicone, methyl hydrogen silicone, fluorine-modified silicone, epoxy-modified silicone, carboxy-modified silicone, carbinol-modified silicone, amino-modified silicone, etc. Is mentioned. From the viewpoint of the softening effect, dimethyl silicone, amino-modified silicone and polyether-modified silicone are preferred, and dimethyl silicone and amino-modified silicone are more preferred. These can be used alone or as a mixture of two or more.

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

  The pH adjusting agent used for adjusting the pH of the softener of the present invention includes, for example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, formic acid, acetic acid, lactic acid, glycolic acid, oxalic acid, succinic acid, and citric acid. Organic acids such as maleic acid, fumaric acid, propionic acid, malonic acid, glutaric acid, adipic acid, malic acid, crotonic acid, benzoic acid, paratoluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, polyacrylic acid, Inorganic bases such as sodium hydroxide, potassium hydroxide, triethanolamine and the like, or organic bases can be mentioned. The pH adjuster is preferably used so that the pH of the liquid softener composition falls within the range described below.

  The viscosity of the liquid softener composition of the present invention at 30 ° C. is preferably 100 mPa · s or less, more preferably 60 mPa · s or less, more preferably 55 mPa · s or less, from the viewpoint of handleability during use. Further, the viscosity is preferably 5 mPa · s or more. The viscosity was obtained by measuring the liquid softener composition at 30 ° C. with a B-type viscometer (model number: TVB-10, manufactured by Toki Sangyo Co., Ltd., using a No. 2 rotor, 60 r / min) and stirring. Use the value 1 minute after the start.

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

  The liquid softener composition of the present invention may be in an emulsion state. In the present invention, an emulsified liquid softener composition is a liquid softener composition that forms visible particles in the liquid softener composition to form particles that are large enough to scatter visible light. 1 shows a liquid softener composition in a closed state. Specifically, when a glass cell having an optical path length of 10 mm was used as a measurement cell and ion-exchanged water was placed in a control cell, the visible light transmittance (wavelength) of the sample was measured using an ultraviolet-visible spectrophotometer. 660 nm) is less than 25%.

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

Hereinafter, components used in Examples and Comparative Examples are shown.
[(A) component]
(A-1): Esterification reaction product obtained in the following synthesis example a-1 (a-2): Esterification reaction product obtained in the following synthesis example a-2

<Synthesis Example a-1: Synthesis of (a-1)>
Triethanolamine and a fatty acid (mixed fatty acid, the composition is shown below) are subjected to an esterification reaction at a reaction molar ratio (fatty acid / triethanolamine) of 1.65 / 1 to give an amine compound represented by the general formula (1) An esterification reaction product containing was obtained.
The mz of the esterification reaction product (the number average of m in the general formula (1) in the entire component (A)) was 1.57. The esterification reaction product contained 5% by mass of unreacted fatty acids. A quaternization reaction was performed with dimethyl sulfate so that the methyl group was 0.96 equivalent to the amine of the amine compound in the esterification reaction product. After the quaternization reaction, 10% by mass of ethanol based on the mass of the reaction product was added, and mixed uniformly.
The obtained esterification reaction product was analyzed by HPLC for the composition ratio of each component, and quantified using tetraoctylammonium bromide as an internal standard substance. As a result, the obtained esterification reaction product was (A1) The mixture contained a tertiary amine compound as the component, a quaternized product as the component (A2), and an unreacted fatty acid in a total amount of 90% by mass. Since 2% by mass of the fatty acid was contained in the mixture, the total of the components (A1) and (A2) in the mixture was 90% by mass = 2% by mass = 88% by mass. The mass ratio of the component (A1) / the component (A2) in the mixture is 13/87, and the acyl group R ¹ -C (ＣO) in the general formula (1) of the component (A1) and the component (A2) is used. ) Were each composed of a fatty acid having a mass ratio of unsaturated fatty acid / saturated fatty acid of 0.4.

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

The composition of the fatty acid is shown below.
Palmitic acid: 45% by mass
Stearic acid: 25% by mass
Fatty acid having 18 carbon atoms and one unsaturated bond: 27% by mass
Fatty acid having 18 carbon atoms and having two unsaturated bonds: 3% by mass
The composition was analyzed by gas chromatography for fatty acids used as raw materials, and the area% of each fatty acid was regarded as mass%. The cis / trans ratio of the unsaturated group is 85/15 (integration ratio by ¹ H-NMR).

<Synthesis Example a-2: Synthesis of (a-2)>
Triethanolamine and fatty acid (mixed fatty acid, the composition is shown below) are subjected to an esterification reaction at a reaction molar ratio (fatty acid / triethanolamine) of 1.86 / 1 to give an amine compound represented by the general formula (1) An esterification reaction product containing was obtained.
The mz of the esterification reaction product [the number average of m in the general formula (1) in the entire component (A)] was 1.77. The esterification reaction product contained 5% by mass of unreacted fatty acids. A quaternization reaction was performed with dimethyl sulfate so that the methyl group was 0.98 equivalent to the amine of the amine compound in the esterification reaction product. After the quaternization reaction, 10% by mass of ethanol based on the mass of the reaction product was added, and mixed uniformly.
The obtained esterification reaction product was analyzed by HPLC for the composition ratio of each component, and quantified using tetraoctylammonium bromide as an internal standard substance. As a result, the obtained esterification reaction product was (A1) It was a mixture containing a total of 85% by mass of the tertiary amine compound of the component, the quaternized product of the component (A2), and the unreacted fatty acid. Since 2% by mass of the fatty acid was contained in the mixture, the total of the components (A1) and (A2) in the mixture was 85% by mass = 2% by mass = 83% by mass. Further, the mass ratio of the component (A1) / the component (A2) in the mixture is 9/91, and the acyl group R ¹ -C (中 O) in the general formula (1) of the component (A1) and the component (A2). ) Were each composed of a fatty acid having a mass ratio of unsaturated fatty acid / saturated fatty acid of 0.64.

  In preparing the liquid softener composition, (a-2) is blended as a mixture containing the component (A1), the component (A2), fatty acid, ethanol, and other trace components. The mass% of 2) indicates mass% based on the amounts of the component (A1) and the component (A2), and the other components were added to the rest of the ion-exchanged water.

The composition of the fatty acid is shown below.
Myristic acid: 2% by mass
Palmitic acid: 27% by mass
Palmitoleic acid: 3% by mass
Stearic acid: 32% by mass
Fatty acid having 18 carbon atoms and having one unsaturated bond: 33% by mass
Fatty acid having 18 carbon atoms and having two unsaturated bonds: 3% by mass
The composition was analyzed by gas chromatography for fatty acids used as raw materials, and the area% of each fatty acid was regarded as mass%. The cis / trans ratio of the unsaturated group is 85/15 (integration ratio by ¹ H-NMR).

[(B) component]
(B-1): Cetyl 2-ethylhexanoate (b-2): 2-ethylhexyl stearate (b-3): 2-ethylhexyl palmitate

[(C) component]
(C-1): Pentaerythritol stearic acid ester (Exepearl PEMS, Kao Corporation)
(C-2): glycerin fatty acid ester obtained in the following Synthesis Example c-2

<Synthesis Example c-2: Synthesis of (c-2)>
158 g of glycerin, 932 g of fatty acid (lauric acid / myristic acid / palmitic acid / stearic acid / others = 51% by mass / 23% by mass / 7% by mass / 17% by mass / 2% by mass) 44 mol) and 1.7 g of NaOH were charged into a four-necked flask, and heated at 220 ° C. for 5 hours while heating while introducing nitrogen gas to remove water generated in the reaction. It was confirmed that the acid value of the reaction product was 0.3 mgKOH / g or less and the hydroxyl value was between 32 and 38 mgKOH / g, and thus (c-2) was synthesized.
In (c-2), the proportion of the monoester structure was 7% by mass in the total amount of (c-2), and the total of the fatty acid diester structure and the fatty acid triester structure was 93% by mass. The ratio of the fatty acid monoester, fatty acid diester, fatty acid triester, and fatty acid tetraester was measured using a high-speed GPC device HCL-8220GPC (manufactured by Tosoh Corporation) under the following conditions.
<HPLC conditions>
Column: TSKgel G1000HXL + G2000HXL (series connection)
Mobile phase: THF (tetrahydrofuran)
Flow rate: 0.7ml / min
Temperature: 25 ° C
Detector: RI
Sample concentration and injection volume: 1% THF solution, 20 μl

[(D) component]
(D-1): the cationic polymer obtained in the following synthesis example d-1 (d-2): the cationic polymer (d-3) obtained in the following synthesis example d-2: the following synthesis example d-3 The cationic polymer (d-4) obtained in the following: The cationic polymer (d-5) obtained in the following Synthesis Example d-4: The cationic polymer obtained in the following Synthesis Example d-5

<Synthesis Example d-1: Synthesis of (d-1)>
A 1-L four-neck separable flask equipped with a propeller stirrer, a nitrogen inlet tube, a Dimroth reflux condenser, and a thermometer was purged with nitrogen for a certain period of time. 73.3 g of propylene glycol monomethyl ether was added thereto, and the content was heated to 80 ° C. while stirring and maintained.
Separately, a monomer solution was prepared by uniformly mixing 213.6 g (1.36 mol) of dimethylaminoethyl methacrylate, 86.4 g (0.34 mol) of lauryl methacrylate, and 164.1 g of propylene glycol monomethyl ether.
An initiator solution obtained by uniformly mixing 4.22 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (v-65B: manufactured by Wako Pure Chemical Industries, Ltd.) and 40.11 g of propylene glycol monomethyl ether Was also prepared separately.
The monomer solution and the initiator solution were dropped into the separable flask over 3 hours. Next, a solution prepared by dissolving 8.44 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (v-65B, manufactured by Wako Pure Chemical Industries, Ltd.) in 75.9 g of propylene glycol monomethyl ether was added to the flask. The solution was dropped at a constant rate over 4 hours. After the completion of the dropwise addition, the mixture is kept at 80 ° C. for 2 hours, and then propylene glycol monomethyl ether is added, whereby a copolymer of dimethylaminoethyl methacrylate and lauryl methacrylate as the component (D) [cationic polymer (d-1)] 1563 g of a polymer solution containing was obtained. The weight average molecular weight (Mw) of the obtained cationic polymer was 14,000. The composition of this copolymer analyzed by ¹ H-NMR was dimethylaminoethyl methacrylate / lauryl methacrylate = 8/2 (molar ratio). The composition of the polymer solution was 20% by mass of a cationic polymer (d-1), which is a copolymer of dimethylaminoethyl methacrylate and lauryl methacrylate, and 80% by mass of propylene glycol monomethyl ether. This polymer solution was used so that the amount of the copolymer (d-1) was as shown in the table.

<Synthesis Example d-2: Synthesis of (d-2)>
50.0 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM), 200.0 g of a polymerization solvent isopropyl alcohol, and a polymerization initiator V- were added to a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube. 6.0 g of 65B (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and a polymerization reaction was carried out at 85 ° C. for 6 hours. Thereafter, the precipitate was reprecipitated with 3000.0 g of acetone and then dried to obtain a cationic polymer, poly (2-methacryloyloxy-ethyltrimethylammonium chloride) (d-2) (Mw 10,000).

<Synthesis Example d-3: Synthesis of (d-3)>
In a reactor equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, 50.0 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM), 50.0 g of water as a polymerization solvent, and a polymerization initiator were added. 2.3 g of sodium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was charged, and a polymerization reaction was performed at 80 ° C. for 6 hours. Thereafter, the precipitate was reprecipitated with 3000.0 g of acetone and then dried to obtain a cationic polymer, poly (2-methacryloyloxy-ethyltrimethylammonium chloride) (d-3) (Mw 58000).

<Synthesis Example d-4: Synthesis of (d-4)>
In a reactor equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube, 100.0 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM), 150.0 g of a polymerization solvent ethanol, and a polymerization initiator V-65B 0.4 g (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and a polymerization reaction was carried out at 70 ° C. for 6 hours. Thereafter, the precipitate was reprecipitated with 3000.0 g of acetone and then dried to obtain a cationic polymer, poly (2-methacryloyloxy-ethyltrimethylammonium chloride) (d-4) (Mw 100,000).

<Synthesis Example d-5: Synthesis of (d-5)>
A reactor equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was charged with 100.0 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM), 66.7 g of ethanol as a polymerization solvent, and a polymerization initiator V-. 0.1 g of 65B (manufactured by Wako Pure Chemical Industries, Ltd.) was charged and a polymerization reaction was carried out at 85 ° C. for 6 hours. Thereafter, the precipitate was reprecipitated with 3000.0 g of acetone and then dried to obtain a cationic polymer, poly (2-methacryloyloxy-ethyltrimethylammonium chloride) (d-5) (Mw 230,000).

[(E) component]
(E-1): Nonionic surfactant (polyoxyethylene lauryl ether having an average number of moles of added oxyethylene group of 30 mol)

[(F) component]
(F-1): Methyl glycine diacetate 3Na (Torylon M Liquid, BASF Japan K.K.) (The effective amount of methyl glycine diacetate 3Na was used so as to have the values shown in Tables 2 and 3.)
(F-2): citric acid

[(G) component]
(G-1): calcium chloride

[(H) component]
(H-1): ethylene glycol

[(I) component]
(I-1): Perfume composition i1 shown in Table 1
(I-2): Perfume composition i2 shown in Table 1

[Other components]
(J-1): 1,2-benzisothiazolin-3-one (Proxel BDN (Lonza Japan Co., Ltd.))
(K-1): Highly polymerized dimethicone emulsion: 60% by mass of dimethylpolysiloxane having a kinematic viscosity at 25 ° C. of 500,000 mm ² / s, and the average number of moles of oxyethylene groups added (hereinafter referred to as the average number of moles of EO added). Is 1.5 mol% of polyoxyethylene lauryl ether having 5 mol, 4.5 mass% of polyoxyethylene lauryl ether having an average number of moles of added EO of 23 mol, 0.1 mass% of sodium salt of lauryl sulfate, and an emulsion of the remainder of water, The average particle diameter of the dispersed particles is 500 nm (the effective amount of dimethylpolysiloxane was used so as to have the values shown in Tables 2 and 3).

<Method for producing liquid softener composition in emulsion state>
The liquid softener composition in an emulsion state was prepared by mixing the components so as to have the composition shown in Table 2. Specifically, it is as follows.
In a 300 mL beaker, 90% by mass of ion-exchanged water equivalent to the amount required for the final mass of the emulsified liquid softener composition to be 200 g, component (E) (nonionic surfactant), ( The component (F) (chelating agent), the component (H) (ethylene glycol), and the component (j-1) (antibacterial agent) were added, and the temperature of ion-exchanged water was adjusted to 60 ± 2 ° C. using a water bath. Next, after adding the component (D) (cationic polymer), a pH adjuster (hydrochloric acid) was added to obtain an aqueous composition. The pH of this aqueous composition was 2.5 to 3.5 at 65 ° C. If necessary, stirring was performed using the following stirring blades so that these components were uniformly dissolved in ion-exchanged water.
Ion-exchanged water containing the above components, which has been adjusted to a temperature of 60 ± 2 ° C., is stirred with a stirring blade (blade) whose long side is oriented at 90 degrees with respect to the rotation center axis of a stirring rod having a diameter of 5 mm. No .: 3, blade long side / short side: 3 cm / 1.5 cm, installation of blade: 45 ° angle with respect to rotating surface) at 65 ° C. while stirring (450 r / m) (B) The component (A) dissolved by heating together with the component and the component (C) was added over 3 minutes. After completion of the addition, the mixture was stirred for 15 minutes.
A 35% by mass aqueous solution of the component (G) (calcium chloride) was charged and stirred for 10 minutes. Using a 5 ° C water bath, the contents were cooled until the temperature of the contents reached 30 ± 2 ° C to obtain an emulsified composition.
The component (I) (fragrance composition) was added to the obtained emulsion composition, and the mixture was stirred for 5 minutes. Next, the component (k-1) (highly polymerized dimethicone emulsion) was added and stirred for 5 minutes to obtain a liquid flexible composition for clothing having the composition shown in Table 2.

<Evaluation method>

(1) Viscosity 30 g of the liquid softener composition shown in Table 2 was filled in a container (glass wide-mouthed bottle No. 6), and the temperature of the composition was adjusted to 30 ° C. Using a B-type viscometer (model number: TVB-10, manufactured by Toki Sangyo Co., Ltd., using a No. 2 rotor, 60 r / min), measurement of the viscosity of the liquid softener composition was started at the above-mentioned temperature and 1 minute The subsequent value was read (the unit of viscosity was “mPa · s”). Table 2 shows the results. In this evaluation, the viscosity is preferably 50 mPa · s or less.
In addition, long-term storage was carried out by allowing to stand in a constant temperature room at 30 ° C. for one year. The viscosity of the liquid softener composition after storage was measured by the above method. The viscosity is preferably 100 mPa · s or less. The results are shown in Table 2.

(2) Evaluation method of softness effect (I) Pretreatment method of evaluation towel Using a commercially available powder detergent (manufactured by Kao Corporation, “Attack” manufactured in May 2015), a commercially available cotton towel (manufactured by Takei Towel) , "TW-220"), a series of washing steps was repeated five times using Hitachi fully automatic washing machine NW-6CY (attack usage: 34 g, standard course, water volume: 45 L, water temperature: 20 ° C., washing time: 10 minutes) , Rinse twice). Thereafter, drying was performed under the conditions of 20 ° C. and 45% RH.

(II) Flexible treatment method of evaluation towels 4.5 L of water at 20 ° C. was injected into an electric bucket type washing machine (MiniMini, model number “NA-35”) manufactured by National, and the cotton was pretreated by the method (1). Two towels were charged and stirred for 1 minute. After stirring, the liquid softener composition which had been stored for one year under the condition (1) was charged in an amount of 7 ml per 1.5 kg of cotton towel, and treated for 5 minutes with stirring. After the treatment, the mixture was dehydrated in a dehydration tank for 2 minutes and dried at 20 ° C. and 45% RH.
(III) Evaluation The softening effect was determined by changing the softness of a cotton towel treated and dried with a liquid softener composition having the composition shown in Table 2 to the softness of a dried cotton towel treated with the liquid softener composition of Comparative Example 5. Was evaluated in comparison with
Of the two cotton towels treated and dried with the liquid softener composition of each example or comparative example, 10 panelists, respectively, of the cotton towels treated and dried with the liquid softener composition of Comparative Example 5 Was compared with the softness when touched with a hand, and a score was given based on the following criteria. Table 2 shows the results. The numerical values of the softening effect in Table 2 represent the average values of 10 panelists. In this evaluation, the average score of the softness is preferably 1.5 or more.
Evaluation criteria for flexibility effect:
0: Not softer than Comparative Example 5 1: Softness equivalent to Comparative Example 5 2: Softer than Comparative Example 5

<Formulation example>
Table 3 shows a formulation example of the liquid softener composition of the present invention.

Claims (5)

(A) A tertiary amine or a neutralized or quaternized product thereof having an ester group and having at least one hydrocarbon group having 9 to 23 carbon atoms in the molecule, in an amount of 10% by mass to 30% by mass. ,
(B) 0.1% by mass or more of an ester compound of a fatty acid having 2 to 10 carbon atoms and a monohydric alcohol having 12 to 20 carbon atoms, wherein the total number of carbon atoms is 16 to 24. 5% by mass or less,
(C) 0.1% by mass or more and 5% by mass or less of an oil agent other than the component (B);
(D) A liquid softener composition comprising from 0.1% by mass to 1.5% by mass of a cationic polymer and water. (A) is (A1) a tertiary amine compound represented by the following general formula (1) and an acid salt thereof, and (A2) a quaternary amine compound represented by the following general formula (1) The liquid softener composition according to claim 1, which is at least one compound selected from the group consisting of:
^{_{[R 1 -C (= O) -O-}} (C p H 2p O) r -C q H 2q ] ^{_{m N (R 2) 3-}} m (1)
Wherein, ^{R 1} is a hydrocarbon group having 11 to 23 carbon atoms, ^{R 2} is a hydrocarbon group having 1 to 3 carbon atoms, and _{HO- (C p H 2p O)} r -C q H 2q group M is a number of 1 or more, 3 or less, p and q are numbers of 2 or 3, and r is a number of 0 or more and 5 or less. ^{If R 1,} R ₂ in the same _{molecule, HO- (C p H 2p O} ) r -C q H 2q group, p, q, r there are a plurality, they may be the same or different. ] The liquid softener according to claim 1 or 2, wherein (C) is an ester compound of a polyhydric alcohol having 2 to 10 carbon atoms having 2 to 6 hydroxy groups and a fatty acid having 12 to 24 carbon atoms. Composition.   The liquid softener composition according to any one of claims 1 to 3, further comprising (E) a nonionic surfactant.   The liquid softener composition according to any one of claims 1 to 4, further comprising (F) a chelating agent.