JP2014125692A - Softener composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid softener composition that is excellent in storage stability, that can suppress the precipitation of solids even when exposed to sun light under the condition of being packed in a bag-shaped container, and that can maintain viscosity suitable for use even when subjected to vibration.SOLUTION: A liquid softener composition, containing (A) a particular tertiary amine compound or acid salt or quarternary thereof, (B) a particular quaternary ammonium salt having one hydrocarbon group of 8 or more and 12 or less carbon atoms, (C) particular polyoxyethylene alkyl ether, (D) an inorganic salt, and water, and having a pH at 30°C of 2.5 or more and 4.0 or less.

Description

  The present invention relates to a liquid softener composition.

Even when discharged into the environment, a flexible base having an ester group in the molecule is used for the purpose of quickly decomposing and reducing the burden on the environment.
Patent Document 1 contains a fatty acid, a flexible base having an ester group in the molecule, and a single long-chain quaternary ammonium salt, and suppresses a decrease in flexibility due to storage, resulting in storage stability at various temperatures. Excellent liquid softener compositions are disclosed.
Patent Document 2 contains a soft base having an ester group in the molecule and a single long-chain quaternary ammonium salt, and can provide a preferable soft performance even if the rinse is insufficient at the time of washing. Finishing agents are disclosed.

  In recent years, due to increasing environmental awareness, it has become common to purchase a refill product filled in a bag-like container and refill it into a bottle for use.

  Patent Document 3 includes one or more layers selected from a softener composition containing a nonionic surfactant and a softener, selected from a polyethylene terephthalate layer, a plastic layer on which an aluminum vapor deposition layer is formed, and an aluminum layer. Further, a bag-containing softener filled in a bag-like container formed from a laminated material having a thickness of 100 to 250 μm is disclosed.

JP-A-8-81881 JP 2004-525271 A JP 2010-222711 A

  In general, a liquid softening agent composition containing a softening base containing an ester group in the molecule is prepared as an emulsion-like appearance composition. However, it can be seen that such a liquid softener composition in an emulsion state freezes when exposed to conditions of −10 ° C. or lower in winter and the like, and then returns to room temperature to increase in viscosity and become a gel. Has been issued. Furthermore, when a bag-like container filled with an emulsion liquid softener composition is exposed to sunlight, the emulsion liquid softener composition in contact with the light-exposed surface of the container It has been clarified that a phenomenon occurs in which solid matter is precipitated. To improve this, a single long-chain quaternary ammonium salt, which has only one long-chain hydrocarbon group and the other is a hydrophilic group or a short-chain hydrocarbon group, is effective. The present inventors have found that, as a new problem, as an evaluation method assuming that the composition is transported as a product, when a vibration is applied to the composition, a single long chain A new problem of increased viscosity, which is thought to be caused by quaternary ammonium salts, has been found.

  The present invention is excellent not only in storage stability but also in freezing recovery, and can suppress precipitation of solid matter even when exposed to sunlight in a state of being filled in a bag-like container, and even if vibration is applied. A liquid softener composition capable of maintaining a viscosity suitable for use is provided.

The present invention relates to a liquid softener composition comprising the following component (A), component (B), component (C) and water, and having a pH at 30 ° C. of 2.5 or more and 4.0 or less. .
Component (A): (a1) Tertiary amine compound represented by the following general formula (1), its acid salt (hereinafter referred to as (a1) component) and (a2) its quaternized product (hereinafter referred to as (a2) A compound selected from “components” or a mixture containing them 3% by mass to 20% by mass [R ¹ —C (═O) —O— (C _p H _2p O) _r —C _q H _2q ] _m N (R ² ) _3-m (1)
[Where,
R ¹ is a hydrocarbon group having 11 to 23 carbon atoms,
R ² is a group selected from a hydrocarbon group having 1 to 3 carbon atoms and a HO— (C _p H _2p O) _r —C _q H _2q group,
m is a number of 1 or more and 3 or less, p and q are 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. ]
Component (B): Compound represented by the following general formula (2) 0.1% by mass or more and 1.0% by mass or less R ³ —N ⁺ (R ⁴ ) ₃ · X ⁻ (2)
[Wherein R ³ is a hydrocarbon group having 8 to 12 carbon atoms, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and — (C ₂ H ₄ O) is a group selected from _S— H groups, and s is an average added mole number, which is a number of 2 or more and 5 or less. X ^- is an anionic group. ]
Component (C): Polyoxyethylene alkyl ether in which ethylene oxide is added to an aliphatic alcohol having 9 or more and 12 or less carbon atoms in an average of 15 or more and 50 or less mols in an amount of 3.0 to 5.0% by mass ( D) Component: Inorganic salt 0.1% by mass or more and 1.0% by mass or less

  The present invention also relates to a bag-like softener article in which a bag-like container is filled with the liquid softener composition of the present invention.

  According to the present invention, the viscosity is excellent in storage stability, can suppress the precipitation of solids even when exposed to sunlight in a state filled in a bag-like container, and is suitable for use even when subjected to vibration. A liquid softener composition capable of maintaining The liquid softener composition of the present invention can provide such an effect even when it is in an emulsion state.

[Component (A)]
The component (A) is a compound selected from (a1) a tertiary amine compound represented by the following general formula (1), an acid salt thereof, and (a2) a quaternized product thereof, or a mixture containing them.
^{[R 1 -C (= O) -O-} (C p H 2p O) r -C q H 2q ] _{^{m N (R 2) 3-}} m (1)
[Where,
R ¹ is a hydrocarbon group having 11 to 23 carbon atoms,
R ² is a group selected from a hydrocarbon group having 1 to 3 carbon atoms and a HO— (C _p H _2p O) _r —C _q H _2q group,
m is a number of 1 or more and 3 or less, p and q are 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 compound represented by the general formula (1) can be produced, for example, by an esterification reaction between a predetermined alkanolamine compound and a fatty acid or a transesterification reaction between a predetermined alkanolamine compound and a fatty acid ester. R ¹ in the general formula (1) preferably contains a saturated hydrocarbon group and an unsaturated hydrocarbon group from the viewpoint of the availability of fatty acids. Further, from the viewpoint of the availability of fatty acids, saturated fatty acids having 14 or more and 18 or less carbon atoms and unsaturated fatty acids having 14 or more and 18 or less carbon atoms, unsaturated fatty acids having 14 to 18 carbon atoms / 14 carbon atoms. It is preferable to contain in the molar ratio of -18 saturated fatty acid = 0.1 or more and 3 or less. The molar ratio is preferably 3 or less from the viewpoint of suppressing discoloration of the liquid softening agent composition. R ¹ in the general formula (1) is preferably a molar ratio of unsaturated hydrocarbon group having 14 to 18 carbon atoms / saturated hydrocarbon group having 14 to 18 carbon atoms = 0.1 or more and 3 or less.

  Saturated fatty acid represents a fatty acid having no unsaturated group in the molecule. Examples of saturated fatty acids include linear or branched saturated fatty acids.

Unsaturated groups contained in unsaturated fatty acids exist in cis and trans forms. Specific examples of the cis isomer / trans isomer ratio include cis isomer / trans isomer in a molar ratio of 30/70 or more and 99/1 or less. From the viewpoint of availability of the alkenyl group, the cis isomer / trans isomer is preferably 50/50 or more and 97/3 or less in terms of molar ratio. In the present invention, the ratio of the cis form to the trans form can be calculated by the integral ratio of ¹ H-NMR.

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

  Among the compounds represented by the general formula (1) as the component (a1), the tertiary amine compound may be partly or wholly contained in the form of an acid salt depending on the pH of the liquid softener composition. good.

  Examples of the acid in the case where the tertiary amine compound is present as an acid salt include inorganic acids and organic acids. As specific examples of the inorganic acid, hydrochloric acid and sulfuric acid can be used. Specific examples of the organic acid include monovalent carboxylic acids having 1 to 10 carbon atoms, monovalent or polyvalent sulfonic acids having 1 to 20 carbon atoms, and monoalkyl sulfates having 1 or 2 carbon atoms. Can be mentioned. More specifically, glycolic acid, benzoic acid, salicylic acid, p-toluenesulfonic acid, (o-, m-, p-) xylenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, monomethyl sulfate ester, monoethyl sulfate ester Can be mentioned.

  Although the manufacturing method in particular which obtains the tertiary amine compound represented by General formula (1) which is (a1) component is not restrict | limited, For example, the alkanolamine compound and fatty acid represented by the following general formula (1-1) It can be obtained by an esterification reaction or a transesterification reaction between an alkanolamine compound represented by the general formula (1-1) and a fatty acid short-chain alkyl (methyl, ethyl or propyl) ester.

_{[HO- (C p H 2p O)} r -C q H 2q ] ^{_{n N (R 5) 3-}} n (1-1)
[Wherein R ⁵ is a group selected from a hydrocarbon group having 1 to 3 carbon atoms, n is a number of 1 to 3 and p, q, and r are the same as those in the general formula (1). Represents meaning. ]

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

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

  The quaternized product of the tertiary amine compound represented by the general formula (1) as the component (a2) is a quaternary compound using a tertiary amine compound represented by the general formula (1) and an alkylating agent. It can be obtained by a chemical reaction.

  Examples of the alkylating agent include methyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, diethyl sulfate and the like. As an example of the quaternization reaction, for example, the method described in paragraph [0017] to paragraph [0023] of JP-A-7-138211, or the production method described in JP-A-66-66 can be applied. .

The component (A) is preferably a compound in which R ² is a HO— (C _p H _2p O) _r —C _q H _2q group in the general formula (1) from the viewpoint of suppressing precipitation of solids upon exposure to light. . The component (A) may be a mixture of a plurality of compounds. In that case, as the component (A), in the general formula (1), R ² is HO— (C _p H _2p O) _r —C _q H _2q It is preferable that the compound which is group is included.

  When the component (A) is a mixture of two or more types of compounds, a mixture having a number average number of m of 1.2 or more and 2.5 or less can be used. From the viewpoint of softening the textile, the number average number of m is preferably 1.3 or more, more preferably 1.4 or more, and is preferably 2.0 or less, and more preferably 1.9 or less.

  In obtaining a mixture satisfying the number average number of m, the compound of the general formula (1-1) used as the raw material may be a mixture of compounds having different structures, but the general formula (1-1) may be used. In the case where the compound is prepared using a compound with n = 3 in the formula (1), it is preferable that the number average numerical range of the m is in the range.

The component (A) is a mixture of one or more compounds selected from the acid salt of the component (a1) and the component (a1), and a component (a2). The mixture can be obtained by obtaining each component and then mixing them.
Further, when the component (a1) is subjected to a quaternization reaction to obtain the component (a2), it can be used as a mixture containing the component (a1) as an unreacted product or side reaction product and its acid salt.
Moreover, the mixture containing the acid salt of (a1) component and (a1) component can be obtained intentionally by adjusting the quaternization reaction rate.

The ratio of the mass of the component (a1) and the salt of the component (a1) and the mass of the component (a2) is represented by [(a1) component + acid salt of the component (a1)] / [(a2) component].
The mass of the component (a1) is the mass of the tertiary amine compound itself in the case of the tertiary amine compound represented by the general formula (1), and in the case of the acid salt of the tertiary amine compound. The mass is converted to the tertiary amine compound.
The mass of the component (a2) is a mass including a counter ion derived from the quaternizing agent used for quaternization of the tertiary amine compound (for example, methyl sulfate ion when quaternized with dimethyl sulfate). is there.
The mass ratio is [(a1) component + (a1) component acid salt] / [(a2) component] = 0.01 or more, and more preferably 0.1 or more, in terms of suppression of solid precipitation upon exposure to light. It is preferably 0.6 or less, more preferably 0.5 or less, and further preferably 0.3 or less.

[(B) component]
The component (B) is one or more compounds represented by the following general formula (2).
R ³ −N ⁺ (R ⁴ ) ₃ · X ⁻ (2)
[Wherein R ³ is a hydrocarbon group having 8 to 12 carbon atoms, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and — (C ₂ H ₄ O) is a group selected from _S— H groups, and s is an average added mole number, which is a number of 2 or more and 5 or less. X ^- is an anionic group. ]

In the structure of the general formula (2), R ³ is a group corresponding to a long chain and functions as a hydrophobic group. On the other hand, in the structure of the general formula (2), R ⁴ is a group that functions as a group corresponding to a short chain or a hydrophilic group. R ³ is a hydrocarbon group having 8 or more and 12 or less carbon atoms, preferably a hydrocarbon group having 10 or more and 12 or less carbon atoms, from the viewpoint of suppressing solid precipitation during light exposure. The hydrocarbon group is preferably a group selected from an alkyl group and an alkenyl group. An alkyl group is more preferable from the viewpoint of easy availability of the component (B). Further, a group selected from linear alkyl groups and alkenyl groups having 10 to 12 carbon atoms is preferred.
Specific examples of R ⁴ include a methyl group, an ethyl group, a hydroxyethyl group, and a — (C ₂ H ₄ O) _s —H group (where s is a number of 2 or more and 5 or less, preferably 4 or less. 1) or more groups selected from: In the compound represented by the general formula (2), R ⁴ in the same molecule may be the same group or different groups. In general formula (2), it is preferable that at least two of R ⁴ are the same group.

From the viewpoint of ease of production of the component (B), R ⁴ is preferably a group selected from a methyl group, an ethyl group and a hydroxyethyl group.

X ⁻ represents an anionic group, and specific examples include halogen ions such as chlorine ions, bromine ions, or alkyl sulfate ions having 1 or 2 carbon atoms such as methyl sulfate ions and ethyl sulfate ions.

[Component (C)]
Component (C) is a polyoxyethylene alkyl ether obtained by adding an average of 15 to 50 moles of ethylene oxide to an aliphatic alcohol having 9 to 12 carbon atoms. From the viewpoint of chain freezing recovery, the aliphatic alcohol is preferably at least one selected from linear primary alcohols, branched primary alcohols and linear secondary alcohols. Here, the primary alcohol is a compound in which the carbon atom to which the hydroxyl group is bonded is the first carbon atom, and the secondary alcohol is a compound in which the carbon atom to which the hydroxyl group is bonded is the second carbon atom. Furthermore, in the present invention, the straight chain and the branched chain indicate the structure of an alkyl group, and the case where the alkyl group has a branched structure of a hydrocarbon group is defined as a branched chain. In the present invention, for example, an aliphatic alcohol having no branched structure other than a hydroxyl group is a linear secondary alcohol.

  From the viewpoint of suppressing thickening when the softening agent composition is vibrated, the average added mole number of ethylene oxide is 15 or more, preferably 20 or more, and 50 or less, preferably 40 or less. .

  In the present invention, as the component (C), polyoxyethylene alkyl ether in which ethylene oxide is added to an average of 20 mol or more and 40 mol or less to a linear secondary alcohol having 9 to 11 carbon atoms is more preferable.

[Component (D)]
(D) A component is an inorganic salt. The inorganic salt is preferably a water-soluble inorganic salt. In the present invention, a compound that dissolves 10 g or more in 100 g of deionized water at 20 ° C. is defined as a water-soluble inorganic salt. Preferred inorganic salts include inorganic salts selected from alkali metal chlorides and alkaline earth metal chlorides. Furthermore, one or more inorganic salts selected from the group consisting of sodium chloride, potassium chloride, calcium chloride and magnesium chloride are preferred from the viewpoint of the storage stability of the composition. From the viewpoint of viscosity adjustment, one or more inorganic salts selected from the group consisting of calcium chloride and magnesium chloride are more preferable.

[Liquid softener composition]
In the liquid softening agent composition of the present invention, the content of the component (A) is 3% by mass or more and 20% by mass or less. The content of the component (A) is preferably 5% by mass or more, and more preferably 7% by mass or more in the composition from the viewpoint that the usage amount per wash can be reduced. In addition, the content of the component (A) is preferably 20% by mass or less, more preferably 18% by mass or less in the composition from the viewpoint of suppressing solid precipitation during light exposure.

  In the liquid softener composition of the present invention, the content of the component (B) is 0.1% by mass or more, and preferably 0.2% by mass or more, from the viewpoint of suppressing solid precipitation during light exposure. From the viewpoint of separation suppression and economic efficiency due to long-term storage, it is 1.0% by mass or less, and preferably 0.8% by mass or less.

  In the liquid softener composition of the present invention, the content of the component (C) is 3.0% by mass or more, and preferably 3.5% by mass or more, from the viewpoint of suppressing the increase in viscosity when applying vibration. From the viewpoint of suppression of separation by long-term storage and economical efficiency, it is 5.0% by mass or less, and preferably 4.5% by mass or less.

  In the liquid softener composition of the present invention, the content of the component (D) is 0.1% by mass or more, and preferably 0.2% by mass or more from the viewpoint of viscosity reduction of the composition. From the viewpoint of separation suppression and economic efficiency due to long-term storage, it is 1.0% by mass or less, and preferably 0.8% by mass or less.

  The viscosity (30 ° C.) of the liquid softening agent composition of the present invention is preferably 5 mPa · s or more, more preferably 10 mPa · s or more, and more preferably 100 mPa · s or less, more preferably 80 mPa · s or less, from the viewpoint of ease of use. . The viscosity of the composition was measured using a B-type viscometer. 1-No. Using one of the three rotors, the indicated value is one minute after the start of measurement at 60 r / min. The liquid softener composition is measured by adjusting the temperature to 30 ± 1 ° C.

  The liquid softening agent composition of the present invention has a pH of 2.5 or more and 4.0 or less at 30 ° C. from the viewpoint of hydrolytic stability of the component (A). The pH is preferably 3.5 or less. The pH is measured at 30 ° C. according to item 8.3 of JIS K 3362; 2008.

  The liquid softener composition of the present invention is preferably an emulsion (emulsion) liquid softener composition for reasons of storage stability. In the present invention, the liquid softener composition in an emulsion state means that the component (A) forms large particles that scatter visible light in the liquid softener composition, so that the visible light is scattered and visually observed. The above represents a liquid softener composition having a cloudy appearance. Specifically, when a glass cell having an optical path length of 10 mm is used as a measurement cell and ion-exchanged water is added to the control cell, the visible light transmittance (wavelength) of the sample measured using an ultraviolet-visible spectrophotometer. 660 nm) refers to a liquid softener composition that is less than 25%.

[Optional ingredients]
The liquid softener composition in an emulsion state can contain an oil agent, a pH adjuster, a fragrance, an antioxidant, a chelating agent, a dye, an antiseptic, a silicone compound, and the like as optional components.

  The oil agent used in the present invention is used for imparting further excellent softness performance to the fiber product. Examples include esterified products of polyhydric alcohols and fatty acids, and preferred examples include glycerin fatty acid esters, pentaerythritol fatty acid esters, sorbitan fatty acid esters, and the like. From the viewpoint of improving the softness performance, the fatty acid is preferably palmitic acid, stearic acid, or a mixture thereof.

  The pH adjuster used in the present invention is used to adjust the softener composition to an optimum pH for the purpose of inhibiting hydrolysis of the component (A). For example, inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid, lactic acid, glycolic acid, oxalic acid, succinic acid, citric acid, maleic acid, fumaric acid, propionic acid, malonic acid, glutaric acid, adipic acid , Malic acid, crotonic acid, benzoic acid, paratoluenesulfonic acid, cumenesulfonic acid, metaxylenesulfonic acid, polyacrylic acid and other organic acids, sodium hydroxide, potassium hydroxide, triethanolamine and other inorganic bases, or An organic base is mentioned.

  The fragrance | flavor used in this invention is used in order to give a consumer high palatability with respect to a softening agent composition. Preference is not only the effect of giving a pleasant feeling such as exhilaration, sedation, exhilaration, but also the effect of deodorizing unpleasant odors such as sweat odor, cigarette odor, fresh odor, cooling action, heat action, hypnosis It may also include functional effects such as action, aphrodisiac action, antidepressant action, antibacterial action, and diet action. As the fragrance component, for example, the fragrance described in “Basic knowledge of fragrance and fragrance, edited by Motoki Nakajima, published by Sangyo Tosho Co., Ltd., April 20, 2005,” No. 10-507793. Perfume can be used.

  Perfume ingredients are appropriately selected and used from the standpoints of fragrance quality and strength, and stability in softener systems. Hereinafter, the compounds that can be blended in the present invention and that are used as a perfume component are classified into the categories shown in the perfume field and are as follows. Examples of terpene compounds include limonene, p-cymene, α-pinene, β-pinene, and β-caryophyllene, and alcohol compounds include cis-3-hexenol, trans-2-hexenol, methyltrimethylcyclopentenylbutenol, and dihydromil. Senol, l-menthol, phenylethyl alcohol, citronellol, geraniol, nerol, linalool, terpineol, tetrahydrolinalol, tetrahydrogeraniol, dimethylbenzyl carbinol, β-phenylethyl alcohol, benzyl alcohol, cinnamic alcohol, anis alcohol, farnesol, Nerolidol, dimethylphenylethyl carbinol, o, t-butylcyclohexanol, p, t-butylcyclohexanol, sandalma Sole core (2-methyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol) (manufactured by Kao Corporation), bagdanol (manufactured by IFF), jabanol (Product of Dibodan Co., Ltd.), and ester compounds such as benzyl acetate, dimethylbenzylcarbvinyl 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, styryl acetate, cis-3-hexenyl acetate, trans-2-hexenyl acetate Hexyl acetate, cinnamyl acetate, isobutyl propionate, 2-phenylethyl propionate, Citronellyl onion, benzyl propionate, tricyclodecenyl propionate, geranyl propionate, allyl propionate, geranyl butyrate, citronellyl butyrate, isoamyl butyrate, amyl butyrate, allyl butyrate, phenoxyethyl isobutyrate, geranyl isobutyrate, isoyoshichi Geranyl herbate, ethyl caproate, allyl caproate, ethyl enanthate, allyl enanthate, ethyl octoate, methyl anthranilate, cis-3-hexenyl benzoate, benzyl benzoate, amyl salicylate, isoamyl salicylate, benzyl salicylate, cis salicylate -3-hexenyl, hexyl salicylate, 2-phenylethyl salicylate, methyl dihydrojasmonate, coumarin, γ-octalactone, γ-undecalactone, γ-decalactone, γ-nonalacto , Δ-nonalactone, δ-decalactone, δ-undecalactone, δ-dodecalactone, cyclopentadecanolide, cyclopentadecenolide (Havanolide, manufactured by Firmenich), cyclohexadecanolide, amblet lidide, 11-oxa-16-hexadecanolide (Musk R-1, manufactured by Dibodan), 10-oxa-16-hexadecanolide (Oxalide, manufactured by Takasago International Corporation), 12-oxahexadecanolide, ethylene brushate, ethylenedodecanedio Aldehyde (musk C-14), and aldehyde compounds include octanal, nonanal, decanal, undecanal, 10-undecenal, dodecanal, citral, citronellal, anisaldehyde, phenylacetaldehyde, mylacaldehyde, lilyal, rilal, dimethyltetra Hi Robenzaldehyde, amylcinnamic aldehyde, hexylcinnamic aldehyde, cyclamenaldehyde, vanillin, ethyl vanillin, heliotropin, helional are mentioned, and ketone compounds include florarozone, l-carvone, menthone, cis jasmon, geranylacetone, damascones, Damasenones, α-dynascon, ionones, methylionones, β-methylnaphthyl ketone, iso-E super, raspberry ketone, maltol, ethyl maltol, cachemelan (manufactured by IFF), 5-cyclohexedenon-1-one (Musk ™ -II), and ether compounds such as anethole, eugenol, methyl eugenol, methyl isoeugenol, diphenyl oxide, 1,8-cineole, cedryl methyl ether, a Broxan (3α, 6,6,9α-tetramethyldodecahydronaphtho [2,1-b] furan), ethoxymethylcyclododecyl ether (boasambrenforte, manufactured by Kao Corporation), geranyl nitrile as a nitrogen-containing compound Citronellyl nitrile, indole, acetyl cedrene, methyl anthranilate, methyl N-methylanthranylate, auranthiol, peonyl (manufactured by Dibodan) and the like.

  The fragrance | flavor used for such a composition may mix | blend a fragrance | flavor by encapsulating the fragrance | flavor for the purpose of the fragrance sustainability and the remaining fragrance property. The fragrance microcapsule is a spherical substance that is made by wrapping the fragrance of the core material with a wall material. Its role is to protect the fragrance of the core material, and when the capsule is subjected to physical force, the capsule wall breaks and the core It releases the fragrance of the substance.

Further, for the purpose of scent sustainability and residual fragrance, an ester of silicic acid and an alcohol used as a fragrance (hereinafter referred to as “alcoholic fragrance”), for example, a general formula (Japanese Unexamined Patent Publication No. 2009-256818) ( The compound represented by 1) can be used. As alcoholic fragrance | flavors, the alcohol of following i) -iii) is mentioned.
i) Aliphatic alcohols having a log P of 1 to 5 Specifically, cis-3-hexenol (1.4), geraniol (2.8), nerol (2.8), 2,6-dimethyl-2- Heptanol (3.0), menthol (3.2), citronellol (3.3), rosinol (3.3), 9-decenol (3.5), tetrahydrolinalool (3.5), tetrahydrogeraniol (3. 7), 4-methyl-3-decen-5-ol (3.7), tetrahydrogeraniol (3.7) and the like. Here, the values in () are logP values (the same applies to the following ii) and iii).

ii) Aromatic alcohol having a log P of 1 to 5 Specifically, anis alcohol (1.0), raspberry ketone (1.1), phenylethyl alcohol (1.2), eugenol (2.4), isoeugenol ( 2.6), dimethylbenzyl carbinol (3.0), phenylethylmethylethyl carbinol (3.0), 3-methyl-5-phenylpentanol (3.2), thymol (3.4) and the like. Can be mentioned.

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

  In the present invention, the log P value is a coefficient indicating the affinity of an organic compound for water and 1-octanol. 1-octanol / water partition coefficient P is a distribution equilibrium when a trace amount of compound is dissolved as a solute in a two-liquid solvent of 1-octanol and water, and is a ratio of the equilibrium concentration of the compound in each solvent. It is common to show them in the form of their logarithm logP relative to the base 10. Log P values of many compounds have been reported, and many values are listed in databases available from Daylight Chemical Information Systems, Inc. (Daylight CIS), etc., and can be referred to. When there is no measured log P value, it can be calculated by a program “CLOGP” or the like available from Daylight CIS. This program outputs the value of “calculated logP (ClogP)” calculated by the fragment approach of Hansch, 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 in place of the actual logP value in selecting a compound. In the present invention, if there is a measured value of logP, the ClogP value calculated by the program CLOGP v4.01 is used.

  The antioxidant used in the present invention is, for example, an antioxidant having a phenol group in the molecule. An antioxidant having a phenol group in the molecule is used to suppress a change in the odor of the fragrance. When an antioxidant is used in combination with a fragrance, the change in odor can be suppressed, but since the antioxidant having a phenol group that has been oxidized is colored, the discoloration of the softener composition is promoted. The compounding amount of the agent is used after sufficiently confirming with the perfume component that is susceptible to oxidation and its content.

  From the viewpoint of easy availability, 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol are antioxidants having a phenol group in the molecule. And one or more antioxidants selected from butylhydroxyanisole are preferred. From the viewpoint of suppressing discoloration, one or more antioxidants selected from 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol are preferable. .

  The chelating agent used in the present invention is used for suppressing discoloration of the softening agent composition and discoloration of the dye due to storage. For example, ethane-1-hydroxy-1,1-diphosphonic acid, ethylenediaminetetraacetic acid, methylglycine diacetate, hydroxyethyliminodiacetic acid, ethylenediamine disuccinic acid, L-glutamic acid-N, N-diacetic acid, N-2- One or more selected from hydroxyethyliminodiacetic acid, citric acid, succinic acid and salts thereof are preferred.

  The dye used in the present invention is used to give consumers a high preference for the softener composition. For example, one or more dyes selected from a color index acidic red dye, a color index acidic yellow dye and a color index acidic blue dye.

Specific examples of the color index acidic red dye include CIAcid Red 18 CIAcid Red 27, CIAcid Red 52, CIAcid Red 82, CIAcid Red 114, 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. Also, dyes available as polymer dyes can be used.

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

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

  The silicone compound used in the present invention is used for imparting further excellent softness performance to a textile product. For example, dimethyl silicone, polyether modified silicone, methylphenyl silicone, alkyl modified silicone, higher fatty acid modified silicone, methyl hydrogen silicone, fluorine modified silicone, epoxy modified silicone, carboxy modified silicone, carbinol modified silicone, amino modified silicone, etc. Is mentioned. From the viewpoint of the softening effect, dimethyl silicone, amino-modified silicone, and polyether-modified silicone are particularly preferable, and dimethyl silicone and amino-modified silicone are more preferable. These can be used alone or as a mixture of two or more.

  The liquid softening agent composition of the present invention is suitable for textile products, and examples of the textile products include clothing, fabrics, bedding, towels and the like.

[Bag-like softener article]
The bag-like softener article of the present invention is a bag-like container filled with the above-described liquid softener composition.
The bag-like container is composed of a laminated material in which at least two plastic layers are laminated. As the bag-like container, a bag-like container described in paragraphs [0019] to [0022] of JP-A No. 2001-098300 or JP-A 2011-122093 can be used.

  Laminated materials for manufacturing bag-like containers include stretched nylon (ONy), polyethylene terephthalate (PET), stretched polypropylene (OPP), high-density polyethylene (HDPE), etc. on the outermost layer (layer where light first enters) A base material layer [Layer I] is disposed, and a sealant layer [Layer II] composed of unstretched polypropylene (CPP), linear low density polyethylene (L-LDPE), low density polyethylene (LDPE), etc. is disposed on the inside. The ones made are preferred. The base layer [Layer I] made of stretched nylon (ONy) is disposed as the outermost layer, and a linear low density polyethylene (L-LDPE) is arranged on the inner side in that it is easier to obtain a solid precipitation suppressing effect in sunlight exposure. A laminate material in which a sealant layer [Layer II] is formed is preferred.

  The thickness of the base material layer [Layer I] may be any thickness that can be held to the minimum necessary for rigidity and the like, and can be determined taking into account bag-making processability, cost, and strength, but is 10 μm or more and 50 μm. The following is preferred. The thickness of the entire laminated material can also be determined in consideration of bag-making processability, cost, strength and rigidity, and is preferably 100 μm or more and 300 μm or less.

  Lamination of each layer of the film is performed using an adhesive such as polyurethane or ester or a water-soluble adhesive such as casein.

  The bag-like container is obtained by laminating the above-described laminated material (composite film base material) with the innermost layer as the inner layer and bonding the peripheral edge thereof by heat sealing or the like to form a bag shape. .

[Component (A)]
The component (A) used in the examples is shown below.
(A-1) Component Fatty acid represented by R ¹ COOH with triethanolamine is subjected to esterification reaction at a reaction molar ratio (fatty acid / triethanolamine) of 1.65 / 1. An esterification reaction product containing the represented amine compound was obtained.
The esterification reaction product contained 5% by mass of unreacted fatty acid (composition as described later). 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.

  As a result of analyzing the composition ratio of each component of the obtained reaction product by HPLC method and using tetraoctyl ammonium bromide as an internal standard substance, the obtained reaction product was obtained from the following component (a11-1): It was a mixture (100 mass% in total) consisting of the component (a11-3), the component (a21-1) to the component (a21-3), and the unreacted fatty acid. The quaternization rate was 92%. The quaternization rate can be determined from the amine value.

() Content in the, (a11-1) component ~ (A11-3) component, (A21-1) quaternary ammonium ion moiety of component ~ (A21-3) component (CH ₃ OSO ₃ ^- excluding Part) and the content ratio of each component in the total of unreacted fatty acids.

Unreacted fatty acid: (2% by mass)
The composition of R ¹ COOH used for production 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 one unsaturated group: 33% by mass
Fatty acid with 18 carbon atoms and two unsaturated groups: 3% by mass
The composition was analyzed for the fatty acid used as a raw material by gas chromatography, and the area% of each fatty acid was regarded as mass%. The mass ratio of the cis / trans isomer of the unsaturated group is 85/15 (integral ratio by ¹ H-NMR).

(A-2) Component The fatty acid represented by N-methyldiethanolamine and R ¹ COOH is esterified with a reaction molar ratio (fatty acid / triethanolamine) of 1.9 / 1, and the general formula (1) An esterification reaction product containing the represented amine compound was obtained.
The esterification reaction product contained 5% by mass of unreacted fatty acid (composition as described later). After adding 10% by mass of ethanol to the amine of the amine compound in the esterification reaction product and mixing them uniformly, methyl chloride is added to the amine so that the methyl group becomes 0.98 equivalents. A grading reaction was performed. The quaternization rate was 90%.
As a result of analyzing the composition ratio of each component of the obtained reaction product by HPLC method and using tetraoctylammonium bromide as an internal standard substance, the obtained reaction product was the following component (a12-1): It was a mixture (100 mass% in total) consisting of the component (a22-1), the component (a22-2), and the unreacted fatty acid.
The number in parentheses, (a12-1) component, (A22-1) component, (A22-2) quaternary ammonium ion portion of the component ^- in the total of (Cl portions excluding), and unreacted fatty acids The content ratio of each component is shown.

Unreacted fatty acid: (8.7% by mass)
The composition of R ¹ COOH used for production is shown below.
Palmitic acid: 10% by mass
Stearic acid: 60% by mass
Fatty acid having 18 carbon atoms and one unsaturated group: 30% by mass
The composition was analyzed for the fatty acid used as a raw material by gas chromatography, and the area% of each fatty acid was regarded as mass%. The cis / trans isomer ratio of the unsaturated group is 1/1 (integral ratio by ¹ H-NMR).

[(B) component]
(B-1): N-lauryltrimethylammonium chloride (b-2): N-octyltrimethylammonium chloride (b-3): N-lauryl-N-hydroxyethyl-N, N-dimethylammonium methylsulfate

[(B ′) component]
(B′-1): N-tetradecyltrimethylammonium chloride (b′-2): N-hexadecyltrimethylammonium chloride

[Component (C)]
(C-1): Polyoxyethylene lauryl ether obtained by adding 21 moles of ethylene oxide to lauryl alcohol on average (c-2): Emulgen 1135S-70 [Exxal 11 alcohol (branched primary alcohol having 9 to 11 carbon atoms, Polyoxyethylene alkyl ether obtained by adding an average of 35 moles of ethylene oxide to ExxonMobil Corp., manufactured by Kao Corporation]
(C-3): Softanol 400 [polyoxyethylene alkyl ether obtained by adding an average of 40 moles of ethylene oxide to a linear secondary alcohol having 9 to 11 carbon atoms, manufactured by Nippon Shokubai Co., Ltd.]

[(C ′) component]
(C′-1): Neodol 91-8 [polyoxyethylene alkyl ether obtained by adding an average of 8 mol of ethylene oxide to a linear alcohol having 9 to 11 carbon atoms, manufactured by Shell Chemicals Japan Co., Ltd.]

[Component (D)]
(D-1): Calcium chloride (d-2): Magnesium chloride

[Optional ingredients]
(E-1): stearic acid mono, di, triglyceride mixture (mono / di / tri = 60/35/5, molar ratio)
(F-1): citric acid (g-1): sodium hydroxide (h-1): perfume composition of Table 2 (i-1): 1,2-benzisothiazolin-3-one (proxel BDN (arch)・ Chemical Japan Co., Ltd.))
(J-1): Highly polymerized dimethicone emulsion: 60% by mass of dimethylpolysiloxane having a kinematic viscosity at 25 ° C. of 500,000 mm ² / s and an average ethylene oxide (hereinafter referred to as EO) addition of 5 mol of polyoxyethylene lauryl ether 1.5% by mass, average EO addition mole number 23 mol of polyoxyethylene lauryl ether 4.5% by mass, lauryl sulfate sodium salt 0.1% by mass, remaining emulsion, average particle diameter of dispersed particles 500 nm

[Bag-like container]
A bag-like container (length: 200 mm, width 90 mm) formed using a laminated material having the following configuration was used. Layer I was an outer layer, and layer II was an inner layer (a layer in contact with the composition).
(Layer I) Stretched nylon (ONy), thickness 15 μm, back surface (surface in contact with layer II) gravure printed (white solid twice) (layer II) linear low density polyethylene (L-LDPE), heat 150 μm

<Method for producing emulsion liquid softener composition>
An emulsion type liquid softening agent composition was prepared by mixing each component so as to have a blending composition shown in Table 1 (numbers in blending amount are mass%. Each component is expressed in effective amount). Specifically, it is as follows.

In a 300 mL beaker, 90% by mass of ion-exchanged water and component (B) (or component (B ′)), (C), which are necessary for the final mass of the emulsion-type liquid softening agent composition to be 200 g. ) Component [or (C ′) component] and (i-1) component were added, and the temperature of ion-exchanged water was adjusted to 60 ± 2 ° C. using a water bath. (B) Component [or (B ′) component] and (C) Component [or (C ′) component] were stirred using the following stirring blade as necessary so that they were uniformly dissolved in ion-exchanged water. .
Ion exchange water containing (B) component [or (B ′) component], (C) component [or (C ′) component], (i-1) component adjusted to a temperature of 60 ± 2 ° C. Is a stirring blade (the number of blades: three, the long side / short side of the blade: 3 cm / 1.5 cm, with the long side being in the direction of 90 degrees with respect to the rotation center axis of the stirring rod of 5 mm. Installation of blades: While stirring (300 r / m) at an angle of 45 degrees with respect to the rotating surface, the component (A) heated and dissolved together with the component (e-1) at 65 ° C. was added over 3 minutes. After completion of the addition, the mixture was stirred for 15 minutes.
(D) The 10 mass% aqueous solution of a component was thrown in and it stirred for 10 minutes. Using a 5 ° C. water bath, the contents were cooled to 30 ± 2 ° C. Thereafter, the (f-1) component, the (g-1) component, the (h-1) component, and the (j-1) component were sequentially added and stirred for 5 minutes. Ion exchange water was added so that the mass (200 g) was completed, and the mixture was stirred for 5 minutes, and then the pH was adjusted with hydrochloric acid or an aqueous sodium hydroxide solution to obtain a liquid softener composition.

  It confirmed that it was an emulsion type about the liquid softening agent composition of the Example of Table 1, and a comparative example. That is, a liquid softening agent composition measured using an ultraviolet-visible spectrophotometer (UV-2500PC manufactured by Shimadzu Corporation) using a glass cell having an optical path length of 10 mm as a measurement cell, putting ion-exchanged water into a control cell. The visible light transmittance (wavelength 660 nm) was less than 10%, confirming that it was an emulsion liquid softener composition of an emulsion. The composition of the emulsion liquid softener composition is shown in Table 2.

<Evaluation method>
(1) Appearance stability No. of liquid softener composition. A sample for evaluation was prepared by placing 40 ml in a 6-glass transparent wide-mouth standard bottle and capping with a polyethylene cap and a polypropylene screw cap. The appearance of the sample for evaluation after storage for 20 days at room temperature, specifically in the range of 20 to 25 ° C., was observed. The case where the appearance did not change was designated as “◯”, and the case where the upper layer or the lower layer was separated in the aqueous phase was designated as “separation”.

(2) Light stability (2-1) Exposure test The test machine used was a low-temperature cycle xenon fade meter (model number: XL75, manufactured by Suga Test Instruments Co., Ltd.).
In the test machine, 300 g of the liquid softening agent composition was filled and the maximum area of the bag-like container sealed with a heat sealer was placed facing the lamp, and irradiated with light under the following irradiation conditions. The operation was stopped and left as it was for 18 hours (one cycle). After 11 cycles of this cycle, the seal part on the upper side of the container was picked and carefully taken out from the testing machine so as not to move the liquid softener composition inside.
* Irradiation conditions and set irradiance: 42 W / m ²
・ Set radiation time: 6 hours (integrated irradiance: 0.9 MJ / m ² )
・ Black panel temperature: 45 ℃

(2-2) Measurement of Weight of Precipitated Solid Material The seal part on the upper side of the container is cut with scissors, the container is turned upside down, and the content (liquid softener composition) is made of stainless steel mesh (200 mesh opening 75 μm). And filtered. After filtration, the weight of the solid precipitate remaining on the mesh after standing for 1 minute was measured (the weight of the stainless steel mesh before filtration was measured in advance, and the difference was defined as the weight of the solid precipitate). The results are shown in Table 1.

(3) Freezing recovery property The freezing recovery property of the liquid softening agent composition was evaluated by the viscosity after freezing recovery.
The test machine used the low temperature thermostat (model number; PU-3K, Espec Co., Ltd. make). An operation in which a bag-like container filled with 300 g of the liquid softening agent composition was placed in the test machine and allowed to stand at −20 ° C. for 12 hours and at 20 ° C. for 12 hours was set as one cycle, and this cycle was repeated three times.
After the completion, 90 g of the liquid softener composition The product was transferred to an 11 standard bottle, sealed with a special cap, adjusted to a content temperature of 30 ° C. using a 30 ° C. water bath, and then allowed to stand for 1 hour while maintaining the content temperature at 30 ° C. Start viscosity measurement of each liquid softener composition using a B-type viscometer (model number; TVB-10 manufactured by Toki Sangyo Co., Ltd., using any of No. 1-3 rotors, 60 r / min), The value after 1 minute was read (the unit of viscosity is “mPa · s”). In this evaluation, the viscosity after freeze recovery is preferably 500 mPa · s or less. The results are shown in Table 1.

(4) Shaking stability The shaking stability of the liquid softening agent composition was evaluated by the viscosity after shaking storage.
The testing machine used was a powerful shaker (model number; reciprocating shaker SR-II, manufactured by Taitec Corporation). No. 30 g was sealed in a 6 standard bottle, shaken at 360 rpm for 20 seconds, and allowed to stand at room temperature for one week. After adjusting the content temperature to 30 ° C. using a 30 ° C. water bath, the content temperature was kept at 30 ° C. for 1 hour. Start viscosity measurement of each liquid softener composition using a B-type viscometer (model number; TVB-10 manufactured by Toki Sangyo Co., Ltd., using any of No. 1-3 rotors, 60 r / min), The value after 1 minute was read (the unit of viscosity is “mPa · s”). In this evaluation, the viscosity after shaking storage is preferably 100 mPa · s or less. The results are shown in Table 1.

Claims (2)

A liquid softener composition comprising the following component (A), component (B), component (C), and water, and having a pH at 30 ° C. of 2.5 or more and 4.0 or less.
(A) Component: (a1) A tertiary amine compound represented by the following general formula (1), its acid salt and (a2) a compound selected from its quaternized product, or a mixture containing them: 3% by mass or more, 20 wt% or less ^{[R 1 -C (= O) -O-} (C p H 2p O) r -C q H 2q ] _{^{m N (R 2) 3-}} m (1)
[Where,
R ¹ is a hydrocarbon group having 11 to 23 carbon atoms,
R ² is a group selected from a hydrocarbon group having 1 to 3 carbon atoms and a HO— (C _p H _2p O) _r —C _q H _2q group,
m is a number of 1 or more and 3 or less, p and q are 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. ]
Component (B): Compound represented by the following general formula (2) 0.1% by mass or more and 1.0% by mass or less R ³ —N ⁺ (R ⁴ ) ₃ · X ⁻ (2)
[Wherein R ³ is a hydrocarbon group having 8 to 12 carbon atoms, R ⁴ is an alkyl group having 1 to ⁴ carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, and — (C ₂ H ₄ O) is a group selected from _S— H groups, and s is an average added mole number, which is a number of 2 or more and 5 or less. X ^- is an anionic group. ]
Component (C): Polyoxyethylene alkyl ether in which ethylene oxide is added to an aliphatic alcohol having 9 or more and 12 or less carbon atoms in an average of 15 or more and 50 or less mols in an amount of 3.0 to 5.0% by mass ( D) Component: Inorganic salt 0.1% by mass or more and 1.0% by mass or less   A bag-like softener article, wherein the liquid softener composition according to claim 1 is filled in a bag-like container.