JP6163053B2 - Bag softener article - Google Patents

Description

  The present invention relates to bagging softener articles.

  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.

  In order to impart a scent to a textile product, the softener composition is blended with a fragrance composition containing various fragrance materials. In particular, aldehyde fragrances are frequently used as base fragrances, and can impart a rich fragrance to textiles.

  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 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 discloses a plastic finishing agent containing a plastic sachet containing a compound such as polyethylene glycol and suppressing the occurrence of lumps during outdoor storage.

  Patent Document 3 discloses that a softening agent obtained by filling a softening agent composition containing a specific perfume into a container made of a laminated material including an aluminum layer is excellent in preventing leakage of aromatic substances to the outside. Has been.

JP-A-8-81881 JP-A-8-35174 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, a product in which a bag-like container is filled with a liquid softener composition in an emulsion state containing a softening base containing an ester group in the molecule and an aldehyde perfume having an aromatic group in the molecule is exposed to sunlight. As a result, it was clarified that a solid precipitates in the emulsified liquid softening agent composition in contact with the surface exposed to light of the container. As described above, an aldehyde fragrance having an aromatic group in the molecule can impart a rich scent to the fiber product, and is therefore a preferred component for blending into a softener, and it is possible to precipitate solids as described above. A technology that can prevent this is desired.

  The present invention relates to a bag softener article in which a liquid softener composition is filled in a bag-like container, and relates to the stability of the liquid softener composition upon exposure to light, specifically, the suppression of solid precipitation and the maintenance of viscosity. It is an object of the present invention to provide a packaged softener article that is excellent and can suppress discoloration of the appearance of a liquid softener composition due to storage.

The present invention includes the following (A) component 5 mass% or more, 25 mass% or less, the following (B) component 0.05 mass% or more, 1.5 mass% or less, the following (C) component 0.05 mass% or more, 2 mass% or less, the following (D) component 1.0 mass% or more, 5.0 mass% or less, the following (E) component and water are contained, and the viscosity in 30 degreeC is 5 mPa * s or more and 200 mPa * s or less The emulsified liquid softening agent composition relates to a bagging softening article filled in a bag-like container.
Component (A): (a1) One or two selected from tertiary amine compounds represented by the following general formula (1) and acid salts of tertiary amine compounds represented by the following general formula (1) One or more compounds selected from the above compounds [hereinafter referred to as the component (a1)] and (a2) quaternized tertiary amine compounds represented by the following general formula (1) [hereinafter, (Referred to as “component (a2)”) wherein the component (a1) and component (a2) have a mass ratio of (a1) / (a2) of 0.01 or more and 0.6 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 —C (═O) is an acyl group derived from a fatty acid having 12 to 22 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, 2 or 3, p and q are numbers of 2 or 3, respectively, 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): One or more compounds selected from divalent or trivalent carboxylic acids having a hydroxyl group in the molecule and salts thereof (C) Component: represented by the following general formula (2) Compound R ³ —N ⁺ (R ⁴ ) ₃ · X ⁻ (2)
[Wherein R ³ is a hydrocarbon group having 8 to 16 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 _s H _2s O) _t —H group (where s is a number of 2 or 3, t is a number of 2 or more and 15 or less), and X ⁻ is an anionic group. is there. R ⁴ may be the same or different. ]
(D) Component: One or more glycol compounds selected from ethylene glycol, propylene glycol and glycerin.
(E) Component: Aldehyde fragrance having an aromatic group in the molecule

  The bag softener article of the present invention is excellent in the stability of the liquid softener composition when exposed to light. Specifically, it is excellent in suppressing solid precipitation of the liquid softening agent composition upon exposure to light and maintaining the viscosity of the liquid softening agent composition upon exposure to light. The bagging softener article of the present invention, for example, is capable of suppressing precipitation of solids and increasing viscosity so that it can be used at home even when stored by being irradiated with sunlight or light having a strength corresponding to sunlight. It is suppressed. Moreover, the discoloration of the external appearance after high temperature storage is also suppressed.

<Emulsion liquid softener composition>
In the present invention, an emulsion liquid softener composition means that visible light can be obtained by forming large particles such that the compounding component such as the component (A) scatters visible light in the liquid softener composition. It represents a liquid softener composition that is scattered and visually turbid. Specifically, when a glass cell having an optical path length of 10 mm is used as a measurement cell and ion-exchanged water is put into a control cell, the visible light transmittance (wavelength) of the sample measured using an ultraviolet-visible spectrophotometer. 660 nm) represents a liquid softener composition with less than 25%.

[Component (A)]
The component (A) is (a1) one or two selected from a tertiary amine compound represented by the following general formula (1) and an acid salt of a tertiary amine compound represented by the following general formula (1) One or more compounds selected from the quaternized product of the tertiary amine compound represented by the following general formula (1): (a2) one or more compounds [hereinafter referred to as component (a1)] , (Component a2)]. In the component (A), the mass ratio of the component (a1) to the component (a2) is 0.01 or more and 0.6 or less in terms of (a1) / (a2).

^{[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 —C (═O) is an acyl group derived from a fatty acid having 12 to 22 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, 2 or 3, p and q are numbers of 2 or 3, respectively, 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 components (a1) and (a2) are the masses of unsaturated fatty acid / saturated fatty acid, respectively, wherein the acyl group R ¹ —C (═O) in the general formula (1) of the component (a1) and component (a2) It is preferably composed of fatty acids having a ratio of 0.1 or more and 3 or less. Further, the mass ratio of unsaturated fatty acid / saturated fatty acid is preferably 0.1 or more, more preferably 0.3 or more, more preferably 0.6 or more, and preferably 3 or less, more preferably 2 Below, more preferably 1.5 or less.

In addition, the (a1) component and the (a2) component have the acyl group R ¹ —C (═O) in the general formula (1) of the (a1) component and the (a2) component, respectively (with 14 or more carbon atoms, 18 or less unsaturated fatty acid) / (saturated fatty acid having 14 or more carbon atoms and 18 or less carbon atoms) = 0.1 or more and preferably 3 or less. The mass ratio of (unsaturated fatty acid having 14 to 18 carbon atoms) / (saturated fatty acid having 14 to 18 carbon atoms) is preferably 0.1 or more, more preferably 0.3 or more, and still more preferably. It is 0.6 or more, and preferably 3 or less, more preferably 2 or less, still more preferably 1.5 or less.

  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. The fatty acid used for the synthesis of the tertiary amine compound of the general formula (1) is composed of a saturated fatty acid having 12 to 22 carbon atoms and an unsaturated fatty acid having 12 to 22 carbon atoms. It is preferable that the fatty acid is a mixed fatty acid having a mass ratio of 0.1 or more and 3 or less. This mass ratio is preferably 0.1 or more from the viewpoint of softening performance, and preferably 3 or less from the viewpoint of suppressing discoloration of the liquid softening agent composition after high-temperature storage.

  Moreover, the fatty acid used for the synthesis | combination of the tertiary amine compound of General formula (1) is a mixed fatty acid containing C14-C18 saturated fatty acid and C14-C18 unsaturated fatty acid. The mass ratio of (saturated fatty acid having 14 to 18 carbon atoms) / (unsaturated fatty acid having 14 to 18 carbon atoms) is preferably 0.1 or more and 3 or less. This mass ratio is preferably 3 or less from the viewpoint of suppressing discoloration of the liquid softening agent composition after high-temperature storage. Furthermore, the mixed fatty acid is preferably composed of a fatty acid having 14 to 18 carbon atoms.

  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.

An unsaturated fatty acid represents a fatty acid having an unsaturated group in the molecule. When the unsaturated group contained in the unsaturated fatty acid is a carbon-carbon double bond, a cis isomer and a trans isomer are present. The unsaturated fatty acid may be a mixed unsaturated fatty acid including a cis isomer and a trans isomer. In that case, the ratio of the cis isomer to the trans isomer is such that the molar ratio of cis isomer / trans isomer is 30/70 or more and 99/1 or less. From the viewpoint of availability of alkenyl groups, the molar ratio of cis isomer / trans isomer is preferably 50/50 or more and 97/3 or less. The ratio of the cis isomer to the trans isomer of the unsaturated mixed fatty acid can be calculated by the integral ratio of ¹ H-NMR.

  Moreover, in general formula (1) of (A) component, p and q are the numbers of 2 or 3, respectively. From the viewpoint of suppressing solid precipitation upon exposure to light (meaning solid precipitation of the liquid softening agent composition; hereinafter the same unless otherwise specified), p is preferably a number of 2. (A) From the viewpoint of ease of production of the component, 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.

  The tertiary amine compound represented by the general formula (1), which is the component (a1), may be partly or wholly contained in the form of an acid salt depending on the pH of the emulsified 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 a monovalent carboxylic acid having 1 to 10 carbon atoms, a monovalent sulfonic acid having a hydrocarbon group having 1 to 20 carbon atoms, and a monoalkyl sulfuric acid having 1 or 2 carbon atoms. Examples include esters. 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.

  The production method for obtaining the tertiary amine compound among the compounds represented by the general formula (1) as the component (a1) is not particularly limited. For example, an alkanolamine compound represented by the following general formula (1-1) By an esterification reaction with a fatty acid having 12 to 22 carbon atoms, or an ester exchange reaction between an alkanolamine compound represented by the general formula (1-1) and a fatty acid ester having an acyl group having 12 to 22 carbon atoms. Can be obtained.

_{(HO-C q H 2q)} m 'N (R 2') 3-m '(1-1)
[Wherein R ^{2 ′} represents a hydrocarbon group having 1 to 3 carbon atoms, m ′ represents 1, 2 or 3 and q represents the same meaning as in the general formula (1). ]

  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 [0013] to [0016] of JP-A-7-138211 can be applied.

  The component (a2) is one or more compounds selected from quaternized compounds of the tertiary amine compound represented by the general formula (1). The component (a2) can be obtained by a quaternization reaction using a tertiary amine compound represented by the general formula (1) and an alkylating agent. Examples of the alkylating agent include methyl chloride, dimethyl sulfate, diethyl sulfate and the like. As an example of the quaternization reaction, for example, the method described in [0017] to [0023] of JP-A-7-138211, or the production method described in JP-A-11-106366 can be applied. .

The component (A) is a group selected from HO— (C _p H _2p O) _r —C _q H _2q as R ² in the general formula (1) from the viewpoint of suppressing solid precipitation during light exposure (here And p, q, and r have the same meaning as in general formula (1), respectively.

  (A) In general formula (1) of a component, m is a number of 1, 2 or 3. The component (A) preferably includes a plurality of compounds having different m in the general formula (1), and preferably includes all of a compound in which m is 1, a compound in which m is 2, and a compound in which m is 3. When the component (A) is a plurality of compounds having different m in the general formula (1), it is preferable that the number of compounds with m = 2 is the largest. When the component (A) is a plurality of compounds having different m, the total number of these compounds, that is, the number average of m in the entire component (A) (hereinafter sometimes referred to as mz) is preferably 1.2 or more. From the viewpoint of softening the textile, more preferably 1.3 or more, still more preferably 1.4 or more, and preferably 2.5 or less, more preferably 2 from the viewpoint of softening the textile. 0.0 or less, more preferably 1.9 or less.

  As the component (A), a mixture containing a plurality of compounds having different m in the general formula (1) can be used. In obtaining a mixture satisfying the number average number mz of m, the compound of the general formula (1-1) used as the raw material may be a mixture of compounds having structures different in m. It is preferable to prepare a mixture in which mz is in the above range using a compound of m ′ = 3 in 1-1). In that case, the molar ratio of the fatty acid or fatty acid lower alcohol ester to the amine compound of m ′ = 3 in the general formula (1-1) is preferably 1.2 or more, more preferably 1.3 or more, and preferably 2.5. Less than. More preferably, a mixture having an mz of 1.2 or more and 2.5 or less can be prepared by esterification or transesterification at a ratio of 2.0 or less.

  (A) component is (a1) component and (a2) component, and may be used for preparation of a composition as a mixture containing these. The mixture containing the component (a1) and the component (a2) can be obtained by obtaining the respective components and then mixing them. In the liquid softener composition according to the present invention, as the component (A), the component (a1) and the component (a2) are mixed at a mass ratio of (a1) / (a2) = 0.01 to 0.6. It contains.

In addition, the mixture containing the component (a1) and the component (a2) is obtained by subjecting the component (a1) to a quaternization reaction to obtain the component (a2). It can also be obtained by adjusting so as to obtain a mixture containing.
Moreover, the mixture containing (a1) component can be obtained intentionally by adjusting the quaternization reaction rate.

  In the component (A) of the present invention, the mass ratio (a1) / (a2) of the components (a1) and (a2) is 0.01 or more and 0.6 or less. The mass ratio of (a1) / (a2) is preferably 0.05 or more, more preferably 0.07 or more, and preferably 0.5 or less, from the viewpoint of suppressing solid precipitation during light exposure. More preferably, it is 0.3 or less.

  Here, among the (a1) component, the acid salt of the tertiary amine compound represented by the general formula (1), the mass is converted into the tertiary amine compound represented by the general formula (1). Find the mass ratio. Moreover, about the (a2) component, the said mass ratio is calculated | required with the mass as a quaternization thing of the tertiary amine compound represented by General formula (1). That is, the mass of the component (a2) includes 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). Mass.

The component (A) is preferably such that the acyl group R ¹ —C (═O) in the general formula (1) of the component (a1) and the component (a2) has a carbon number of 14 or more and 18 or less. (Saturated fatty acid) / (saturated fatty acid having 14 to 18 carbon atoms) mass ratio is 0.1 or more, preferably 0.3 or more, more preferably 0.6 or more, and 3 or less, preferably 2 or less, More preferably, it is composed of a fatty acid that is 1.5 or less, and the mass ratio of the (a1) component to the (a2) component is 0.01 or more in terms of (a1) / (a2), preferably 0.05 or more, 0 0.07 or more, and 0.6 or less, preferably 0.5 or less, more preferably 0.3 or less.

[(B) component]
Component (B) is one or more compounds selected from divalent or trivalent carboxylic acids having a hydroxyl group in the molecule and salts thereof.

  The molecular weight of the component (B) is preferably 100 or more, more preferably 120 or more, and preferably 500 or less, more preferably 300 or less, in terms of acid structure, that is, in terms of acid type compound. is there. The component (B) is preferably a compound having one hydroxy group in the molecule.

  In the present invention, the combined use of the component (B) and the component (C) in the system containing the component (A) suppresses solid precipitation upon exposure to light, and changes the appearance of the liquid softener composition due to storage. Is suppressed. Although the reason is not necessarily clear, the present inventors presume as follows. The carboxyl group in component (B) is a quaternary ammonium group in component (a1) of component (A), a tertiary amino group in component (a2) or a cation group of an acid salt of the tertiary amine, Or, even if a complex is formed by ionic bonding with the quaternary ammonium group of component (C), the dispersibility in water can be maintained because the component (B) has a hydroxyl group in the molecule, and light exposure It is considered that solid precipitation at the time is suppressed and discoloration of the appearance of the liquid softening agent composition during storage can be suppressed.

  The component (B) is one or two selected from tartaric acid, malic acid, citric acid and salts thereof from the viewpoint of suppressing solid precipitation upon exposure to light and suppressing discoloration of the appearance of the liquid softening agent composition due to storage. The above compounds are preferred. More preferably, it is 1 type, or 2 or more types of compounds chosen from tartaric acid, a citric acid, and these salts, More preferably, it is a citric acid or its salt. From the viewpoint of ease of handling, monovalent metal salts, alkanolamine salts having 2 to 6 carbon atoms and quaternary ammonium salts having 2 to 6 carbon atoms having an alkanol group are preferred. Specifically, monovalent metal salts such as sodium salt and potassium salt, N-methyldiethanolamine salt, triethanolamine salt, N, N-dimethyl-N, N-diethanolammonium salt, N-methyl-N, N, N-triethanolammonium salt is mentioned.

[Component (C)]
The component (C) of the present invention is a compound effective for suppressing solid precipitation upon exposure to light, and is a compound 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 16 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 _s H _2s O) _t —H group (where s is a number of 2 or 3, t is a number of 2 or more and 15 or less), and X ⁻ is an anionic group. is there. R ⁴ may be the same or different. ]

In general formula (2), R ³ is a hydrocarbon group having 8 or more and 16 or less carbon atoms, and preferably a hydrocarbon group having 10 or more and 16 or less carbon atoms, from the viewpoint of suppressing solid precipitation during light exposure. The hydrocarbon group is a group selected from an alkyl group and an alkenyl group. In the present invention, an alkyl group is preferred.

In the general formula (2), specific examples of R ⁴ include a methyl group, an ethyl group, a hydroxyethyl group, and a — (C ₂ H ₄ O) _{t ′} —H group (where t ′ is 2 or more, 15 1 or more groups selected from the following numbers): R ⁴ is preferably a group selected from a methyl group, an ethyl group, and a hydroxyethyl group from the viewpoint of easy production of the component (C).

X ⁻ is an anionic group, specifically, an anionic group selected from halogen ions such as chlorine ions, bromine ions, and alkyl sulfate ions having 1 or 2 carbon atoms such as methyl sulfate ions and ethyl sulfate ions. It is done. Preferably it is a chlorine ion.

[Component (D)]
(D) component of this invention is a compound effective in solid precipitation suppression at the time of light exposure, and is 1 or more types of glycol compounds chosen from ethylene glycol, propylene glycol, and glycerin. Component (D) is preferably ethylene glycol.

[(E) component]
(E) A component is an aldehyde fragrance | flavor which has an aromatic group in a molecule | numerator. The aldehyde fragrance | flavor which has an aromatic group in a molecule | numerator means the compound used as a fragrance | flavor among the aldehyde compounds which have an aromatic group in a molecule | numerator.

  The aldehyde fragrance having an aromatic group in the molecule used as the component (E) is, for example, “Basic knowledge of fragrance and fragrance, edited by Motoki Nakajima, published by Sangyo Tosho Co., Ltd., April 20, 2005, 4th printing”. The fragrance | flavor of description and the fragrance | flavor of Japanese Patent Publication No.10-507793 can be used.

  As the component (E), a structure in which an aromatic group and an aldehyde group are connected by a divalent hydrocarbon group having 2 or more and 4 or less carbon atoms in terms of imparting a durable scent to the fiber product. The aldehyde fragrance | flavor which has an aromatic group in a molecule | numerator which has is preferable.

  Examples of the aldehyde fragrance having an aromatic group in the molecule having a structure in which an aromatic group and an aldehyde group are linked by a divalent hydrocarbon group having 2 or more and 4 or less carbon atoms include phenylpropyl aldehyde, cinnamic Aldehyde, α-amylcinnamic aldehyde, α-hexylcinnamic aldehyde, cyclamenaldehyde, 3- (pt-butylphenyl) -propylaldehyde, p-ethyl-2,2-dimethylhydrocinnamaldehyde, 2-methyl- Examples include fragrances selected from 3- (p-methoxyphenyl) -propylaldehyde and pt-butyl-α-methylhydrocinnamic aldehyde.

〔water〕
The liquid softening agent composition according to the present invention contains water. Water is contained in an amount that makes the entire composition 100% by mass. Deionized water is preferably used as the water, and more preferably sterilized with a small amount of hypochlorite.

[Other ingredients]
<(F) component>
The liquid softener composition according to the present invention preferably contains an antioxidant having a phenol group in the molecule as the component (F). (F) component is used in order to suppress the change of the odor of the said (E) component. In the present invention, when used in combination with the component (E), the change in odor can be suppressed, but the discoloration of the liquid softener composition is promoted by coloring the antioxidant having an oxidized phenol group. It became clear. However, it was found that by using the component (B) in combination, it is possible to obtain a liquid softener composition in which coloring is suppressed and change in odor is suppressed.

  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 two antioxidants selected from 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol are preferable.

<(G) component>
The liquid softener composition according to the present invention contains, as component (G), one or more dyes selected from color index acidic red dyes, color index acidic yellow dyes and color index acidic blue dyes. Can do.

  Specific examples of the color index acidic red dye include C.I.Acid Red 18 C.I.Acid Red 27, C.I.Acid Red 52, C.I.AcidRed 82, C.I.Acid Red 114, C.I.Acid Red 138, and C.I.Acid Red 186.

  Specific examples of the color index acidic yellow dye include C.I. Acid Yellow 1, C.I. Acid Yellow 3, C.I. Acid Yellow 7, C.I. Acid Yellow 23, and C.I. Acid Yellow 141.

  Specific examples of the color index acidic blue dye include C.I.Acid Blue 5, C.I.Acid Blue 9, and C.I.Acid Blue 74.

  (G) Component suppresses discoloration after high-temperature storage of the liquid softening agent composition containing (E) component or (E) component and (F) component by using together with said (B) component. I can do it. One or more dyes selected from color index acidic red dyes and color index acidic yellow dyes are preferred in terms of inhibiting discoloration after high temperature storage.

  In the present invention, dyes other than the component (G) can also be used. Examples of dyes other than the component (G) include alkoxylated anthraquinone polymer colorants, alkoxylated triphenylmethane polymer colorants, and alkoxylated thiophene polymer colorants.

<(H) component>
The liquid softening agent composition according to the present invention is selected from a nonionic surfactant, a cationic surfactant other than the component (A), and a cationic surfactant other than the component (C) as the component (H). One or more surfactants can be included. As the component (H), a nonionic surfactant is preferred from the viewpoint of storage stability. Examples of the nonionic surfactant include polyoxyethylene alkyl ethers having an alkyl group having 12 to 18 carbon atoms and an average addition mole number of ethyleneoxy groups of 10 to 50.

<Other optional components>
The emulsified liquid softener composition includes, as optional components, pH adjusters, water-soluble inorganic chlorides such as calcium chloride and magnesium chloride, antibacterial and antifungal agents commercially available as proxel, and components other than (E) Other perfume ingredients, water-soluble solvents other than the component (D) such as phenoxyethanol, ethanol, and isopropanol, an antifoaming agent, or a silicone fiber such as dimethylsiloxane as a texture modifier for textiles can be contained.

[Composition of liquid softener composition, etc.]
The content of component (A) in the emulsified liquid softener composition is 5% by mass or more and 25% by mass or less, and is 5% by mass or more from the viewpoint that the amount of use per washing can be reduced. , Preferably it is 7 mass% or more. From the point which is excellent in the solid precipitation suppression at the time of light exposure, Preferably it is 20 mass% or less, More preferably, it is 18 mass% or less.

  Content of (B) component in the liquid softening agent composition of an emulsion state is 0.05 mass% or more and 1.5 mass% or less. From the viewpoint of suppressing discoloration of the liquid softening agent composition after high temperature storage, the content of the component (B) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, further preferably in the composition. Is 0.3% by mass or more. From the economical point, the content of the component (B) is preferably 1.3% by mass or less, more preferably 1.0% by mass or less in the composition. In addition, in this invention, content of (B) component represents content of (B) component converted into an acid type. For example, even if trisodium citrate is used, the content represents a value converted as citric acid.

  Content of (C) component in the liquid softening agent composition of an emulsion state is 0.05 mass% or more and 2 mass% or less. From the viewpoint of suppressing solid precipitation during light exposure, the content of component (C) is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and further preferably 0.2% by mass in the composition. % Or more. From the viewpoint of suppressing separation of the liquid softening agent composition when exposed to light, the content of the component (C) is preferably less than 2% by mass, more preferably 1.5% by mass or less, and still more preferably 1 in the composition. It is below mass%.

  Content of (D) component in a liquid softening agent composition is 1.0 mass% or more and 5.0 mass% or less. The content of the component (D) in the composition is preferably 1.2% by mass or more, more preferably 1.5% by mass or more, and still more preferably 2.0% by mass or more. From the viewpoint of suppressing separation of the liquid softening agent composition, the content of the component (D) is 5.0% by mass or less, preferably 4.5% by mass or less, more preferably 4.0% by mass in the composition. % Or less.

  The content of the component (E) in the emulsified liquid softener composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of imparting fragrance to the fiber product. Preferably it is 0.1 mass% or more. Further, from the viewpoint that discoloration of the appearance hardly occurs, the content of the component (E) is preferably 1% by mass or less, more preferably 0.8% by mass or less, and further preferably 0.5% by mass or less in the composition. It is.

  When the component (F) is contained, the content of the component (F) in the liquid softener composition in the emulsion state is a mass ratio with the component (E) in terms of suppressing the odor change of the component (E). However, it is (F) component / (E) component, Preferably it is 0.1 or more, More preferably, it is 0.2 or more, More preferably, it is 0.3 or more. From the economical viewpoint, the mass ratio of the component (F) / the component (E) is preferably less than 5, more preferably 4 or less, and still more preferably 3 or less.

  When the component (G) is contained, the content of the component (G) in the emulsified liquid softener composition is preferably 0.01 mg / kg or more, more preferably from the viewpoint of suppressing discoloration after high-temperature storage. Is 0.05 mg / kg or more, more preferably 0.1 mg / kg or more, still more preferably 0.3 mg / kg or more. From the viewpoint of aesthetics, it is preferably 10 mg / kg or less, more preferably 5 mg / kg or less, still more preferably 3 mg / kg or less, still more preferably 2 mg / kg or less, and even more preferably 1 mg / kg or less.

  The emulsion liquid softener composition according to the present invention has a viscosity at 30 ° C. of 5 mPa · s or more, preferably 10 mPa · s or more, and 200 mPa · s or less, preferably from the viewpoint of ease of use. 150 mPa · s or less. This viscosity is the viscosity before filling the bag-like container, and is measured by the method of “initial viscosity” in the examples.

  Moreover, the liquid softening agent composition according to the present invention preferably has a viscosity that does not increase even after light irradiation. Specifically, those having a viscosity after light irradiation of 600 mPa · s or less are preferred, and in terms of ease of use, 350 mPa · s or less is preferred, 300 mPa · s or less is more preferred, and 250 mPa · s or less is preferred. More preferred is less than 150 mPa · s. This viscosity was measured by the method of “viscosity after storage under light irradiation” in the Examples.

  The pH of the emulsified liquid softener composition according to the present invention is 25 ° C., preferably 2 or more, and preferably 7 or less, more preferably, from the viewpoint of hydrolytic stability of the component (A). Is 5 or less. The pH is measured at 25 ° C. according to item 8.3 of JIS K 3362; 2008.

[Bag-like container]
The bag-packed softener article of the present invention is formed by filling a bag-like container with the above-described predetermined emulsion liquid softener composition. The bag-like container used in the present invention is preferably a bag-like container formed of a laminated material including one or more layers made of plastic. For example, a bag-like container described in [0030] to [0039] of JP-A-2009-154915 can be used, and the structure shown in FIGS. 1 and 2 or FIG. 3 of JP-A-8-26297 is used as the structure. be able to.

The bag-like container is preferably configured to include a laminated material in which at least two plastic layers are laminated. As a specific configuration of the bag-like container formed by including the laminated material, stretched nylon (ONy), polyethylene terephthalate (PET), stretched polypropylene (OPP), high A base material layer [Layer I] made of density polyethylene (HDPE) or the like is disposed, and then a sealant layer made of unstretched polypropylene (CPP), linear low density polyethylene (L-LDPE), low density polyethylene (LDPE), or the like [ A configuration in which the layer II] is arranged and laminated can be exemplified.
The thickness of the base material layer [Layer I] may be a thickness that can be kept to the minimum necessary for rigidity and the like, and can be determined in consideration of bag-making processability, cost, and strength. A typical thickness is 10 μm or more and 50 μm or less. The thickness of the entire laminated material can also be determined in consideration of bag-making processability, cost, strength and rigidity. A typical thickness is 100 μm or more and 300 μm or less.

  The bag-packing softener article of the present invention can suppress solid deposition upon exposure to light without using a bag-like container having an aluminum layer with excellent light-shielding properties as described in Patent Document 3. it can. If necessary, a bag-like container having an aluminum layer can also be used. In that case, the aluminum layer can be made thinner than before, and for example, the manufacturing cost can be reduced to about 3 μm or less.

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

  The bag-like container used in the present invention is formed by laminating the composite film substrate as described above 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. can get.

[Component (A)]
The component (A) used in the examples is shown below.

(A-1): Esterification reaction product obtained in Synthesis Example 1 below <Synthesis Example 1: Production method of (a-1)>
An amine compound represented by the general formula (1) is obtained by esterifying triethanolamine and a fatty acid (mixed fatty acids, composition is shown below) at a reaction molar ratio (fatty acid / triethanolamine) of 1.86 / 1. An esterification reaction product containing was obtained.
The mz of the esterification reaction product was 1.77. The esterification reaction product contained 5% by mass of unreacted fatty acid. 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 with respect to the mass of the reaction product was added and mixed uniformly.
As a result of analyzing the composition ratio of each component of the obtained esterification reaction product by HPLC and using tetraoctylammonium bromide as an internal standard substance, the obtained esterification reaction product was (a1) The mixture contained a tertiary amine compound as a component, a quaternized product as a component (a2), and 85% by mass of an unreacted fatty acid. Since 2 mass% of fatty acids were contained in the mixture, the total of the components (a1) and (a2) in the mixture was 85 mass% -2 mass% = 83 mass%. In addition, the mass ratio of the component (a1) / component (a2) in the mixture is 0.10, and the acyl group R ¹ —C (═O in the general formula (1) of the component (a1) and component (a2) ) Were each composed of fatty acids having an unsaturated fatty acid / saturated fatty acid mass ratio of 0.64.

  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 a-1) indicates mass% based on the amounts of the components (a1) and (a2), and the other components were added to the balance of the ion exchange 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 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 cis / trans isomer ratio of the unsaturated group is 85/15 (integral ratio by ¹ H-NMR).

(A-2): Esterification reaction product obtained in Synthesis Example 2 below <Synthesis Example 2: Production method of (a-2)>
N-methyldiethanolamine and a fatty acid (mixed fatty acids, composition is shown below) are esterified at a reaction molar ratio (fatty acid / N-methyldiethanolamine) of 1.9 / 1, and represented by the general formula (1). An esterification reaction product containing an amine compound was obtained.
The mz of the esterification reaction product was 1.72. The esterification reaction product contained 9.5% by mass of unreacted fatty acid. 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 was added so that the methyl group would be 0.98 equivalent to the amine. A quaternization reaction was performed.
As a result of analyzing the composition ratio of each component of the obtained esterification reaction product by HPLC and using tetraoctylammonium bromide as an internal standard substance, the obtained esterification reaction product was (a1) The mixture contained a tertiary amine compound as a component, a quaternized product as a component (a2), and 88% by mass of an unreacted fatty acid. Since the fatty acid was contained in the mixture in an amount of 8.7% by mass, the total of the components (a1) and (a2) in the mixture was 88% by mass-8.7% by mass = 79.3% by mass. Met. Further, the mass ratio of the component (a1) / the component (a2) is 0.18, and the acyl group R ¹ -C (═O) in the general formula (1) of the component (a1) and the component (a2) is Each was composed of fatty acids with an unsaturated fatty acid / saturated fatty acid mass ratio of 0.42. In addition, the mass% of (a-2) of Tables 1 and 2 was also expressed in mass% based on the amounts of the (a1) component and the (a2) component.

The composition of the fatty acid 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 85/15 (integral ratio by ¹ H-NMR).

[(B) component]
(B-1): Citric acid (molecular weight 192)
(B-2): Malic acid (molecular weight 134)
(B-3): Tartaric acid (molecular weight 150)

[(B ′) Component: Comparative Compound of Component (B)]
(B′-1): Malonic acid (molecular weight 104)

[Component (C)]
(C-1): N-lauryltrimethylammonium chloride (c-2): N-lauryl-N-methyl-N, N-bis- (polyoxyethylene (average 3 mol addition)) ammonium methylsulfate

[(C ′) Component: Comparative Compound of (C) Component]
(C′-1): N-octadecyltrimethylammonium chloride

[Component (D)]
(D-1): Ethylene glycol (d-2): Glycerin

[(E) component]
(E-1): α-amylcinnamic aldehyde (e-2): α-hexylcinnamic aldehyde (e-3): cyclamenaldehyde

[(F) component]
(F-1): 2,6-di-tert-butyl-4-methylphenol

[(G) component]
(G-1): CI Acid Yellow 3
(G-2): CI Acid Red 52
(G-3): CI Acid Blue 9

[(H) component]
(H-1): Nonionic surfactant (average 21 moles of ethylene oxide adduct of lauryl alcohol)

[Bag-like container]
A standing pouch having the structure shown in FIG. 3 of JP-A-8-26297, which is a bag-like container (height: 260 mm, upper end and lower end width: 130 mm) formed using a laminated material having the following configuration: The bottom portion has a spindle-shaped cross section parallel to the axis, and the major axis is 100 mm and the minor axis is 60 mm.
Laminate material: Layer I is an outer layer and layer II is an inner layer (a layer in contact with the composition). Layer I is stretched nylon (ONy) and a flexible film with a thickness of 15 μm. The back surface of layer I (the surface in contact with layer II) is printed with white ink twice on the entire surface by gravure printing. Layer II is laminated on the substrate. The layer II is a linear low density polyethylene (L-LDPE), a flexible film having a thickness of 150 μm.

<Method for Producing Emulsion Liquid Softener Composition>
An emulsion liquid softener composition was prepared by mixing the components so as to have the blending compositions shown in Tables 1 and 2. Specifically, it is as follows. In a 1 L beaker, 90% by mass of ion-exchanged water and (B) component or (B ′) component and (C) of the amount necessary for the finished mass of the emulsified liquid softening agent composition to be 600 g. Component (C ′), component (D) and component (G) were added, and the temperature was adjusted to 60 ° C. ± 2 ° C. using a water bath. (B) Component or (B ′) component and (C) component or (C ′) component and (G) component are stirred using the following stirring blade as necessary so that they are uniformly dissolved in the ion exchange water. did. A (B) component or (B ′) component adjusted to a temperature of 60 ° C. ± 2 ° C. and ion-exchanged water containing the component (C) or (C ′) component and the component (G) are mixed with a stirring bar having a diameter of 5 mm. Stirrer blades arranged so that the long side is in the direction of 90 degrees with respect to the rotation center axis (number of blades: 3, blade long / short sides: 3 cm / 1.5 cm, blade installation: rotation While stirring (300 r / m) at an angle of 45 degrees with respect to the surface, a mixture of the components (A) and (H) dissolved by heating at 65 ° C. was added over 3 minutes. After completion of the addition, the mixture was stirred for 15 minutes. A 10% by mass aqueous solution of the calcium chloride component was added and stirred for 10 minutes. Using a 5 ° C. water bath, the contents were cooled to 30 ° C. ± 2 ° C. A mixture in which the component (E) and the component (F) were mixed in advance was added and stirred for 5 minutes. Ion exchange water was added so that the mass (600 g) was completed, and the mixture was stirred for 5 minutes. It was confirmed that the liquid softening agent compositions of Examples and Comparative Examples were all in an emulsion state. In addition, pH (30 degreeC) of the liquid softening agent composition was adjusted to the value in a table | surface with hydrochloric acid or sodium hydroxide aqueous solution.

<Bagging softener article>
500 g of the liquid softening agent composition was filled in the bag-like container to prepare a bagging softening product.

<Evaluation>
[1] Storage Stability under Light Irradiation The storage stability of a bag-filled softener article under light irradiation was evaluated by the amount of solid precipitated from the liquid softener composition after storage under light irradiation.
The testing machine used was a low-temperature cycle xenon fade meter (model number: XL75, manufactured by Suga Test Instruments Co., Ltd.).
The maximum area surface of the bag-filled softener article was placed in the test machine facing the lamp, irradiated with light under the following irradiation conditions, then the test machine was stopped and left as it was for 18 hours (1 cycle). The irradiation conditions at that time were a set irradiance of 42 W / m ² , a set irradiance time of 6 hours (integrated irradiance: 0.9 MJ / m ² ), and a black panel temperature of 45 ° C.
After performing this cycle for 11 cycles, 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 emulsion liquid softener composition inside.
The seal part on the upper side of the container was cut with scissors, the container was turned upside down, and the contents were filtered with a stainless steel mesh (200 mesh opening 75 μm). After filtration, the mass of the solid precipitate remaining on the mesh after being left for 1 minute was measured (the mass of the stainless steel mesh before filtration was measured in advance, and the difference was taken as the mass of the solid precipitate). The results are shown in Tables 1 and 2.
A mass of less than 1 g of solid precipitate is acceptable, preferably 0.8 g or less, more preferably 0.5 g or less, still more preferably 0.3 g or less, and particularly preferably less than 0.2 g. Most preferred is 0 g (no solid is measured).

[2] Viscosity (2-1) Initial viscosity The viscosity of the liquid softener composition immediately after preparation was measured. About the liquid softening agent composition adjusted to 30 ± 1 ° C., each emulsion state was measured using a B-type viscometer (TOKI SANGYO Co., LTD, VISCOMETER TVB-10, No. 2 rotor, 60 r / m). The viscosity measurement of the liquid softener composition was started, and the value after 1 minute was read.

(2-2) Viscosity after storage under light irradiation In the storage stability test of [1] above, 90 g of the filtered liquid softener composition after storage was subjected to No. It was put into an 11 standard bottle, sealed with a dedicated 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.
Using a B-type viscometer (TOKI SANGYO Co., LTD, manufactured by VISCOMETER TVB-10, No. 2 rotor, 60 r / m), the viscosity measurement of the liquid softener composition in each emulsion state was started, and after 1 minute (The unit of viscosity is “mPa · s”). No viscosity is high. If measurement is not possible with 2 rotors, no. The measurement was conducted in the same manner after replacing the three rotors.

[3] Change in appearance after high-temperature storage After filling the bag-like softener article of the liquid softener composition for clothing blended with each component by the above preparation method in a thermostatic chamber at 40 ° C. for 20 days, it is used by five panelists. Visual observation was performed, and changes in appearance (discoloration of the liquid softener composition in an emulsion state) were determined according to the following criteria. The lighting in the temperature-controlled room is not used except when entering the temperature-controlled room. Tables 1 and 2 show the average values of five panelists, with 2.0 or more being acceptable values.
Evaluation criteria:
3: No change in appearance (discoloration) compared to immediately after blending.
2: Appearance slightly changed (slightly discolored) compared to immediately after compounding. (Within the acceptable range)
1: Appearance changed (discolored) compared to immediately after blending. (Outside tolerance)
0: Appearance changed remarkably (remarkably discolored) compared to immediately after compounding. (Outside tolerance)

* In the table, the unit of the amount of component (G) is mg / kg.

Claims (6)

The following (A) component 5 mass% or more, 25 mass% or less, the following (B) component 0.05 mass% or more, 1.5 mass% or less, the following (C) component 0.05 mass% or more, 2 mass% or less The following (D) component 1.0% by mass or more and 5.0% by mass or less, the following (E) component and water, an emulsion state having a viscosity at 30 ° C. of 5 mPa · s or more and 200 mPa · s or less A bag softener article in which a liquid softener composition is filled in a bag-like container.
Component (A): (a1) One or two selected from tertiary amine compounds represented by the following general formula (1) and acid salts of tertiary amine compounds represented by the following general formula (1) One or more compounds selected from the above compounds [hereinafter referred to as the component (a1)] and (a2) quaternized tertiary amine compounds represented by the following general formula (1) [hereinafter, (Referred to as “component (a2)”) wherein the component (a1) and component (a2) have a mass ratio of (a1) / (a2) of 0.01 or more and 0.6 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 —C (═O) is an acyl group derived from a fatty acid having 12 to 22 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, 2 or 3, p and q are numbers of 2 or 3, respectively, 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): One or more compounds selected from divalent or trivalent carboxylic acids having a hydroxyl group in the molecule and salts thereof (C) Component: represented by the following general formula (2) Compound R ³ —N ⁺ (R ⁴ ) ₃ · X ⁻ (2)
[Wherein R ³ is a hydrocarbon group having 8 to 16 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 _s H _2s O) _t —H group (where s is a number of 2 or 3, t is a number of 2 or more and 15 or less), and X ⁻ is an anionic group. is there. R ⁴ may be the same or different. ]
(D) Component: One or more glycol compounds selected from ethylene glycol, propylene glycol and glycerin (E) Component: Aldehyde fragrance having an aromatic group in the molecule   The bagging softener article according to claim 1, wherein the component (B) is one or more compounds selected from tartaric acid, malic acid, citric acid, and salts thereof. The component ( E ) is an aldehyde fragrance having an aromatic group in the molecule, having a structure in which an aromatic group and an aldehyde group are linked by a divalent hydrocarbon group having 2 to 4 carbon atoms. The bag-filling softener article according to claim 1 or 2.   Furthermore, as component (G), one or more acidic dyes selected from color index acidic red dyes, color index acidic yellow dyes and color index acidic blue dyes are contained in an amount of 0.01 mg / kg to 10 mg / kg. The bagging softener article according to any one of claims 1 to 3.   The bagging softener article according to claim 4, wherein the component (G) is one or more acidic dyes selected from a color index acidic red dye and a color index acidic yellow dye.   The bag-like softener article according to any one of claims 1 to 5, wherein the bag-like container is a bag-like container configured to include a laminated material in which at least two plastic layers are laminated.