JP2008162901A - New methoxylated quaternary ammonium salt, additive for liquid softener containing the compound and liquid softener composition containing the compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new compound imparting a liquid softener composition with antiseptic effect and freeze restoration stability and a liquid softener composition containing the compound. <P>SOLUTION: The invention provides a monomethoxylated compound comprising N-methyl-N-methoxyethyl-N,N-dihydroxyethyl ammonium methyl sulfate and a dimethoxylated compound comprising N-methyl-bis(N-methoxyethyl)-N-hydroxyethyl ammonium methyl sulfate as the new methoxylated quaternary ammonium salt and a softener composition containing the compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel methoxylated quaternary ammonium salt, an additive for liquid softener containing the compound, and a liquid softener composition used for various fiber products containing the compound. In particular, the present invention contains a useful novel methoxylated quaternary ammonium salt which can be blended in a liquid softening agent composition and can provide excellent antiseptic power and freeze-restoration stability with a single agent, and the compound. The present invention relates to an additive for a liquid softener and a liquid softener composition containing the compound.

Currently, commercially available softener products for home use have advantages for both consumers and manufacturers, and therefore, reduction and weight reduction of containers and concentration of contents are progressing. For consumers, it is possible to reduce the labor for taking home from the purchaser, and for manufacturers, it is possible to greatly reduce packaging material costs and logistics costs. Moreover, since the amount of plastic as a container material can be greatly reduced, it is preferable from the viewpoint of environment. However, the concentration of contents can cause troubles during washing. For example, when softening is performed using the charging port of a fully automatic washing machine, the concentrated softener may remain at the charging port. There is no problem if it is washed away immediately, but it may dry and solidify if left untreated. This is not only unsightly at the time of the next washing, but is not preferable for hygiene purposes. Some washing machine manufacturers recommend diluting the composition in order to eliminate such troubles. On the other hand, there are also consumers who use tap water in a bottle container to dilute the contents in order to increase the feeling of use or avoid excessive use. Furthermore, in recent years, many refill products using pouch containers have been distributed, and washing and diluting of containers with tap water is routinely performed at the time of transfer to bottles.
However, due to such dilution or content transfer action, microorganisms derived from the environment are mixed in the content, and there is a risk of its proliferation. Therefore, for the purpose of preventing the growth of microorganisms derived from the natural environment in the softener container, an antiseptic / disinfectant is used together with the softener component in the commercially available softener.

For example, Patent Document 1 proposes a softener composition containing a poorly water-soluble quaternary ammonium salt type cationic surfactant and a 3-isothiazolone antibacterial agent, and a preferred 3-isothiazolone antibacterial agent is 5-chloro Examples are 2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one. Patent Document 2 and the like also exemplify the above compound or 2-bromo-2-nitropropane-1,3-diol as an arbitrary antibacterial preservative. Patent Document 3 discloses a liquid softener composition containing a cationic surfactant and a specific organic sulfur compound such as 1,2-benzisothiazolin-3-one and having a pH of 1.5 to 5.5. Has been proposed. Furthermore, in Patent Document 4, three types of compounds such as isothiazolone organic sulfur compounds are used in combination with a cationic surfactant having at least one ester group-containing hydrocarbon group in the molecule, which is a biodegradable softening base. An antiseptic softener composition has been proposed.
However, it is considered that the above-described dilution and contents transfer work increase the possibility that microorganisms derived from the environment will grow in the container, which in turn adversely affects quality such as fragrance. In addition, with the progress of product concentration, divalent metal inorganic salts are frequently used for the purpose of reducing the viscosity of the composition. As a result, the antibacterial and antiseptic power is reduced. Even in such a case, for the purpose of preventing the growth of microorganisms derived from the environment, it is necessary to impart a stronger antibacterial and antiseptic power to the composition. Furthermore, preservatives are generally expensive, and blending them in large amounts is not preferable from the viewpoint of safety such as skin irritation.

On the other hand, the aqueous liquid softener composition has ethanol, ethylene glycol, propylene glycol as so-called hydrotrope agents for the purpose of preventing gelation and phase separation when frozen and thawed under storage conditions in winter. In many cases, lower monohydric or polyhydric alcohols such as are mixed. Furthermore, for the purpose of imparting such freeze-restoration stability, a softener composition mainly comprising a cationic surfactant having at least one biodegradable ester group-containing hydrocarbon group in the molecule as described above. On the other hand, neutralized short-chain alkyl tertiary amines having functional groups such as hydroxyl groups have also been proposed. (Patent Document 5)
However, an additive that can impart antiseptic power and freeze-restoration stability to a liquid softening agent composition as a single agent has not yet been proposed.

JP 62-263380 A (Lion) JP-A-3-113077 (Unilever) JP 11-181681 A (Kao) JP 2001-192966 A (Lion) JP-A-6-228868 (Lion)

  The present invention is a novel quaternary ammonium salt that can be added to a liquid softener composition to give excellent preservative power and freeze-restoration stability with a single agent, and a liquid softener containing the compound An object is to provide an additive and a liquid softener composition containing the compound.

As a result of intensive studies, the present inventors have found that the above object can be achieved by using a novel methoxylated quaternary ammonium salt, and have made the present invention.
That is, this invention provides the compound represented by following formula (1).

（式中、Ｒは水素原子又はメチル基である。）

(In the formula, R is a hydrogen atom or a methyl group.)

The present invention also provides an additive for a liquid softening agent containing at least one of the above compounds.
The present invention also provides a liquid softener composition containing at least one of the above compounds.

  According to this invention, it can add to a liquid softening agent composition, and can provide the antiseptic | preserving power which was excellent in one agent, and freeze-restoration stability.

[Component (A): monomethoxylated TEA quaternary salt, dimethoxylated TEA quaternary salt]
The methoxylated quaternary ammonium salt of the present invention which is a novel compound is represented by the above structural formula (1). The compound of the formula (1) is a methyl-N-methoxyethyl-N, N-dihydroxyethylammonium methyl sulfate represented by the following formula (I) (hereinafter abbreviated as “monomethoxylated TEA quaternary salt”) (a -1) or methyl-bis (N-methoxyethyl) -N-hydroxyethylammonium methyl sulfate represented by the following structural formula (II) (hereinafter abbreviated as “dimethoxylated TEA quaternary salt”) (a-2) It is.

The compounds of the present invention can be used as additives in liquid softener compositions and surprisingly have two properties as preservatives and freeze-recovery stabilizers. Although the softening base which comprises a liquid softening agent composition is not specifically limited, (B) mentioned later is preferable.
The additive of the present invention is preferably contained in an amount of 0.5% by mass or more, more preferably 1 to 5% by mass, based on the total mass of the liquid softening agent composition. By being contained in such a range, sufficient antiseptic power and freeze-restoration stabilizing effect can be imparted.
The production method of the compound of the present invention will be described by taking a monomethoxylated TEA quaternary salt as an example. Monomethoxylated TEA quaternary salt can be obtained by the following main reaction process.

  In this reaction, unreacted tertiary amine and monomethyl sulfate of the amine are included as by-products. In the quaternization step, the reaction molar ratio of methoxyethyldihydroxyethylamine: dimethylsulfuric acid is set to 1: 2 or more, and the aging time is lengthened to sufficiently ripen, whereby the content of dimethoxylated TEA quaternary salt is increased. A high “mixture of monomethoxylated TEA quaternary salt and dimethoxylated TEA quaternary salt” is obtained.

[Component (B): Hydrocarbon group-containing cationic surfactant containing an ester group]
The cationic surfactant which is the component (B) used in the present invention comprises an amine compound containing an ester group and one or more long chain hydrocarbon groups having 12 to 24 carbon atoms in the molecule and an organic or inorganic acid thereof. And a quaternized product thereof. Any of these may be used as a single type or a mixture of two or more types. In order to improve the flexibility of the textile processed with the liquid softener composition of the present invention, the mass ratio of the cationic surfactant having two or three long-chain hydrocarbon groups in the cationic surfactant mixture is It is preferable that it is 50% or more. Since the component (B) used in the present invention contains an ester group in the middle of the long chain hydrocarbon group, it is biodegraded after being discarded into the natural environment after use. Specific examples of the component (B) that can be used in the present invention include compounds of the following formulas (III) to (IX).

The long chain hydrocarbon group constituting the cationic surfactant is a hydrocarbon group having 12 to 24 carbon atoms. R ¹ —COO is a residue esterified from a fatty acid having 10 to 22 carbon atoms and an ethanolamine group, and is a long-chain hydrocarbon derived from any of saturated fatty acid, unsaturated fatty acid, linear fatty acid, and branched fatty acid. It is a group. In the case of an unsaturated fatty acid, a cis isomer and a trans isomer are present, and the cis / trans mass ratio = 25/75 to 100/0 is preferable, and 40/60 to 95/5 is particularly preferable. Examples of the fatty acid that is the basis of R ¹ —COO include the following. Examples include stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, partially hydrogenated palm oil fatty acid (iodine value 10 to 60), partially hydrogenated beef tallow fatty acid (iodine value 10 to 60), and the like. Of these, stearic acid, palmitic acid, and oleic acid are combined in a predetermined amount, and the saturated / unsaturated mass ratio is 95/5 to 50/50, and the cis / trans isomer mass ratio of the unsaturated bond is 40/60 to 90 /. It is preferable to use a fatty acid composition adjusted so that the iodine value is 10 to 60 and the ratio of 18 carbon atoms is 60% by mass or more. Here, all R ¹ —COO present in the formula may be the same or different.

  The compounds of the general formulas (III) and (IV) can be synthesized by a condensation reaction of the above fatty acid composition or fatty acid methyl ester composition and methyldiethanolamine. In that case, it is preferable to synthesize | combine so that the abundance ratio of the compound of (III) and (IV) may become 99/1-50/50 by mass ratio from a viewpoint of making a softness | flexibility favorable. Further, when the quaternized product is used, methyl chloride or dimethyl sulfuric acid is used as the quaternizing agent, and the latter is more preferable. In that case, it is preferable to synthesize | combine so that the abundance ratio of the quaternized product of the ester amine represented by (III) and (IV) may be 99/1 to 50/50 in mass ratio from the viewpoint of flexibility.

  The compounds of general formulas (V), (VI), and (VII) can be synthesized by a condensation reaction of the above fatty acid composition or fatty acid methyl ester composition and triethanolamine. At that time, the content ratio of each component to the total mass of (V), (VI), and (VII) is 1 to 60 mass% for (V) and 5 to 98 mass% for (VI) from the viewpoint of flexibility. , (VII) is preferably present in a ratio of 0.1 to 40% by mass, (V) is 30 to 60% by mass, (VI) is 10 to 55% by mass, and (VII) is 5 to 35% by mass. More preferably, it is present in the ratio of Furthermore, when the quaternized product is used, methyl chloride, dimethyl sulfate or the like is used as the quaternizing agent, but dimethyl sulfate is more preferable in that the quaternization reaction is sufficiently advanced. At that time, the abundance ratio of the quaternized product of the ester amine represented by (V), (VI), or (VII) is also from 1 to 60 mass% (VI) in terms of mass ratio from the viewpoint of flexibility. 5 to 98% by mass, (VII) is preferably present in a ratio of 0.1 to 40% by mass, (V) is 30 to 60% by mass, (VI) is 10 to 55% by mass, and (VII) is More preferably, it is present at a ratio of 5 to 35% by mass. When (V), (VI), or (VII) is quaternized, esteramine that is not quaternized remains after the quaternization reaction. At that time, the ratio of quaternized / non-quaternized esteramine may be any of 70/30 to 99/1.

The compounds represented by the general formulas (VIII) and (IX) are prepared from the above fatty acid composition, an adduct of N-methylethanolamine and acrylonitrile, as described in “J. Org. Chem., 26, 3409 (1960)”. It can be synthesized by a condensation reaction with N- (2-hydroxyethyl) -N-methyl-1,3-propylenediamine synthesized in (1). In that case, it is preferable to synthesize | combine so that the abundance ratio of the compound of (VIII) and (IX) may become 99/1-50/50 by mass ratio. Further, when the quaternized product is used, it is quaternized with methyl chloride. The abundance ratio of the quaternized product of the ester amine represented by (VIII) and (IX) is 99/1 to 50/50 by mass ratio. It is preferable to synthesize. In addition, when (VIII) and (IX) are quaternized, esteramine that has not been quaternized remains after the quaternization reaction. In that case, it is preferable that the ratio of the quaternized / non-quaternized ester amine is a mass ratio of 99/1 to 70/30 in terms of mass ratio from the viewpoint of hydrolysis stability of the ester group.
In the present invention, it is preferable to use a mixture of quaternized compounds of the general formulas (V), (VI) and (VII).

  The amount of component (B) is preferably 3 to 40% by mass, more preferably 5 to 25% by mass, based on the total amount of the composition. When the blending amount of the component (B) is in such a range, both the cotton product and the synthetic fiber have a softening effect, and it is easy to adjust the viscosity to an appropriate level for use.

[(C) component: alkylene oxide addition type nonionic surfactant]
In addition to the components (A) and (B) described above, the liquid softener composition of the present invention contains an alkylene oxide addition-type nonionic surfactant as the component (C), and stability of the composition, particularly emulsion dispersion stability. It is preferably used for the purpose of improving the stability and freeze-recovery stability, more particularly freeze-restore stability.
The nonionic surfactant is preferably a higher alcohol or higher fatty acid ester represented by the following general formula (X), or an alkylene oxide adduct of a higher amine represented by the following general formula (XI). Preferred are alkylene oxide adducts of higher alcohols.

[R ^2: C10~20 group carbonyl group a hydrocarbon group of a hydrocarbon group, or 10 to 20 carbon atoms are linked, R ^3: an alkyl group of hydrogen or C1 -3, A: Number 2-3 carbon An alkylene group, n and p + q are numbers from 10 to 100. ]
The higher alcohol may be primary or secondary, and the long-chain hydrocarbon chain portion may be branched or straight chain, may be unsaturated, or may have a distribution in carbon chain length. The carbon chain length is preferably 10-20, more preferably 10-18. When the hydrocarbon chain contains an unsaturated group, those having 16 to 18 carbon atoms are preferable, and the stereoisomeric structure of the unsaturated group may be a cis isomer or a trans isomer, but a mixture of both. May be.
On the other hand, the alkylene oxide added to the higher alcohol is preferably ethylene oxide (EO) alone, but propylene oxide (PO) may be used in combination with ethylene oxide, and the average number of added moles of these alkylene oxides is 10 to 100. 80 is preferable, and more preferably 30 to 60 mol.

  More specifically, as the alkylene oxide addition type nonionic surfactant, an average EO 20 mol adduct of lauryl alcohol, an average EO 20 mol adduct of primary isodecyl alcohol, an average EO 40 mol adduct of primary isotridecyl alcohol, Examples include an average EO 45 mol adduct of isotridecyl alcohol, an average EO 60 mol adduct of primary isohexadecyl alcohol, an average EO 60 mol adduct of tallow alkylamine, and an average EO 30 mol adduct of lauric acid. Specific examples include Emulex series from Nippon Emulsion Co., Ltd., Emalmin series from Sanyo Chemical Co., Ltd., TDA series from Lion Chemical Co., Ltd., Esomin series, Softanol series such as Softanol 300 from Nippon Shokubai Co., Ltd. A BASF Lutensol series or the like can be used. In addition, the above-mentioned compound may contain 10% by mass or less of the raw material alcohol, amine, polyalkylene glycol such as polyethylene glycol, polypropylene glycol and the like as an unreacted component in the nonionic surfactant. They can be used alone or as a mixture of two or more.

  As the raw material alcohol of the higher alcohol alkylene oxide adduct suitable as a nonionic surfactant, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, 2-butyloctanol, isotridecyl alcohol, isohexadecyl alcohol Natural or synthetic higher alcohols such as 2-butyldecanol, 2-hexyloctanol, 2-hexyldecanol, 2-octyldecanol, 2-hexyldecanol, 2-octadecanol, 2-dodecylhexadecanol Can be used.

  By containing an alkylene oxide addition type nonionic surfactant, the stability of the liquid softening agent composition, in particular, the emulsification dispersion stability and the freeze / restoration stability, and particularly the freeze / restoration stability are improved. The blending amount is preferably 0.1 to 15% by mass, particularly 0.5 to 10% by mass, and more preferably 1 to 5% by mass with respect to the total mass of the composition. By making the blending amount above the lower limit value, the effect of improving the freeze-recovery stability can be made sufficient. On the other hand, by making the blending amount less than the upper limit value, the excess when the effect reaches saturation Therefore, it is possible to reduce the amount of excessive foaming during the flexible processing.

  In the liquid softener composition of the present invention, in addition to the above-described components, in addition to the above-described components, in addition to the above components, a normal liquid is used for the purpose of functional addition, viscosity stabilization, productivity improvement, appearance improvement, aroma improvement, and the like. The following optional components can be blended as known components blended in the softener composition. Further, the liquid softener composition of the present invention is preferably an aqueous composition, and water used for formulation preparation can be any of tap water, ion-exchanged water, pure water, distilled water and the like. However, ion-exchanged water is optimal considering the cost.

[Optional component: Water-soluble inorganic or organic salt]
Furthermore, the composition of the present invention suppresses the viscosity of the liquid softener composition, and is a stable emulsion that does not cause a sudden increase in viscosity such as gelation even after freezing or storage for a long period of time. In addition, it is more desirable to use a water-soluble inorganic salt or organic salt in combination. Examples of the water-soluble salt include sodium chloride, potassium chloride, calcium chloride, magnesium chloride and the like, as well as inorganic salts such as an alkali metal salt or alkaline earth metal salt of sulfuric acid or nitric acid, p-toluenesulfonic acid, Alkali metal salts of organic acids such as glycolic acid and lactic acid can be used. Preferably, they are calcium chloride, magnesium chloride, and sodium chloride.
The water-soluble salt is suitably added in an amount of 0 to 3% by mass, preferably 0.01 to 2% by mass, more preferably 0.05 to 1% by mass, based on the total amount of the composition. Even if it is below the lower limit or above the upper limit, the viscosity suppressing effect is insufficient and the emulsion dispersion stability is deteriorated. The addition of inorganic or organic water-soluble salts may be added at any step in the production of the composition.

[Optional component: Lower monohydric or polyhydric alcohol]
A monovalent or divalent alcohol having 1 to 8 carbon atoms can be blended for the purpose of improving the handleability of the raw materials for the production of the composition and improving the freeze / restoration stability of the composition. These mono- or dihydric alcohols may be used as a reaction solvent or diluent for improving the handling properties of the component (A) or the component (B), or a liquid softener composition may be produced. In some cases, it is blended.

Specific examples of the monohydric or polyhydric alcohol having 1 to 8 carbon atoms include ethanol, isopropanol, propylene glycol, ethylene glycol, diethylene glycol, dipropylene glycol, 1,2-pentanediol, hexylene glycol, trimethylpentanediol, Benzyl alcohol, glycerin, 2-phenoxyethanol, 2-phenylethanol and the like. These 1 type can be used individually or in combination of 2 or more types as appropriate.
The monovalent or polyhydric alcohol having 1 to 8 carbon atoms is usually 0 to 15% by mass, preferably 0.5 to 10% by mass, based on the total amount of the composition.

[Optional components: sequestering agent and / or antioxidant]
For the purpose of improving the stability of the fragrance and color tone of the softener composition, a sequestering agent and / or an antioxidant can be contained.
Examples of sequestering agents that can be incorporated into the composition of the present invention include aminocarboxylates such as ethylenediaminetetraacetate and diethylenetriaminepentaacetate, citric acid, succinic acid, hydroxyiminodisuccinic acid, and tripolyphosphoric acid. Examples thereof include inorganic phosphorus compounds typified by salts, and organic phosphorus compounds typified by 1-hydroxyethylidene-1,1-diphosphonate. Of the sequestering agents, 1-hydroxyethylidene-1,1-diphosphonate is particularly preferred. In addition, when mix | blending a sequestering agent with a liquid softening agent, you may mix | blend as a free acid and may mix | blend as a salt.
The compounding amount of the sequestering agent is preferably 0.0001 to 1% by mass, more preferably 0.0005 to 0.5% by mass, based on the total amount of the composition. If the amount is too small, the effect may be weakened. If the amount is too large, phase separation may occur.

On the other hand, examples of the antioxidant include propyl gallate, BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), p-hydroxyanisole, tea extract and the like. Of these, BHT is particularly preferred.
The compounding quantity of antioxidant is 0-1 mass% with respect to the composition whole quantity, Preferably it is 0.0001-0.5 mass%, More preferably, it is 0.001-0.1 mass%. If the blending amount is too small, the effect may be weakened, and if it is too much, the production cost is increased.

[Optional component: Preservative other than component (A)]
The composition of the present invention can be used in combination with a preservative usually used in an aqueous liquid softener composition in order to further enhance the antiseptic property during long-term storage. Specific examples include isothiazolone-based organic sulfur compounds, benzisothiazolone-based organic sulfur compounds, benzoic acids, and 2-bromo-2-nitropropane-1,3-diol.
Examples of isothiazolone-based organic sulfur compounds include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, 2-phenyl-3 -Isothiazolone, 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazoline-3-one, and mixtures thereof. A more preferred antiseptic / disinfectant is an aqueous mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, more preferably about 77%. An aqueous mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and about 23% 2-methyl-4-isothiazolin-3-one. Commercial products such as Caisson CG / ICP (approximately 1.5% by mass aqueous solution) manufactured by Rohm and Haas and Juncide 5 manufactured by Pure Chemical Co., Ltd. can be used.
Examples of benzisothiazoline-based organic sulfur compounds include 1,2-benzisothiazolin-3-one and 2-methyl-4,5-trimethylene-4-isothiazolin-3-one. Dithio-2,2-bis (benzmethylamide) and the like can also be used, and they can be used in any mixing ratio. Of these, 1,2-benzisothiazolin-3-one is particularly preferred. As such a compound, commercially available products such as Proxel series (BDN, BD20, XL-2, GXL) manufactured by Arch Chemicals Japan can be used.
Examples of benzoic acids include benzoic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, benzyl paraoxybenzoate, and the like. it can.

  The compounding amount of the preservative which is an optional component is 0.00001 to 1% by mass, preferably 0.0001 to 0.05% by mass, more preferably 0.0001 to 0.01% by mass with respect to the total amount of the composition. is there.

[Optional ingredients: Colorant]
Arbitrary dyes and / or pigments can be blended for the purpose of improving the appearance of the liquid softening agent composition. Preferably, it is one or more of red, blue, yellow or purple water-soluble dyes selected from acid dyes, direct dyes, basic dyes, reactive dyes, and mordant / acid mordant dyes. Specific examples of the dyes that can be added are described in the Dye Handbook (edited by the Society of Synthetic Organic Chemistry, published on July 20, 1970, Maruzen Co., Ltd.).

From the viewpoint of the storage stability of the liquid softening agent composition and the dyeing property to fibers, an acid dye or a direct dye having at least one functional group selected from a hydroxyl group, a sulfonic acid group, an amino group, and an amide group in the molecule A reactive dye is preferred, and its blending amount is preferably 1 to 50 ppm, more preferably 1 to 30 ppm, based on the entire composition.
Examples of the dye used in the liquid softener composition of the present invention include JP-A-6-123081, JP-A-6-123082, JP-A-7-18573, JP-A-8-27669, and JP-A-9. The dyes described in JP-A-25-250085, JP-A-10-77576, JP-A-11-43865, JP-A-2001-181972, JP-A-2001-348784, and the like can also be used.

[Optional ingredients: perfume composition]
Perfume compositions include aliphatic and aromatic ethers, aliphatic and terpene oxides, acetals, phenols, phenol ethers, fatty acids, acids such as terpene carboxylic acids and aromatic carboxylic acids, amides One or two or more kinds of blended fragrances including synthetic and / or natural fragrances such as nitriles, nitriles, amines, quinolines, nitrogen-containing compounds such as pyrrole and indole can be used.
The fragrance component contained in the fragrance is not particularly limited, and a list of the fragrance components to be used is, for example, “Perfume and Flavor Chemicals” Vol. IandII, Stephen Arctander, Allured Pub. Co. (1994), “Synthetic fragrance chemistry and product knowledge”, Motoichi Into, Chemical Industry Daily (1996), “Perfume and Flavor Materials of Natural Origin”, Stephen Arctander, Allred Pub. Co. (1994), “Performerial Material Performance V.3.3”, Boelens Aroma Chemical Information Service (1996), and the like can be used.

[Optional component: Silicone compound]
A silicone selected from dimethylpolysiloxane and modified dimethylpolysiloxane having various organic functional groups is used singly or in combination of two or more for the purpose of improving the physical properties of the fiber such as wrinkle resistance, water absorption, and iron sliding properties. It can be used in any proportion as a mixture. In particular, polyether-modified silicones containing a polyoxyalkylene group in the molecule represented by the following general formula (XII) are suitable.

In the formula, —Z ¹ and —Z ² are each independently —R, —O—R, —OH, —O—X—R, and —O—X—H. R may be the same as or different from each other, and each is a saturated or unsaturated linear or branched hydrocarbon group having 1 to 4 carbon atoms, and X is a polyoxyalkylene group. —Y is —R ⁴ —O—X—R ⁵ or —O—X—R ⁵ , R ⁴ is a saturated or unsaturated linear or branched hydrocarbon group having 1 to ⁴ carbon atoms, R ⁵ is a hydrogen atom or a saturated or unsaturated linear or branched hydrocarbon group having 1 to 4 carbon atoms.

In the general formula (XII), -Z ¹ and -Z ² are preferably each independently -R and -OH. R is preferably a short-chain saturated hydrocarbon group having 1 to 4 carbon atoms, and particularly preferably a methyl group. R ⁴ is preferably a short-chain saturated hydrocarbon group having 1 to 4 carbon atoms, and particularly preferably a propylene group. When R ⁵ is a hydrocarbon group, a short-chain saturated hydrocarbon group having 1 to 4 carbon atoms is preferable. Particularly preferred R ⁵ is a hydrogen atom or a methyl group.

  In the general formula (XII), X represents a polyoxyalkylene group, but oxyethylene units, oxypropylene units, oxybutylene units, and the like may be arranged in a block or randomly. However, the mass ratio of the polyoxyethylene chain portion in X is 10% or more and less than 60%, preferably 20% to 35%, based on the mass of the whole molecule. Moreover, it is preferable that the mass ratio of the polyoxyethylene chain part in the polyoxyalkylene group X is 50% to 100%.

  Furthermore, in the said general formula (XII), L, M, and N all represent the average value of the number of each repeating unit, L is 0-50, Preferably it is 0-3, M is 1-1000, Preferably it is 1-50, N is 10-10000, Preferably it is 20-500. The polyether-modified silicone represented by the general formula (XII) may have a block copolymer structure in which each repeating unit is arranged in a block shape, and each repeating unit is randomly arranged. It may have a structure.

The kinematic viscosity at 25 ° C. of silicone is preferably in the range of 100 to 100,000 mm ² / s (B-type viscometer, manufactured by TOKIMEC, 25 ° C., the same applies hereinafter), more preferably 100 to 10,000 mm ² / s. . Various silicones may be used as an oil, an emulsion, or a dispersion. These silicone compounds are preferably added in an amount of 0 to 10% by mass, more preferably 2 to 8% by mass, based on the total amount of the liquid softening agent composition.

[Optional ingredients: pH adjuster and pH]
Although the pH of the liquid softening agent composition of the present invention is not particularly limited, the pH is set in the range of 1.0 to 6.0 for the purpose of suppressing hydrolysis in the ester group composition of the component (B). In particular, a pH range of 2.0 to 4.0 is preferable. For the pH adjustment, any inorganic or organic acid and alkali can be used. Specifically, hydrochloric acid, sulfuric acid, phosphoric acid, alkyl sulfuric acid, benzoic acid, p-toluenesulfonic acid, acetic acid, citric acid, ring Examples thereof include carboxylic acids such as acid, succinic acid, lactic acid and glycolic acid, sodium hydroxide, diethanolamine, and triethanolamine. Among these, hydrochloric acid, methyl sulfuric acid, sodium hydroxide, diethanolamine, and triethanolamine are preferable.

[viscosity]
The viscosity of the liquid softening agent composition of the present invention is not particularly limited, but is approximately 1,500 mPa · s (B-type viscometer, TOKIMEC, from the viewpoint of dischargeability from a container, handling property when charged into a washing machine, and the like. It is preferable that the viscosity is 10 to 100 mPa · s immediately after blending, considering the increase in viscosity due to storage days, and preferably 10 to 50 mPa · s. Is more preferable. Within such a range, even after long-term storage or freeze-restoration, an abnormal phenomenon such as phase separation or gelation does not occur, and the above usability is favorable.

[Mixing method]
The method of blending the liquid softening agent is not particularly limited, and various methods can be used, and in particular, JP-A-2-68137, JP-A-5-32788, JP-A-5-32789, and JP-A-10-10. The method described in 237762 is preferred. That is, a high concentration cationic surfactant is prepared by adding a part of the aqueous phase to the oil phase containing the components (A) and (B) or adding the oil phase to a part of the aqueous phase. The aqueous liquid softener composition of the present invention can be prepared by a method of forming a liquid crystal phase containing, then adding the remaining aqueous phase to the liquid crystal phase and inverting the liquid crystal phase to an O / W emulsion. it can.

  The alkylene oxide addition type nonionic surfactant blended for the purpose of improving emulsification dispersion stability such as freeze-recovery stability may be added to either the aqueous phase or the oil phase. The organic or inorganic salts that are viscosity modifiers can be added in several divided portions during production. The optional component is selected to be added to either the aqueous phase or the oil phase from the viewpoint of ease of dissolution in the aqueous phase or oil phase and handling properties. However, those having poor solubility can be added to any phase in combination with an emulsifier or a solvent. In general, it is preferable to add a highly water-soluble one to the aqueous phase and a poorly water-soluble one to the oil phase.

[Packaging container for liquid softener composition]
The packaging container to be filled with the liquid softening agent composition of the present invention is not particularly limited, but it is generally filled in a polyethylene or polypropylene, polyethylene terephthalate bottle container, polyethylene or nylon pouch container. In recent years, polyethylene and polyethylene terephthalate films on which aluminum or alumina is vapor-deposited may be used as the pouch material in order to suppress moisture evaporation of the composition and to suppress changes in properties such as viscosity, color tone, and aroma. A multilayer film in which two or more layers are bonded together can be used. Among these, it is particularly desirable to use a combination of two or more of nylon, polyethylene, polypropylene, and polyethylene terephthalate. Further, these may contain pigments, antistatic agents, ultraviolet absorbers, slipping agents and the like.

[Method of using liquid softener composition]
The softener composition of the present invention is used for rinsing after washing in normal laundry. However, the softener composition may be used alone without the washing step. The detergent in the washing process may be an anionic or non-ionic detergent, and may contain other surfactants and function improvers. Can be used. From the viewpoint of imparting flexibility to the textile product, the concentration used when finishing the textile product is the component (A) alone or the amount of water used when finishing the textile product filled in the washing bath in the rinsing step, or It is desirable to use it in such an amount that the concentration of the total amount of the component (A) and the component (B) is 10 to 100 ppm. More preferably, it is 20-100 ppm. However, it is most preferable that the user adjusts the amount to his or her preference in consideration of the laundry model, the amount of textiles, the amount of water, and the like.
The softener composition of the present invention can be used in all commercially available washing machines such as a two-layer washing machine, a fully automatic washing machine, and a washing machine with a drying function.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.

Example 1. (A) Synthesis of Component and Identification Analysis Example 1-1. [Component (a-1): Synthesis of Monomethoxylated TEA Salt]
[Synthesis of methoxyethyl dihydroxyethylamine]
In a 1 L pressure vessel equipped with a thermometer and a stirrer, 300 g (4.0 mol) of methoxyethylamine (manufactured by Kanto Chemical) was charged. When the liquid temperature reaches 100 ° C, ethylene oxide (manufactured by Mitsubishi Chemical) is gradually added while gradually increasing the liquid temperature, and a total of 349 g (7.93 mol) of ethylene oxide is controlled while controlling the temperature to 150 to 170 ° C. The reaction pressure was 0.5 MPa · G (gauge pressure) or less. After completion of the preparation of ethylene oxide, the mixture was aged for 1 hour while maintaining at 170 ° C. After completion of aging, the liquid temperature was cooled to 60 ° C. As a result of measuring the amine value of the obtained methoxyethyldihydroxyethylamine, it was 342 mgKOH / g.
[Component (a-1): Synthesis of N-methyl-N-methoxyethyl-N, N-dihydroxyethylammonium methyl sulfate]
200 g (Mw: 163.4, 1.22 mol) of methoxyethyl dihydroxyethylamine obtained by the above method was charged into a 1 L four-necked flask equipped with a thermometer, a cooling device, and a stirrer, and the temperature was adjusted to 50 to 60 ° C. While maintaining the liquid temperature, dimethyl sulfate (154.2 g, 1.22 mol) was added to carry out the reaction. The amount of residual amine in the obtained quaternary ammonium salt was 0.29%, and amine monomethyl sulfate was 1.02%.

Example 1-2. [Synthesis of mixture of component (a-1) and component (a-2)]
200 g (Mw: 163.4, 1.22 mol) of methoxyethyl dihydroxyethylamine obtained by the above method was charged into a 1 L four-necked flask equipped with a thermometer, a cooling device, and a stirrer, and the temperature was adjusted to 50 to 60 ° C. Dimethyl sulfuric acid (308.4 g, 2.44 mol) was added over 2 hours while maintaining the liquid temperature, and then aging reaction was performed at 60 ° C. The amount of residual amine of the obtained quaternary ammonium salt was 0.05%. The resulting quaternary ammonium salt was neutralized by adding KOH / methanol (56.1 g (1.0 mol) / 200 g), and the resulting precipitate was filtered off at 60 ° C. Subsequently, the methanol in the composition was distilled off from the obtained filtrate at 60 ° C. under reduced pressure (1.3 kPa or less) to obtain the title quaternary ammonium salt composition. It was 1 / 2.6 as a result of calculating the ratio of a monomethoxy body: (a-1) component / dimethoxy body: (a-2) component by proton NMR.
The chemical structure analysis results of the monomethoxylated TEA quaternary salt and dimethoxylated TEA quaternary salt obtained in Examples 1-1 and 1-2 are shown in Chemical Formula 7 and FIGS. Note that the encircled numbers in Chemical Formula 7 correspond to the encircled numbers in FIGS. 1 and 2.

The synthesized sample said component (a-1) ^{alone, 1 H-NMR (300MHz,} D 2 O) in FIG. 1-1 (Figure 1 bottom) ^{spectra, 13 C-NMR (300MHz,} D 2 O ) Spectrum in FIG. 2, mass spectrum in FIG. 3, infrared absorption spectrum in FIG. 4, sample of a mixture of component (a-1) and component (a-2), ¹ H-NMR (300 MHz, D ₂ O) spectrum is shown in FIG. 1-2 (upper right of FIG. 1), and mass spectrum is shown in FIG.

¹ H-NMR (300 MHz, D ₂ O) monomethoxylated TEA salt: δ = 3.1-3.2 (3H, s), 3.25-3.35 (3H, s), 3.5-3.6 (4H, t), 3.6-3.7 ( 2H, t), 3.6-3.67 (CH ₃ SO ₄ ⁻ ), 3.75-3.85 (2H, t), 3.9-4.0 (4H, t), dimethoxylated TEA salt: δ = 3.1-3.2 (3H, s), 3.25-3.35 (3H, s), 3.5-3.6 (2H, t), 3.6-3.7 (4H, t), 3.6-3.67 (CH 3 SO 4 -), 3.75-3.85 (4H, t), 3.9-4.0 (2H, t).
¹³ C-NMR (300 MHz, D ₂ O) δ = 50.5-50.8, 55.9-56.2, 56.1-56.3 (CH ₃ SO ₄ ⁻ ), 58.9-59.1, 63.1-63.3, 65.0-65.2, 66.0-66.2.
MS (ESI +) monomethoxylated TEA salt: m / z = 178 [M] ⁺ , 134 [M-CH ₂ CH ₂ OH + H] ⁺ , 120 [M-CH ₂ CH ₂ OCH ₃ + H] ⁺ , 102 [M-CH ₂ CH ₂ OCH ₃ —OH] ⁺ , 59 [CH ₂ CH ₂ OCH ₃ ] ⁺ , dimethoxylated TEA salt: m / z = 192 [M] ⁺ , 134 [M-CH ₂ CH ₂ OCH ₃ + H] ⁺ , 116 [M-CH ₂ CH ₂ OCH ₃ —OH] ⁺ , 59 [CH ₂ CH ₂ OCH ₃ ] ⁺ .
IR (Transmission FT-IR) 754cm ^-1 1457-1473cm ^-1 2950cm ^-1 CH bond, 1006cm ^-1 1212-1251cm ^-1 C-0 bond, 3384cm ^-1 0-H bond, 2850cm ^-1 CH ₃ -O CH bond.

Manufacturing example. Preparation of Component (B) Component (B) used for blending softener described in Table-4: Mono long chain / di long chain / tri long chain hydrocarbon group containing ester group which is (b-1) The quaternary ammonium salt mixture was prepared according to the following method.
<Synthesis of ester amine>
To a 2 L 4-neck flask equipped with a stirrer, a condenser, a thermometer, a cooling device and a vacuum set, a partially hydrogenated palm oil fatty acid methyl ester (methyl stearate 40% + methyl oleate 40% + methyl palmitate 20 %, A mixture of 5% pastel M180, pastel M181, pastel M16), 186 g (1.24 mol) triethanolamine, 0.4 g magnesium oxide as a catalyst, and A 25% aqueous sodium hydroxide solution (1.5 g) was charged. After carrying out nitrogen substitution, the pressure was reduced to 70 kPa. Thereafter, the temperature was raised to 185 ° C. at a rate of 1.5 ° C./min, the pressure was gradually reduced to 3 kPa, and the reaction was carried out for 7 hours. After confirming that the unreacted methyl ester was 1% or less, the reaction was stopped. The fatty acid salt derived from the catalyst was removed by filtration from the obtained product to obtain an intermediate ester amine. The average molecular weight determined from the measured amine value was 606.
<Quaternization>
303 g (0.50 mol) of the resulting ester amine was charged into a 1 L four-necked flask equipped with a thermometer, a dropping funnel and a cooling device, and purged with nitrogen. Then, it heated at 90 degreeC and 61.7 g (0.49 mol) of dimethyl sulfuric acid was dripped over 1 hour. After completion of dropping, the mixture was further stirred for 1 hour. Next, the solution was cooled while dropping about 64 g of ethanol as a solvent, and an ethanol solution of a mono long chain ester / di long chain ester / tri long chain ester quaternary ammonium methyl sulfate mixture (b-1) (concentration of nonvolatile content: About 85%). In the obtained quaternary ammonium salt mixture, the mass of mono long chain ester quaternary ammonium salt / di long chain ester quaternary ammonium salt / tri long chain ester quaternary ammonium salt was 25/55/20. The iodine value was 34. Furthermore, the mass ratio of the cis isomer / trans isomer of the unsaturated bond was cis isomer / trans isomer = 45/55. The ethanol solution contains about 9% in total of mono-long chain ester tertiary amine, di-long chain ester tertiary amine and tri-long chain ester tertiary amine which are not quaternized, The mass ratio was mono / di / tri = 1/9/90.

Formulation and Evaluation of Aqueous Liquid Softener Composition [Formulation Examples 1 to 8, Formulation Comparative Examples 1 to 3]
Using the components shown in Tables 1 to 4, 1 kg of a liquid softener composition was blended. First, an oil phase mixture and an aqueous phase mixture are prepared. However, the aqueous phase mixture was divided into two so as to have a mass ratio of 3: 7, and a first aqueous phase mixture and a second aqueous phase mixture were obtained, respectively. Then, the aqueous phase mixture was balanced with purified water so that the total of the oil phase mixture, the first aqueous phase mixture and the second aqueous phase mixture was 990 g. Thereafter, if necessary, hydrochloric acid (reagent 5 mol / L, manufactured by Kanto Chemical Co., Inc.) or sodium hydroxide (reagent 5 mol / L, manufactured by Kanto Chemical Co., Ltd.) is added to the aqueous phase mixture to obtain a predetermined pH. In addition, ion exchange water was added so that the total mass became 1000 g, and the liquid softening agent compositions shown in Table 4 were obtained. Unless otherwise specified, the amount is shown as% by mass with respect to the total softener composition in each case, but is abbreviated as%.
Formulation is (A) component, (B) component (previously mixed with 0.001% of an appropriate amount of synthetic ethanol and 1-hydroxyethylidene-1,1-diphosphonic acid as an optional component) and an additional amount of ethanol and a fragrance composition A first aqueous phase containing a component (hereinafter simply referred to as “aqueous phase”), which is blended with an aqueous phase in an oil phase mixture composed of a polyether-modified silicone as necessary (previously mixed with 0.01% BHT) The mixture was added to form a liquid crystal phase of a cationic surfactant, and then the liquid crystal phase and the second aqueous phase mixture were mixed to invert the liquid crystal phase. The oil phase mixture was heated to about 55 ° C and the aqueous phase mixture was heated to about 40 ° C and mixed. In preparing the composition, a paddle mixer was used and mixed for 5 minutes at 1000 rpm before and after liquid crystal phase inversion.
In addition, the softener composition described in Table 4 includes an alkylene oxide addition-type nonionic surfactant (aqueous phase) as component (C) and an optional component calcium chloride (half amount in the first aqueous phase). Then, after mixing the oil phase mixture and the aqueous phase mixture, the liquid crystal phase was added in the remaining half amount at the time of phase inversion), and the dye (aqueous phase) was blended according to each composition. Further, a predetermined amount of isothiazolone liquid (aqueous phase) was also added as required. In addition, (C) component used for mixing | blending is shown in Table-1, respectively, Table-2 shows a fragrance | flavor composition, Table-3 shows common arbitrary components other than a fragrance | flavor, respectively. About the obtained liquid softening agent composition, according to the evaluation method shown below, antiseptic | preservative power and freeze restoration stability were evaluated. The composition and evaluation results of the softener are shown in Table-4. In blending, the blending amount of calcium chloride as a viscosity modifier was adjusted so that the viscosity immediately after blending was in the range of 10 to 50 mPa · s.

[Production method of test polyether-modified silicone]
828 g of hydrogensiloxane represented by (CH3) 3SiO (CH3CH3SiO) 210 (CH3HSiO) 9Si (CH3) 3, 210 g of allylated polyether represented by average composition CH2 = CHCH2O (CH2CH2O) 9H, 726 g of ethyl alcohol and platinum chloride The acid, which was neutralized with Cl, was weighed so that platinum was 5 ppm by weight with respect to the allylated polyether, stirred at a reaction temperature of 80 ° C., and reacted for 5 hours. After completion of the reaction, a polyether-modified silicone was obtained by distilling off under reduced pressure. 10 g of diethylene glycol monobutyl ether was added to 90 g of this polyether-modified silicone.

[Method for evaluating liquid softener composition]
(1) Freezing and restoring stability About 100 mL of softening agent composition is put in a 100 mL glass bottle, and -15 ° C (40 hours, freezing) ⇔25 ° C (8 hours, restoring) is repeated three times, and then according to the following criteria. The presence or absence of changes in viscosity and liquid appearance was determined. The viscosity was measured at a sample temperature of 25 ° C. and using a B-type viscometer (BL Viscometer manufactured by TOKIMEC) at a rotation speed of 30 rotations / minute and at the 10th rotation. A No. 2 rotor was used when the viscosity was 1000 mPa · s or less, and a No. 3 rotor was used when the viscosity exceeded 1,000 mPa · s.
<Criteria>
(Double-circle): The viscosity after 3 times freezing restoration is 300 mPa * s or less, and there is no abnormality in a liquid external appearance.
○: Viscosity after 3 times of freeze-recovery is more than 300 to 800 mPa · s, and the liquid appearance is not abnormal.
(Triangle | delta): The viscosity more than 800-1,500 mPa * s or less after three times of freezing restorations, or the liquid external appearance has some signs of non-uniform gelation.
X: Viscosity after 1500 times of freezing restoration, more than 1500 mPa · s, gelled within 3 times.
(2) Preservative power After producing the softener composition, the test sample that was allowed to stand at 25 ° C. for 1 day was inoculated with Burkhorderia cepacia bacteria at a density of 10 6 / mL. Stored at ° C. Then, the number of bacteria surviving in the sample over time was measured by the plate pour method. The number of days (days of death) when the number of bacteria was less than 10 / g was determined. The measurement was carried out 1 day, 4 days, 7 days, 14 days later (after 21 days and 28 days depending on the result), and the number of days when the number of bacteria was less than 10 cells / g was defined as the number of killed days. The smaller the number of days, the stronger the antiseptic power.
The results are shown in Table-4.

FIG. 1-1 shows the ¹ H-NMR (300 MHz, D ₂ O) spectrum of the component (a-1) synthesized in Example 1-1, and FIG. 1) A ¹ H-NMR (300 MHz, D ₂ O) spectrum of a mixture of the component and the component (a-2) is shown. The ¹³ C-NMR (300 MHz, D ₂ O) spectrum of the component (a-1) synthesized in Example 1-1 is shown. The mass spectrum of (a-1) component synthesize | combined in Example 1-1 is shown. The infrared absorption spectrum of (a-1) component synthesize | combined in Example 1-1 is shown. The mass spectrum of the mixture of (a-1) component and (a-2) component synthesize | combined in Example 1-2 is shown.

Claims (4)

A compound represented by the following formula (1).

(In the formula, R is a hydrogen atom or a methyl group.)   An additive for liquid softeners, comprising at least one compound according to claim 1.   A liquid softener composition comprising at least one compound according to claim 1.   Further, (B) 1 selected from the group consisting of an amine compound containing one or more hydrocarbon groups having 12 to 24 carbon atoms including an ester group in the molecule, or a neutralized product or quaternized product thereof. The liquid softening agent composition according to claim 3, comprising at least one kind of cationic surfactant.

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