JP4451413B2 - Liquid softener composition - Google Patents

Description

  The present invention relates to a liquid softener composition. In particular, the present invention relates to a liquid softener composition capable of imparting excellent flexibility to various synthetic fibers.

  Conventionally, commercial products that are marketed as liquid softener compositions for household use can obtain a good softening effect in a small amount, so that a fourth compound having 1 to 2 long-chain alkyl or alkenyl groups in one molecule. A composition mainly composed of a quaternary ammonium salt has been used. Such a liquid softener composition using a quaternary ammonium salt imparts a sufficient softening effect to cotton. However, it is difficult to say that such a liquid softener composition is sufficiently effective for synthetic fibers such as acrylics, polyesters, and polyamides, and the texture of clothing is impaired when processed at a higher concentration. There was a problem that it might be. On the other hand, in order for the liquid softening agent composition to effectively exhibit its softening finishing effect, it is necessary to stably disperse the base quaternary ammonium salt in the aqueous medium. In addition, the soft finish may be frozen by being exposed to a low temperature during transportation or storage, but once it has been frozen and thawed back to room temperature, it must still have dispersion stability. is there. In recent years, a quaternary ammonium salt having three alkyl groups in one molecule has attracted attention as a base for a softener for the purpose of improving the softness of synthetic fibers (for example, Japanese Patent Laid-Open No. Hei 10). -77575). However, since such a quaternary ammonium salt has strong crystallinity, it is very difficult to stably disperse it in an aqueous medium, and there is a problem. JP-A-3-287866 and JP-A-3-287867 disclose various fibers by using a soft finish obtained by mixing mono, di, triester quaternary ammonium salt and imidazoline compound at a specific ratio. A technique for improving the flexible performance with respect to the above has been disclosed. However, although these softening agent compositions have improved softening performance, there is a problem with the dispersion stability during freezing and restoration as described above.

  Furthermore, in consideration of the influence on the environment, in recent years, it is desired to use a base for a liquid softening agent composition having excellent biodegradability and the like having little influence on the environment. For example, JP-A-6-228877 and JP-A-7-3649 describe softener compositions containing a quaternary ammonium salt containing an ester group. In order to prevent such quaternary ammonium salts, many have an ester bond in the carbon chain for the purpose of obtaining good biodegradability, and hydrolysis tends to proceed. Furthermore, it is necessary to maintain the pH of the composition on the acidic side. On the other hand, in order to increase the commercial value as a softening agent, the liquid softening agent composition is generally colored by adding a pigment as a component of the liquid softening agent composition. When the pH of the composition is acidic, problems such as dyeing of the fibers on the fibers during processing and fading during storage occur. For this reason, attempts have been made to obtain a liquid softener composition that is biodegradable, colored, and highly stable in color by blending a stable pigment even when the pH is acidic. For example, Japanese Patent Application Laid-Open No. 7-18574 discloses the use of a specific blue dye in combination with a specific chelating agent, and Japanese Patent Application Laid-Open No. 7-18573 discloses a fourth long di-chain. It is disclosed that a combination of a quaternary ammonium salt and a specific red pigment is used. However, in any of these methods, usable dyes are limited to the above-mentioned specific dyes, so that the degree of freedom in selecting the dye composition is low, and it cannot be said that this point is sufficient.

  Accordingly, the present invention provides a liquid softening agent composition that imparts excellent flexibility to various synthetic fibers and that is excellent in dispersibility, particularly dispersion stability during freeze-restoration. Objective.

  The present invention also provides a liquid softener composition having a high biodegradability of the base and capable of performing desired coloring by using various pigments and having high color stability. Is the second purpose.

  As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that specific tri-long-chain alkyl (or alkenyl) quaternary ammonium salts, di-long-chain alkyl (or alkenyl) quaternary ammonium salts and mono-long chains. It has been found that the first problem can be solved by using a mixture of an alkyl (or alkenyl) quaternary ammonium salt together with a nonionic active agent having a specific structure.

  The present inventors can also solve the second problem by using a mixture of the quaternary ammonium salt together with a dye having a specific structure and a metal chelating agent and / or an antioxidant. I found it.

That is, the present invention provides, as its first aspect, (A) a quaternary ammonium salt mixture comprising the following components (a-1), (a-2) and (a-3), Based on the total mass of the mixture, it comprises 5 to 30% by weight of the (a-1) component, 35 to 70% by weight of the (a-2) component, and 10 to 45% by weight of the (a-3) component. A mixture of quaternary ammonium salts, and (B) a nonionic activator obtained by adding an average of 10 to 100 moles of alkylene oxide to a primary alcohol having a branched alkyl group or branched alkenyl group having 8 to 20 carbon atoms, A liquid softener composition is provided.
Component (a-1): It has three long-chain alkyl or alkenyl groups in the molecule, and has the following general formula (I):

A quaternary ammonium salt represented by
Component (a-2): It has two long-chain alkyl or alkenyl groups in the molecule, and has the following general formula (II):

A quaternary ammonium salt represented by
(A-3) Component: It has one long-chain alkyl or alkenyl group in the molecule, and has the following general formula (III):

A quaternary ammonium salt represented by
(In the formulas (I) to (III), R _{1 to} R ₃ and R _{5 to} R ₇ each represent a linear or branched saturated or unsaturated hydrocarbon group having 10 to 24 carbon atoms, and they are the same as each other. Or R ₄ represents an alkyl group having 1 to ₄ carbon atoms or a hydroxyalkyl group, n is an integer of 2 to 4, m is an integer of 0 to 3, and p is 2 to 4 And each n, m and p may be the same or different from each other, X ⁻ is a softener compatible anion.)

  The second aspect of the present invention also includes, as a second embodiment, one or two kinds selected from the above-mentioned component (A), (C) a red dye having a sulfonic acid group or a salt thereof, a blue dye, a yellow dye, and a purple dye. Provided is a liquid softener composition comprising a dye and (D) a metal chelator and / or an antioxidant.

  First, the component (A) common to the first and second aspects of the present invention will be described.

The component (A) used in the present invention is a base of the liquid softening agent composition, and is a tri long chain alkyl (or alkenyl) quaternary ammonium salt ((a-1) represented by the above general formula (I). ) Component), a di long chain alkyl (or alkenyl) quaternary ammonium salt represented by general formula (II) (component (a-2)) and a mono long chain alkyl represented by general formula (III) (or Alkenyl) quaternary ammonium salt (component (a-3)) in a specific ratio. In the general formulas (I) to (III), R _{1 to} R ₃ and R _{5 to} R ₇ are each an alkyl or alkenyl group having 10 to 24 carbon atoms, preferably 14 to 20 carbon atoms. R _{1 to} R ₃ and R _{5 to} R ₇ are such that the mass ratio of fatty acid residues having 17 or more carbon atoms in the molecules of the components (a-1) to (a-3) is 50% or more. It is desirable to select it, preferably 70% or more, particularly preferably 80% or more. R _{1 to} R ₃ and R _{5 to} R ₇ are such that only saturated higher fatty acid residues or unsaturated higher fatty acid residues are present in the molecules of the components (a-1) to (a-3). It may be a thing, or both may exist together. The ratio of saturated / unsaturated fatty acid residues in the molecule of each component is desirably in the range of 10/0 to 1/9, preferably 10/0 to 3/7, particularly preferably 10 in terms of mass ratio. / 0 to 5/5. When an unsaturated group is present as R _{1 to} R ₃ and R _{5 to} R ₇ , the stereoisomer structure may be either a cis isomer or a trans isomer, or both may be present together. Also good. The ratio of cis isomer / trans isomer in the unsaturated group is preferably in the range of 25/75 to 100/0 in terms of mass ratio. Specifically, R _{1 to} R ₃ and R _{5 to} R ₇ are, for example, residues derived from unsaturated higher fatty acids such as oleic acid, elaidic acid, linoleic acid, and linolenic acid, or stearic acid, palmitic acid, and myristic acid. It may be a residue derived from a saturated higher fatty acid such as acid or lauric acid. These residues may be residues derived from fatty acids and fatty acid esters obtained by degrading and purifying natural fats such as beef tallow, lard, palm oil, soybean oil, safflower oil, sunflower oil, olive oil and the like. It may be hydrogenated after decomposition.

In the general formula (I) ~ (III), R 4 is an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms. Specific examples of R ₄ include a methyl group, an ethyl group, a propyl group, a butyl group, and a hydroxyethyl group, and a methyl group and an ethyl group are particularly preferably used. In the general formulas (I) to (III), p is an integer of 2 to 4, preferably 2 or 3, and when p is 3, the group represented by C _p H _2p is: An isopropyl group is desirable. N is an integer of 2 to 4, and is preferably 2. Furthermore, m is an integer of 0 to 3, preferably 0 or 1. Each n, m and p may be the same or different from each other. Further, X ⁻ is a softener compatible anion, ie any anion such that the quaternary ammonium salts of general formulas (I) to (III) can function as a base for a liquid softener composition. Specific examples of softener compatible anions represented by X ⁻ include halogen atom anions such as chlorine, bromine and iodine, and anions such as methyl sulfate, ethyl sulfate and methyl carbonate. X ⁻ is preferably an anion of chlorine, bromine or methyl sulfate, and particularly preferably methyl sulfate anion.

Specific examples of quaternary ammonium salts that can be used as the components (a-1) to (a-3) of the present invention are shown below.
(A-1) Component:

(A-2) Component:

(A-3) Component:

  (A) component used by this invention is a mixture of the quaternary ammonium salt obtained by combining the said (a-1) component, (a-2) component, and (a-3) component by a specific ratio. . From the viewpoint of imparting flexibility to various synthetic fibers of the liquid softener composition, the proportion of the component (a-1) is 5% by mass or more based on the mass of the entire component (A), and the component (a-2) The proportion is 70% by mass or less, and the proportion of the component (a-3) is 45% by mass or less, preferably 35% by mass or less. Moreover, from the viewpoint of obtaining the effect of the liquid softening agent composition of the present invention, the proportion of the component (a-1) is 30% by mass or less, preferably 25% by mass or less, based on the mass of the entire component (A). The proportion of the component a-2) is 35% by mass or more, preferably 45% by mass or more, and the proportion of the component (a-3) is 10% by mass or more, preferably 15% by mass or more. Each component of (a-1) to (a-3) can be produced by any ordinary method known to those skilled in the art as a method for producing a quaternary ammonium salt. For example, it can be obtained by quaternizing a long-chain ester amine obtained by a condensation reaction between the corresponding short-chain tertiary amine and a fatty acid or a fatty acid methyl ester with a quaternizing agent such as dimethyl sulfate. is there. In this case, the unreacted short-chain tertiary amine, fatty acid, fatty acid methyl ester, quaternized product of short-chain tertiary amine, mono-, di-, and tri-long-chain ester amine are represented by (a-1) to (a- 3) Even if it is contained in an amount of 0.05 to 20% by mass relative to the component, there is no particular problem. The blending amount of the component (A) is from the viewpoint of obtaining sufficient flexibility imparting performance with a small amount of the liquid softener composition, and from the viewpoint of making the product viscosity and handling properties of the liquid softener composition suitable. In the liquid softening agent composition of the present invention, it is desirable that the amount be 3% by weight to 50% by weight, preferably 3% by weight to 40% by weight, and more preferably 3% by weight based on the weight of the entire liquid softening agent composition. % -30 mass% is mix | blended.

  Next, other components in the first aspect of the present invention will be described.

  The component (B) used in the present invention is a nonionic active agent obtained by adding an alkylene oxide to a primary alcohol having a specific structure. Specifically, the component (B) is a nonionic active agent obtained by adding an average of 10 to 100 moles of alkylene oxide to a primary alcohol having a branched alkyl group or branched alkenyl group having 8 to 20 carbon atoms. The primary branched alcohol preferably has 10 to 16 carbon atoms, particularly preferably 13 carbon atoms. The primary branched alcohol is used as the raw material alcohol of the component (B) used in the present invention because it is liquid flexible compared to the case of using a linear alcohol or a secondary alcohol even if branched. It is because it is excellent in the viewpoint of ensuring the dispersion stability after freeze-restoration of an agent composition. As the alkylene oxide added to the primary branched alcohol, ethylene oxide is preferably used alone, but propylene oxide may be added together with ethylene oxide. When both ethylene oxide and propylene oxide are added to the primary branched alcohol, any of them may be added first. The average number of moles of alkylene oxide added is preferably 20 to 80 moles, particularly preferably 30 to 60 moles. Moreover, when adding propylene oxide with ethylene oxide, the average addition mole number of propylene oxide can be made into 1-5 mol, Preferably it is 1-3 mol.

  Specific examples of the component (B) that can be used in the present invention include a product obtained by adding an average of 20 moles of ethylene oxide (EO) to primary isodecyl alcohol, a product obtained by adding an average of 40 moles of EO to primary isotridecyl alcohol, Examples include an average of 60 mol of EO added to tridecyl alcohol and an average of 60 mol of EO added to primary isohexadecyl alcohol.

  Component (B) used in the present invention is prepared, for example, using propylene or butylene as a raw material, and preparing an n-mer thereof (3-6 mer in the case of propylene, 2-4 mer in the case of butylene, etc.). It can be prepared by adding an alkylene oxide to a primary alcohol obtained by hydrogenation using an oxo reaction by a conventional method known to those skilled in the art.

  From the viewpoint of obtaining a liquid softening agent composition having good dispersion stability after freezing and restoring the viscosity of the liquid softening agent composition, the blending amount of the component (B) is that of the present invention. In a liquid softening agent composition, it is desirable to set it as 0.1 mass%-10 mass% on the basis of the mass of the whole liquid softening agent composition, Preferably it is 0.1 mass%-5 mass%, More preferably, it is 0 .3 mass%-2 mass% is mix | blended.

  The pH of the liquid softening agent composition of the present invention is within the range of 2 to 5 in order to suppress cleavage of the ester bond contained in the components (a-1) to (a-3) and hydrolysis. It is desirable that it is within the range of 2 to 4.5. Examples of the acid blended to adjust the pH of the liquid softener composition of the present invention include inorganic salts such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and carbons such as acetic acid, lactic acid, glycolic acid, citric acid, and maleic acid. An organic acid having a number of 6 or less can be used, and hydrochloric acid and sulfuric acid are particularly preferable. Moreover, you may use alkali compounds, such as sodium hydroxide and potassium hydroxide, as needed for the purpose of adjustment of pH of a liquid softening agent composition.

  In the liquid softener composition of the present invention, dimethylpolysiloxane and / or a partial amino group is used for the purpose of imparting appropriate elasticity to the softened synthetic fiber and further improving the slipperiness of the iron. A silicone compound such as dimethylpolysiloxane modified with a carboxyl group or a polyoxyethylene group can be blended. When blending these silicone compounds, the blending amount can be 0.1 to 10% by weight, preferably 0.3 to 5% by weight, especially based on the weight of the entire liquid softener composition. Preferably it is 0.5-3 mass%.

  Furthermore, in the liquid softener composition of the present invention, as other optional components, known components that are usually blended in the softener composition can be blended within a range that does not interfere with the effects of the present invention. As such an optional component, for example, 0.1 to 2% by mass of a di-long-chain alkyldimethyl quaternary ammonium salt and a mono-long-chain alkyltrimethyl quaternary ammonium salt based on the mass of the entire liquid softening agent composition 0.01 to 0.5% by mass of higher fatty acids such as stearic acid, oleic acid, and palmitic acid, and 0.01 to 3% of higher alcohols such as stearyl alcohol, palmityl alcohol, oleyl alcohol, and primary isotridecyl alcohol. % By mass, 0.01-2% by mass of fatty acid methyl esters such as stearic acid methyl ester, oleic acid methyl ester, palmitic acid methyl ester, 0.01-1% by mass of nonionic active agent such as fatty acid glycerin ester, chloride Calcium, sodium chloride, potassium chloride, sodium sulfate, ammonium chloride Ethanol, propylene glycol, ethylene glycol, butanediol, helium containing 0.01 to 2% by mass of a water-soluble salt such as um, magnesium chloride, and a trace amount of denaturing agents such as desodium benzoate, 8-acetylated sucrose, and brucine. Solvents such as xylene glycol, 2,2,4-trimethyl-1,3-pentanediol and benzyl alcohol are 1 to 20% by mass, antibacterial agents such as caisson CG are 0.001 to 0.1% by mass, 2,6- 0.001-0.1% by mass of an antioxidant such as di-tert-butyl-4-methylphenol and 0.01-2.0% by mass of hydrocarbons such as paraffin and liquid paraffin can be blended, Furthermore, urea, pigments, dyes, cellulose derivatives, ultraviolet absorbers, fluorescent brighteners, fragrances, and the like can be blended.

  Perfumes include ethers such as aliphatic ethers and aromatic ethers, oxides such as aliphatic oxides and terpene oxides, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogen Synthetic fragrances such as fluorinated aromatic carboxylic acids, acids such as aromatic carboxylic acids, acid amides, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, indoles, etc., natural from animals and plants One kind or two or more kinds of blended fragrances including fragrances, natural fragrances and / or synthetic fragrances can be mixed and used. For example, in 1996, Motoichi Into, published by Chemical Industry Daily, “Synthetic Fragrance Chemistry and Product Knowledge”, 1969 MONTCLAIR, N. J. et al. Fragrances described in “Perfume and Flavor Chemicals” by STEFEN Arctander can be used. The main fragrance names are shown below. Eugenol, geraniol, bacdanol, dipropylene glycol, linalool, phenylethyl alcohol, 9-decen-1-ol, citronellol, isoeugenol, cedrol, cis-3-hexenol, nerol, terpineol, borneol, cis-3-hexenyl salicylate, Dibutylhydroxytoluene, methyl atrate, menthol, tetrahydrolinalol, dimethylbenzyl carbinol, geranyl acetate, citronellyl acetate, phenylethyl acetate, methyl dihydrojasmonate, benzyl acetate, linalyl acetate, terpinyl acetate, acetyl cedrene, p-tert-butylcyclohexyl acetate, 2-tert-butylcyclohexyl acetate, methyl acetate Slanilate, dimethylbenzylcarvinyl acetate, nonanal, decanal, undecanal, 2-methylundecanal, anisaldehyde, heliotropin, hexylcinnamic aldehyde, lyial, rilal, vanillin, ethyl vanillin, muscone, cyclohexadecenone, musk ketone, Tonalide, ionone, methylionone, iso-super, β-methylnaphthyl ketone, cacimelan, damascon, limonene, pinene, myrcene, caryophyllene, cyclopentadecanolide, γ-decalactone, γ-undecalactone, coumarin, galaxolide, ambroxan , Cedryl methyl ether, farenal, indole, benzyl alcohol, benzyl salicylate, para tertiary butyl cyclohexanol, ortho Tertiary butylcyclohexanol, cinnamic alcohol, phenoxyethanol, dihydrolinalol, myrcenol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, 3-octanol, 1-octen-3-ol, 9-decenol, trans-2-cis- 6-nonadienol, farnesol, nerolidol, bisabolol, patchoulol alcohol, vetiverol, p-tertiary butylcyclohexanol, ambrinol, 1- (2-t-butylcyclohexyloxy) -2-butanol, dihydromyrsenol, dimethol, Dimyrcetol, Fentyl alcohol, Hexyl salicylate, Hydrotropic alcohol, Mayol, Methyl salicylate, Mugor, Nopi Alcohol, nerol, oxyphenylone, lavandulol, sandaroa, sandera, santarex, bramanol, polysanthol, evanol, dimethylbenzylcarbinol, tetrahydromumol, tetrahydrogeraniol, thymol, carvacrol, allylamylglyco Rate, allylcyclohexane propionate, amyl valeric acid, amyl salicylate, isoamyl acetate, isoamyl salicylate, acetyl yugenol, benzyl salicylate, bergamyl acetate, bornyl acetate, butyl butyrate, benzyl formate, cedryl acetate, citronellyl Formate, cyclaset, cyclaprop, cinnamyl acetate, flutate, phenylethylphenylacetate, gel Nilfomate, cis-3-hexenyl acetate, hexyl salicylate, isobornyl acetate, isononyl acetate, jasmar, menthyl acetate, methyl salicylate, nopylacetate, neryl acetate, methylphenylacetate, neobergamate , Ethyl-2-methylpentanoate, styraryl acetate, styraryl propionate, tetrahydrolinalyl acetate, tetrahydrogeranylacetate, bellodox, cis-3-hexenal, trans-2-hexenal, heheptanal, octanal, Adoxal, amyl cinnamic aldehyde, benzaldehyde, cinnamic aldehyde, citral, citrusal, citronellal, cyclamenaldehyde, p-ethyl- 2,2-dimethylhydrocinnamaldehyde, 3- (pt-butylphenyl) -propylaldehyde, cuminaldehyde, dupical, helional, hyacinthaldehyde, hydroxycitronellal, isocyclocitral, ligustral, mugealdehyde, miracaldehyde , Tripral, 4-tricyclodecylidenebutanal, trimethylcyclohexene methylbutanal, safranal, perilaldehyde, α-methylene citronellal, undecylene aldehyde, dimethyl octanal, trimethylundecenal, trans-2-nonenal, acetophenone, Carvone, Celestorid, Cis jasmon, Caron, Dihydro jasmon, Diphenyl oxide, Coabon, Methyl lavender ketone, Sibeto , Cyclopentadecanone, oxahexadecen-2-one, olibon, oxyphenylone, traceolide, acetyl cedrene, methyl lavender ketone, isocyclemon, iron, α-dynascon, isodamascone, damasenone, neron, 3,3-dimethylcyclohexylmethyl Ketone, p-tertiary-butylcyclohexanone, cycloten, trimethylcyclopentanone, hexylcyclopentanone, maltol, ethylmaltol, sotron, 2,5-dimethyl-4-hydroxy-3 (2H) -furanone, terpinene, ferrandrene, p- Cymene, farnesene, 3-carene, terpinolene, camphene, sabinene, bisabolen, cedrene, guaien, diphenyl, diphenylmethane, amblet lid, n-butyl Talide, propylidenephthalide, butylidenephthalide, δ-hexalactone, δ-octalactone, δ-nonalactone, δ-2-decenolactone, δ-undecalactone, δ-dodecalactone, δ-tetradecalactone, lactoskatone, γ-hexalactone, γ-octalactone, γ-nonalactone, whiskey lactone, angelica lactone, γ-dodecalactone, γ-jasmolactone, jasmine lactone, cisjasmon lactone, cyclohexyl lactone, ε-decalactone, ε-dodecalactone, Ethylene dodecanedioate, cyclohexadecanolide, 10-oxahexadecanolide, 11-xahexadecanolide, 12-oxahexadecanolide, ethylene brushate, 14-methyl-hexadecenolide, 14-methyl -Hexa Canolide, oximene epoxide, paracresyl methyl ether, rose oxide, cinnamyl nitrile, cuminyl nitrile, quinoline, isoquinoline, p-methylquinoline, 6-isopropylquinoline, isobutylquinoline, yarayara, acetic acid, heptanoic acid, octanoic acid, decane Acid, gellanic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, benzoic acid, phenylacetic acid, cinnamic acid, hydrocinnamic acid, vanillic acid, anise oil, bay oil, boadrose oil, cananga oil , Cardamom oil, cassia oil, cedarwood oil, orange oil, mandarin oil, tangerine oil, basil oil, nutmeg oil, citronella oil, clove oil, coriander oil, elemi oil, eucalyptus oil, fennel oil, galvanum oil, geranium oil, Ba oil, camellia oil, jasmine oil, lavandin oil, lavender oil, lemon oil, lemongrass oil, lime oil, neroli oil, oak moss oil, okotia oil, patchouli oil, peppermint oil, perilla oil, petitgren oil, pine oil, rose Oil, rosemary oil, ginger brain oil, melamine oil, clary sage oil, sandalwood oil, spearmint oil, spike lavender oil, star anise oil, thyme oil, turpentine bean tincture, turpentine oil, vanilla bean tincture, vetiver oil, ylang ylang Oil, grapefruit oil, citron oil, benzoin, peruvian balsam, trubalsam, tuberose oil, mustin tincture, castrium tincture, civet tincture, ambergris tincture. Moreover, diethyl phthalate, benzyl benzoate, isopropyl myristate, hercorin, isopentane, orange terpene, etc. can be used as a perfume solvent or as a retaining agent. In addition, a fragrance | flavor is not limited to the fragrance | flavor of an Example.

  Furthermore, other components in the second aspect of the present invention will be described.

The component (C) used in the present invention is one or two or more kinds of dyes selected from a red dye, a blue dye, a yellow dye, and a purple dye having a sulfonic acid group or a salt thereof. When the sulfonic acid group forms a salt, the salt may be, for example, a sodium salt (—SO ₃ Na). As the pigment, direct dyes, acid dyes, reactive dyes, and the like can be used, but are not limited thereto.

Specific examples of the dye that can be used in the present invention include the following.
Red pigment:
CIAcid Red 18 CIAcid Red 27 CIAcid Red 52C.I.Acid Red 82 CIAcid Red 114 CIAcid Red 138C.I.Acid Red 186C.I.Direct Red 2 CIDirect Red 23 CIDirect Red 31C.I.Direct Red 79 CIDirect Red 81C.I .Reactive Red 6 CIReactive Red 17
Blue pigment:
CIAcid Blue 9 CIAcid Blue 40 CIAcid Blue 45C.I.Acid Blue 62 CIAcid Blue 74 CIAcid Blue 113C.I.Acid Blue 127C.I.Direct Blue 1 CIDirect Blue 15 CIDirect Blue 71C.I.Direct Blue 78 CIDirect Blue 86 CIDirect Blue 106C.I.Direct Blue 168C.I.Reactive Blue 4 CIReactive Blue 19 CIReactive Blue 83C.I.Reactive Blue 231
Yellow pigment
CIAcid Yellow 1 CIAcid Yellow 7 CIAcid Yellow 23C.I.Acid Yellow 141C.I.Direct Yellow 12 CIDirect Yellow 44C.I.Direct Yellow 50C.I.Reactive Yellow 3 CIReactive Yellow 17
Purple pigment
CIAcid Violet 7 CIAcid Violet 9 CIAcid Violet 43C.I.Acid Violet 49 CIAcid Violet 97 CIAcid Violet 106C.I.Direct Violet 48C.I.Reactive Violet 2 CIReactive Violet 4

  (C) The compounding quantity of a component can be suitably determined according to the color tone of a desired liquid softening agent composition. From the viewpoint that the color tone of the liquid softening agent composition is within a preferable range in appearance, the liquid softening agent composition of the present invention is 0.1 to 100 ppm based on the total mass of the liquid softening agent composition. It is desirable to add 1 to 50 ppm, more preferably 2 to 40 ppm.

  The component (D) used in the present invention is a metal chelating agent and / or an antioxidant. Examples of metal chelating agents that can be used in the present invention include aminocarboxylic acids typified by ethylenediaminetetraacetic acid salt, diethylenetriaminepentaacetic acid salt, etc., inorganic phosphorus compounds typified by tripolyphosphate, pyrophosphate, 1-hydroxy Examples include ethane-1,1-diphosphonate, polyphosphonic acids typified by compounds represented by the following general formulas (IV) to (VII), and organic phosphoric acids typified by phytic acid. Of these, 1-hydroxyethane-1,1-diphosphonate is particularly preferred. Moreover, when mix | blending a metal chelating agent with a liquid softening agent composition, you may mix | blend as a free acid and may mix | blend as a salt.

  Examples of the antioxidant include antioxidants such as 2,6-di-tert-butyl-4-methylphenol, butylated hydroxyanisole, and 2,6-di-tert-butyl 4-ethylphenol. Of these, 2,6-di-tert-butyl-4-methylphenol is preferred. When the metal chelating agent and the antioxidant are used in combination, the ratio is desirably 1/99 to 50/50 by mass ratio, preferably 5/95 to 35/65, particularly preferably 5/95 to 20 / 80. From the viewpoint that the liquid softening agent composition is stable over time without causing thickening and the like, and from the viewpoint of obtaining a sufficient dye fading inhibiting effect, In the liquid softener composition, it is desirable that the liquid softener composition is 1 to 500 ppm, preferably 10 to 500 ppm, more preferably 50 to 400 ppm, based on the total mass of the liquid softener composition.

  The pH of the liquid softening agent composition of the present invention is within the range of 2 to 5 in order to suppress cleavage of the ester bond contained in the components (a-1) to (a-3) and hydrolysis. It is desirable that it is within the range of 2 to 4.5. Examples of the acid blended to adjust the pH of the liquid softener composition of the present invention include inorganic salts such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and carbons such as acetic acid, lactic acid, glycolic acid, citric acid, and maleic acid. An organic acid having a number of 6 or less can be used, and hydrochloric acid and sulfuric acid are particularly preferable. Moreover, you may use alkali compounds, such as sodium hydroxide and potassium hydroxide, as needed for the purpose of adjustment of pH of a liquid softening agent composition.

  In the liquid softener composition of the present invention, dimethylpolysiloxane and / or a partial amino group is used for the purpose of imparting appropriate elasticity to the softened synthetic fiber and further improving the slipperiness of the iron. A silicone compound such as dimethylpolysiloxane modified with a carboxyl group or a polyoxyethylene group can be blended. When blending these silicone compounds, the blending amount can be 0.1 to 10% by weight, preferably 0.3 to 5% by weight, especially based on the weight of the entire liquid softener composition. Preferably it is 0.5-3 mass%.

Furthermore, in the liquid softener composition of the present invention, as other optional components, known components that are usually blended in the softener composition can be blended within a range that does not interfere with the effects of the present invention. As such an optional component, for example, 0.1 to 2% by mass of a di-long-chain alkyldimethyl quaternary ammonium salt and a mono-long-chain alkyltrimethyl quaternary ammonium salt based on the mass of the entire liquid softening agent composition N, N, N triacylyloxyethylamine 0.05 to 4.5% by mass, N, N diacyloxyethyl-N-hydroxyethylamine 0.03 to 2% by mass, N-acyloyloxyethyl 0.03 to 1% by mass of N, N-dihydroxyethylamine, 0.05 to 10% by mass of tertiary amines such as triethanolamine and methyldiethanolamine, neutralized products and quaternized products thereof, stearic acid and olein 0.01-0.5% by mass of higher fatty acids such as acid and palmitic acid, stearyl alcohol, palmityl alcohol, oleyl alcohol 0.01-3 mass% of higher alcohols such as ruthenium, 0.01-2 mass% of fatty acid methyl esters such as stearic acid methyl ester, oleic acid methyl ester, palmitic acid methyl ester, fatty acid glycerin ester, polyoxyethylene ( 5-100 mole) linear alkyl or alkenyl (C ₁₂ ~C _24: linear) 0.01 to 10 wt% of nonionic surfactant such as ether, calcium chloride, sodium chloride, potassium chloride, sodium sulfate, ammonium chloride , Ethanol, propylene glycol, ethylene glycol, butanediol, hexylene containing 0.01 to 2% by weight of a water-soluble salt such as magnesium chloride, and a trace amount of a denaturing agent such as desodium benzoate, 8-acetylated sucrose, and brucine Glycol, 2,2,4-trimethyl-1,3 pen 1 to 20% by mass of a solvent such as tandiol or benzyl alcohol, 0.001 to 0.1% by mass of an antibacterial agent such as caisson CG, 0.01 to 2% by mass of hydrocarbon such as paraffin or liquid paraffin In addition, urea, cellulose derivatives, ultraviolet absorbers, fluorescent brighteners, fragrances, and the like can be blended.

  Perfumes include ethers such as aliphatic ethers and aromatic ethers, oxides such as aliphatic oxides and terpene oxides, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogen Synthetic fragrances such as fluorinated aromatic carboxylic acids, acids such as aromatic carboxylic acids, acid amides, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, indoles, etc., natural from animals and plants One kind or two or more kinds of blended fragrances including fragrances, natural fragrances and / or synthetic fragrances can be mixed and used. For example, in 1996, Motoichi Into, published by Chemical Industry Daily, “Synthetic Fragrance Chemistry and Product Knowledge”, 1969 MONTCLAIR, N. J. et al. Fragrances described in “Perfume and Flavor Chemicals” by STEFEN Arctander can be used. The main fragrance names are shown below. Eugenol, geraniol, bacdanol, dipropylene glycol, linalool, phenylethyl alcohol, 9-decen-1-ol, citronellol, isoeugenol, cedrol, cis-3-hexenol, nerol, terpineol, borneol, cis-3-hexenyl salicylate, Dibutylhydroxytoluene, methyl atrate, menthol, tetrahydrolinalol, dimethylbenzyl carbinol, geranyl acetate, citronellyl acetate, phenylethyl acetate, methyl dihydrojasmonate, benzyl acetate, linalyl acetate, terpinyl acetate, acetyl cedrene, p-tert-butylcyclohexyl acetate, 2-tert-butylcyclohexyl acetate, methyl acetate Slanilate, dimethylbenzylcarvinyl acetate, nonanal, decanal, undecanal, 2-methylundecanal, anisaldehyde, heliotropin, hexylcinnamic aldehyde, lyial, rilal, vanillin, ethyl vanillin, muscone, cyclohexadecenone, musk ketone, Tonalide, ionone, methylionone, iso-super, β-methylnaphthyl ketone, cacimelan, damascon, limonene, pinene, myrcene, caryophyllene, cyclopentadecanolide, γ-decalactone, γ-undecalactone, coumarin, galaxolide, ambroxan , Cedryl methyl ether, farenal, indole, benzyl alcohol, benzyl salicylate, para tertiary butyl cyclohexanol, ortho Tertiary butylcyclohexanol, cinnamic alcohol, phenoxyethanol, dihydrolinalol, myranol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, 3-octanol, 1-octen-3-ol, 9-decenol, trans-2-cis-6 Nonadienol, farnesol, nerolidol, bisabolol, patchouliol, vetiverol, p-tertiary butylcyclohexanol, ambrinol, 1- (2-t-butylcyclohexyloxy) -2-butanol, dihydromyrsenol, dimethol, dimyrcetol, Fentyl alcohol, hexyl salicylate, hydrotropic alcohol, mayol, methyl salicylate, mugor, nopi Alcohol, nerol, oxyphenylone, lavandulol, sandaroa, sandera, santarex, bramanol, polysanthol, evanol, dimethylbenzylcarbinol, tetrahydromumol, tetrahydrogeraniol, thymol, carvacrol, allylamylglyco Rate, allylcyclohexane propionate, amyl valeric acid, amyl salicylate, isoamyl acetate, isoamyl salicylate, acetyl yugenol, benzyl salicylate, bergamyl acetate, bornyl acetate, butyl butyrate, benzyl formate, cedryl acetate, citronellyl Formate, cyclaset, cyclaprop, cinnamyl acetate, flutate, phenylethylphenylacetate, gel Nilfomate, cis-3-hexenyl acetate, hexyl salicylate, isobornyl acetate, isononyl acetate, jasmar, menthyl acetate, methyl salicylate, nopylacetate, neryl acetate, methylphenylacetate, neobergamate Ethyl-2-methylpentanoate, styraryl acetate, styraryl propionate, tetrahydrolinalyl acetate, tetrahydrogeranyl acetate, bellodox, cis-3-hexenal, trans-2-hexenal, heheptanal, octanal, adxal, Amyl cinnamaldehyde, benzaldehyde, cinnamaldehyde, citral, citrusal, citronellal, cyclamenaldehyde, p-ethyl- 2,2-dimethylhydrocinnamaldehyde, 3- (pt-butylphenyl) -propylaldehyde, cuminaldehyde, dupical, helional, hyacinthaldehyde, hydroxycitronellal, isocyclocitral, ligustral, mugealdehyde, miracaldehyde , Tripral, 4-tricyclodecylidenebutanal, trimethylcyclohexene methylbutanal, safranal, perilaldehyde, α-methylene citronellal, undecylene aldehyde, dimethyl octanal, trimethylundecenal, trans-2-nonenal, acetophenone, carvone , Celestorid, cis jasmon, caron, dihydro jasmon, diphenyl oxide, coabon, methyl lavender ketone, sibeto , Cyclopentadecanone, oxahexadecen-2-one, olibon, oxyphenylone, traceolide, acetyl cedrene, methyl lavender ketone, isocyclemon, iron, α-dynascon, isodamascone, damasenone, neron, 3,3-dimethylcyclohexylmethyl Ketone, p-tertiary butylcyclohexanone, cycloten, trimethylcyclopentanone, hexylcyclopentanone, maltol, ethylmaltol, sotron, 2,5-dimethyl-4-hydroxy-3 (2H) -furanone, terpinene, ferrandrene, p- Cymene, farnesene, 3-carene, terpinolene, camphene, sabinene, bisabolen, cedrene, guaien, diphenyl, diphenylmethane, amblet lid, n-butyl Talide, propylidenephthalide, butylidenephthalide, δ-hexalactone, δ-octalactone, δ-nonalactone, δ-2-decenolactone, δ-undecalactone, δ-dodecalactone, δ-tetradecalactone, lactoskatone, γ-hexalactone, γ-octalactone, γ-nonalactone, whiskey-lactone, angelica lactone, γ-dodecalactone, γ-jasmolactone, jasmine lactone, cisjasmon lactone, cyclohexyl lactone, ε-decalactone, ε-dodecalactone , Ethylenedodecandioate, cyclohexadecanolide, 10-oxahexadecanolide, 11-oxahexadecanolide, 12-oxahexadecanolide, ethylene brushate, 14-methylhexadecenolide, 14- Methyl-hexa Canolide, oximene epoxide, paracresyl methyl ether, rose oxide, cinnamyl nitrile, cuminyl nitrile, quinoline, isoquinoline, p-methylquinoline, 6-isopropylquinoline, isobutylquinoline, yarayara, acetic acid, heptanoic acid, octanoic acid, decane Acid, gellanic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, benzoic acid, phenylacetic acid, cinnamic acid, hydrocinnamic acid, vanillic acid, anise oil, bay oil, boadrose oil, cananga oil , Cardamom oil, cassia oil, cedarwood oil, orange oil, mandarin oil, tangerine oil, basil oil, nutmeg oil, citronella oil, clove oil, coriander oil, elemi oil, eucalyptus oil, fennel oil, galvanum oil, geranium oil, Ba oil, camellia oil, jasmine oil, lavandin oil, lavender oil, lemon oil, lemongrass oil, lime oil, neroli oil, oak moss oil, okotia oil, patchouli oil, peppermint oil, perilla oil, petitgren oil, pine oil, rose Oil, rosemary oil, ginger brain oil, melamine oil, clary sage oil, sandalwood oil, spearmint oil, spike lavender oil, star anise oil, thyme oil, turpentine bean tincture, turpentine oil, vanilla bean tincture, vetiver oil, ylang ylang Oil, grapefruit oil, citron oil, benzoin, peruvian balsam, trubalsam, tuberose oil, mustin tincture, castrium tincture, civet tincture, ambergris tincture. Moreover, diethyl phthalate, benzyl benzoate, isopropyl myristate, hercorin, isopentane, orange terpene, etc. can be used as a perfume solvent or as a retaining agent. In addition, a fragrance | flavor is not limited to the fragrance | flavor of an Example.

  There are no particular restrictions on the method for preparing the composition of the present invention, and various methods can be used, but the method described in JP-A-2-68137 is particularly preferred. That is, a part of the aqueous phase is added to the oil phase containing the quaternary ammonium salt type cationic surfactant, or the oil phase is added to a part of the aqueous phase to change the liquid crystal phase of the cationic surfactant. The composition of the present invention can be prepared by a method of forming and then mixing the liquid crystal phase and the remaining aqueous phase to invert the liquid crystal phase.

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-4
These examples and comparative examples relate to the first aspect of the present invention.

(1) Method for evaluating softness performance After washing a commercially available acrylic cloth twice at 40 ° C. using a washing machine “Super Top” (trade name, manufactured by Lion Co., Ltd.) with a commercial laundry detergent, and at room temperature tap water And rinsed thoroughly to obtain a test cloth. Next, it shows in Table 1-5 and Table 1-6 so that (a-1) + (a-2) + (a-3) component may be 1 g with respect to 30 liters of 30 degreeC tap water. The blended composition was added and dispersed uniformly. Each test cloth was immersed in this solution at a bath ratio of 30 times, treated for 3 minutes, and then dehydrated for 1 minute. The fabric thus treated was air-dried and then allowed to stand for 24 hours at 20 ° C. and 45% RH. The evaluation of the softness performance of these fabrics was made by comparing a pair of a mixture containing 13% by mass of Arcac 2HT-75 manufactured by Lion Akzo Co., Ltd. and 0.5% by mass of calcium chloride under the same conditions as a control. And evaluated according to the following criteria.
A: Softer than the control.
○: Slightly softer than the control.
Δ: Same as control ×: The control is softer.

(2) Evaluation method of freeze / restoration stability As an evaluation of freeze / restoration stability, the same amount of sample was added to a 100 ml glass bottle container, frozen at −15 ° C. for 40 hours, and restored at 25 ° C. for 8 hours as one cycle. The change in viscosity of the sample after 6 cycles, separation, and the presence or absence of precipitates were evaluated according to the following criteria.
A: There is almost no change in viscosity after 6 cycles, and there is no separation or precipitate.
○: Viscosity changes up to 5 cycles, and no separation or precipitation occurs.
Δ: Viscosity changes up to 4 cycles, and no separation or precipitation occurs.
X: Viscosity changes after 3 cycles, or separation or precipitation is observed.

(3) Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-4
Using the components (a-1) to (a-3) and the component (B) shown in Table 1-1 to Table 1-4 below, the liquid softener was formulated according to the formulation shown in Tables 1-5 and 1-6. Compositions were prepared and evaluated for softness performance and freeze / restoration stability. The results are shown in Table 1-5.

＊Ｉ−１〜Ｉ−５のＲ₁〜Ｒ₃は、２種又は３種以上の脂肪酸残基の混合物である。
＊ＣｘＦｙは脂肪酸残基を表し、ｘは炭素数、ｙは二重結合の数をそれぞれ意味する。

* R ₁ to R ₃ of I-1 to I-5 is a mixture of two or more fatty acid residues.
* CxFy represents a fatty acid residue, x represents the number of carbon atoms, and y represents the number of double bonds.

＊II−１〜II−５のＲ₅〜Ｒ₆は、２種又は３種以上の脂肪酸残基の混合物である。

* R ₅ to R ₆ of II-1 to II-5 is a mixture of two or more fatty acid residues.

＊III-１〜III-５のＲ₇は、２種又は３種以上の脂肪酸残基の混合物である。

* R- _{7 in} III-1 to III-5 is a mixture of two or more fatty acid residues.

＊Ｂ−１：協和発酵株式会社製のオキソコールＣ１３に、エチレンオキシドを付加したもの。
＊Ｂ−２：協和発酵株式会社社製のトリデカノールに、エチレンオキシドを付加したもの。
＊Ｂ−３：株式会社日本触媒社製の、ソフタノール３００。
＊Ｂ−４：日光ケミカルズ株式会社社製のもの。

* B-1: A product obtained by adding ethylene oxide to oxocol C13 manufactured by Kyowa Hakko.
* B-2: Tridecanol produced by Kyowa Hakko Co., Ltd. added with ethylene oxide.
* B-3: Softanol 300 manufactured by Nippon Shokubai Co., Ltd.
* B-4: manufactured by Nikko Chemicals Co., Ltd.

＊（）内の数値は液体柔軟剤組成物全体の質量を基準とした配合量（質量％）である。
＊ｐＨは塩酸及び水酸化ナトリウムを用いて調整した。

* Numerical values in parentheses are blending amounts (% by mass) based on the mass of the entire liquid softening agent composition.
* PH was adjusted using hydrochloric acid and sodium hydroxide.

＊ジメチルシリコーン：（ＢＹ２２−０２９）東レ・ダウコーニング・シリコーン株式会社製。
＊イソチアゾロン液：５−クロロ−２−メチル−４−イソチアゾリン−３−オン、２−メチル−４−イソチアゾリン−３−オン、マグネシウム塩、水の混合液
香料：表１−７の組成で配合したもの。

* Dimethyl silicone: (BY22-029) manufactured by Toray Dow Corning Silicone Co., Ltd.
* Isothiazolone liquid: 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, magnesium salt, water mixed fragrance: blended in the composition of Table 1-7 thing.

＊配合量は香料全体の質量を基準とした量である。

* The blending amount is based on the total mass of the fragrance.

  From the results, it is clear that the liquid softening agent composition of the present invention imparts excellent flexibility to the synthetic fiber and is excellent in terms of dispersion stability during freezing and restoration.

Examples 2-1 to 2-6 and comparative examples 2-1 to 2-3
These examples and comparative examples relate to the second aspect of the present invention.

(1) Method for evaluating softness performance After washing a commercially available acrylic cloth twice at 40 ° C. using a washing machine “Super Top” (trade name, manufactured by Lion Co., Ltd.) with a commercial laundry detergent, and at room temperature tap water And rinsed thoroughly to obtain a test cloth. Next, it shows in Table 2-6 and Table 2-7 so that (a-1) + (a-2) + (a-3) component becomes 1 g with respect to 30 liters of tap water at 30 ° C. The blended composition was added and dispersed uniformly. Each test cloth was immersed in this solution at a bath ratio of 30 times, treated for 3 minutes, and then dehydrated for 1 minute. The fabric thus treated was air-dried and then allowed to stand for 24 hours at 20 ° C. and 45% RH. The evaluation of the softness performance of these fabrics was made by comparing a pair of a mixture containing 13% by mass of Arcac 2HT-75 manufactured by Lion Akzo Co., Ltd. and 0.5% by mass of calcium chloride under the same conditions as a control. And evaluated according to the following criteria.
A: Softer than the control.
○: Slightly softer than the control.
Δ: Same as control ×: The control is softer.

(2) Evaluation Method of Color Tone Stability As an evaluation of the color tone stability, the same amount of sample was added to a 100 ml glass bottle container and stored at 50 ° C. for one month to evaluate the change in color tone of the sample.
A: Almost no change in color tone.
○: The color tone changed slightly.
X: The color tone changed remarkably.

(3) Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-3
Using the components (a-1) to (a-3), (C) and (D) shown in Tables 2-1 to 2-5 below, Tables 2-6 and 2-7 show A liquid softener composition was prepared by blending and evaluated for softness performance and color stability, and the results are shown in Table 2-6.

＊α−１〜α−５のＲ₁〜Ｒ₃は、２種又は３種以上の脂肪酸残基の混合物である。
＊ＣｘＦｙは脂肪酸残基を表し、ｘは炭素数、ｙは二重結合の数をそれぞれ意味する。

* R ₁ to R ₃ of the α-1~α-5 is a mixture of two or more fatty acid residues.
* CxFy represents a fatty acid residue, x represents the number of carbon atoms, and y represents the number of double bonds.

＊β−１〜β−５のＲ₅〜Ｒ₆は、２種又は３種以上の脂肪酸残基の混合物である。

* R ₅ to R ₆ of the β-1~β-5 is a mixture of two or more fatty acid residues.

＊γ−１〜γ−５のＲ₇は、２種又は３種以上の脂肪酸残基の混合物である。

* R- ₇ of γ-1 to γ-5 is a mixture of two or more fatty acid residues.

Table 2-4
(C) component
Symbol Dye Mixing ratio (mass ratio)
C-1 CIAcid Red 52
C-2 CIAcid Red 138
C-3 CIAcid Blue 9
C-4 CIDirect Blue 86 / CIAcid Yellow 23 50/50
C-5 CIReactive Blue 231 / CIAcid Yellow 141 50/50
C-6 CIBasic Blue 24

Table 2-5
(D) component
Symbol Metal chelating agent Antioxidant Mixing ratio (mass ratio)
D-1 d-1
D-2 d-1 d-3 10/90
D-3 d-1 d-3 20/80
D-4 d-2 d-4 30/70
* Metal chelating agent:
d-1: 1-hydroxyethane-1,1-diphosphonic acid d-2: sodium ethylenediaminetetraacetate * antioxidant:
d-3: 2,6-di-tert-butyl-4-methylphenol d-4: 2,6-di-tert-butyl-4-ethylphenol

Table 2-6
Evaluation results
Example 2-1 Example 2-2 Example 2-3
(A-1) Component α-1 α-2 α-3
(2.4) (2.4) (0.5)
(A-2) Component β-1 β-2 β-3
(8.6) (7.0) (3.6)
(A-3) Component γ-1 γ-2 γ-3
(4.0) (2.6) (1.9)
(a-1) / (a-2) / (a-3) 16/57/27 20/58/22 8/60/32
(A) component (15.0) (12.0) (6.0)
(C) Component C-1 C-2 C-1
(0.001) (0.001) (0.0005)
(D) Component D-2 D-2 D-1
(0.025) (0.025) (0.015)
pH 3.0 3.0 2.5
Flexible performance ◎ ◎ ◎
Color stability ◎ ◎ ○
* Numerical values in parentheses are blending amounts (% by mass) based on the mass of the entire liquid softening agent composition.
* PH was adjusted using hydrochloric acid and sodium hydroxide.

Table 2-6 (continued)
Evaluation results (continued)
Example 2-4 Example 2-5 Example 2-6
(A-1) Component α-4 α-5 α-4
(7.2) (2.2) (2.4)
(A-2) Component β-4 β-3 β-5
(16.5) (13.8) (10.9)
(A-3) Component γ-4 γ-5 γ-4
(6.3) (4.0) (2.7)
(a-1) / (a-2) / (a-3) 24/55/21 11/69/20 15/68/17
(A) component (30.0) (20.0) (16.0)
(C) Component C-4 C-5 C-3
(0.001) (0.001) (0.001)
(D) Component D-2 D-3 D-4
(0.035) (0.03) (0.025)
pH 3.0 3.0 2.5
Flexible performance ◎ ○ ○
Color stability ◎ ◎ ○

Table 2-6 (continued)
Evaluation results (continued)
Comparative Example 2-1 Comparative Example 2-2 Comparative Example 2-3
(A-1) Component α-4 α-1 α-1
(1.5) (8.0) (2.4)
(A-2) Component β-4-β-1
(1.5)-(8.6)
(A-3) Component γ-4 γ-1 γ-1
(12.0) (8.0) (4.0)
(a-1) / (a-2) / (a-3) 10/10/80 50/0/50 16/57/27
(A) component (15.0) (16.0) (15.0)
(C) Component C-2 C-2 C-6
(0.001) (0.001) (0.001)
(D) Component-D-1 D-4
− (0.02) (0.015)
pH 3.0 3.0 3.0
Flexible performance × × ◎
Color stability × ○ ×

Table 2-7
Composition of optional and common ingredients
Examples 2-1 to 2-3, Example 2-4
2-5 to 2-6 and
Comparative Examples 2-1 to 2-3
Nonionic activator 1% by mass 6% by mass
Ethylene glycol 10% by mass 4% by mass
Calcium chloride 0.5% by mass 1% by mass
Hexylene glycol-3% by mass
2,2,4-trimethyl-5% by mass
-1,3 pentanediol brucine modified ethanol 4% by mass
Dimethyl silicone 0.5% by mass
Isothiazolone solution 0.015% by mass
Fragrance 1.0% by mass
Water balance amount
* Nonionic activator: alcohol ethoxylate obtained by adding 40 mol of ethylene oxide on average to oxocol C13 manufactured by Kyowa Hakko Co., Ltd.
* Dimethyl silicone: (BY22-029) manufactured by Toray Dow Corning Silicone Co., Ltd.
* Isothiazolone liquid: 5-chloro-2-methyl-4-isothiazolin-3-one, 2-methyl-4-isothiazolin-3-one, magnesium salt, water mixed fragrance: formulated with the composition shown in Table 2-8 thing.

Table 2-8
Fragrance composition
Ingredient Amount (% by mass)
Eugenol 0.5
Geraniol 1.0
Vacdanol 2.0
Dipropylene glycol 3.0
Linalool 3.0
Phenylethyl alcohol 5.0
9-decen-1-ol 0.1
Citronellol 2.0
Isoeugenol 0.1
Cedrol 0.4
Cis-3-hexenol 3.0
Nellore 1.0
Turpineol 3.0
Borneol 0.2
Cis-3-hexenyl salicylate 3.0
Dibutylhydroxytoluene 0.5
Methyl atrate 0.1
Menthol 0.3
Nonanal 0.2
Decanal 0.2
Undecanal 0.2
2-Methylundecanal 0.1
Anisaldehyde 2.0
Heliotropin 1.0
Hexylcinnamic aldehyde 2.0
Lilianal 4.0
Lilar 2.0
Vanillin 0.1
Ethyl vanillin 0.1
Muscon 0.1
Cyclohexadecenone 1.0
Musk ketone 0.5
Tonalid 5.0
Yonon 0.2
Methyl ionone 3.0
IsoEsper 6.0
β-methylnaphthyl ketone 0.1
Kashmeran 0.2
Damascon 0.3
Geranyl acetate 0.2
Citronellyl acetate 0.5
Phenylethyl acetate 1.0
Methyl dihydrojasmonate 5.0
Benzyl acetate 4.0
Linalyl acetate 2.0
Turpinyl acetate 2.0
Acetyl cedrene 2.0
p-tert-butylcyclohexyl acetate 2.0
2-tert-butylcyclohexyl acetate 0.3
Methyl anthranilate 0.2
Dimethylbenzyl car vinyl acetate 2.0
Limonene 6.0
Pinene 2.0
Myrcene 1.0
Caryophyllene 1.0
Cyclopentadecanolide 1.0
γ-decalactone 0.1
γ-undecalactone 0.2
Coumarin 1.0
Galaxolide 6.0
Orange oil 2.0
Amproxan 0.3
Farenar 0.2
Geranil nitrile 0.3
Labandin oil 1.0
Indole 0.2
* The blending amount is based on the total mass of the fragrance.

  From the results, it is clear that the liquid softener composition of the present invention imparts excellent flexibility to the synthetic fiber and is excellent in terms of color tone stability.

Claims (5)

(A) A mixture of quaternary ammonium salts comprising the following components (a-1), (a-2) and (a-3), and 5 to 30% by mass based on the mass of the whole mixture A mixture of a quaternary ammonium salt comprising the component (a-1), 35 to 70% by mass of the (a-2) component, and 10 to 45% by mass of the (a-3) component;
(C) one or two or more dyes selected from a red dye, a blue dye, a yellow dye, and a purple dye having a sulfonic acid group or a salt thereof; and
(D) metal chelating agent and / or antioxidant,
A liquid softener composition containing a diethylenetriamine and a saturated or unsaturated fatty acid having 12 to 22 carbon atoms, which does not contain a dehydration cyclocondensation reaction product .
Component (a-1): It has three long-chain alkyl or alkenyl groups in the molecule, and has the following general formula (I):

A quaternary ammonium salt represented by
Component (a-2): It has two long-chain alkyl or alkenyl groups in the molecule, and has the following general formula (II):

A quaternary ammonium salt represented by
(A-3) Component: It has one long-chain alkyl or alkenyl group in the molecule, and has the following general formula (III):

A quaternary ammonium salt represented by
(In the formulas (I) to (III), R1 to R3 and R5 to R7 each represent a linear or branched saturated or unsaturated hydrocarbon group having 10 to 24 carbon atoms, and they may be the same as each other. R4 represents an alkyl group having 1 to 4 carbon atoms or a hydroxyalkyl group, n is an integer of 2 to 4, m is an integer of 0 to 3, p is an integer of 2 to 4, n, m and p may be the same or different from each other, and X − is a softener-compatible anion.) The component ( c) is selected from CIAcid Red 52, CIAcid Red 138, CIDirect Blue 86, CIAcid Yellow 23, CIAcid Reactive Blue 231, CIAcid Yellow 141, CIBasic Blue 24, and is contained in an amount of 0.1 to 100 ppm. 2. The liquid softener composition according to 1 . The liquid softener composition according to claim 1 or 2 , wherein the component (a-3) is contained in an amount of 15 to 45 mass% based on the mass of the entire mixture. (D) The liquid softening agent composition of any one of Claims 1-3 which contains a metal chelating agent and antioxidant by the mass ratio of 1 / 99-50 / 50. Furthermore, 0.01-10 mass% of polyoxyethylene (5-100 mol) linear alkyl or alkenyl (C12-C24) ether is contained on the basis of the total mass of a composition, Any one of Claims 1-4 . The liquid softener composition according to claim 1.