JP2008063681A - Emulsified liquid softener composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain an emulsified liquid softener composition which prevents adhesion of smells such as smell of sweat, cigarette smell, etc., in use of a textile product subjected to softening treatment in washing. <P>SOLUTION: The emulsified liquid softener composition includes (A) one or more kinds of cationic surfactants selected from the group consisting of a 10-22C tertiary amine which contains divided groups and a long-chain hydrocarbon group divided by an ester group, the neutralized tertiary amine and the quaternized tertiary amine, and (B) ≥0.1 mass% of benzyl benzoate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an emulsion-type liquid softener composition. Specifically, by using it when washing textile products such as clothing, it gives the fabric a texture such as flexibility and smoothness, and at the same time, by using benzyl benzoate, odors such as sweat odor and tobacco odor It is related with the emulsion type liquid softening agent composition which can prevent adhesion of water.

Quaternary ammonium having a long-chain hydrocarbon group in the molecule in order to impart flexibility and smoothness to the textile product and also to prevent static electricity during the winter season when washing the textile product. Soft finishes based on salt have been used in the past. Moreover, it is a known technique to introduce an ester group or an amide group into a quaternary ammonium salt molecule for the purpose of facilitating biodegradation in the natural environment after being discarded in the environment after use. (Patent Documents 1, 3, 4)
However, in Patent Document 3, in contrast to a composition in which an unsaturated ester-type cationic surfactant is used in combination with a lower alcohol ester of an unsaturated fatty acid, benzyl benzoate is used as a scent retention agent in the softener composition. Only about 0.01-0.04 mass% is included, and the subject effect of adding benzyl benzoate is clearly different from the present application.
On the other hand, as one of the additional functions of the softening agent, an attempt to contain a specific component other than the softening base in the softening finish with the aim of preventing the unpleasant odor such as food odor and tobacco odor from attaching to the textile product. Has been made recently. (Patent Documents 4 and 5)
In the former, a fragrance composition containing a specific fragrance component is used in combination with an ester group-containing quaternary ammonium salt, while in the latter, metal oxide fine particles mainly exhibit its deodorizing effect. In particular, in the former embodiment, in addition to the specific fragrance component, a fragrance composition containing 1% by mass of benzyl benzoate as the component (B) of the present application as a fragrance retention agent is added to the liquid softener composition in an amount of 0. 5 to 1.0 mass% is blended, and therefore benzyl benzoate is contained in the composition only in an amount of 0.005 to 0.01 mass%. On the other hand, in the present application, since the above-mentioned specific perfume component is not included and benzyl benzoate is contained in the composition at a higher concentration, the deodorizing effect is clearly stronger than Patent Document 4.

  On the other hand, in Patent Document 1, two kinds of specific perfume ingredients such as benzyl benzoate are used for a softening base composed of an ester amide type tertiary amine, a neutralized product thereof, or a quaternized product thereof and a higher fatty acid. It proposes a composition in which 0.02 to 1.0% by mass of the above is blended in the composition, and the fragrance of the composition hardly changes even when stored over time. In this case as well, the subject effect is different from the proposal of the present application aiming at imparting deodorization properties, and in this patent document, a cationic softening base containing a long-chain hydrocarbon group containing an ester group and an amide group is used. Since fatty acids are used in combination within a certain ratio range, the biodegradability in the natural environment is inferior to that of the composition of the present invention.

  Furthermore, in Patent Document 2, a main solvent having a ClogP value within a certain range and a main solvent extender selected from polar hydrophobic substances such as benzyl benzoate are used in combination with a fabric softener. A concentrated stable translucent or transparent fabric softening composition has been proposed. However, this patent document is aimed at a translucent or transparent composition at a low solvent amount and a low perfume addition amount level. On the other hand, the present application has a low solvent amount and an emulsion type liquid softener composition. Obviously, the amount of benzyl benzoate added, the effect of the problem, and the appearance of the composition are completely different.

JP-A-8-013335 (Kao) Special Table 2002-505391 (P & G) JP 2003-105668 A (Lion) JP 2005-232637 A (Lion) JP 2006-063499 A (Lion)

  An object of the present invention is to provide an emulsion type capable of imparting a good texture such as flexibility to a textile product such as clothing treated at the time of washing, and preventing the attachment of odors such as sweat odor and tobacco odor when the textile product is used. The object is to provide a liquid softener composition.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problem can be achieved by using a specific cationic surfactant in combination with a specific amount or more of benzyl benzoate. That is, according to the present invention, an emulsion-type liquid softener composition characterized by containing an emulsion-type liquid softener composition characterized by containing the following components (A) and (B): provide:
(A) A tertiary amine having a long chain hydrocarbon group having 10 to 22 carbon atoms, including a splitting group, which is split by an ester group, a neutralized product of the tertiary amine, and a quaternized product of the tertiary amine 1 or more types of cationic surfactant (B) selected from the group which consists of benzyl benzoate: 0.1 mass% or more.

  According to the present invention, it is possible to impart a good texture such as flexibility to a textile product, to prevent the attachment of odors such as sweat odor and tobacco odor when the textile product is used, and to biodegrade in the environment after use. An easy-to-use emulsion liquid softener composition can be provided. The composition of the present invention also has good emulsion dispersion stability in that the increase in viscosity is small even after long-term storage.

In the present invention, “emulsion” means that when a glass cell having an optical path length of 10 mm is used as a measurement cell and ion-exchanged water is added to a control cell, the visible light transmittance (wavelength 660 nm) of the sample is less than 30%. It means that.
[(A) component: cationic surfactant]
The component (A) used in the present invention is a tertiary amine having one or more long-chain hydrocarbon groups separated by an ester group having 10 to 22 carbon atoms, preferably 18 to 20 carbon atoms including the dividing group, A neutralized product or quaternized product with an organic or inorganic acid, or a mixture thereof. Any of these may be used as a single type or a mixture of two or more types. Examples of the long chain hydrocarbon group include a linear or branched alkyl group or an alkenyl group. Since the long-chain hydrocarbon group has an ester group, it exhibits good biodegradability. Therefore, the liquid detergent composition of the present invention is preferably disposed in the natural environment and then has a small load on the environment. .
The component (A) is a cationic surfactant mixture containing the above tertiary amine, or a neutralized product or quaternized product thereof, and the long chain hydrocarbon group is converted based on the total amount of the cationic surfactant mixture. It is preferable that the content of the cationic surfactant having 2 or 3 is 50% or more, preferably 60% or more, more preferably 70% or more, since the flexibility of the treated fiber product becomes better.

  As the cationic surfactant that can be used in the present invention, commercially available products may be used, or those that can be produced by a known method may be used. When manufacturing by a well-known method, it can use as it is, without isolate | separating unreacted raw materials. Specifically, a tertiary amine represented by the following formulas (I) to (V), a neutralized product or a quaternized product thereof with an organic or inorganic acid, or a mixture thereof can be used. In the present invention, it is preferable to use a mixture of quaternized compounds of the general formulas (III), (IV) and (V).

  R1COO constituting the component (A) is a residue of a fatty acid having 8 to 20 carbon atoms, and is a long-chain hydrocarbon group derived from any of a saturated fatty acid, an unsaturated fatty acid, a linear fatty acid, and a branched fatty acid. In the case of an unsaturated fatty acid, a cis isomer and a trans isomer are present, and the mass ratio is preferably cis / trans = 25/75 to 100/0, particularly preferably 40/60 to 80/20. Examples of the fatty acid serving as the R1COO group include the following. Stearic acid, palmitic acid, myristic acid, lauric acid, oleic acid, elaidic acid, linoleic acid, partially hydrogenated palm oil fatty acid (iodine value 10-60), partially hydrogenated tallow fatty acid (iodine value 10-60), etc. It is done. Of these, stearic acid, palmitic acid, myristic acid, oleic acid, elaidic acid, and linoleic 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 is 40/60 to 80/20, iodine value is 10 to 50, carbon number ratio is 70 mass% or more, carbon number 20 fatty acid is 2 mass%, carbon number 22 fatty acid is 1 mass It is preferable to use a fatty acid composition adjusted to be%. Here, all R1 present in the formula may be the same or different.

  Examples of the acid used for neutralizing the tertiary amine include hydrochloric acid, sulfuric acid, and methyl sulfuric acid. The tertiary amine used in the present invention is preferably used in the form of an amine salt neutralized with hydrochloric acid, sulfuric acid or methyl sulfuric acid. In the neutralization step, a tertiary amine previously neutralized may be dispersed in water, or the tertiary amine may be introduced into the acid aqueous solution in liquid or solid form. Of course, a tertiary amine and an acid component may be added simultaneously. Examples of the quaternizing agent used for the quaternization of the tertiary amine include methyl chloride, dimethyl sulfate, and diethyl sulfate.

  The compounds of the general formulas (I) and (II) can be synthesized by a condensation reaction of the fatty acid composition or the fatty acid methyl ester composition and methyldiethanolamine. At that time, from the viewpoint of improving the emulsification and dispersion stability in the liquid softening agent composition, the abundance ratio of the compounds of (I) and (II) is synthesized such that the mass ratio is 99/1 to 50/50. It is preferable to do. Further, when the quaternized product is used, methyl chloride, dimethyl sulfate or the like is used as a quaternizing agent. In that case, it is preferable to synthesize | combine so that the abundance ratio of the quaternized esteramine represented by (I) and (II) may be 99/1 to 50/50 by mass from the viewpoint of dispersion stability. Moreover, when quaternizing (I) and (II), generally the esteramine which is not quaternized remains after 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.

  The compounds of the general formulas (III), (IV) and (V) can be synthesized by a condensation reaction of the above fatty acid composition or fatty acid methyl ester composition and triethanolamine. At that time, from the viewpoint of improving the emulsion dispersion stability in the liquid softening agent composition, the abundance ratio of the compounds of [(III) + (IV)] and (V) is preferably 99/1 to It is preferable to synthesize so as to be 50/50, more preferably 70/30 to 80/20. Further, when the quaternized product is used, methyl chloride, dimethyl sulfate or the like is used as a quaternizing agent, and dimethyl sulfate is more preferable from the viewpoint of reactivity. In that case, the abundance ratio of the quaternized product of the ester amine represented by [(III) + (IV)] and (V) is also 99/1 to 50/50, more preferably from the viewpoint of dispersion stability. It is preferable to synthesize so as to be 70/30 to 80/20. When (III), (IV), and (V) are quaternized, esteramine that is not 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.

  The compounding quantity of (A) component in the composition of this invention is 1-50 mass%, Preferably it is 3-30 mass%, More preferably, it is 5-20 mass%. If the amount of component (A) is too large, the viscosity of the composition becomes too high, making it difficult to control the viscosity. On the other hand, if the blending amount is small, it is necessary to use a large amount of the composition in order to impart flexibility and a deodorizing effect. Further, since an extra space is required from the transportation of the product to the storage stage, the efficiency is lowered, which is not preferable.

[(B) component: benzyl benzoate]
The essential component (B) in the present invention is benzyl benzoate. In general, benzyl benzoate is very readily available because it is synthesized from benzaldehyde by the Cannizzaro reaction or is industrially produced by esterifying benzyl alcohol with benzoic acid.

  As described above, the compound is widely used as a solvent or a retention agent for a fragrance component, and in most cases (Patent Documents 3 to 5), about 1% by mass in the fragrance composition and approximately 0 in terms of the softener composition. 0.05% by mass is added as the upper limit. In order to impart a deodorizing effect which is one of the problems of the present invention, benzyl benzoate is 0.1% by mass or more, preferably 0.1 to 5% by mass, more preferably 0.00%, based on the softener composition. It is necessary to mix | blend 3 to 3 mass%, More preferably, 0.5 to 2 mass%. If the amount is less than the above lower limit amount, the deodorizing effect is insufficient, while if it exceeds the upper limit amount, the cost becomes high, and even if a fragrance composition is added, the base odor itself is not noticeably masked, and The emulsion dispersion stability also tends to deteriorate.

[Optional component (C): Nonionic surfactant]
In order to obtain a stable liquid softening agent composition that does not separate into an emulsified dispersion state even when stored for a long period of time and has no significant increase in viscosity, in addition to the above components (A) and (B), a nonionic interface It is preferable to add an activator, and among them, higher alcohol, higher amine or higher fatty acid alkylene oxide adduct can be used, and higher alcohol alkylene oxide adduct is particularly preferable. 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 8-20, 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.

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, etc. Can be used.
On the other hand, the alkylene oxide added to the higher alcohol is preferably ethylene oxide (EO) alone, but propylene oxide (PO) or butylene oxide (BO) may be used in combination with ethylene oxide, and the average number of added moles of these alkylene oxides is 30 to 30. 100 is preferable, More preferably, it is 30-80 mol.

  More specifically, as an alkylene oxide addition type nonionic surfactant, an average EO 30 mol adduct of lauryl alcohol, an average EO 30 mol adduct of primary isodecyl alcohol, an average EO 45 or 60 mol addition of primary isotridecyl alcohol Products, an average EO 60 mol adduct of primary isohexadecyl alcohol, an average EO 60 mol adduct of tallow alkylamine, an average EO 30 mol adduct of lauric acid, and the like. Specific examples include Emulex series from Nippon Emulsion Co., Ltd., Emalmine series from Sanyo Chemical Co., Ltd., TA series from Lion Corporation, and Esomin series from Lion Akzo Corporation, Softanol series from Nippon Shokubai Co., Ltd. BASF's Lutensol series and the like can be used. In addition, the above-mentioned compound may contain alcohol or amine as raw materials, polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol, etc. as unreacted components in the nonionic surfactant at 10% by mass or less. Good. They can be used alone or as a mixture of two or more.

  The addition amount of the nonionic surfactant is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass with respect to the total amount of the composition. If the amount added is too much, the initial viscosity will increase too much, and the cost will be useless. On the other hand, when there is too little addition amount, the emulsification dispersion stability of the obtained emulsion-type liquid softening agent composition will deteriorate.

  The composition of the present invention can further contain other components usually contained in a liquid softener composition for textiles. Specifically, it can contain water, a solvent, inorganic or organic water-soluble salts, silicone compounds, polymer compounds, dyes, fragrances, ultraviolet absorbers, antibacterial agents, deodorants, skin care ingredients, and the like.

[Arbitrary component (D)]
The composition of the present invention is preferably an aqueous composition, and tap water, ion-exchanged water, pure water, distilled water, etc. can be used as the water used, but ion-exchanged water is preferred.
The solvent is one or more aqueous solvents selected from the group consisting of lower (C1-4) alcohols, glycol ether solvents, and polyhydric alcohols. Specifically, a solvent component selected from ethanol, isopropanol, glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, hexylene glycol, polyoxyethylene phenyl ether, and a water-soluble solvent represented by the general formula (VI) It is preferable to mix.
R2-O- (C2H4O) y- (C3H6O) z-H (VI)
[Wherein, R 2 represents an alkyl group or alkenyl group having 1 to 6 carbon atoms, preferably 2 to 4 carbon atoms. y and z are average addition mole numbers, y is 1-10, Preferably it is 2-5, z shows the number of 0-5, Preferably it is 0-2. ]
Among them, preferred examples include ethanol, ethylene glycol, butyl carbitol, propylene glycol, diethylene glycol monopropylene glycol monobutyl ether and the like.
These solvents are blended in the composition in an amount of 0 to 30% by mass, preferably 0.01 to 25% by mass, more preferably 0.1 to 20% by mass.

[Optional component (E)]
Inorganic or organic water-soluble salts can be used for the purpose of controlling the viscosity of the composition. Examples of inorganic or organic water-soluble salts include sodium chloride, potassium chloride, calcium chloride, magnesium chloride, alkali metal salts or alkaline earth metal salts of sulfuric acid or nitric acid, p-toluenesulfonic acid, glycolic acid, Examples include alkali metal salts of organic acids such as lactic acid. Preferably, they are calcium chloride, magnesium chloride, and sodium chloride. The compounding amount of the inorganic or organic water-soluble salt is 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. The addition of inorganic or organic water-soluble salts may be added at any step in the production of the composition.

[Optional component: Silicone compound]
A silicone selected from dimethylpolysiloxane and modified dimethylpolysiloxane having various organic functional groups is used singly or in combination for the purpose of improving wrinkle resistance in the washing process, fiber water absorption improvement, iron sliding property, and the like. It can be used in any proportion as a mixture of seeds or more.
In particular, polyether-modified silicones containing a polyoxyalkylene group in the molecule represented by the following general formula (1) 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. L is 0-50, M is 1-1000, and N is 10-10000. However, the mass ratio of the polyoxyethylene chain portion in X is 10% or more and less than 60% based on the mass of the whole molecule.

In the general formula (1), -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 (1), X represents a polyoxyalkylene group, but an oxyethylene unit, an oxypropylene unit, an oxybutylene unit, or 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 (1), 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 (1) 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, 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 component; polymer compound]
In the composition of the present invention, a polymer compound, preferably a cationic polymer compound, can be used in combination for the purpose of changing the texture of the treated fiber product. The cationic polymer is a polymer of dimethyldiallylammonium chloride, such as MERQUAT100 (Nalco), Adekathioace PD-50 (Asahi Denka Kogyo), Daidol EC-004, Daidol HEC, Daidoru Chemical Industries, Ltd., MERQUAT550 Dimethyldiallylammonium chloride / acrylamide copolymer such as JL5 (Nalco), dimethyldiallylammonium chloride / acrylic acid copolymer such as MERQUAT280 (Nalco), cationized cellulose such as Leogard KGP (Lion), LUVIQUAT-FC905 ( BASF) and other imidazolinium chloride-vinylpyrrolidone copolymers, LUGALVAN-G15000 (BASF) and other polyethyleneimines, Poval CM318 (Kuraray) and others Examples include natural polymer derivatives having amino groups such as conjugated polyvinyl alcohol and chitosan, and copolymers with vinyl monomers having hydrophilic groups to which diethylamino methacrylate / ethylene oxide has been added. Any high molecular compound may be used.

[Optional component: sequestering agent and / or antioxidant]
For the purpose of improving the stability of the fragrance and color tone of the liquid softening agent composition, a metal ion 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 represented by salts, and organic phosphorus compounds represented by 1-hydroxyethane-1,1-diphosphonate. Of the sequestering agents, 1-hydroxyethane-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 ingredients; antibacterial agents or bactericides]
For the purpose of enhancing the antiseptic and sterilizing power of the liquid softening agent composition, the compounds described in 1) to 4) below can be used singly or in combination of two or more.

1) As the isothiazolone-based organic sulfur compound, a compound containing a 3-isothiazolone group is preferable. These compounds are disclosed in Lewis et al., US Pat. No. 4,265,899, issued May 5, 1981. Examples 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-isothiazolin-3-one and mixtures thereof. A more preferred antiseptic / disinfectant is a water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, more preferably about 77% by mass. Water-soluble mixture of 5-chloro-2-methyl-4-isothiazolin-3-one and about 23% by weight of 2-methyl-4-isothiazolin-3-one. Commercially available products such as Ron & Haas's Caisson CG / ICP (approximately 1.5 mass% aqueous solution) and Junside series such as Junside 5 manufactured by Junsei Kagaku can be used.

2) Examples of benzisothiazoline-based organic sulfur compounds include 1,2-benzisothiazolin-3-one, 2-methyl-4,5-trimethylene-4-isothiazolin-3-one, and dithio- 2,2-bis (benzmethylamide) and the like can also be used, and they can be used in any mixing ratio. Examples of such compounds include Proxel series [BDN (effective content 33% by mass), BD20 (effective content 20% by mass), XL-2 (effective content 10% by mass), GXL (effective content) manufactured by Avicia Co., Ltd. 20% by mass), etc.], and commercially available products such as Denide BIT / NIPA can be used.

3) 5-Bromo-5-nitro-1,3-dioxane, 2-bromo-2-nitropropane-1,3-diol, 5-chloro-5-nitro-1,3-dioxane, or 2-chloro- 2-Nitropropane-1,3-diol and the like can be used. Commercial products such as Bronidox L from Henkel, Bronopol from Inolex, Bronopol from Yoshitomi Pharmaceutical, Myaside BT from Boots, Myaside Pharma BP from BASF, etc. can be used.

4) Benzoic acids or phenol compounds include benzoic acid or salts thereof, salicylic acid or salts thereof, parahydroxybenzoic acid or salts thereof, paraoxybenzoic acid derivatives, 3-methyl-3-isopropylphenol, o-phenylphenol, 2- Isopropyl-5-methylphenol, resorcin, cresol, 2,6-di-tert-butyl-p-cresol and the like can be used.

  The compounding amount of the compounds 1) to 3) is suitably 0 to 0.1% by mass, preferably 0.00001 to 0.05% by mass, more preferably 0.0001 to 0. 0% by mass relative to the total amount of the composition. 01% by mass. The compounding amount of the compound 4) is suitably 0 to 3% by mass, preferably 0.01 to 1.5% by mass, based on the total amount of the composition. Moreover, antiseptic | preservative power and bactericidal power can be strengthened by using together 2 or more types of the said compound of 1) -4), and the usage-amount of the said expensive compound can also be reduced. Among these, it is particularly preferable to use two or more of caisson CG / ICP, proxel series BDN, myaside BT, and benzoic acid.

  The above compounds 1) to 3) must be added to the composition as a solution of ethylene glycol, propylene glycol, or dipropylene glycol for stabilization, in the presence of metal ions such as zinc, copper, calcium, and magnesium. Is preferred.

[Optional component; Dye]
Any coloring matter which is a dye and / or pigment 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-25-250085, JP-A-10-77576, JP-A-11-43865, JP-A-2001-181972, and JP-A-2001-348784 can also be used.

[Optional ingredients; perfume]
The fragrance composition of the present invention composition includes aliphatic and aromatic ethers, aliphatic and terpene oxides, acetals, phenols, phenol ethers, fatty acids, terpene carboxylic acids and aromatic carboxylic acids. Mixing and using one or more kinds of blended fragrances including synthetic and / or natural fragrances, such as acids such as amides, nitriles, amines, quinolines, nitrogen-containing compounds such as pyrrole and indole, etc. Can do.
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; pH adjuster]
The liquid softener composition of the present invention may contain the following pH adjuster. That is, the liquid softener composition of the present invention preferably has a pH in the range of 1.0 to 6.0, particularly in the range of pH 2.0 to 4.0 for the purpose of suppressing hydrolysis of the ester group. Is preferred. 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.

[Optional ingredients; Function improvers, etc.]
In addition to the above-mentioned compounds, as a function improver, a shrinkage inhibitor, an anti-wrinkle agent, a shape retention agent, a drape retention agent, an iron property improvement agent, an oxygen bleaching inhibitor, a whitening agent, a whitening agent, and a fabric softening Clay, antistatic agent, polyvinylpyrrolidone, alkylene terephthalate and / or nonionic polymer compound composed of alkylene isophthalate unit and polyoxyalkylene unit, stain transfer agent, soil release agent, scum dispersant, 4,4- Fluorescent brighteners such as bis (2-sulfostyryl) biphenyl disodium (Cinospecial Chemicals' Chino Pearl CBS-X), dye fixing agents, anti-fading agents such as 1,4-bis (3-aminopropyl) piperazine, and stain removal Agents such as cellulase, amylase, protease, lipase, keratinase, Foams, silk protein powder as a silk texture and functions such as moisture absorbing and releasing property can be imparted, their surface reformate, can be blended and emulsified dispersion.

[PH, viscosity]
As described above, the pH of the composition of the present invention is preferably 1 to 6, more preferably 2 to 4. Since the cationic surfactant of component (A) has an ester group in the molecule, the pH of the composition is preferably within this range in order to suppress hydrolysis of the cationic surfactant.
On the other hand, the initial viscosity of the composition of the present invention is not particularly limited, but in the case of a product to be added to rinse water in the rinse process of washing, 5 to 100 mPa · s (B-type viscometer, manufactured by TOKIMEC, 25 ° C., the same applies hereinafter) It is preferably 20 to 50 mPa · s. Within such a range, the degree of thickening is small even after storage, and this is preferable.

[Method for Preparing Emulsion Type Liquid Softener Composition]
The method for preparing the liquid softening agent is not particularly limited, and various methods can be used. Particularly, JP-A-2-68137, JP-A-5-32788, JP-A-5-32789, and JP-A-10- The method described in 237762 is preferred. That is, a part of the aqueous phase is added to the oil phase containing the components (A) and (B), and optionally the fragrance composition, or the oil phase is added to a part of the aqueous phase, The aqueous liquid softener of the present invention is formed by forming a liquid crystal phase containing a cationic surfactant at a concentration, and then adding the remaining aqueous phase to the liquid crystal phase to invert the liquid crystal phase into an O / W emulsion. A composition can be prepared.

  On the other hand, a nonionic surfactant such as a higher alcohol alkylene oxide adduct added for the purpose of improving the emulsion dispersion stability of the emulsion liquid softener composition may be added to either the aqueous phase or the oil phase. The organic or inorganic salts that are viscosity control agents can be added in several portions during the 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.

[Package presentation]
The container for storing the liquid softening agent composition of the present invention is not particularly limited, but it is generally stored 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. Furthermore, these may contain pigments, antistatic agents, ultraviolet absorbers, slipping agents and the like.

[How to use for textile products]
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 nonionic detergent, and may contain other surfactants and function improvers. It is used in the rinsing process of all detergents marketed in Japan and overseas. can do. The concentration of the component (A) used for the finishing of the textile product is the amount of water used for finishing the textile product filled in the washing bath in the rinsing process from the viewpoint of imparting flexibility to the textile product. It is desirable to use it in an amount of 10 to 300 ppm. More preferably, it is 30-100 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-tub washing machine, a fully automatic washing machine, and a washing machine with a drying function.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this. In the examples, the component blending amounts are all expressed by mass% (in terms of pure content, unless otherwise specified).

[Method for preparing liquid emulsion softener composition]
[Examples 1-6, Comparative Examples 1-2]
The components (A) and (B), which were previously heated to 55 ° C. and melted, were placed in a glass container having an inner diameter of 120 mm and stirred at 1000 rpm using a three-one motor (manufactured by Shinto Kagaku Co., Ltd.). In Examples 3 to 6, the component (C) was dissolved, and then the component (C) was added to the mixture of the component (A) and the component (B) to form an oil phase. Ion exchange water preheated to 50 ° C. was added to the oil phase, and the mixture was stirred for 3 minutes while the concentration of component (A) was 35% by mass. Thereafter, ion-exchanged water was further added so that the concentration of the component (A) was a predetermined concentration, followed by stirring for 2 minutes to obtain a liquid emulsion softener composition. As the stirring blade, a paddle blade having three blades having a length of 100 mm at intervals of 30 mm was used.

[Examples 7 to 12]
The components (A), (B) and common components (4) to (6), which were previously heated to 55 ° C. and melted, were placed in a glass container having an inner diameter of 120 mm, and three-one motor (Shinto Scientific Co., Ltd.) The product was stirred at 1000 rpm. Next, the component (C) was dissolved and added to the mixture of the component (A), the component (B) and the common components (4) to (6) and mixed to obtain an oil phase. Further, common components (1) to (3) (excluding inorganic salts in common components 1 to 3) are dissolved in ion-exchanged water, and an aqueous phase heated to 50 ° C. is added to the oil phase. The mixture was stirred for 3 minutes in a state where the concentration of component (A) was 35% by mass. Thereafter, the aqueous phase was further added and stirred for 2 minutes so that the concentration of the component (A) became a predetermined concentration. Finally, an inorganic salt in the common components (1) to (3) previously prepared to a concentration of 15% using ion-exchanged water is added (while stirring at 100 rpm), and a liquid emulsion softener composition I got a thing. As the stirring blade, a paddle blade having three blades having a length of 100 mm at intervals of 30 mm was used.

[Flexible processing method]
Twelve commercially available cotton towels (Moraltex, manufactured by Japan Towel Inspection Association), and a commercially available T-shirt (BVD round neck short sleeve T-shirt M product number GNO132 manufactured by Fuji Spinning Co., Ltd.) Ten sheets were used. The test garment was subjected to pretreatment washing using a household washing machine (NA-F80SD1, manufactured by Matsushita Electric Industrial Co., Ltd.) and then subjected to the test. Here, 50 g of a commercial detergent (Top, manufactured by Lion Co., Ltd.) was used as a detergent for the pretreatment washing, the household washing machine was set to gossip course, and washing was repeated twice with a water volume of 57 L. 12 cotton towels and 10 T-shirts that were pretreated and washed were washed and softened using 25 g of a commercially available detergent (Top, manufactured by Lion Corporation) and 20 mL of the liquid emulsion softener composition of the present invention. gave. A household washing machine (NA-F80SD1, manufactured by Matsushita Electric Industrial Co., Ltd.) was used for the treatment, and a gossip course and a water volume of 57 L were set. The commercial detergent and the liquid softener of the present invention were respectively stored in the detergent inlet and the softener (soft finish) inlet installed in the washing machine, and were automatically added to the washing bath by the washing machine. After the treatment, the test fiber product was dried for 16 hours under the conditions of 20 ° C. and 45% RH, and subjected to the performance evaluation test shown below.

[Evaluation of flexibility]
The softness of the cotton towel that had been washed, softened and dried under the above conditions was evaluated by the following method. Using a cotton towel treated with the composition described in Comparative Example 1 as a control, evaluation was performed according to the following criteria in a sensory pair comparison by 10 professional panels, and the results were shown as average values of 10 people.
〔Evaluation criteria〕
+2: Clearly softer than the control +1: Slightly softer than the control 0: Almost the same as the control -1: Slightly softer than the control -2: Clearer softer than the control The evaluation result list shows the average value of the above scores Is expressed by the following criteria.
+2.0 or less, +0.0 or more: ◎
Less than +0.0, -0.5 or more: ○
-0.5 or less, -2.0 or more: ×

[Evaluation of deodorizing effect against tobacco odor]
The following method evaluated the deodorizing performance with respect to the tobacco smell of the cotton towel which performed washing | cleaning, a softening process, and drying on the above conditions.
The evaluation cloth was hung on a hanger in a small room of (1 m × 2 m × 2 m), in which a commercial cigarette “Mild Seven” was sucked for 1 minute, and a cigarette smell was given to the evaluation cloth.
Immediately after collecting the evaluation cloth, five expert panelists evaluated the strength of the tobacco odor attached to the evaluation cloth. As a control, a fabric treated with the softener composition described in Comparative Example 1 was used. Evaluation was performed according to the following criteria.
Compared to the control, there is not much smell of tobacco: +2
Slight tobacco smell: +1
Equivalent: 0
Slight tobacco odor: -1
I feel quite a cigarette smell: -2
As the average score of the evaluation results of five professional panelists,
+1.0 or more and +2 or less: ◎
+0.2 or more and less than +1.0: ○
-0.5 or more and less than +0.2: △
-2.0 or more and less than -0.5: x
It was described in the evaluation result according to the criteria.

[Evaluation of deodorizing effect against sweat odor]
The following method evaluated the deodorizing performance with respect to the sweat odor of the T-shirt which performed washing | cleaning, softening treatment, and drying on the above conditions.
T-shirts were worn by five men in their 30s and sweated for 30 minutes in a constant temperature room at 40 ° C. After the sweat was dried in a constant temperature room at 25 ° C. for 30 minutes, the presence or absence of sweat odor of the T-shirt was evaluated according to the following criteria.
Compared to the control, there is not much sweat odor: +2
I do not feel a little sweaty odor: +1
Equivalent: 0
I feel a little sweaty odor: -1
I feel a lot of sweat odor: -2
As the average score of the evaluation results of 5 people,
+1.0 or more and +2 or less: ◎
+0.2 or more and less than +1.0: ○
-0.5 or more and less than +0.2: △
-2.0 or more and less than -0.5: x
It was described in the evaluation result according to the criteria.

[Evaluation of emulsion dispersion stability]
The prepared liquid emulsion softener composition was put into a 100 mL glass bottle, and after sealing, left at 40 ° C. for 4 months. The viscosity after 4 months was measured, and the results of evaluation according to the following criteria are shown in the examples. From the viewpoint of usability, it is preferably ◯ or more.
<Criteria>
Viscosity is 200 mPa · s or less: ◎
Viscosity is over 200 mPa · s and 500 mPa · s or less: ○
Viscosity is over 500 mPa · s and 1,000 mPa · s or less: Δ
Viscosity exceeds 1,000 mPa · s: ×

[Sample properties and evaluation results]
Tables 1 to 4 on the attached sheets show the properties of the test samples such as the components (A), (B), and (C).
Table 5 on the attached sheet shows the evaluation results regarding the liquid softening agent composition.
The softness of Examples 1 to 12, which were comparatively evaluated using Comparative Example 1 as a control, and the effects of suppressing tobacco odor and sweat odor are all superior to Comparative Example 1.
Further, the emulsion dispersion stability is improved when (C) is blended, and further improved when an inorganic electrolyte such as calcium chloride, sodium chloride, or magnesium chloride is used in combination.

Claims (3)

An emulsion-type liquid softening agent composition comprising the following component (A) and component (B):
(A) A tertiary amine having a long chain hydrocarbon group having 10 to 22 carbon atoms, including a splitting group, which is split by an ester group, a neutralized product of the tertiary amine, and a quaternized product of the tertiary amine 1 or more types of cationic surfactant (B) benzyl benzoate selected from the group which consists of: 0.1 mass% or more   Furthermore, a nonionic surfactant is added as (C) component, The emulsion type liquid softening agent composition of Claim 1 characterized by the above-mentioned.   The emulsion type liquid softening agent composition of Claim 1 or 2 whose nonionic surfactant of (C) component is an alkylene oxide (AO) addition type, and the average added mole number of AO is 30-100.