JP2006200116A - Liquid softener composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid softener composition which can improve a softening effect, when used for clothes. <P>SOLUTION: This liquid softener composition comprises (a) a dimethylpolysiloxane emulsion having an average particle diameter of 50 to 900 nm and produced by emulsifying a dimethylpolysiloxane compound (a1) having a viscosity of 100,000 to 10,000,000 mm<SP>2</SP>/s at 25°C in water in the presence of a surfactant (a2) selected from a polyoxyalkylene alkyl ether type nonionic surfactant (a21) and an anionic surfactant (a22) having a sulfonate in the molecule, (b) a quaternary ammonium salt compound having one to three 12 to 24C hydrocarbon groups divided with ester groups and/or amide groups and the residual one to three 1 to 3C alkyl groups or the like, and (c) water, wherein the mass ratio of (a1) component / (b) component is 1/100 to 1/1. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a liquid softener composition.

Techniques for applying silicone compounds to softeners are known, and are described in, for example, Patent Documents 1 to 4. Patent Document 5 describes a method for producing a silicone emulsion.
JP 2004-131895 A JP 2004-131896 A JP 2004-263347 A JP-A-10-219567 JP 7-173294 A

  Usually, the softener composition contains a quaternary ammonium type softening base as a main component, and also uses a silicone compound for the purpose of imparting smoothness and lubricity to the fiber product. Silicone compounds are generally lipophilic substances and are insoluble in water, so they are used by emulsifying silicone compounds for blending into liquid softener compositions. There are sexual challenges.

  Therefore, in Patent Documents 1 to 3, a silicone compound modified with a hydrophilic group such as an amino group or a polyoxyalkylene group or a relatively low viscosity dimethylpolysiloxane is used. In addition, the silicone compound imparts a texture such as lubricity and smoothness to the garment, while giving the garment a greasy feel and a slimy feeling peculiar to the silicone compound. Furthermore, Patent Documents 1 to 3 do not describe at all that a specific silicone emulsion can significantly improve the softening effect.

  Patent Document 4 discloses a softener composition containing a silicone compound emulsified with a specific cationic surfactant, which can improve the adsorptivity to clothes and impart smoothness to clothes. However, it does not improve the softening effect, and has problems from the viewpoint of blending stability and storage stability.

  Patent Document 5 describes a technique for applying a nonionic surfactant or an anionic surfactant to the production of a silicone emulsion, which was made for the purpose of improving the stability of the silicone emulsion. No mention is made of the point that the softening effect can be remarkably improved when applied to a softening agent.

  Accordingly, an object of the present invention is to provide a liquid softening agent composition which has no problem in blending stability and storage stability, has no oiliness and slimy feeling peculiar to silicone, and can remarkably improve the softening effect. .

As a means for solving the problems, the present invention
(A) a dimethylpolysiloxane compound (a1) having a viscosity at 25 ° C. of 100,000 to 10,000,000 mm ² / s,
It is emulsified in water by a surfactant (a2) containing a polyoxyalkylene alkyl ether type nonionic surfactant (a21) and an anionic surfactant (a22) having one sulfonate or sulfate ester salt in the molecule. The
Dimethylpolysiloxane emulsion having an average particle size of 50 to 900 nm,
(B) 1 to 3 hydrocarbon groups having a total carbon number of 12 to 24 separated by ester groups and / or amide groups, and the rest are quaternary alkyl groups or hydroxyalkyl groups having 1 to 3 carbon atoms. One or more compounds selected from an ammonium salt compound and a tertiary amine salt compound and (c) a liquid softness containing water, wherein (a1) component / (b) component is 1/100 to 1/1 by mass ratio An agent composition is provided.

  The liquid softening agent composition of the present invention has an excellent softness-imparting effect on clothes and has excellent storage stability.

<(A) component>
The component (a) of the present invention is a dimethylpolysiloxane emulsion having an average particle size of 50 to 900 nm obtained by emulsifying the component (a1) in water with the component (a2) including the component (a21) and the component (a22). It is.

The component (a1) is a dimethylpolysiloxane compound having a viscosity at 25 ° C. of 100,000 to 10,000,000 mm ² / s. (A1) the viscosity of the components, from the viewpoint of improving the softening effect, from 500,000 to 9,000,000 mm ² / s are preferred, from 800,000 to 7,000,000 mm ² / s and more preferably, especially 1000000 to 6000000 mm ² / s is preferred. The component (a1) is preferably a straight-chain polymer compound, and a crosslinked silicone compound or a branched silicone compound is not preferred because the effect of improving the softening effect is low.

(A1) when the viscosity as a component used dimethylpolysiloxane compound of from 1,000,000 to 10,000,000 mm ² / s, from the viewpoint of industrial handling, a viscosity at 25 ° C., preferably 5~300mm ² / s, more It is preferable to use a dimethylpolysiloxane compound having a low molecular weight of preferably 10 to 200 mm ² / s, particularly preferably 20 to 100 mm ² / s. The viscosity can be measured with an Ubbelohde viscometer.

  As the component (a21), a compound represented by the following general formula (1) is suitable.

R ^1a —O— (AO) _n —H (1)
[Wherein R ^1a is a hydrocarbon group having 10 to 16 carbon atoms, A is an ethylene group or a propylene group, and n is an average added mole number of 1 to 100. ]
R ^1a is preferably an alkyl group having 12 to 16 carbon atoms, A is preferably an ethylene group, and n is preferably 1 to 80, more preferably 2 to 50, and particularly preferably 2 to 40.

Moreover, in this invention, it is preferable to use together lipophilic (a21) component and hydrophilic (a21) component as (a21) component from the point of the mixing | blending stability of (a) component. Specifically, in general formula (1), n is 1 to 10, preferably 2 to 8 (hereinafter referred to as “component (a21o)”), and in general formula (1), n is 10 to 50, preferably 20 to 40 , particularly preferably 20 to 35 compounds [hereinafter referred to as “component (a21w)”] are preferably used in combination.

  When the component (a21o) and the component (a21w) are used in combination, the component (a21o) / (a21w) = 1/10 to 10/1, preferably 1/5 to 2/3 is preferably contained.

  As the component (a22), a compound represented by the following general formula (2) is suitable.

R ^2a -X (2)
[Wherein R ^2a is an alkyl group having 10 to 16 carbon atoms or an alkylaryl group having 10 to 16 carbon atoms, and X is —SO ₃ M or — (OB) _m —OSO ₃ M. (B is an ethylene group or a propylene group, m is an average added mole number, and is a number from 0 to 4. M is an inorganic or organic cation.)]
Specifically, an alkylbenzene sulfonate having 10 to 16 carbon atoms, an alkyl sulfate ester salt having 10 to 16 carbon atoms, preferably 10 to 14 carbon atoms, and an average addition mole number of an oxyethylene group (a compound in which B is an ethylene group). A polyoxyethylene alkyl ether sulfate salt having 1 to 4 preferably 1.5 to 3 and an alkyl group having 10 to 16 carbon atoms, preferably 10 to 14 carbon atoms is suitable. The salt is preferably a sodium salt, potassium salt or alkanolamine salt.

  The component (a2) is a combination of the component (a21) and the component (a22), and the component (a21) / component (a22) is preferably in a mass ratio of 300/1 to 2/1, more preferably 200/1. It is preferable for the purpose of improving the softening effect to contain 10/1.

  In the component (a), the content of the component (a1) is 5 to 70% by mass, preferably 20 to 70% by mass, and particularly preferably 40 to 70% by mass. In the component (a), the content of the component (a2) is 0.1 to 10% by mass, preferably 1 to 10% by mass, and particularly preferably 3 to 10% by mass. The ratio of (a1) / (a2) is preferably 4/1 to 50/1, particularly preferably 5/1 to 30/1, in terms of mass ratio.

  In the component (a), the content of water is 10 to 80% by mass, preferably 20 to 70% by mass, and particularly preferably 30 to 60% by mass.

  (A) As a preparation method of a component, the method of emulsifying using the stirring apparatus which can provide a high-speed shearing force like a homomixer, a high-pressure homogenizer, etc. is applicable. In addition, a so-called emulsion polymerization method in which a low-molecular cyclic polysiloxane is used as a starting material and is polymerized using a strong acid or strong alkali as a catalyst in an emulsified dispersion state can also be employed. Preferably, after preparing the silicone emulsion of component (a), it can be filtered by a known method to remove the non-emulsified dimethylpolysiloxane compound.

  Preferably, the component (a1) is added to the aqueous solution containing part or all of the component (a2) and part or all of water while applying high-speed shearing force with a device such as a homomixer or a high-pressure homogenizer. (A2) A method of mixing the component and water is applied. The amount of the component (a2) used in the step of adding the component (a1) while applying high-speed shearing force is 20 to 100% by mass, preferably 20 to 70% by mass, particularly preferably 20% of the total (a2) component. -50 mass%.

  The average particle size of the dimethylpolysiloxane emulsion as component (a) is 50 to 900 nm, preferably 100 to 700 nm, more preferably 200 to 600 nm, and particularly preferably 200 to 500 nm. The particle diameter can be measured by a dynamic light scattering method.

  The pH of the dimethylpolysiloxane emulsion as component (a) at 20 ° C. is 2 to 8, preferably 3 to 7. Examples of the pH adjuster include citric acid, acetic acid, malic acid, succinic acid, and benzoic acid. Organic acids, inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid can be used.

<(B) component>
The component (b) is composed of 1 to 3 hydrocarbon groups having 12 to 24 carbon atoms separated by an ester group and / or an amide group, and the remainder being an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms. It is a quaternary ammonium salt compound and a tertiary amine salt compound. Specific examples of suitable component (b) include compounds of the following general formula (3).

[Where:
R ^3a , R ^3b , and R ^3c may be the same or different from each other, and the alkyl group having 14 to 26 carbon atoms separated by an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or an ester group or an amide group. Group or an alkenyl group. However, at least one is an alkyl group having 14 to 26 carbon atoms or an alkenyl group separated by an ester group or an amide group. R ^3d is hydrogen, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group, and X ⁻ represents an anion group. ]
More specifically, the compound of general formula (4) is preferable.

[Where,
R ^4a is an alkyl group having 14 to 24 carbon atoms, preferably 16 to 20 carbon atoms, or an alkenyl group,
R ^4b is an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or a group represented by R ^4f — [E—R ^4g ] _d — (wherein R ^4f is an alkyl group having 14 to 24 carbon atoms). Group or alkenyl group, R ^4g is an alkylene group having 1 to 6 carbon atoms, E is a group selected from —COO—, —OCO—, —CONH— and —NHCO—, and d is a number of 0 or 1 ),
R ^4c is a group represented by R ^4h — [F—R ^4g ] _i — (where R ^4h is an alkyl group having 14 to 24 carbon atoms or an alkenyl group, and R ^4g is a group having 1 to 6 is an alkylene group, F is a group selected from —COO—, —OCO—, —CONH—, and —NHCO—, i is a number of 0 or 1), or an alkyl group having 1 to 3 carbon atoms. Or a hydroxyalkyl group,
R ^4d is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group,
R ^4e is an alkylene group having 1 to 6 carbon atoms,
D is a group selected from -COO-, -OCO-, -CONH- and -NHCO-,
c is a number of 0 or 1,
X ^- is an anionic group. ]
In the compound of the general formula (4), R ^4a is preferably an alkyl group having 15 to 19 carbon atoms or an alkenyl group, and R ^4b is preferably a group represented by R ^4f- [ ^{ER 4g} ] _d- ^4f is preferably an alkyl group having 15 to 19 carbon atoms or an alkenyl group, D and E are preferably —COO— and —CONH—, and c and d are at least one of 1, and preferably all are 1. It is preferable that R ^4c is preferably a methyl group or a hydroxyethyl group. R ^4d is preferably hydrogen or a methyl group, and R ^4e or R ^4g is preferably an ethylene group or a propylene group. X ⁻ is preferably a halogen ion, an alkyl sulfate ester ion having 1 to 3 carbon atoms, or a fatty acid ion having 1 to 18 carbon atoms.

<(C) component>
The component (c) of the present invention is water, preferably water from which hardness components such as calcium and magnesium present in trace amounts and heavy metals such as iron are removed, and ion-exchanged water or distilled water can be used. Moreover, you may contain a small amount of chlorine compounds for the purpose of disinfecting or sterilizing water.

<Other ingredients>
The liquid softener composition of the present invention has a surfactant selected from fatty acids having 12 to 24 carbon atoms and nonionic surfactants as component (d) from the viewpoint of further improving the softening effect and storage stability. It is preferable to contain an agent.

  As the fatty acid (hereinafter referred to as the component (d1)), lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, erucic acid, and behenic acid are preferable, and palmitic acid, stearic acid, oleic acid are particularly preferable. Linoleic acid is preferred.

  As the nonionic surfactant (hereinafter referred to as component (d2)), polyoxyethylene alkyl ether having an alkyl group or alkenyl group having 8 to 20 carbon atoms is preferable, and in particular, the nonionic surfactant represented by the following general formula (5) Is good.

^R5a- F-[( ^R5bO ) _e- ^R5c ] _g (5)
[Where,
R ^5a is an alkyl group having 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms, or an alkenyl group,
R ^5b is an alkylene group having 2 or 3 carbon atoms, preferably an ethylene group,
R ^5c is an alkyl group having 1 to 3 carbon atoms or a hydrogen atom,
e is a number of 2 to 100, preferably 5 to 80, more preferably 5 to 40, particularly preferably 10 to 60;
F is —O—, —COO—, —CON— or —N—, and when F is —O— or —COO—, g is 1, and when F is —CON— or —N—, g is 1 or 2. ]
Specific examples of the compound of the general formula (5) include the following compounds.

R ^5a —O— (C ₂ H ₄ O) _h —H
[Wherein R ^5a has the above-mentioned meaning. h is a number of 8 to 100, preferably 10 to 60. ]
_{^{R 5a -O- (C 2 H 4}} O) i - (C 3 H 6 O) j -H
[Wherein R ^5a has the above-mentioned meaning. i and j are each independently a number of 2 to 40, preferably 5 to 40, and (C ₂ H ₄ O) and (C ₃ H ₆ O) may be random or block adducts. ]

[Wherein R ^5a has the above-mentioned meaning. k and l are each independently a number from 0 to 40, and k + 1 is a number from 5 to 60, preferably from 5 to 40. R ^5d and R ^5e are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]
In addition, (d) component may be similar or the same as (a21) component in (a) component, and cannot be distinguished in a composition. However, the component (a21) is used in the step of emulsifying the component (a1) and has the effect of improving the softening effect of the present invention. The component (d) is a composition together with the components (a) to (c). It is used in the manufacturing process and has the effect of improving the storage stability of the softening agent. Therefore, the component (d) and the component (a21) are used at different stages in the production process of the composition, and the effects expressed by the addition of the components are also different.

  The composition of the present invention can contain an inorganic salt as the component (e) as necessary. As the inorganic salt, sodium chloride, calcium chloride, and magnesium chloride are preferable from the viewpoint of storage stability.

  The composition of the present invention is a combination of a saturated or unsaturated fatty acid having 8 to 22 carbon atoms and a polyhydric alcohol as a component (f) for the purpose of imparting an effect of further improving flexibility by being used together with the component (a). An ester compound may be contained, but in order to obtain good storage stability, it is desirable to pay attention to the type and content. Examples of the component (f) that can be blended include triglyceride, diglyceride, monoglyceride, and mono, di, triester, and sorbitan ester of pentaerythritol. The reaction molar ratio between the fatty acid and the hydroxyl group in the polyhydric alcohol is preferably 1/3 to 1/1, more preferably 1/2 to 1/1, and particularly preferably 1/2 to 0.9 / 1.

  The composition of this invention may contain a solvent as a (g) component as needed. Specifically, it is a solvent selected from ethanol, isopropanol, glycerin, ethylene glycol, and propylene glycol, and ethanol is particularly preferable from the point of smell.

  The composition of the present invention is a fragrance ((h) component, particularly preferably a fragrance shown in components (c) and (d) described in JP-A No. 8-113871) used in ordinary fiber treatment agents. (Combination of components).

  The composition of the present invention has an azo group, a phthalocyanine group, a triphenylmethane group, a xanthan group, an anthraquinone group as a chromophore in the molecule, and a sulfonic acid group, a functional group that improves water solubility and water dispersibility, A dye having an amino group, a carboxyl group, or a polyoxyalkylene group (component (i)) may be contained.

  The composition of the present invention can contain a chelating agent (component (j)) for the purpose of improving odor stability and hue stability. The component (j) is a compound selected from aminopolycarboxylic acid, phosphonic acid, and salts thereof.

As the aminopolycarboxylic acid, a compound having a molecular weight of 180 to 1000, preferably 250 to 600 having at least one, preferably 1 or 2, iminodiacetic acid groups represented by —N (CH ₂ COOM) ₂ in the molecule. Is preferred. More specifically, nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aspartic acid diacetic acid, glutamic acid diacetic acid, glycol etherdiaminetetraacetic acid, hydroxyethyliminodiacetic acid, triethylenetetramine hexaacetic acid, and diencoric acid. In particular, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, aspartic acid diacetic acid, and glutamic acid diacetic acid are preferred.

  Examples of phosphonic acid include ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid and its derivatives, ethanehydroxy-1,1,2- Triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, ethylenediaminetetra (methylenephosphonic acid), diethylenetriaminepenta (methylenephosphonic acid), trimethylenephosphonoamine, Particularly preferred are ethane-1,1-diphosphonic acid and ethylenediaminetetramethylenephosphonic acid.

  As the salt, sodium salt, potassium salt, magnesium salt, alkanolamine salt, iron salt, nickel salt, chromium salt and zinc salt are preferable, and sodium salt, potassium salt and iron salt are particularly preferable.

  In the present invention, ethylenediaminetetraacetic acid and its sodium salt, potassium salt, and iron salt are most preferred as the component (j). Further, it may contain an antifoaming silicone, an antioxidant and a preservative in amounts that do not affect the effects of the present invention.

<Liquid softener composition>
The content of the component (a) is preferably 0.2 to 5.0 mass%, more preferably 0.3 to 2.0 mass%, particularly preferably 0.5 to 0.5 mass% as the content of the silicone compound (a1). 1.5% by mass.

  (B) As for content of a component, 3-30 mass% is preferable, More preferably, it is 4-25 mass%, Most preferably, it is 10-25 mass%.

  Further, the (a1) component / (b) component is preferably 1/100 to 1/5, more preferably 1/100 to 1/10 in terms of mass ratio.

  The content of the component (d) is preferably from 0.1 to 10% by mass, more preferably from 0.5 to 8% by mass, and particularly preferably from 1.5 to 10% by mass from the viewpoint of the storage stability improving effect and the flexibility improving effect. 8% by mass.

  The content of the component (d1) is preferably 0.1 to 8% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass.

  Component (d1) / component (b) has a mass ratio of 1/200 to 1/2, preferably 1/100 to 1/5, more preferably 1/80 to 1/8 in terms of flexibility improvement effect. Is preferred.

  The content of the component (d2) is preferably 0.1 to 10% by mass, more preferably 0.1 to 8% by mass, and particularly preferably 1 to 6% by mass for the purpose of improving storage stability.

  The content of the component (e) and the component (g) is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, for the purpose of improving storage stability. (G) A component becomes like this. Preferably it is 0.01-5 mass%, More preferably, it is 0.1-3 mass%. For the purpose of further improving the softening effect, the content of (f) component is preferably contained in an amount such that the mass ratio of (a1) component / (f) component is 1/10 to 8/1, more preferably. Is 1/5 to 5/1, particularly preferably 1/3 to 3/1. (H) A component becomes like this. Preferably it is 0.1-5 mass%, More preferably, it is 0.1-3 mass%. Particularly preferably 0.2 to 1.5% by mass, component (i) is preferably 0.1 to 100 mg / kg, more preferably 0.1 to 80 mg / kg, particularly preferably 1 to 60 mg / kg. . (J) A component becomes like this. Preferably it is 0.001-0.05 mass%, More preferably, it is 0.001-0.03 mass%, Most preferably, it is 0.005-0.02 mass%.

  In addition, although surfactants such as fatty acid salts include sodium salts and potassium salts, the inorganic salt mixed into the composition by using such surfactants is the content of the component (e). There are no restrictions.

  The composition of the present invention is in the form of an aqueous solution in which the components (a) and (b) described above are dissolved or dispersed in the water (c), and the content of the component (c) in the composition 30-95 mass% is preferable, More preferably, it is 50-85 mass%. In addition, content of (c) component is also what combined the quantity of the water contained in (a) component.

  In the composition of the present invention, the pH of the composition at 20 ° C. is preferably adjusted to 2 to 8.5, more preferably 2 to 8, particularly 2 to 5 from the viewpoint of storage stability. The pH was measured using a pH meter D-52S manufactured by HORIBA, Ltd. and a pH electrode 6367-10D. As the pH adjuster, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid and the component (d1) can be used as acid agents, and sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, etc. can be used as alkaline agents. it can.

<Method for producing softener composition>
In the composition of the present invention, for example, the component (d2) and the component (g) are dissolved in the water of the component (c) and heated to 40 to 70 ° C., preferably 45 to 65 ° C. Depending on the case, (d1) component, (f) component is premixed with (b) component and melted, and the mixture is stirred and mixed, adjusted to a predetermined pH, and then (e) component is added. . Next, after adding component (h) and component (i) and cooling, a method of adding component (a) prepared in advance can be applied. In addition, you may add a part or whole quantity of (g) component previously mixed with (b) component.

  With the composition obtained by such a production method, the effects of the present invention that the flexibility improving effect, the blending stability, and the storage stability are good can be obtained, but the components (a1) and (a2) The effects of the present invention cannot be obtained with a composition obtained by emulsifying after individually adding at the time of preparation of the composition.

  The liquid softener composition of the present invention is supplied to general consumers as a product filled in an ordinary plastic packaging container. Moreover, the display which gives the softness | flexibility to the clothing which is the effect of this invention can be given to these containers.

  The liquid softener composition of the present invention can be used not only for clothing, bedding (comforter covers, mattress covers, blanket covers, pillow covers, towels, etc.), various towels, foot-wiping mats, etc., but also at home. It can be applied to all necessary textile products.

<Preparation of emulsion of component (a)>
Ultra-Turrax T-20 (manufactured by IKA, shaft generator S25-25F) was used as the high shear force when preparing the following components (a-1) to (a-5). The particle diameter was adjusted by changing the rotation speed.

(A-1): 5 g of polyoxyethylene lauryl ether having an average addition mole number of 5 mol was added to 300 g of a silicone compound (viscosity 5,000,000 mm ² / s at 25 ° C.) Ultra Turrax T-20 (manufactured by IKA, shaft Generator S25-25F) was applied while applying a high shearing force, and stirring was continued for 10 minutes with a high shearing force. Thereafter, 30 g of ion-exchanged water was added, and then 2 g of polyoxyethylene lauryl ether sodium sulfate having an average addition mole number of 2 mol and 15 g of polyoxyethylene myristyl ether having an average addition mole number of 40 mol were added. Stirring was continued for 30 minutes, and then 248 g of water was added and stirred. The average particle size of this product was 500 nm.

(A-2): 500 g of a silicone compound (viscosity 500,000 mm ² / s at 25 ° C.) is added to 500 ml of an aqueous solution containing 10% of the B5 component described in the examples of JP-A-10-219567. A silicone emulsion having an average particle diameter of 400 nm obtained by continuing stirring for 90 minutes below.

  (A-3): A silicone emulsion having an average particle size adjusted to 2000 nm in the component (a-1).

(A-4): A silicone emulsion using a silicone compound having a viscosity of 50,000 mm ² / s at 25 ° C. in the component (a-1). The average particle size is 2000 nm.

(A-5): 8.2 g of polyoxyethylene lauryl ether having an average addition mole number of 4 mol was added to 300 g of a silicone compound (viscosity 5,000,000 mm ² / s at 25 ° C.) Ultra Turrax T-20 (manufactured by IKA) The shaft generator S25-25F) was used while applying a high shearing force, and stirring was continued for 10 minutes with a high shearing force. Thereafter, 30 g of ion-exchanged water was added, and then 0.27 g of polyoxyethylene lauryl ether sodium sulfate having an average addition mole number of 3 mol and 24.5 g of polyoxyethylene lauryl ether having an average addition mole number of 23 mol were added. Stirring was continued for 30 minutes under shear force, and then 237 g of water was gradually added and stirred. This had an average particle size of 400 nm.

  The components (a-1) to (a-5) were used after filtration with a 400 mesh wire net under normal pressure.

Production of (b-1) N- (3-aminopropyl) -N- (2-hydroxyethyl) -N-methylamine and hardened beef tallow fatty acid are dehydrated and condensed according to a known method at a molar ratio of 1 / 1.9. It was. The reaction was terminated when the fatty acid content in the reaction product reached 5%. The structure of the main component is as follows. The content as component (b) was 95%.

Production of (b-2) Triethanolamine and hardened beef tallow fatty acid were dehydrated and condensed according to a known method at a molar ratio of 1 / 1.8. The reaction was terminated when the fatty acid content in the reaction product reached 3%. Next, 10% equivalent amount of ethanol was added to the dehydrated condensate. Next, quaternization was carried out according to a known method using 0.98 equivalents of dimethyl sulfate to the amine. Thereafter, ethanol was added so that the solid content was 90%. The structure of the main component is as follows. The content as component (b) was 88%.

Production of (b-3) 10% by mass of ethanol was added to (c-1), and quaternization was carried out by a known method using 0.98 equivalents of methyl chloride with respect to the amine. Thereafter, ethanol was added so that the solid content was 90%. The structural formula of the main component is as follows. The content as component (b) was 84%.

Manufacture of (b-4) It manufactured according to the manufacturing method of (b-2) except having used oleic acid as a fatty acid. The content as component (b) was 87%.

The compounds (b-1) to (b-4) were produced by a known method or a method described in JP-A-11-229273.
(D1-1): stearic acid (d1-2): oleic acid (d2-1): 20 moles of EO added to C12 saturated alcohol on average (d2-2): EO averaged over isotridecyl alcohol 30 mol added (e-1): calcium chloride (f-1): dehydrated condensate of hardened beef tallow fatty acid and glycerin, molar ratio of hardened beef tallow fatty acid / glycerin is 1.8 / 1 (g- 1): Ethanol (h-1): Perfume mixture (mixture of component (c-1) and component (d-1) described in JP-A-8-113871 (mass ratio 3/2))
(I-1): Food blue No. 1 (j-1): Ethylenediaminetetraacetic acid tetrasodium salt <Method for producing liquid softener composition>
The following components were used so that the final softening agent composition was 300 g, and a softening agent composition was produced. A 500 mL glass beaker in which a stirring blade with three turbine blades each having a length of 2.5 cm is installed 1 cm above the bottom of the beaker is charged with a necessary amount of 95 mass% ion-exchanged water (c), The temperature was raised to 62 ° C. with a water bath. While stirring at 500 rpm, the melted component (d2) was added.
Next, a premixture in which the components (b), (d1), (f), and (g) were premixed and melted at 70 ° C. was added. Next, a 35% aqueous hydrochloric acid solution and / or a 48% aqueous sodium hydroxide solution necessary to obtain a predetermined pH were then added. Further, the component (e) was added with stirring, and the mixture was stirred for 10 minutes.

  Then, (h) component and (i) component were added and stirred for 5 minutes, then cooled to 30 ° C. in a 5 ° C. water bath, added with (j) component and (a) component, and further mixed for 5 minutes. . Finally, the pH was checked again and adjusted with a 35% aqueous hydrochloric acid solution and / or a 48% aqueous sodium hydroxide solution as necessary. Within the stated range, almost all the component (b-1) is present in the composition in the form of hydrochloride.

(1) Stability evaluation method of liquid softener composition An 800 mL polyethylene resin container was filled with 600 mL of the liquid softener composition shown in Table 1 and stored at 40 ° C for 1 month. After storage, the mixture was cooled to 30 ° C., and the contents were filtered through a 400 mesh metal wire mesh. The metal wire mesh was washed with 100 g of ion exchange water, and after drying, the state of the wire mesh was visually observed.

Evaluation criteria (appearance)
○: Nothing remains on the wire mesh.
□ ... Slightly adhering gel-like material on the wire net, but at an acceptable level.
X: It is observed that gel-like substances are clearly attached on the wire mesh.

(2) Treatment method with liquid softener composition (evaluation of softness and texture)
Put 1.5 kg of a commercially available cotton towel (100% cotton) and 0.5 kg of cotton underwear (100% cotton) into a fully automatic washing machine (National NA-F60E), and use a commercially available weak alkaline detergent (trade name Attack, Kao Corporation )) For 5 times (standard course, detergent concentration 0.0667% by weight, 40 L of tap water, water temperature 20 ° C.). After each washing, it was naturally dried at 25 ° C. and 40% RH.

  Next, it was washed again with a fully automatic washing machine (standard course, detergent concentration 0.0667 mass%, softener composition amount 10 g, tap water 40 L used, water temperature 20 ° C.). The softening agent composition was put into a washing tub and subjected to softening treatment. After dehydration, the towel was naturally dried under conditions of 25 ° C. and 40% RH. In addition, a cotton towel and cotton underwear that were similarly softly processed using a reference composition (Table 1) for evaluating softness and texture were also prepared.

* 1: Blending amount including carry-over from component (b) * 2: Blending amount of component (c) is blended as solid content * 3: pH adjustment is 0.1N hydrochloric acid aqueous solution and 0.1N hydroxylation Performed with aqueous sodium.

(Flexibility evaluation criteria)
The towels treated with the respective compositions shown in Table 2 by 10 panelists (male in their 30s) with the flexibility of the cotton towel treated as described above, and the component (a) is not blended Were determined by a paired comparison based on the following criteria with the reference composition of Table 1 having the same composition (the blending amount of the component (a) is balanced with ion-exchanged water), and the average score was obtained. An average score of 0 or more and less than 1 was evaluated as ◯, 1 or less than 1.5 as Δ, and 1.5 or more as x.

Compared with cotton towel, it finished very soft: 0
Finished slightly softer than the comparative cotton towel: 1
Same softness as a comparative cotton towel: 2
(Texture evaluation criteria)
The texture of the above-treated cotton underwear was determined by 10 panelists (male in their 30s) according to the following criteria, and the average score was obtained. An average score of 0 or more and less than 1 was evaluated as ◯, 1 or less than 1.5 as Δ, and 1.5 or more as x.

I feel only the same level of slimness as the comparative cotton underwear: 0
A feeling of sliminess is felt from the comparison cotton underwear: 1
From the comparison cotton underwear, there is a clear feeling: 2

  * 1, * 2, * 3 are the same as in Table 1.

Claims (7)

(A) a dimethylpolysiloxane compound (a1) having a viscosity at 25 ° C. of 100,000 to 10,000,000 mm ² / s,
It is emulsified in water by a surfactant (a2) containing a polyoxyalkylene alkyl ether type nonionic surfactant (a21) and an anionic surfactant (a22) having one sulfonate or sulfate ester salt in the molecule. The
Dimethylpolysiloxane emulsion having an average particle size of 50 to 900 nm,
(B) 1 to 3 hydrocarbon groups having a total carbon number of 12 to 24 separated by ester groups and / or amide groups, and the rest are quaternary alkyl groups or hydroxyalkyl groups having 1 to 3 carbon atoms. One or more compounds selected from an ammonium salt compound and a tertiary amine salt compound and (c) a liquid softness containing water, wherein (a1) component / (b) component is 1/100 to 1/1 by mass ratio Agent composition. The liquid softener composition according to claim 1, wherein the component (a21) is a compound of the following general formula (1).
R ^1a —O— (AO) _n —H (1)
[Wherein, R ^1a is a hydrocarbon group having 10 to 16 carbon atoms, A is an ethylene group or a propylene group, and n is an average added mole number of 1 to 100. ] The liquid softener composition according to claim 1 or 2, wherein the component (a22) is a compound of the following general formula (2).
R ^2a -X (2)
[Wherein, R ^2a is an alkyl group having 10 to 16 carbon atoms or an alkylaryl group having 10 to 16 carbon atoms, and X is —SO ₃ M or — (OB) _m —OSO ₃ M. . (B is an ethylene group or a propylene group, and m is an average added mole number of 0 to 4. M is an inorganic or organic cation.)]   The liquid softener composition according to any one of claims 1 to 3, wherein the component (a) contains the component (a1) / the component (a2) at a mass ratio of 3/1 to 100/1.   The liquid softener composition according to any one of claims 1 to 4, wherein the component (a2) contains the component (a21) / the component (a22) at a mass ratio of 500/1 to 1/1.   The liquid softener composition according to any one of claims 1 to 5, which comprises (a1) component / (b) component at a mass ratio of 1/100 to 1/3. (A1) component, (a2) component, and water are mixed beforehand, and after preparing the dimethylpolysiloxane emulsion (a) whose average particle diameter is 50-900 nm, the component containing (b) component and (c) component And a method for producing a liquid softener composition.