JP2003096674A - Modified silicone emulsion, softening and finishing agent for clothes and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a modified silicone emulsion which makes it possible to suitably use a modified silicone that is gelled and hardly emulsified in water, as a base agent or as a performance-imparting agent for fiber treating agents and softening and finishing agents for clothes, to obtain the softening and finishing agent for the clothes, and to provide a method for producing the same. SOLUTION: The modified silicone emulsion is characterized by being obtained by mixing and dissolving (a) a modified silicone which is gelled in water, (b) an organic solvent, and (c) a cationic surfactant and/or a nonionic surfactant and then emulsifying and dispersing the mixture in water. The softening and finishing agent for the clothes is obtained by compounding the emulsion. The method for producing the softening and finishing agent for the clothes is also provided.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a modified silicone which can be suitably used as a base or performance-imparting agent for a fiber treating agent or a softening agent for clothing, which is a modified silicone which gels when contacted with water and is difficult to emulsify. The present invention relates to an emulsion, a softening agent for clothing, and a method for producing the same.

[0002]

2. Description of the Related Art Modified silicone has a structure in which a dimethylpolysiloxane skeleton is provided with functional groups such as amino groups, epoxy groups and polyoxyalkylene groups. When emulsifying a polyether-modified silicone having high water-solubility among such modified silicones, as described in JP-A-2-191774, it is directly dissolved or dispersed in an aqueous phase to easily obtain an emulsion. And can be easily incorporated into a fabric softening agent.

However, in the case of a modified silicone which gels when contacted with water, a strong gel is formed at the moment of contact with water during emulsification, which hinders atomization, so that emulsification is very difficult. Have difficulty. This is a phenomenon peculiar to the modified silicone, which does not occur with other unmodified dimethyl silicone and gels when contacted with water.

For the preparation of such modified silicone emulsions, modified silicones and nonionics are used as described in "Silicone for Fibers Catalog" (published in December 1989) issued by Toray Dow Corning Silicone Co., Ltd. A method in which a surfactant is premixed and then emulsified and dispersed in water under high shear using a homogenizer, homomixer, or colloid mill, or water is gradually added to a mixture of a modified silicone and a nonionic surfactant. A method of preparing a W / O emulsion and then performing phase inversion emulsification in water under high shear is used, but in these methods, an emulsifier that generates high shear is indispensable, and the emulsion can be more easily produced. Is desired.

Further, Japanese Patent Laid-Open No. 9-316331 proposes a method of emulsifying an organopolysiloxane with a cationic surfactant. In this proposal, the organopolysiloxane, the cationic surfactant and water are mixed. The mixture is mixed and phase-inverted from a W / O type to an O / W type under high shearing force, and only large particles having a particle size of several tens of μm are obtained.

Further, Japanese Patent Application Laid-Open No. 11-21587 proposes an example in which polyorganosiloxane is emulsified by using a sorbitan-based surfactant. In this proposal as well, polydimethylsiloxane is used as the polyorganosiloxane. It is emulsified and dispersed by applying high shearing force.

Further, Japanese Patent Laid-Open No. 11-12286 and Japanese Patent Laid-Open No. 11-148011 propose a method for producing a silicone emulsion, both of which are methods that require high shearing force.

As described above, at present, a production method capable of obtaining an emulsion under low shear has not been realized yet.

On the other hand, as to the method of blending the modified silicone with the softening agent for clothing, Japanese Patent Laid-Open No. 112481/1990 discloses that a 1% amino modified product of dimethylpolysiloxane is an ethylene oxide 11 mol adduct of stearyl alcohol. Although an emulsified emulsion is prepared and blended with the softening agent, no preparation such as using an organic solvent is found in the preparation of this emulsion.

[0010]

SUMMARY OF THE INVENTION Under such circumstances, it is an object of the present invention to solve various problems in the prior art and achieve the following objects. That is, the present invention is a modified silicone emulsion which can easily obtain an emulsion of a modified silicone that gels when contacted with water and is difficult to emulsify without adding high shear, and a soft finish for clothing containing the modified silicone emulsion. An object of the present invention is to provide a simple method for producing an agent and a softening agent for clothing.

[0011]

In order to achieve the above-mentioned object, the inventors of the present invention have earnestly studied a method for easily obtaining an emulsion of a modified silicone which gels when contacted with water and is difficult to emulsify. As a result, (a) A modified silicone that gels when contacted with water and is difficult to emulsify; and (b) an organic solvent,
(C) By mixing and dissolving the cationic surfactant and / or the nonionic surfactant, of course, under high shearing force,
It was found that it can be easily emulsified in water even under low shear force.

Further, the modified silicone emulsion of the present invention is blended with a softening agent for clothing, or (a)
A mixed melt obtained by mixing and dissolving a modified silicone that gels when contacted with water and is difficult to emulsify, (b) an organic solvent, and (c) a cationic surfactant and / or a nonionic surfactant, ) Emulsified in a separately prepared soft base dispersion for clothing or an emulsified dispersion concentrate of a soft base for clothing, or
Alternatively, (ii) it was found that a softening agent for clothing containing an emulsion of a modified silicone can be easily obtained by simultaneously adding and emulsifying the softening agent for clothing in an emulsifying / dispersing step, and thus completed the present invention. It was

In order to solve the above problems, the present invention provides the following modified silicone emulsion, softening agent for clothing and a method for producing the same.

According to the first aspect of the present invention, (a) a modified silicone that gels when contacted with water, (b) an organic solvent,
(C) A modified silicone emulsion obtained by mixing and dissolving a cationic surfactant and / or a nonionic surfactant, and emulsifying and dispersing in water. The invention of claim 2 is a softening agent for clothing, which comprises the modified silicone emulsion of claim 1. The invention of claim 3 mixes and dissolves (a) a modified silicone that gels when contacted with water, (b) an organic solvent, and (c) a cationic surfactant and / or a nonionic surfactant, This mixed solution is emulsified in (i) a separately prepared soft base dispersion for clothing or an emulsified dispersion concentrate of a soft base for clothing, or (ii) in an emulsification / dispersion step of a soft base for clothing. A softening agent for clothing, which is obtained by simultaneously adding and emulsifying. The invention of claim 4 mixes and dissolves (a) a modified silicone that gels when contacted with water, (b) an organic solvent, and (c) a cationic surfactant and / or a nonionic surfactant, This mixed solution is mixed with (i) a modified silicone emulsion obtained by emulsifying and dispersing in water with a flexible base dispersion for clothing or an emulsion dispersion concentrate of a soft base for clothing, or (ii) separately prepared clothing Softening agent dispersion or emulsifying dispersion concentrate of softening agent for clothing, or (iii) softening agent for clothing characterized by being simultaneously added to the emulsifying and dispersing step of the softening agent for clothing and emulsifying It is a method of manufacturing a finishing agent.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. <Modified Silicone Emulsion> The modified silicone emulsion of the present invention comprises (a) a modified silicone that gels when contacted with water, (b) an organic solvent, (c) a cationic surfactant and / or a nonionic surfactant. It is obtained by mixing and dissolving and and emulsifying and dispersing in water.

The modified silicone, which is gelled when it comes into contact with water as the component (a) and is difficult to emulsify, has an increased viscosity and gels when mixed with water. Considering from this property, it is at least hydrophilic. It has been modified with a functional group of. As the hydrophilic functional group, a polyether group such as a polyoxyethylene chain or a polyoxypropylene chain,
An amino group etc. are mentioned. Regarding the arrangement of the functional groups in the silicone skeleton, the repeating units may have a structure of a block copolymer in which each repeating unit is arranged in a block form, or of a random copolymer in which each repeating unit is randomly arranged. It may have a structure.

Examples of such modified silicones include polyether modified silicones, amino modified silicones, amino / polyether modified silicones, alkyl / polyether modified silicones, and amide / polyether modified silicones. Water-soluble modified silicone is not included because it does not cause gelation on contact with water.

As a specific example of the modified silicone that is difficult to emulsify when it comes into contact with water as the component (a), a polyether modified silicone manufactured by Toshiba Silicone Co., Ltd. (product numbers TSF4445, TSF4446, TSF446) is used.
0), polyether-modified silicone manufactured by Shin-Etsu Chemical Co., Ltd. (Part numbers KF353A, KF945A, KF601)
3, KF6015, KF6016, KF6017), polyether modified silicone (product number SH3775C, SH3775M, manufactured by Toray Dow Corning Silicone Co., Ltd.)
SH3772C, SH3748, SH3749), an amino-modified silicone (product number TS) manufactured by Toshiba Silicone Co., Ltd.
F4700, TSF4701, TSF4702, TSF
4703), amino-modified silicone manufactured by Toray Dow Corning Silicone Co., Ltd. (SF8417, BY16-82).
8, BY16-849, BY16-850), Toray Dow Corning Silicone Co., Ltd. alkyl aralkyl polyether modified silicone (product number SF8419), and the like. Among these, preferred is HLB
Is 3 to 8 and is a polyether-modified silicone.

The kinematic viscosity of the modified silicone as the component (a) is 100 to 100,000 mm ^{2 in} terms of handling property.
/ S is preferable, and more preferably 100 to 5,0.
It is 00 mm ² / s.

The proportion of the modified silicone as the component (a) in the emulsion is 1% by mass to 50% by mass, preferably 5% by mass to 40% by mass, more preferably 10% by mass to 3%.
It is 0 mass%. If the blending ratio of the modified silicone as the component (a) is too large, aggregation and separation may occur and the stability may deteriorate, while if it is too small, the economical efficiency may deteriorate.

As the organic solvent of the component (b),
There is no particular limitation as long as it is compatible with the modified silicone as the component (a), but in consideration of its use as a softening agent for clothing, it should be avoided that it is highly harmful to the human body. Depending on the type of modified silicone, it is preferable to combine an organic solvent compatible with this modified silicone.

Specific examples of the organic solvent as the component (b) include lower alcohols such as ethanol, isopropyl alcohol and propyl alcohol, propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol, sorbitol and sugar. Examples include polyhydric alcohols such as alcohol. Of these, ethanol and isopropyl alcohol are preferable.

The compounding ratio of the organic solvent of the component (b) to the modified silicone of the component (a) is a mass ratio of the modified silicone of the component (a) / the organic solvent of the component (b) = 100 /
5-100 / 100, preferably 100 / 30-100
/ 80, and more preferably 100/40 to 100/60. If the blending ratio of the organic solvent of the component (b) is too large, the economical efficiency may deteriorate, while if it is too small, the modified silicone may gel during emulsification.

Among the cationic surfactants and / or nonionic surfactants as the component (c), the cationic surfactants include quaternary ammonium salts represented by the following general formula (I), and the following general formulas: Examples include neutralized products of amines represented by the formula (II), neutralized products of imidazolines represented by the following general formula (III), imidazolinium salts, and amino acid-based cationic surfactants. The seeds may be used alone or in combination of two or more.

[0025]

[Chemical 1] [However, in the formula, at least one group and three or less groups of R ^{1 to} R ⁴ are an alkyl group or an alkenyl group having 10 to 26 carbon atoms, and even if it is unsubstituted, -O-,- CO
It may be divided by a functional group such as NH-, -NHCO-, -COO-, -OCO- or substituted by a functional group such as -OH. The remaining groups of R ^{1 to} R ⁴ are an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or — (CH
During _{2 -CH (Y) -O) n} -H ( wherein, Y is hydrogen atom or CH _3, n is group or a benzyl group represented by a is) number of 2 to 10, X is a halogen It is an atom or a monoalkyl sulfate group. ]

[0026]

[Chemical 2] [However, in the formula, at least one group and two or less groups of R ^{5 to} R ⁷ are an alkyl group or an alkenyl group having 10 to 26 carbon atoms, and even if it is unsubstituted, -O-,- CO
It may be divided by a functional group such as NH-, -NHCO-, -COO-, -OCO- or substituted by a functional group such as -OH. The remaining groups of R ^{5 to} R ⁷ are an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or — (CH ₂ —C
_{H (Y) -O) n -H} ( wherein, Y is a hydrogen atom or CH ₃
And n is a number of 2 to 10). ]

[0027]

[Chemical 3] [Wherein, R ⁸ is an alkyl or alkenyl group having 10 to 26 carbon atoms, and even if it is unsubstituted, -O-,-
It may be divided by a functional group such as CONH-, -NHCO-, -COO-, -OCO- or substituted by a functional group such as -OH. R ⁹ is R ⁸ or an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or — (CH ₂ —CH
(Y) _-O) n -H (wherein, Y is hydrogen atom or CH _3, n is a group represented by a number of 2 to 10). ]

Specific examples of the quaternary ammonium salt of the general formula (I) include octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, tallow trimethylammonium chloride, coconut oil trimethylammonium chloride, octyldimethylbenzyl. Ammonium chloride, decyldimethylbenzylammonium chloride, dioctadecyldimethylammonium chloride, distearoyloxyethyldimethylammonium chloride, dioleoyloxyethyldimethylammonium chloride, N-stearoyloxyethyl-N-, N-dimethyl-N- (2- Hydroxyethyl) ammonium methylsulfate, N, N-distearoyloxyethyl-N-methyl- - (2-hydroxyethyl) ammonium methylsulfate,-N-N-oleoyl-oxyethyl, N- dimethyl-N-(2-hydroxyethyl) and ammonium methylsulfate and the like,
These 1 type can be used individually or in combination of 2 or more types.

For neutralizing the amine of the general formula (II) or the imidazoline of the general formula (III), a usual acid can be used. Specific examples of the acid include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and organic acids such as benzoic acid, citric acid, malic acid, succinic acid and acrylic acid.

Examples of the neutralized product of the amine include distearylmethylamine hydrochloride, dioleylmethylamine hydrochloride, distearylmethylamine sulfate, N- (3
-Octadecanoylaminopropyl) -N- (2-octadecanoyloxyethyl-N-methylamine hydrochloride and the like can be mentioned, and one of these can be used alone or two or more can be used in combination.

Specific examples of the imidazoline salt include 1
-Octadecanoylaminoethyl-2-heptadecyl imidazoline hydrochloride, 1-octadecenoylaminoethyl-2-heptadecenyl imidazoline hydrochloride and the like. Examples of the imidazolinium salt include methyl-1-
Beef tallow amide ethyl-2-beef tallow alkylimidazolinium methylsulfate, methyl-1-hexadecanoylamidoethyl-2-pentadecylimidazolinium chloride, ethyl-1-octadecenoylamidoethyl-2
-Heptadecenyl imidazolinium ethyl sulphate and the like. These may be used alone or in combination of two or more.

Among these cationic surfactants, mono-long-chain alkyltri-short-chain alkyl type quaternary ammonium salts are preferable from the viewpoint of emulsifying power.

Among the cationic surfactants and / or nonionic surfactants as the component (c), the nonionic surfactants are generally polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl Examples include ethers, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, and the like. HLB of these nonionic surfactants is
About 8 to 20 is suitable for the purpose of forming an emulsion.

Specific examples of such nonionic surfactants include hexaglyceryl monolaurate, decaglyceryl monolaurate, decaglyceryl monostearate, decaglyceryl monoisostearate, decaglyceryl diisostearate, and POE (1 monooleate).
5) Glyceryl, POE (20) monoisostearate
Sorbitan, monococonut oil fatty acid POE (20) sorbitan, monooleic acid POE (20) sorbitan, trioleic acid POE (20) sorbitan, tetraoleic acid POE (40) sorbit, tetraoleic acid POE
(60) Sorbit, POE (40) Castor oil, POE
(50) Castor oil, POE (40) Hardened castor oil, PO
E (60) hydrogenated castor oil, POE (100) hydrogenated castor oil, polyethylene glycol monostearate (25E
O), polyethylene glycol monostearate (40
EO), POE (20) cetyl ether, POE (3
0) cetyl ether, POE (40) cetyl ether,
POE (20) oleyl ether, POE (20) isodecyl ether, POE (60) isohexadecyl ether, POE (40) isotridecyl ether, POE
(50) Isotridecyl ether, POE (20) behenyl ether, POE (25) octyldodecyl ether, POE (20) POP (4) cetyl ether, PO
E (7.5) nonylphenyl ether, POE (15)
Nonyl phenyl ether, POE (15) stearylamine, POE (15) stearic acid amide, etc. are mentioned, and these 1 type can be used individually or in combination of 2 or more types.

The total amount of the cationic surfactant and / or nonionic surfactant as the component (c) is
The compounding ratio of the component (a) to the modified silicone is, in mass ratio, the modified silicone of the component (a) / the surfactant of the component (c) = 100/1 to 100/100. When a modified silicone having a POE chain in the molecule is used, the compounding ratio by mass ratio of the modified silicone of the component (a) / the surfactant of the component (c) = 100/5 to 100/60 is preferable, and 100 / 10 to 100/50 is more preferable. When a modified silicone having an amino group in the molecule is used, the compounding ratio is (a) component modified silicone / mass ratio.
Component (c) surfactant = 100/30 to 100/10
0 is preferable, and 100/50 to 100/100 is more preferable. If the blending ratio of the surfactant of the component (c) is too large, the economical efficiency may be deteriorated, while if it is too small, the modified silicone may gel during emulsification.

When the modified silicone emulsion of the present invention is produced, the components (a), (b) and (c) are mixed and dissolved. In this case, the mixing and dissolving conditions are not particularly limited and are generally Various mixing conditions are acceptable. The mixing temperature varies depending on the melting points of the cationic surfactant and / or nonionic surfactant used, but is usually room temperature to about 50 ° C. Moreover, when using an organic solvent that is easily volatilized, a temperature as low as possible is preferable. The mixing device may be a general stirring tank equipped with a propeller blade and a paddle blade,
A continuous mixer such as a static mixer may be used.

The mixed solution obtained by mixing and dissolving the components (a), (b) and (c) is then emulsified and dispersed in the aqueous phase. Usually, a high-shear type emulsifying device such as a homomixer, an ultramixer, a fill mix, a milder, and a clear mix is used for this emulsification dispersion, but in the present invention, the emulsification can be performed even at low shear. Here, low shear means
It is a level under stirring and shearing by propeller blades and paddle blades used in normal stirring operation. Shear force is the shear rate that normally occurs between a fixed wall and a moving wall. Considering a stirring tank, the tank wall is regarded as the fixed wall and the tip of the stirring blades as the moving wall. Is defined by the formula

<Equation 1> Shear velocity γ = 2π × n × d / (D−d) Unit [1 / s] (where n is blade rotation speed [rps], d is blade diameter [m], and D is It is the stirring tank diameter [m].)

When the high shear level is specifically shown by using the above shear rate, the length of the clearance between the blade and the wall varies depending on the size of the apparatus, but it is 10000 on a laboratory scale.
(1 / s) to 160000 (1 / s), which is 10
000 (1 / s) or less is a medium shear level, and at low shear, the shear rate is 150 (1 / s) or less. Further, the lower limit of the shear rate is, from the viewpoint of flowing the whole liquid,
It is about 5 (1 / s). Further, when a stirring tank equipped with a propeller blade or a paddle blade is used, a baffle plate may be installed to increase the mixing power. In the present invention, it is possible to emulsify without problems not only with high shear but also with low shear, and the emulsification work can be performed simply and efficiently.

Water is mainly used as the water phase component in the emulsification, but as long as the object and effect of the present invention are not impaired, antibacterial agents, antiseptics, bactericides, pH adjusters, pigments, and antioxidants. Agents, inorganic salts, organic acid salts and the like can be arbitrarily mixed. Also,
The components used in the fabric softening agent may be preliminarily mixed in the water phase.

The modified silicone emulsion thus prepared has a semi-transparent to cloudy appearance and no floating separation of the modified silicone is observed. In addition, a transparent emulsion may be obtained depending on the type and blending ratio of the surfactant. The viscosity of the emulsion is affected by the concentration of modified silicone and the type of surfactant, but it is several mPa · s to 5000 mPa at room temperature.
・ It is a level with good handling property of about s.

The volume average particle diameter of the modified silicone emulsion is about 0.01 μm to 10 μm. Considering its use as a softening agent for clothing, it is about 0.01 μm to 5 μm from the viewpoint of preventing separation. It is more preferably about 0.01 μm to 1 μm.

As described above, the modified silicone emulsion of the present invention has a fine particle size and good handleability, and can be used alone as a fiber texture improving agent, a hair glossing treatment agent, etc. It can be easily mixed with liquid products such as agents and hair rinses.

<Softening agent for clothing and method for producing the same>
Next, a softening agent for clothes containing a modified silicone that gels when contacted with water and is difficult to emulsify, and a method for producing the same.

The softening agent for clothing is generally one in which a softening agent for clothing mainly containing a cationic surfactant such as dialkyldimethylammonium salt or dialkylmethylamine salt is emulsified in water. Its constituent components are a cationic surfactant, a low temperature stabilizer, a dispersion stabilizer, an antibacterial agent, a dye, a fragrance, water and the like.

Examples of the cationic surfactant include those described above in the section of emulsion formation of modified silicone. The amount of the cationic surfactant blended is about 3 to 45% by mass.

Examples of the low temperature stabilizer include lower alcohols such as ethanol and isopropanol, and polyhydric alcohols such as ethylene glycol and propylene glycol. In addition, the compounding amount of the low temperature stabilizer is 0 to 1.
It is about 0 mass%.

Examples of the dispersion stabilizer include the nonionic surfactants and water-soluble polymers described in the section of the emulsion formation of the modified silicone. The blending amount of the dispersion stabilizer is about 0.1 to 5% by mass.

In addition, an antibacterial agent, an antiseptic agent, a bactericidal agent, an inorganic acid (or salt), an organic acid (or salt), a dye, a fragrance and the like can be added in an appropriate amount. Among these components, it is preferable that the strongly oily component is dissolved in the oil phase mainly containing the cationic surfactant and the strongly aqueous component is dissolved in the water phase mainly containing water.

In the present invention, further, (a) a modified silicone that gels when contacted with water and is difficult to emulsify is added. The blending amount of the component (a) is preferably about 0.1 to 5% by mass, and more preferably about 0.5 to 3% by mass based on the total amount of the modified softener for clothing, based on the total amount of the modified silicone. is there. If the amount of the modified silicone as the component (a) is too small, the effect may not be sufficiently exerted, while if it is too large, the amount of the organic solvent required for the modified silicone emulsification increases, resulting in aggregation and separation of particles. It may happen.

Here, the method for producing a fabric softener of the present invention comprises: (a) a modified silicone which gels when contacted with water; (b) an organic solvent; (c) a cationic surfactant and / or Alternatively, a modified silicone emulsion obtained by first mixing and dissolving a nonionic surfactant and then emulsifying and dispersing the mixed solution in water is used as a soft base dispersion for clothing or an emulsified dispersion concentration of a soft base for clothing. Mix with the liquid, or second,
Emulsified in a separately prepared soft base dispersion for clothing or an emulsified dispersion concentrate of a soft base for clothing, or thirdly,
It can be produced by three methods of simultaneously adding and emulsifying in the emulsifying and dispersing step of the soft base material for clothing.

The first method for producing a fabric softener is as follows:
The modified silicone emulsion of the present invention is prepared by separately preparing an emulsified dispersion of a soft base for clothing mainly composed of a dialkyldimethylammonium salt, a dialkylmethylamine salt or the like or a concentrated emulsified dispersion of a soft base for clothing with reduced water. It is to be mixed with liquid. In this case, the mixing conditions are mixing emulsions, so no special equipment is required,
Using a continuous mixing device such as a general stirring tank or static mixer equipped with propeller blades and paddle blades,
It can be performed under general conditions.

The second method for producing a fabric softening agent is as follows:
A mixture of (a) a modified silicone that gels when contacted with water and is difficult to emulsify, (b) an organic solvent, and (c) a cationic surfactant and / or a nonionic surfactant is prepared in advance by a dialkyldimethylammonium salt or It is emulsified in an emulsified dispersion of a soft base for clothing which contains a dialkylmethylamine salt or the like as a main component or a concentrated dispersion of a soft base for clothing in which water is reduced. In this case, the emulsification conditions can be performed under high shear or low shear based on the above modified silicone emulsion forming conditions, and the degree of shearing force is
The same level is obtained using the shear rate as an index. The emulsification temperature varies depending on the melting point of the cationic surfactant and / or nonionic surfactant of the component (c) used,
It is usually at room temperature to about 50 ° C. It should be noted that when using an organic solvent that easily volatilizes, the temperature is preferably as low as possible.

A third method for producing a fabric softener is as follows:
A step of emulsifying and dispersing a soft base material for clothing by using a mixture of (a) a modified silicone that gels when contacted with water and is difficult to emulsify, (b) an organic solvent, and (c) a cationic surfactant and / or a nonionic surfactant. Is added at the same time to emulsify. The emulsifying and dispersing step of the soft base material for clothes is described in JP-A-63 / 1988.
The methods described in JP-A-143935, JP-A-5-310660 and the like can be used.

Specifically, the oil phase containing the soft base material for clothing is emulsified and dispersed in the aqueous phase under high shear. Examples of the high shear emulsifying device used at this time include a homomixer, a milder, a clear mix, a fill mix, an ultra mixer, a line mixer, a becomix, and a lexamix. The emulsification temperature is preferably not less than the phase transition temperature of the cationic surfactant used, but the high shear level is high,
When an oil phase addition nozzle is provided in the immediate vicinity of the blade,
Emulsification is possible even below the phase transition temperature of the cationic surfactant used.

In the case of continuous production, (a) a modified silicone which gels when contacted with water and is difficult to emulsify, (b) an organic solvent, and (c) a cationic surfactant and / or a nonionic surfactant. A method is preferred in which the mixture is used as the first fluid and the oil phase containing the cationic surfactant as the second fluid is simultaneously introduced into a high shear emulsifying machine together with the aqueous phase to emulsify and disperse.

In the case of batch production, it is preferable to introduce two oil phases into a high shear emulsifying machine at the same time to emulsify and disperse them, as in the above continuous method, but it is preferable to use a mixture containing the above modified silicone. The order of emulsification with the oil phase containing the cationic surfactant is not particularly limited. After emulsifying and dispersing, an aqueous solution of an inorganic salt for reducing the viscosity, an aqueous solution of a water-soluble polymer for stabilization, or a dye water may be added.

The softening agent for clothing of the present invention thus obtained has a liquid viscosity of several mPa · s to several hundreds.
It is mPa · s. Although the modified silicone emulsion and the emulsified particles of the soft base differ in the existence form depending on the manufacturing method, it is considered that they are either in a dispersed state or both are adsorbed and integrated. To be

The fabric softening agent of the present invention is capable of imparting good smoothness to clothes, reducing the formation of wrinkles formed in the washing step, and preventing the clothes from losing their shape. is there.

[0060]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Examples 1 to 17, Comparative Examples 1 and 2] Table 1,
2, (a) modified silicone, (b) organic solvent,
(C) The cationic surfactant and / or the nonionic surfactant were mixed at the same temperature as the emulsification temperature in Tables 1 and 2 to form an oil phase. At this time, the appearance of the oil phase was transparent to slightly cloudy. Separately, add the water phase to a 200 mL beaker, and
It was adjusted to the same temperature as the emulsification temperature of 2. Next, 38 mmφ
The oil phase was emulsified in the water phase under the shear rate conditions of Tables 1 and 2 for the oil phase addition time of Tables 1 and 2 by using the propeller blade of.

The obtained emulsions were allowed to cool to room temperature, and then the appearance, liquid viscosity and average particle diameter were measured by the following methods. The results are also shown in Tables 1 and 2.

<Evaluation Method> The appearance was visually judged.
The liquid viscosity was measured using a BL type rotational viscometer. 2 rotors,
The value of the 10th rotation was recorded under the condition of 30 rotations. The average particle size of the cloudy state was determined by comparison with a scale using a phase contrast microscope, and the transparent to semitransparent state was measured using a Microtrac UPA particle size distribution analyzer manufactured by Nikkiso Co., Ltd.

[0064]

[Table 1]

[0065]

[Table 2] * 1: SH3 manufactured by Toray Dow Corning Silicone Co., Ltd.
775 * 2: Shin-Etsu Chemical Co., Ltd. KF945A * 3: Toshiba Silicone Co., Ltd. TSF4460 * 4: Toray Dow Corning Silicone Co., Ltd. SF8
417

From the results shown in Tables 1 and 2, the modified silicone which is gelled and hard to emulsify when contacted with the component (a) water,
A modified silicone emulsion obtained by mixing the organic solvent of the component (b) with the cationic surfactant and / or the nonionic surfactant of the component (c) even under low shear at a shear rate of 100 (1 / s) or less. Is obtained.

On the other hand, in the case of emulsifying a mixture of (a) a modified silicone, which gels when contacted with water and is difficult to emulsify, and (b) only an organic solvent, under low shear (Comparative Example 1).
As for the modified silicone, an emulsion was not obtained because the modified silicone gelled. When a mixture of (a) a modified silicone that gels when contacted with water and is difficult to emulsify and (c) only a cationic surfactant and / or a nonionic surfactant is emulsified under low shear (Comparative Example 2 ), The viscosity of the oil phase was high, and it was immediately separated due to poor emulsification.

[Examples 18 to 20] (a) shown in Table 3
A modified silicone that gels when contacted with water and is difficult to emulsify, (b) an organic solvent, and (c) a cationic surfactant and / or a nonionic surfactant are mixed at the same temperature as the emulsification temperature in Table 3. The oil phase was used. This oil phase was emulsified by using the emulsification device of Table 3 to the aqueous phase previously charged in the device under the shear rate condition of Table 3 for the oil phase addition time of Table 3.

The appearance, liquid viscosity, and average particle size of each emulsion thus obtained were measured in the same manner as in Examples 1-17. The results are also shown in Table 3.

[0070]

[Table 3] * 1: SH3 manufactured by Toray Dow Corning Silicone Co., Ltd.
775

From the results shown in Table 3, the modified silicone which is gelled and hard to emulsify when contacted with water as the component (a), the organic solvent as the component (b), and the cationic surfactant and / or nonion as the component (c). It has been found that a good modified silicone emulsion can be formed even under high shearing force by mixing with a hydrophilic surfactant. Further, from the results of Tables 1 to 3, it is recognized that the modified silicone emulsions of the examples according to the present invention can be easily emulsified with water under any conditions of high shearing force or low shearing force.

[Example 21] 10 parts by mass of the modified silicone emulsion of Example 2 was added to 90 parts by mass of a commercially available fabric softening agent Soflan C manufactured by Lion Co., Ltd. at room temperature with paddle stirring and mixed. , A softening agent for clothing was prepared. The liquid viscosity of the obtained softening agent for clothing was 60 mPa · s at room temperature.

Example 22 The modified silicone emulsion of Example 5 and a commercially available fabric softening agent Lion Co., Ltd. Soflan C were mixed in a mass ratio of 10:90 at room temperature using a static mixer. A fabric softener was prepared. The liquid viscosity of the obtained softening agent for clothing was 50 mPa · s at room temperature.

Example 23 Polyether-modified silicone (SH377 manufactured by Toray Dow Corning Silicone Co., Ltd.)
5C) 8g, ethanol 4g, and monostearyl trimethyl ammonium chloride 4g were mixed at 40 degreeC, and the oil phase was prepared. Separately, a commercially available softening agent for clothing, 384 g of Soflan C manufactured by Lion Co., Ltd., was placed in a 500 mL beaker and the temperature was set to 35 ° C. While mixing the liquid at 400 rpm using a 55 mm inclined four-blade paddle blade,
The oily phase was gradually added from the upper surface over 2 minutes to emulsify to obtain a fabric softening agent. The liquid viscosity of the obtained softening agent for clothing was 70 mPa · s.

[Example 24] Polyether-modified silicone (SH377 manufactured by Toray Dow Corning Silicone Co., Ltd.)
5C) 1 part by mass, ethanol 0.3 parts by mass, and monostearyl trimethyl ammonium chloride 0.3 parts by mass were mixed at 40 ° C. to prepare an oil phase 1. Separately, 5 parts by mass of distearyldimethylammonium chloride (Arcard 218P manufactured by Lion Corporation, cation content 75%), 2 parts by mass of ethylene glycol, and 0.2 parts by mass of floral fragrance were mixed at 45 ° C. to obtain an oil phase. I prepared 2. Further, 80 parts by mass of purified water and calcium chloride 0.0
An aqueous phase was prepared by mixing 1 part by mass, 0.5 part by mass of POE (40) isotridecyl ether as a dispersion stabilizer, an antibacterial agent: a trace amount, and a dye: a trace amount at 35 ° C. These are oil phase 1: oil phase 2: water phase = 1.8: 8.0: 90.2
To prepare the softening agent for clothing by adding a nozzle to the oil phase 1 and the oil phase 2 at the same time with a line homomixer having a blade diameter of 25 mm and adding oil to the oil phase 1 and oil phase 2 at a rotation speed of 7,000 rpm so that did. The liquid viscosity of the obtained softening agent for clothing was 120 mPa · s at room temperature.

<Evaluation> Using the fabric softening agent obtained in Example 21, a polo shirt was washed and finished under the conditions of a temperature of 25 ° C., a bath ratio of 1/20 and a liquid input amount of 600 ppm, and was dehydrated and air dried. Then, the appearance of the polo shirt was evaluated, and 9 out of 10 panelists obtained an evaluation that the wrinkle was small and the shape was not lost.

Using the fabric softening agent obtained in Example 24, a polo shirt was washed and finished under the conditions of a temperature of 25 ° C., a bath ratio of 1/20, and a liquid amount of 1500 ppm, and the same procedure as above was carried out. As a result of evaluation, 9 out of 10 panelists evaluated that the washing wrinkle was small and the shape was not lost.

[0078]

As described above, according to the modified silicone emulsion of the present invention, the particle size is fine and the handling property is good, and it can be used alone as a fiber texture improving agent, a hair gloss treating agent and the like.

Further, the modified silicone emulsion of the present invention can be easily mixed with other softening agents for clothes and liquid products such as hair rinses. Furthermore, by using the method for producing a modified silicone emulsion of the present invention, a softening agent for clothing in which a modified silicone emulsion is dispersed can be obtained by a simple method.

The thus obtained softening agent for clothing of the present invention, in addition to imparting good smoothness to clothing, reduces the formation of wrinkles formed by the washing step,
It has the effect of preventing the clothes from losing their shape.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F070 AA60 AB01 AB05 AB08 AB13                       AC43 AC45 AC46 AC50 AC84                       AC96 AE14 CA01 CB01 CB13                 4J002 CH052 CP031 CP091 CP181                       EN016 EN136 EU106 FD312                       FD316 GK02 HA07                 4L033 AB04 AC02 CA59

Claims (4)

[Claims] 1. A mixture of (a) a modified silicone that gels when contacted with water, (b) an organic solvent, and (c) a cationic surfactant and / or a nonionic surfactant, which are dissolved in water. A modified silicone emulsion obtained by emulsion-dispersion. 2. A softening agent for clothing, which comprises the modified silicone emulsion according to claim 1. 3. A modified silicone that gels when contacted with water, (b) an organic solvent, and (c) a cationic surfactant and / or a nonionic surfactant are mixed and dissolved, and this mixture is mixed. The solution is emulsified in (i) a separately prepared soft base dispersion for clothing or a concentrated emulsification dispersion of soft base for clothing, or (ii) added simultaneously to the emulsification / dispersion step of the soft base for clothing. A softening agent for clothing, characterized by being obtained by emulsification. 4. A mixture of (a) a modified silicone which gels when contacted with water, (b) an organic solvent, and (c) a cationic surfactant and / or a nonionic surfactant, which are mixed and dissolved. The dissolved product is mixed with (i) a modified silicone emulsion obtained by emulsifying and dispersing in water, a flexible base dispersion for clothing or an emulsion dispersion concentrate of a soft base for clothing, or
(Ii) emulsification in a separately prepared soft base dispersion for clothing or a concentrated emulsion dispersion of soft base for clothing, or (iii) emulsification by simultaneously adding to the emulsification / dispersion step of soft base for clothing. A method for producing a fabric softener, comprising: