JP5186672B2 - Method for producing oil-in-water silicone emulsion - Google Patents

Description

  The present invention relates to a method for producing an oil-in-water silicone emulsion that can be applied to textiles such as clothing and hair and to impart flexibility. Specifically, a method for producing an oil-in-water silicone emulsion, which comprises emulsifying after mixing a specific solvent and water in a specific ratio with silicone that gels when contacted with water, and using the oil-in-water silicone emulsion The present invention relates to a method for producing a softener for clothing.

  Silicone is a substance useful for preparing a fabric softener, rinse, and conditioner, but some silicones have the property of gelling when contacted with water. Conventionally, oil-in-water silicone emulsions used as clothing softeners, hair rinses, treatments, etc. are mixed with silicone and a cationic surfactant, and then mixed with the mixture and a part of the aqueous phase to form a hard liquid crystal. Since it is manufactured by a method of forming, it is necessary to use a special emulsifier under high shear and high temperature conditions, and it is difficult to say that this is a general-purpose technique.

JP 2003-105091 A

  Therefore, an object of the present invention is to provide a method for easily producing an oil-in-water silicone emulsion.

As a result of intensive studies by the present inventors, even when a modified silicone gels when it comes into contact with water, a fine oil-in-water silicone is obtained when a specific solvent is previously dissolved in the modified silicone in a specific ratio and then emulsified. The inventors found that an emulsion was obtained and completed the present invention.
That is, the present invention includes (a) a modified silicone that gels when contacted with water, (a) a modified silicone and a water-soluble (b) solvent, and a mass ratio of (b) and (a) ( b) / (a) is added within a range of 0.25 or more, and both are mixed to prepare (A) a mixed solution;
(C) Water is added to and mixed in the mass ratio (c) / (b) of 0.05 to 4 to (c) water and (b) solvent to the obtained (A) mixed solution. (B) preparing a mixed solution by
And (C) a step of forming an oil-in-water emulsion by adding (d) an aqueous component to the obtained mixed solution (B) and mixing;
(C) A method for producing an oil-in-water silicone emulsion is provided.
The present invention also provides (E) a softener for clothing obtained by the above production method.

  According to the present invention, (C) the oil-in-water silicone emulsion can be easily produced without using a special apparatus. (C) The oil-in-water silicone emulsion (C) obtained by the production method of the present invention is free from the presence of large particles having a large particle size, in which the component (a) is locally gelled, and the appearance and storage stability are small. Excellent.

(A) Component (a) Modified silicone that gels when contacted with water, which can be used in the present invention, is a viscosity after adding water in an amount corresponding to 10% of the mass of the modified silicone and mixing sufficiently. (BH type viscometer, No. 7 rotor, 2 rpm, 150 sec, 25 ° C.) refers to the one that rises 10 times or more before water is added and causes gelation. The modified silicone acts on fibers such as clothing and hair, and imparts wrinkle prevention and slipperiness. Specific examples include silicones modified with hydrophilic functional groups (EO ethylene oxide, amino, cation, etc.). In particular, the modified silicone is preferably a polyether-modified silicone. Such a modified silicone can be produced by a known method, or a commercially available one can be used. As a commercial item, what is marketed by Toray Dow Corning Silicone Co., Ltd. by the brand name CF1188HV is mentioned, for example.
A polyether-modified silicone is more preferred. 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 10 —O—X—R 11 or —O—X—R 11, R 10 is a C 1-4 saturated or unsaturated linear or branched hydrocarbon group, and R 11 is a hydrogen atom. Or it is a C1-C4 saturated or unsaturated linear or branched hydrocarbon group. 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 above formula, -Z1 and -Z2 are preferably each independently -R and -OH, and more preferably -R. R is preferably a short-chain saturated hydrocarbon group having 1 to 4 carbon atoms, and particularly preferably a methyl group. R10 is preferably a short-chain saturated hydrocarbon group having 1 to 4 carbon atoms, and preferably a propylene group. When R11 is a hydrocarbon group, a short-chain saturated hydrocarbon group having 1 to 4 carbon atoms is preferred. Particularly preferred R11 is a hydrogen atom or a methyl group.

In the above formula, X represents a polyoxyalkylene group, but an oxyethylene unit, an oxypropylene unit, an oxybutylene unit or the like may be arranged in a block shape 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 (VI), 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 above formula may have a block copolymer structure in which each repeating unit is arranged in a block shape, and has a structure in which each repeating unit is randomly arranged. It may be a thing.
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 or an emulsion, and may be used as a dispersion when a silicone elastomer powder is used. Moreover, it can be used alone or as a mixture of two or more.

The component (a) is preferably contained in an amount of 0.1 to 50% by mass, based on the total amount of the (C) oil-in-water silicone emulsion obtained by the production method of the present invention, and 0.5 to 30% by mass. It is more preferable that it is contained in an amount of%, and it is further more preferable that it is contained in an amount of 1 to 25% by mass.
When the amount of the component (a) is less than 0.1% by weight, the effect of preventing wrinkles and the effect of imparting slipperiness when used as a softening agent may be insufficient. When the amount of the component (a) is more than 50% by weight, the viscosity of the (C) oil-in-water silicone emulsion becomes high, and the dispersibility in water may deteriorate during use or handleability may deteriorate.

(B) Component The (b) solvent that can be used in the present invention is soluble in any proportion of (a) modified silicone that gels when contacted with water and water. Specifically, carbon number 2 such as lower alcohol having 1 to 4 carbon atoms such as methanol, ethanol, isopropyl alcohol and propyl alcohol, propylene glycol, ethylene glycol, 1,3-butylene glycol, dipropylene glycol and diethylene glycol monobutyl ether. And polyhydric alcohol having 2 to 6 hydroxyl groups. Of these, lower alcohols having 1 to 4 carbon atoms are preferable from the viewpoints of economy, safety to human bodies, and the environment, and ethanol and isopropyl alcohol are particularly preferable.
As the component (a), when polyether-modified silicone is used, ethanol and diethylene glycol monobutyl ether are particularly preferable.

  In the present invention, by adding the component (b) to the component (a) and mixing both, the component (a) can be present in the solvent in a fine state, and the component (a) is added to the aqueous phase. It can be finely emulsified. By mixing (a) component and (b) component in a mass ratio of (b) / (a) = 0.25 or more, preferably 0.3 or more, the (a) component is sufficiently fine. It can be in a state. Even if the component (b) is used in a large amount, the concentration of the component (a) becomes low and lacks economic efficiency, so it is preferably 10 or less, more preferably 5 or less.

(D) Component The (d) aqueous component for preparing the (C) oil-in-water silicone emulsion that can be used in the present invention serves to disperse the (B) mixed solution. Specific examples include water, an aqueous solution containing a water-soluble component, and an oil-in-water emulsion. As an aqueous solution containing a component soluble in water, other optional components described later are soluble in water, and the oil-in-water emulsion contains (f) a cationic surfactant. (D) Aqueous composition Thing etc. are mentioned.

(E) Component In the present invention, from the viewpoint of preventing phase separation of the (C) oil-in-water silicone emulsion, it is preferable to add (e) a nonionic surfactant to the (A) mixed solution. (E) Nonionic surfactant can also be mixed with (a) component after adding to (b) component. The (e) nonionic surfactant that can be used in the present invention can be used without particular limitation as long as it is usually blended in a softener for clothing, hair rinse, treatment, and the like. Nonionic surfactants derived from alcohols, higher amines, fats and oils or higher fatty acids can be used. Of these, alkylene oxide adducts of higher alcohols are preferred.

The higher alcohol constituting the alkylene oxide adduct of the higher alcohol may be primary or secondary, and the long-chain hydrocarbon chain portion may be branched or linear, may be unsaturated, and has a carbon chain length. There may be a distribution. 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.
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 10 to 10. 100 is preferable, and more preferably 10 to 80 mol.

  Specific examples of alkylene oxide adducts of higher alcohols include average EO 20 mol adduct of lauryl alcohol, average EO 20 mol adduct of primary isodecyl alcohol, average EO 40, 45 or 60 mol adduct of primary isotridecyl alcohol, primary Examples include an average EO 60 mol adduct of isohexadecyl alcohol, an average EO 60 mol adduct of beef tallow alkylamine, and an average EO 30 mol adduct of lauric acid. Among these, an average EO45 mole adduct of isotridecyl ether, a 60 mole adduct, and an average EO 60 mole adduct of primary isohexadecyl alcohol are preferable, and an average EO45 mole adduct of isotridecyl ether is particularly preferable.

Specific examples include AAO series, Leox series and TA series of Lion Chemical Co., Ltd., Emulex series of Nippon Emulsion Co., Ltd., Emalmin series of Sanyo Chemical Co., Ltd., TDA series and Esomin series of Lion Chemical Co., Ltd. , Nippon Shokubai's Softanol series, BASF's Lutensol series, and the like can be used. In addition, the above-mentioned compound contains alcohol and amine as raw materials, polyalkylene glycol such as polyethylene glycol, polypropylene glycol, polybutylene glycol and the like as an unreacted component in a nonionic surfactant at 10% by mass or less. Also good. They can be used alone or as a mixture of two or more.
The component (e) is preferably included in an amount of 0.01 to 10% by mass, based on the total amount of the (C) oil-in-water silicone emulsion obtained by the production method of the present invention. More preferably it is included in an amount. When the amount of the component (e) is less than 0.01% by weight, the (C) oil-in-water silicone emulsion may phase-separate over time. When the amount of the component (e) exceeds 10% by weight, the production cost becomes high.

  When (c) water is added to (A) mixed solution obtained by mixing (a) component and (b) component, water phase formed from (c) water and (b) component However, the water-in-oil emulsion that is dispersed in the oil phase formed from the component (a) and the component (b), the component (a), the component (b), and the component (c) are all continuous. A mixed solution (B) having a bicontinuous structure as a phase is obtained. At this time, (c) water and (b) component are set to mass ratio (c) / (b) = 0.05-4, preferably 0.1-4. (C) By adding water, the modified silicone that gels when it comes into contact with water can be uniformly gelled and then refined, and at the same time, the amount of component (b) can be reduced. The obtained (C) oil-in-water silicone emulsion has good storage stability and is economically advantageous. (C) By adjusting the amount of water so as to be in the above range, (a) the modified silicone that gels when contacted with water is refined, and the component (a) is locally gelled and becomes lumpy. Can be prevented.

Next, (C) an oil-in-water silicone emulsion is obtained by adding and mixing (d) an aqueous component to the obtained (B) mixed solution. The method for adding the component (d) is not particularly limited, and the component (d) may be added all at once, or may be added in several portions. Moreover, (d) component may be added to (B) mixed solution, and (B) mixed solution may be added to (d) component. Furthermore, in the case of divided addition, two or more kinds of the above component (d) may be added.
According to the present invention, the blending ratio of the component (a), the component (b), and the component (c) is specified and mixed in a specific order without using a cationic surfactant or the like. ) The component can be refined. Therefore, the blending amount of the component (d) is not particularly limited because it does not affect the particle size of the (C) oil-in-water silicone emulsion. However, the component (a) is not more than 0.00 on the basis of the total amount of the (C) oil-in-water silicone emulsion. It is desirable to control the amount of component (d) so that an amount of 1 to 50% by mass is included.

The smaller the median diameter of the (C) oil-in-water silicone emulsion obtained by the production method of the present invention, the better the storage stability. The thickness is preferably 200 nm or less, more preferably 100 nm or less, and particularly preferably 50 nm or less. When the median diameter exceeds 100 nm, the storage stability effect is not sufficient. In the present invention, the median diameter can be measured with a dynamic light scattering particle size distribution meter.
(C) The mixing operation in each step of preparing the oil-in-water silicone emulsion is mixing of uniform hydrophilic liquids, so no special equipment is required. Static mixer, propeller mixer, paddle mixer, Ajihomo mixer, Disper mixer For example, a known mixing apparatus can be used.
The silicone emulsion of the present invention is applied to (E) a softener for clothing by adding (D) an aqueous composition containing (f) a cationic surfactant to (B) the mixed solution and mixing them. Can do. The (f) cationic surfactant that can be used in that case is preferably a compound represented by the following general formulas (2) and (3).

[In the formula, one or more and three or less groups of R1 to R4 are alkyl groups or alkenyl groups having 12 to 26 carbon atoms, and even if they are unsubstituted, -O-, -CONH-, -NHCO It may be divided by a functional group such as —, —COO— or —OCO— or substituted with a functional group such as —OH. Among these, a C14-24 alkyl group and an alkenyl group are preferable, and the structure of the functional group to divide and to divide is not limited. The remaining groups of R1 to R4 are a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyalkyl group, or — (CH ₂ —CH (Y) —O) n—H (wherein Y is a hydrogen atom or CH ₃ And n is a number of 2 to 10) or a benzyl group, and among them, a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyalkyl group is preferable. X ⁻ is a halogen ion, a monoalkyl sulfate ion having 1 to 3 carbon atoms, or a fatty acid ion having 1 to 18 carbon atoms. ]

[In the formula, R8 is an alkyl or alkenyl group having 12 to 26 carbon atoms, and even if it is unsubstituted, it is a functional group such as —O—, —CONH—, —NHCO—, —COO—, —OCO—, etc. It may be divided or substituted with a functional group such as —OH. R9 is R8, an alkyl group having 1 to 3 carbon atoms or a hydroxyalkyl group, or — (CH ₂ —CH (Y) —O) n—H (wherein Y is a hydrogen atom or CH ₃ , and n is 2 Is a group of 10 to 10. ]

  Specific examples of the general formulas (2) and (3) include octyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, tallow trimethylammonium chloride, coconut oil trimethylammonium chloride, octyldimethylbenzylammonium chloride, decyldimethyl. Benzylammonium chloride, dioctadecyldimethylammonium chloride, distearoyloxyethyldimethylammonium chloride, dioleoyloxyethyldimethylammonium chloride, N-stearoyloxyethyl-N-, N-dimethyl-N- (2-hydroxyethyl) ammonium methyl Sulfate, N, N-distearoyloxyethyl-N-methyl-N- (2-hydroxyethyl) Ammonium methyl sulfate, N-oleoyloxyethyl-N-, N-dimethyl-N- (2-hydroxyethyl) ammonium methyl sulfate, distearylmethylamine hydrochloride, dioleylmethylamine hydrochloride, distearylmethylamine sulfate N- (3-octadecanoylaminopropyl) -N- (2-octadecanoyloxyethyl-N-methylamine hydrochloride, methyl-1-tallowamidoethyl-2-tallow alkylimidazolinium methyl sulfate, methyl- 1-hexadecanoylamidoethyl-2-pentadecylimidazolinium chloride, ethyl-1-octadecenoylamidoethyl-2-heptadecenylimidazolinium ethyl sulfate, 1-octadecanoylaminoethyl-2- Heptadecylimidazoli Hydrochloride, 1-like octadecenyl alkanoylamino ethyl-2-heptadecenyl imidazoline hydrochloride salts. These may be used alone or in admixture.

  (F) The compounding quantity of a cationic surfactant is 3-30 mass% with respect to (D) aqueous composition whole quantity, Preferably it is 5-25 mass%, More preferably, it is 10-20 mass%. If the amount of component (f) is too small, the preparation efficiency may be lowered. When there are too many compounding quantities, (D) aqueous composition viscosity will rise and (C) mixing with an oil-in-water type silicone emulsion may require time.

(D) In order to improve the dispersion stability of the (f) cationic surfactant in the aqueous composition, (e) a nonionic surfactant can be blended as necessary. (E) The compounding quantity of a component is 0.05 to 10 weight% with respect to (D) aqueous composition whole quantity, Preferably it is 0.1 to 5 weight%. (E) If the blending amount of the component is too small, the dispersion effect may not be sufficiently exhibited, and if it is too large, the component may gel during storage over time.
(D) The aqueous composition may contain (b) a solvent as a solvent of (f) a cationic surfactant. In this case, the ratio of the component (f) to the component (b) is preferably 10: 1 to 1: 1 by mass ratio, and more preferably 8: 1 to 3: 1. When the amount of the component (b) is too large, when the component (f) is emulsified in the aqueous composition (D), it becomes difficult to form particles, so that coarse particles increase and storage stability may decrease. If it is too much, the solvent effect on the component (f) may be lowered.

  (D) The preparation method of the aqueous composition is not particularly limited. However, when the cationic surfactant is emulsified and dispersed, it is described in JP-A Nos. 63-143935 and 5-310660. Can be used. Specifically, (f) an oil phase containing a cationic surfactant is emulsified and dispersed in an aqueous phase under high shear. Examples of the high shear emulsifier used at this time include a homomixer, a milder, a Clare mix, a fill mix, an ultra mixer, a line mixer, Vecomics, and Lexamix. The emulsification temperature is preferably equal to or higher than the phase transition temperature of the component (f) to be used, but when the level of high shear is high and an oil phase addition nozzle is provided in the immediate vicinity of the blade, the phase of the component (f) to be used Emulsification is possible even below the transition temperature.

The (E) softener for clothing of the present invention can be produced by mixing the (B) mixed solution and the (D) aqueous composition separately prepared as described above.
(E) The amount of the (f) cationic surfactant in the softener for clothing is not particularly limited, but a viewpoint of obtaining a sufficient softening effect and a viewpoint of making the viscosity of the softener moderate. Therefore, (E) 3 to 50% by mass is preferably blended in the softener for clothing, and more preferably 5 to 30% by mass.

(Other optional ingredients)
(C) In order to prepare an oil-in-water silicone emulsion, the following components can be added as needed in addition to (e) the nonionic surfactant.
(C) Inorganic or organic water-soluble salts can be used for the purpose of controlling the viscosity of the oil-in-water silicone emulsion. Examples of the inorganic water-soluble salts include alkali metal salts or alkaline earth metal salts of sodium chloride, potassium chloride, calcium chloride, magnesium chloride, sulfuric acid or nitric acid. Examples of the organic water-soluble salts include alkali metal salts of organic acids such as p-toluenesulfonic acid, glycolic acid, and lactic acid. Preferably, they are calcium chloride, magnesium chloride, and sodium chloride. The blending amount of the salt is preferably 0.001 to 3% by mass, preferably 0.01 to 2% by mass, more preferably 0.05 to 1% by mass with respect to the total amount of the (C) oil-in-water silicone emulsion. . These salts may be added at any step in the production of the (C) oil-in-water silicone emulsion, or may be added in divided portions.

(C) A fragrance | flavor component can be used in order to raise the usability | use_condition of an oil-in-water type silicone emulsion. As the fragrance component, hydrocarbons such as aliphatic hydrocarbons, terpene hydrocarbons, aromatic hydrocarbons, alcohols such as aliphatic alcohols, terpene alcohols, aromatic alcohols, ethers such as aliphatic ethers, aromatic ethers, etc. Oxides such as aliphatic oxides, terpene oxides, aliphatic aldehydes, terpene aldehydes, hydrogenated aromatic aldehydes, aldehydes such as thioaldehydes, aromatic aldehydes, aliphatic ketones, terpene ketones, hydrogenated aromatics Ketones such as aromatic ketones, aliphatic cyclic ketones, non-benzene aromatic ketones, aromatic ketones, acetals, ketals, phenols, phenol ethers, fatty acids, terpene carboxylic acids, hydrogenated aromatic carboxylic acids, Acids such as aromatic carboxylic acids, acid amides, aliphatic lactones, Cyclic lactone, terpene lactone, hydrogenated aromatic lactone, lactone such as aromatic lactone, aliphatic ester, furan carboxylic acid ester, aliphatic cyclic carboxylic acid ester, cyclohexyl carboxylic acid ester, terpene carboxylic acid ester Synthetic fragrances such as esters such as aromatic carboxylic acid esters, nitromusks, nitriles, amines, pyridines, quinolines, pyrroles, indoles, etc. and natural fragrances from animals and plants, natural fragrances and / or One or two or more kinds of blended fragrances including synthetic fragrances can be mixed and used. For example, in 1996, Chemical Industry Daily, published by Motoichi Into, “Synthetic Fragrance Chemistry and Product Knowledge”, 1969 MONTCLAIR, N. J. et al. Examples include fragrances described in the publication “Perfume and Flavor Chemicals” by STEFEN Arctander.
Since the fragrance component is mainly an oily component, these fragrance components are preferably mixed with the cationic surfactant during preparation of the aqueous composition (D) containing (f) the cationic surfactant. You may add by the method as described in -270135 gazette.

(C) For the purpose of improving the stability of the aroma and color tone of the oil-in-water silicone emulsion, it can contain a sequestering agent and / or an antioxidant. Examples of sequestering agents include aminocarboxylates typified by ethylenediaminetetraacetate and diethylenetriaminepentaacetate, and inorganic phosphorus compounds typified by citric acid, succinic acid, hydroxyiminodisuccinic acid, and tripolyphosphate. And organophosphorus compounds represented by 1-hydroxyethane-1,1-diphosphonate. 1-hydroxyethane-1,1-diphosphonate is particularly preferred. These compounds may be blended as free acids or as salts.
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 (C) oil-in-water silicone emulsion. If the amount is too small, the effect is not sufficient, and if it is too large, phase separation may occur.

Examples of antioxidants include propyl gallate, BHT (butylated hydroxytoluene), BHA (butylated hydroxyanisole), p-hydroxyanisole, tea extract and the like. BHT is particularly preferred.
The blending amount of the antioxidant is (C) 0 to 1% by mass, preferably 0.0001 to 0.5% by mass, more preferably 0.001 to 0.1% by mass with respect to the total amount of the oil-in-water silicone emulsion. Preferably there is. If the blending amount is too small, the effect is not sufficient, and if it is too large, the production cost increases.

For the purpose of enhancing the antiseptic and bactericidal powers, the compounds described in 1) to 4) below can be used singly or in combination of two or more.
1) Examples of isothiazolone organic sulfur compounds include 5-chloro-2-methyl-4-isothiazolin-3-one, 2-n-butyl-3-isothiazolone, 2-benzyl-3-isothiazolone, and 2-phenyl-3. -Isothiazolone, 2-methyl-4,5-dichloroisothiazolone, 5-chloro-2-methyl-3-isothiazolone, 2-methyl-4-isothiazoline-3-one and mixtures thereof. Specifically, 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. Specifically, Proxel series manufactured by Avicia Co., Ltd. [BDN (effective content 33% by mass), BD20 (effective content 20% by mass), XL-2 (effective content 10% by mass), GXL (effective content 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. Commercially available products such as Bronidox L from Henkel, Bronopol from Inolex, Bronopol from Yoshitomi Pharmaceutical, Myr Side BT from Boots, Myr Side Pharma BP from BASF, etc. can be used.

  4) Benzoic acids or phenol compounds include benzoic acid or a salt thereof, salicylic acid or a salt thereof, parahydroxybenzoic acid or a salt thereof, p-hydroxybenzoic acid derivative, 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 based on the total amount of the (C) oil-in-water silicone emulsion. It is preferable that it is 0.0001-0.02 mass%. The compounding amount of the compound 4) is 0 to 3% by mass, preferably 0.01 to 1.5% by mass, based on the total amount of the (C) oil-in-water silicone emulsion. 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.
These sequestering agents and / or antioxidants may be added in any step of the production of the (C) oil-in-water silicone emulsion, or may be added separately in each production step.

(C) For the purpose of improving the appearance of the oil-in-water silicone emulsion, any dye and / or pigment can be blended. Preferably, an acid dye, a direct dye, a basic dye, a reactive dye, and a mordant / acid mordant dye are selected.
(C) From the viewpoint of storage stability of the oil-in-water silicone emulsion and dyeability to fibers, an acidic 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 Direct dyes and reactive dyes are preferred, and the blending amount thereof is preferably 1 to 50 ppm, more preferably 1 to 30 ppm, based on the entire composition.
These arbitrary dyes and / or pigments may be added at any step of (C) the oil-in-water silicone emulsion, or may be added separately in each production step.

(C) In the oil-in-water silicone emulsion, additives that are used in ordinary softeners for clothing other than the above can be used within the range not impeding the effects of the present invention. Specific examples of such additives include ultraviolet absorbers, fluorescent brighteners, pH adjusters, hydrocarbons, fatty acids, urea, and cellulose derivatives.
The additive may be added in any step of the (C) oil-in-water silicone emulsion, or may be added separately in each production step.

(A) Modified silicone, (b) solvent, (c) water, (d) aqueous component, and (e) nonionic surfactant shown in Tables 4-6 are used in the amounts shown in Tables 1-3. (A) mixed solution, (B) mixed solution, and (C) oil-in-water silicone emulsion were prepared.
(Examples 1-3, 8-10, Comparative Examples 1-3)
25 g of component (a) heated to 40 ° C. is weighed and put in a 100 mL (200 mL for Examples 3, 8, 9, and 10) Pyrex (registered trademark) beaker, and the ratios shown in Table 1 are obtained. Thus, (b) solvent at 25 ° C. was added and sufficiently stirred with a propeller blade having a diameter of 30 mm until uniform, to obtain a mixed solution (A).
To the obtained (A) mixed solution, ion-exchanged water (corresponding to “gel-forming water” in Table 1) was added as water (c) heated to 40 ° C. so as to have the ratio shown in Table 1, and The mixture was stirred with the same propeller blade until uniform to obtain (B) a mixed solution.
In a separately prepared 100 mL Pyrex (registered trademark) beaker, 50 g of ion-exchanged water (corresponding to “dispersed water” in Table 1) heated to 40 ° C. is added, and 4 pieces of inclined paddles 30 mm in diameter and 45 degrees (B) The mixed solution obtained previously so that it may become the ratio in an Example table | surface during stirring in 2 steps | paragraphs was added, and it stirred until the whole became uniform, (C) Oil-in-water silicone emulsion was obtained. .

(Examples 4-7, Comparative Example 4)
25 g of the component (a) heated to 40 ° C. (12.5 g in Example 5) was weighed and put into a 100 mL (200 mL in Example 5) Pyrex (registered trademark) beaker, and as shown in Table 1 The solvent (b) at 25 ° C. was added so as to obtain a ratio, and the mixture was sufficiently stirred with a propeller blade having a diameter of 30 mm until uniform, to obtain (A) a mixed solution.
The obtained (A) mixed solution was heated to 40 ° C. so as to have the ratio shown in Table 1. (c) Ion exchange water (corresponding to “gel-forming water” in Table 1) and 40 ° C. Warmed (e) nonionic surfactant was added and stirred with the same propeller blade until uniform, to obtain (B) a mixed solution.
Separately prepared 100 mL (Example 5 is 200 mL) Pyrex (registered trademark) beaker heated to 40 ° C. (d) As an aqueous component, 50 g of ion-exchanged water (corresponding to “dispersed water” in Table 1) was added. (B) The mixed solution (B) obtained previously was added so that the ratio in the example table was obtained during stirring with four 45-degree inclined paddles with a diameter of 30 mm, and stirred until the whole became uniform. (C) An oil-type silicone emulsion was obtained.

(Example 11)
(A) Weigh 25 g of the component, put it into a 100 mL Pyrex (registered trademark) beaker, add (b) the solvent to the ratio shown in Table 1 and add it to a 30 mm diameter propeller blade until uniform. And sufficiently stirred to obtain a mixed solution (A).
To the obtained (A) mixed solution, ion-exchange water (corresponding to “gel-forming water” in Table 1) is added as water so that the ratio shown in Table 1 is obtained, and uniformly with the same propeller blade The mixture was stirred until the (B) mixed solution was obtained.
(F) 88.2 g of a cationic surfactant (distearoyloxyethyldimethyl (2-hydroxyethyl) ammonium methylsulfate: Lion Akzo “Arcade TES-85E”) and a nonionic surfactant (c-2) 13.3 g and fragrance (see Table 7 for composition) were heated to 55 ° C. and stirred uniformly to obtain an oil phase. 310.9 g of purified water and 0.05 g of an antibacterial agent (Rohm & Haas Co., Ltd. “Kaison CG / ICP”) were uniformly mixed and then heated to 40 ° C. to obtain an aqueous phase. The total amount of the oil phase is charged into a 500 mL poly beaker (diameter 85 mm), and a 45 ° four-sheet inclined paddle (diameter: 45 mm, blade width: 10 mm, thickness: 1.5 mm) is used. Set the blade angle to 45 degrees with respect to the horizontal direction, add 93.3 g of the aqueous phase with stirring at 800 rpm, and add 100 rpm (50 ° C) at 10 rpm for the BH viscometer No.7 rotor 2 rpm. A high viscosity liquid crystal was formed, and then the remaining aqueous phase was added. After cooling to 25 ° C, 5 mg of pigment (CI Acid Red 138: Nippon Kayaku Co., Ltd. “Kayanol Milling Red BW”) and 12.5 g of 15% calcium chloride (reagent special grade) aqueous solution are added and mixed. (D) Aqueous composition I got a thing.
Into a separately prepared 100 mL Pyrex (registered trademark) beaker, add 50 g of the aqueous composition (D) prepared above, and stir with four 30 mm diameter 45 degree inclined paddles in two stages so that the ratio in the example table is reached. The obtained (B) mixed solution was added and stirred until the whole became uniform, and (C) an oil-in-water silicone emulsion was obtained.

(Example 12)
(A) 25 g of component (12.5 g in Example 5) was weighed and charged into a 100 mL Pyrex (registered trademark) beaker, and (b) a solvent was added thereto so that the ratio shown in Table 1 was obtained, The mixture was sufficiently stirred with a propeller blade having a diameter of 30 mm until uniform, to obtain (A) a mixed solution.
In the obtained (A) mixed solution, (c) ion-exchanged water (corresponding to “gel-forming water” in Table 1) as water and (e) a nonionic surfactant so that the ratio shown in Table 1 is obtained. And stirred with the same propeller blade until uniform to obtain (B) a mixed solution.
(F) 88.2 g of cationic surfactant (distearoyloxyethyldimethyl (2-hydroxyethyl) ammonium methylsulfate: Lion Akzo "Arcade TES-85E") and 5.0 g of fragrance (see Table 7 for composition) The oil phase was heated to 55 ° C. 239.0 g of purified water and 0.04 g of an antibacterial agent (Rohm & Haas Co., Ltd. “Caisson CG / ICP”) were uniformly mixed and then heated to 40 ° C. to obtain an aqueous phase. Charge the aqueous phase to Robomics homomixer manufactured by Primics Co., Ltd. (rotor diameter 30mm, clearance 0.5mm from the stator, 500mL vessel), add 65.3g of oil phase to the homomixer at 10000rpm rotation, and uniformly emulsify, then dye (CI Acid Red 138: Nippon Kayaku Co., Ltd. “Kayanol Milling Red BW”) 3.5 mg, 8.8 g of 15% calcium chloride (reagent special grade) aqueous solution was added. Thereafter, the mixture was cooled to 25 ° C. to obtain (D) an aqueous composition.
Into a separately prepared 100 mL Pyrex (registered trademark) beaker, add 50 g of the aqueous composition (D) prepared above, and stir with four 30 mm diameter 45 degree inclined paddles in two stages so that the ratio in the example table is reached. The obtained (B) mixed solution was added and stirred until the whole became uniform, and (C) an oil-in-water silicone emulsion was obtained.

The dispersibility of the obtained (C) oil-in-water silicone emulsion was evaluated as follows. The results are shown in Table 1.
[Confirmation of presence / absence]
After sample preparation, the sample was allowed to stand at 25 ° C. for one day and visually confirmed.
(Particle size measurement)
<Measurement method>
・ Equipment: JGC Micro Truck UPA-150EX
-Dispersion medium: water (refractive index 1.33), dispersoid: oil-in-water silicone emulsion (refractive index 1.48)
・ A sample is added to a measuring instrument and stirred uniformly at 25 ° C. After confirming that the “Sample Loading” value is 1 to 50, measurement is started (measurement time: 600 sec, number of measurements: once). The median diameter (d50 value) on a volume basis was measured.

Claims (6)

(A) The modified silicone that gels upon contact with water, the (a) modified silicone and the water-soluble (b) solvent, and the mass ratio of (b) to (a) (b) / (a) Is added within the range of 0.25 or more, and both are mixed to prepare (A) a mixed solution;
(C) Water is added to and mixed with the obtained (A) mixed solution so that the mass ratio (c) / (b) between (c) water and (b) solvent is 0.05-4. (B) a step of preparing a mixed solution; and (D) a step of forming an oil-in-water emulsion by adding (d) an aqueous component to the obtained mixed solution and mixing.
Including,
The ( a) modified silicone is a compound represented by the following formula:
(C) Method for producing oil-in-water silicone emulsion:

(In the formula, -Z 1 and -Z 2 are independently -R, -O-R, -OH, -O-X-R, and -O-X-H. R may be the same or different from each other. Both are saturated or unsaturated linear or branched hydrocarbon groups having 1 to 4 carbon atoms, and X is a polyoxyalkylene group (the alkylene moiety has 2 to 3 carbon atoms). Is —R 10 —O—X—R 11 or —OX—R 11, R 10 is a saturated or unsaturated linear or branched hydrocarbon group having 1 to 4 carbon atoms, and R 11 is a hydrogen atom or carbon number 1 A saturated or unsaturated linear or branched hydrocarbon group of -4, L is 0-50, M is 1-1000, and N is 10-10000, provided that the polyoxyethylene chain portion in X is (The mass ratio is 10% or more and less than 60% based on the mass of the whole molecule.)   The manufacturing method of Claim 1 including the process of adding (e) nonionic surfactant to the said mixed solution (A). The method according to claim 1 or 2, wherein the solvent (b) is a lower alcohol having 1 to 4 carbon atoms or a polyhydric alcohol having 2 to 6 carbon atoms and 2 to 6 hydroxyl groups. The method according to claim 2 or 3, wherein (e) the nonionic surfactant is an alkylene oxide adduct of a higher alcohol. Wherein (d) as an aqueous component, (f) contains a cationic surfactant (D) method of any one of claims 1-4, characterized by using an aqueous composition. (E) The softening agent for clothes obtained from the manufacturing method of any one of Claims 1-5 .