JP2021191735A - Silicone emulsion composition containing polyvalent acid, method for producing the same and method for stabilizing the composition - Google Patents

Abstract

To provide a silicone emulsion composition that is predominantly composed of at least a predetermined amount of amino-modified silicone, and contains a polyvalent acid, and has excellent temporal stability.SOLUTION: A silicone emulsion composition contains (a) surfactant, (b) amino-modified silicone, and (c) at least one compound selected from a polyvalent acid or a salt thereof. The content of the amino-modified silicone is 5 mass% or more. The content of the at least one compound selected from a polyvalent acid or a salt thereof is 0.1 mass% or more. The emulsion particles have a particle size of less than 1 μm.SELECTED DRAWING: None

Description

The present invention relates to a silicone emulsion composition containing a polyvalent acid and an amino-modified silicone, a method for producing the composition, a method for stabilizing the composition, and a cosmetic, a softener and a fiber treatment containing the composition. Regarding the agent.

Amino-modified silicones are widely used in fiber treatment agents, fabric softeners, cosmetics, etc. because they exhibit excellent conditioning effects. However, since amino-modified silicone deteriorates or discolors over time due to the action with ultraviolet rays, heat, and other components, it is often blended together with an antioxidant or a radical inhibitor. For example, Patent Document 1 and Patent Document 2 disclose a method of adding hydroxyethanediphosphonic acid to an emulsified cosmetic composition or a textile product treatment agent composition containing an amino-modified silicone to suppress discoloration. There is.
When the amino-modified silicone is blended with the fiber treatment agent or the like, it can be blended in an oil state, but it is more preferable to blend it in an emulsion state. Amino-modified silicone in an emulsion state has a lower viscosity and better workability, and can be more easily blended into water-based emulsified products such as cosmetics than when blended in an oil state. Because.
In a silicone emulsion composition containing amino-modified silicone as a main component, which is blended in cosmetics and the like, an acid component is blended in order to obtain a stable emulsion having a small particle size as described in Patent Document 3. However, monovalent acids were mainly used, and it was difficult to mix polyvalent acids.

Japanese Unexamined Patent Publication No. 2008-143817 Japanese Unexamined Patent Publication No. 2006-249604 Japanese Unexamined Patent Publication No. 2011-1419

Hydroxyethanediphosphonic acid and citric acid are substances that act as antioxidants and radical inhibitors. However, polyvalent acids such as etidronic acid and citric acid react and network with amino-modified silicone, especially in the presence of high-concentration amino-modified silicone, and become a factor of destabilization. With a monovalent acid, the above problems are unlikely to occur. Since the polyvalent acid has a plurality of reaction points with the amino-modified silicone, it acts like a cross-linking agent, causes aggregation and precipitation of the amino-modified silicone, and often causes destabilization. In addition, the larger the amount of the polyvalent acid and the amino-modified silicone, the greater the tendency.
Therefore, it has been difficult to combine these in a silicone emulsion composition containing amino-modified silicone as a main component. Therefore, polyvalent acids such as hydroxyethandiphosphonic acid and citric acid are not used in the silicone emulsion composition containing amino-modified silicone as a main component, which is blended in cosmetics and the like, and acetic acid and lactic acid are not used. Monovalent acids such as were mainly used.
In fiber treatment agents, fabric softeners and cosmetics, there are many stable formulations of the combination of amino-modified silicone and hydroxyethanediphosphonic acid or citric acid, but for the above reasons, the combination of amino-modified silicone and polyvalent acid There was a limit to the amount.

Therefore, an object of the present invention is to obtain desired physical properties as an amino-modified silicone emulsion in an amino-modified silicone emulsion containing a polyvalent acid, and to obtain sufficient initial and aging stability. Specifically, it contains a certain amount or more of amino-modified silicone as a main component and contains a polyvalent acid. It is to provide an excellent silicone emulsion composition.

The present inventor of the present invention prepares a silicone emulsion composition containing a certain amount or more of amino-modified silicone as a main component, and depending on the timing of blending a polyvalent acid, a certain amount or more of amino-modified silicone is used as a main component. It was found that the stability of the silicone emulsion composition containing and containing a polyvalent acid with time is dramatically improved. The present invention is based on such findings.

The present invention
(a) Surfactants and
(b) Amino-modified silicone and
(c) Containing at least one compound selected from polyvalent acids or salts thereof,
The blending amount of the amino-modified silicone is 5% by mass or more, and
The blending amount of at least one compound selected from the polyvalent acid or a salt thereof is 0.1% by mass or more.
Provided are silicone emulsion compositions having a particle size of emulsion particles of less than 1 μm.

In the present invention, it is possible to provide a silicone emulsion composition having excellent stability over time, which contains a certain amount or more of amino-modified silicone as a main component and contains a polyvalent acid.

The details of the silicone emulsion composition according to the present invention, the method for producing the same, and the method for stabilizing the silicone emulsion will be described below.

The silicone emulsion composition of the present invention is
(a) Surfactants and
(b) Amino-modified silicone and
(c) Containing at least one compound selected from polyvalent acids or salts thereof,
The blending amount of the amino-modified silicone is 5% by mass or more, and
The blending amount of at least one compound selected from the polyvalent acid or a salt thereof is 0.1% by mass or more.
A silicone emulsion composition in which the particle size of the emulsion particles is less than 1 μm.

Further, the method for producing the silicone emulsion composition of the present invention is:
An emulsification step of emulsifying a mixture of amino-modified silicone and a surfactant and water to obtain a composition for preparing a silicone emulsion.
The composition for preparing a silicone emulsion obtained in the emulsification step comprises an acid blending step of blending an aqueous solution containing at least one compound selected from a polyvalent acid or a salt thereof.
A silicone emulsion composition in which the blending amount of the amino-modified silicone is 5% by mass or more, and the blending amount of at least one compound selected from the polyvalent acid or a salt thereof is 0.1% by mass or more. It is a manufacturing method of a product.

Further, the method for stabilizing a silicone emulsion composition of the present invention is at least selected from a polyvalent acid or a salt thereof in a composition for preparing a silicone emulsion obtained by emulsifying a mixture of an amino-modified silicone and a surfactant and water. Including the step of blending an aqueous solution containing one compound,
The blending amount of the amino-modified silicone in the obtained emulsion composition is 5% by mass or more, and the blending amount of at least one compound selected from the polyvalent acid or a salt thereof is 0.1% by mass. This is a method for stabilizing a silicone emulsion composition, which comprises blending the aqueous solution as described above.

The present invention comprises the step of emulsifying the amino-modified silicone with an arbitrary surfactant and then adding a polyvalent acid, and the surfactant is present between the amino-modified silicone and the polyvalent acid. Therefore, it is considered that the formation of a network by the amino-modified silicone and the polyvalent acid can be prevented, and the polyvalent acid and the amino-modified silicone can coexist stably.
By the above-mentioned production method, the amount of the amino-modified silicone compounded is 5% by mass or more, and the polyvalent acid or a polyvalent acid thereof, which is a region where it was conventionally impossible to make the particle size less than 1 μm. Even if the composition of at least one compound selected from the salt is 0.1% by mass or more, the particle size of the emulsion can be less than 1 μm, and as a result, the silicone emulsion having excellent stability over time. The composition can be provided.
In the present specification, excellent stability over time means that there is no creaming or sedimentation separation at the initial stage (24 hours after preparation) and after 1 month of storage at 40 ° C.

Even if the product of the number of amines (milli equivalent / g) of the amino-modified silicone and the blending amount (% by mass) of the amino-modified silicone is less than 2, a silicone emulsion composition having excellent stability over time can be produced. According to the present invention, a silicone emulsion composition having excellent stability over time can be obtained even if the number of silicone emulsion compositions is 2 or more, which is usually not considered to be stable.

In the present invention, the particle size of the emulsion particles in the silicone emulsion composition means the value of z-average measured by the dynamic light scattering method. For example, the particle size of the emulsion particles can be measured using a Nano-ZS90 type machine manufactured by Malvern. In the present invention, the particle size of the emulsion particles needs to be less than 1 μm, but is preferably 500 nm or less, more preferably 300 nm or less, and even more preferably 150 nm or less. When the particle size is 300 nm or less, creaming and sedimentation separation are less likely to occur, especially over time. When the particle size is 150 nm or less, not only is it excellent in stability over time, but it also has a translucent to transparent appearance, so that it can be suitably used for transparent cosmetics and the like.

In the emulsification step of the composition for preparing a silicone emulsion of the present invention, a suitable conventional mixer such as a homogenizer, a colloid mill, a homomixer, a high-speed stator rotor stirrer and the like can be used.

As the emulsification method, a liquid crystal emulsification method, a phase inversion emulsification method, a phase inversion temperature emulsification method, a D phase emulsification method and the like are known.
The liquid crystal emulsification method is a technique for generating fine emulsified particles that disperse and retain a dispersed phase (oil phase in an O / W emulsion) in a liquid crystal formed by a surfactant.
The phase inversion emulsification method is a method of producing an O / W emulsion by dissolving a surfactant in an oil phase, then stirring while adding an aqueous phase, and reversing the continuous phase from the oil phase to the aqueous phase. Is.
In the phase inversion temperature emulsification method, in a three-component system of nonionic surfactant, oil, and water, the nonionic surfactant is infinitely associated at a certain temperature and separated as a macroscopic phase containing a large amount of oil and water. However, when the temperature is further raised, the nonionic surfactant dissolves in the oil phase to form a reverse micelle, and water is solubilized. Therefore, this method is used for emulsification using this phase inversion temperature.
The D-phase emulsification method is a method of adding a polyhydric alcohol as a fourth component to a surfactant, oil, and water to form a fine O / W emulsion.

The concentration of the amino-modified silicone of the silicone emulsion composition obtained by the production method of the present invention is 5% by mass or more, and as long as the emulsion composition has stability, there is no upper limit, but the concentration of the amino-modified silicone can be set as the concentration of the amino-modified silicone. For example, it is 5 to 60% by mass, preferably 10 to 50% by mass. The concentration of amino-modified silicone in the silicone emulsion composition can be adjusted to a desired value by adding water (diluted water) to the emulsion and mixing them.

The surfactant used in the silicone emulsion composition of the present invention is not particularly limited as long as it is an amino-modified surfactant or one that uniformly disperses the amino-modified silicone and other oil components in water, and is generally surface-active. The agent is usually an agent, and can contain a cationic, anionic, nonionic surfactant, an amphipathic surfactant, as well as silica particles having a surfactant function. Nonionic surfactants are preferable because they do not adversely affect the environment and are less irritating to the human body. For example, polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers and polyoxyethylene polyoxypropylene alkyl ethers; polyoxyethylene alkylphenyl ethers; polyoxyethylene alkyl esters; polyoxyethylene sorbitan esters; glycerin esters, sorbitan fatty acid esters, Examples thereof include polyhydric alcohol fatty acid esters such as sucrose fatty acid esters; ethoxylated fatty acids; ethoxylated fatty acid amides, and polyoxyethylene alkyl ethers and polyoxyethylene polyoxypropylene alkyl ethers are preferable. The total HLB (hydrophilic group / lipophilic group balance) of the nonionic surfactant used is preferably in the range of 8 to 17, and more preferably in the range of 10 to 16.

The content of the surfactant is not limited, but in the emulsion composition of the present invention, a transparent to translucent amino microemulsion having a transmittance of 75% or more at a wavelength of 550 nm after storage at 40 ° C. for 1 month. In the case of preparing the amino-modified silicone, the temporal stability is particularly excellent at 30% by mass or more, and the temporal stability is further improved at 45% by mass or more. On the other hand, if it exceeds 90% by mass, the viscosity of the silicone emulsion composition becomes high and the handleability deteriorates. A more preferable content range is 45 to 90% by mass.

The amino-modified silicone used in the silicone emulsion composition of the present invention is not limited in its structure and properties, but is usually an amino-modified organopolysiloxane whose average composition is represented by the general formula (1). This amino-modified organopolysiloxane is a component in an aqueous emulsion that imparts cosmetic functions, particularly smooth feel and passability to hair.
R ¹ _a R ² _b SiO _{(4-ab) / 2} (1)
In the general formula (1), R ¹ may be the same or different in the molecule, and is selected from an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms or a hydrogen atom or a hydroxyl group. Examples of the unsubstituted monovalent hydrocarbon group include a methyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; an aryl group such as a phenyl group; and an aralkyl group such as 2-phenylethyl and 2-phenylpropyl. be able to. Among these, a methyl group and / or a phenyl group is preferable, and 50 mol% or more is particularly preferable. It ^{does not prevent R 1} from containing an alkoxy group having 1 to 3 carbon atoms as a part.

^{R 2} of the general formula (1) is a hydrocarbon group containing one or more amino groups, and is as represented by the following general formula (2).
-R ³ -[(NR ⁴ ) -R ⁵ ] _t NR ⁶ R ⁷ (2)
In the general formula (2), R ³ and R ⁵ represent divalent C1 to C18 hydrocarbon residues, and R ⁴ , R ⁶ and R ⁷ are hydrogen atoms or unsubstituted C1 to C10 alkyl groups. Represented, t represents an integer of 0 or 1-6.

Examples of divalent C1 to C18 hydrocarbon residues R ³ and R ⁵ include methylene group, ethylene group, n-propylene group, iso-propylene group, n-butylene group, iso-butylene group, t-butylene group, n-pentylene group, iso-pentylene group, hexylene group such as n-hexylene group, heptylene group such as n-heptylene group, octylene group such as n-octylene group and iso-octylene group such as 2,2,4-trimethyl It is a pentylene group, a nonylene group, for example, an n-nonylene group, a decylene group, a dodecylene group, for example, an n-dodecylene group, an octadecylene group. Examples of the alkyl groups of R ⁴ , R ⁶ and R ⁷ are the alkyl groups up to C10 mentioned ^{in R 1.}

Examples of R ² _{groups, -CH 2 -CH 2 -CH 2 -NH} 2, -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -NH 2, -CH 2 -CH 2 -CH _{2 -NH 2 -CH 2 -CH 2 -CH} 2 -NH (CH 3), - CH 2 -CH 2 -CH 2 -N (CH 3) 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 _{-NH 2 -CH 2 -CH 2 -CH 2} -NH (CH 3), - CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -N (CH 3) 2 -CH 2 -CH 2 - _{CH 2 -NH-CH 2 -CH 2} -NH (CH 2 CH 3), - CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -N (CH 2 CH 3) 2, -CH 2 - _{CH 2 -CH 2 -NH-CH 2} -CH 2 -NH (cyclo-C 6 H 11) can be exemplified.
In the amino modified silicone is preferably used as a cosmetic, ^{R 2} _{is, -CH 2 -CH 2 -CH 2 -NH} 2, -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 - NH _2, preferably _{-CH 2 -CH 2 -CH 2 -NH 2} -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -NH 2, particularly _preferably, -CH ₂ -CH ₂ -CH a _{2 -NH-CH 2 -CH 2 -NH} 2.

A general formula (1), b is a natural number, which indicates the average number of amino-modified polyorganosiloxanes substituents attached to the silicon of siloxane ^{R 1, R 2, a +} b is a 1.8 to 2.2 .. It is shown that the molecular structure of the organopolysiloxane may have a branched structure as well as a linear structure, but preferably has a linear structure.

The amino-modified silicone used in the silicone emulsion composition of the present invention may be any as long as it can form a silicone emulsion composition, and its form is not limited, but it is preferably oily. Further, it may be a polymer having a single component or a mixture of a plurality of polymers. A part of the component may be a solid content such as a resin, but it is preferable to exhibit oily fluidity as a whole.

The oily component is not limited to amino-modified silicone, and other components may be used in combination. Any modified oil may be used, including dimethylpolysiloxane. It may also contain a resin component. Further, the type of these oils and resins may be one type or any number of types.
The ratio of amino-modified silicone to these oils and / or resins is not limited at all. It suffices if the desired properties of the amino-modified silicone can be exhibited as an emulsion. However, it is preferable that the amino-modified silicone and the oil and / or the resin as a whole exhibit fluidity in a mixed state. Otherwise, it will be difficult to form an emulsion.

The amino-modified silicone used in the silicone emulsion composition of the present invention is generally known as an amino-modified organopolysiloxane oil, and can be produced by a method known to those skilled in the art, but is a typical amino-modified. The method for synthesizing organopolysiloxane oil is as follows. That is, the introduction of the aminoalkyl group into the silicon atom is usually carried out at the silane stage, and the aminoalkylsilane is first produced. Aminoalkylsilane is hydrolyzed to an amino group-containing siloxane oligomer or amino group-containing disiloxane, and further, a rebalancing reaction of Si—O bond with a linear oligomer or cyclic oligomer of dimethylsiloxane in the presence of an alkali catalyst. To obtain an amino-modified organopolysiloxane oil. If hexamethyldisiloxane is used in the reequilibrium reaction, a terminal trimethylsilyl type amino-modified organopolysiloxane oil can be obtained. By adjusting the amount ratio of oligomers or disiloxanes used in the production, amino-modified organopolysiloxane oil having a specific kinematic viscosity and number of amines can be obtained.

The ratio a / b of ^{the average number a of R 1} having no amino group to ^{the average number b of R 2} containing one or more amino groups is preferably 15 to 600. The ratio a / b is a guideline for the ratio of the siloxane unit having no amino group to the siloxane unit containing an amino group. As an indicator of the total amount of amino groups in the amino-modified organopolysiloxane, the number of amines represented by the volume (mL) of 1N hydrochloric acid required to neutralize 1 g of the siloxane is also used.
The number of amines will vary depending on the number and molecular weight of amino groups in one molecule of amino-modified silicone. The number of amines in the amino-modified organopolysiloxane of the present invention is not particularly limited, but is preferably 0.1 to 3.0, more preferably 0.15 to 2.0. If the number of amines is less than 0.1, the ability to adsorb to the surface of the hair is weakened, and if the number of amines exceeds 3.0, the number of amino groups, which are hydrophilic groups, becomes too large, and it becomes difficult to adsorb to the hair.
The above-mentioned structural factors of amino-modified silicone are preferably in the above range when applied to cosmetics and the like, but they are not limited to the present invention.

The lower limit of the product of the number of amines (milli equivalent / g) and the blending amount (% by mass) is not particularly limited, but is particularly effective when it is 2 or more. The upper limit of the product is preferably 180 or less, more preferably 120 or less.

The polyvalent acid or salt thereof used in the silicone emulsion composition of the present invention is not particularly limited, and is, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid). , Ethylenediaminetetra (methylenephosphonic acid), triethylenetetraminehexacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, ethylenediethyltriamine-N, N, N' , N'', N''-pentacetic acid, hydroxyethylethylenediamine triacetic acid, dihydroxyethylglycine, ethylenediaminetetrakis (methylenephosphonic acid), nitrilotris (methylenephosphonic acid), phosphoric acid, pyrophosphate, metaphosphoric acid, polyphosphoric acid , Citric acid, succinic acid, malic acid, tartrate acid, phthalic acid and salts thereof. Among them, citric acid, succinic acid, phthalic acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, EDTA, EHDP and salts thereof are preferable, and pyrophosphoric acid, polyphosphoric acid, EDTA, HEDP and salts thereof are more preferable.

Examples of the monovalent acid of the present invention include formic acid, lactic acid, acetic acid, propionic acid, hydrochloric acid and the like, and among these, lactic acid and acetic acid are preferable, and lactic acid is more preferable.

The silicone emulsion composition of the present invention may further contain a monovalent acid in addition to the above-mentioned polyvalent acid or a salt thereof. The step of adding the monovalent acid is not particularly limited, but when it is added to the composition for preparing a silicone emulsion (that is, when it is added in the emulsification step), emulsion particles having a smaller particle size are formed. As a result, a silicone emulsion composition having further excellent stability over time can be produced.

The silicone emulsion composition of the present invention may contain water. The water that can be used is not limited, but it is preferable to use ion-exchanged water, preferably pH 2 to 12, and particularly preferably pH 4 to 10. It is not recommended to use mineral water, but when using it, it is desirable to use it in combination with a metal inactivating agent or the like. The amount of water added during emulsification is 40 to 90% by mass, preferably 40 to 60% by mass in the emulsion composition of the present invention. The emulsion composition of the present invention is stable to dilution with water, can be further diluted after the emulsion is prepared, and the amount of water in the diluted emulsion is not particularly limited.

The emulsion composition of the present invention may contain other components that are acceptable depending on the purpose, as long as the object of the present invention is not impaired. For example, other components that are acceptable as compounding components include quaternary ammonium-containing compounds, preservatives such as sodium benzoate, phenoxyethanol, methylparaben, propylparaben, salicylic acid, glycerin, butylene glycol, propylene glycol, and isopropanol, and amino acid-based activators. , Various surfactants, thickeners such as guar gum and xanthan gum, fragrances and the like.

When the emulsion in the silicone emulsion composition of the present invention is blended in a cosmetic, it is possible to suppress a change in the color tone of the cosmetic, particularly yellow coloring. In particular, a remarkable effect appears when it is added to cosmetics such as conditioners, shampoos, and rinses, in which amino-modified silicone is frequently used.
When the silicone emulsion composition of the present invention is blended with a fiber treatment agent, coloring of the fibers can be suppressed.

In the present invention, the transmittance of the silicone emulsion composition can be evaluated by an ultraviolet-visible absorptiometer. In the present invention, the silicone emulsion composition preferably has a light transmittance of 75% or more, more preferably 80% or more at a wavelength of 550 nm.

Next, the present invention will be described by way of examples. The present invention is not limited thereto. Further, the evaluation method for the silicone emulsion composition of the present invention in the examples was carried out as follows. Also, all viscosity values are for temperatures of 25 ° C.

When the prepared silicone emulsion composition is a transparent to translucent amino microemulsion, for example, when the particle size of the emulsion particles is 150 nm or less, stability over time and transparency evaluation are performed. It is a white macroemulsion, for example, when the particle size of the emulsion particles is larger than 150 nm, only the stability over time is evaluated.
<Measurement method of particle size>
As the particle size of the emulsion particles in the emulsion composition, the value of z-average measured using a Nano-ZS90 type machine manufactured by Malvern Co., Ltd. was used as the particle size.
<Method of evaluating stability over time>
80 g of the prepared silicone emulsion composition was placed in a 100 ml PP bottle, and after initial storage (24 hours after preparation) and 1 month after storage at 40 ° C., changes over time with or without creaming and sedimentation separation were visually confirmed.
Evaluation criteria;
◎: No creaming or sedimentation separation ○: Almost no creaming or sedimentation separation △: Tendency of creaming or sedimentation separation ×: Creaming or sedimentation separation Yes .. In a transparent to translucent silicone emulsion composition, the higher the transmittance, the better.
<Transparency evaluation method>
80 g of the prepared silicone emulsion composition was placed in a 100 ml PP bottle, and after storage at 40 ° C. for 1 month, the change in transmittance at a wavelength of 550 nm with time was confirmed.

<Example 1>
As an amino-modified silicone, ethylene oxide is added as a surfactant to 20 parts by mass of N- (2-aminoethyl) -3-aminopropyl group-containing dimethylpolysiloxane having a viscosity of 1000 mPa · s and an amine number of 0.6. Polyoxyethylene cetyl ether 6.4, 8.0, 9.6, 11.3 parts by mass, 0.5 parts by mass of lactic acid as a monovalent acid, and phenoxyethanol 1.3 as an optional component. By mixing 10 parts by mass and 10 parts by mass of glycerin, an oily mixture without phase separation was obtained (three kinds having a polyoxyethylene cetyl ether content of 13 mol and different contents of polyoxyethylene cetyl ether).
Next, purified water is added to each oily mixture and mixed, and the composition is stirred at 3000 rpm for 20 minutes at room temperature using an IKA Ultratarax T50 Basic Shaft Generator G45G to prepare a silicone emulsion. Got
Subsequently, an aqueous solution containing 1.0 part by mass of 1-hydroxyethane-1,1-diphosphonic acid, which is a tetravalent acid, was added to the composition for preparing a silicone emulsion to obtain a silicone emulsion composition. The prescriptions are shown in Table 1. The obtained silicone emulsion composition was a microemulsion having a translucent to transparent appearance, and the transmittance of light at a wavelength of 550 nm was 95% or more.
In Example 1, four kinds of silicone emulsion compositions having different surfactant contents were obtained. All of these four types were obtained by emulsifying to obtain a composition for preparing a silicone emulsion, and then adding 1-hydroxyethane-1,1-diphosphonic acid, which are polyvalent acids. The particle size of the emulsion particles was 20 to 35 nm, and all of them had no or almost no creaming or sedimentation separation, and were excellent in stability over time.
When the compounding ratio of the surfactant to the amino-modified silicone was relatively high, 48% or 57%, the particle size became smaller (25 nm and 20 nm, respectively), and the particles were stored at a temperature of 40 ° C. for one month. A highly transparent silicone emulsion composition with higher permeability was obtained.

<Example 2>
Ethylene oxide is added as a surfactant to 36 parts by mass of N- (2-aminoethyl) -3-aminopropyl group-containing dimethylpolysiloxane having a viscosity of 5000 mPa · s and an amine number of 0.14 as an amino-modified silicone. 4.0 parts by mass of polyoxyethylene dodecyl ether having a number of 10 mol and a propylene oxide addition number of 4 mol was mixed to obtain an oily mixture without phase separation. Purified water was added to the oily mixture and mixed, and the mixture was stirred at 3000 rpm at room temperature for 20 minutes using an Ultratarax T50 Basic Shaft Generator G45G manufactured by IKA to obtain a composition for preparing a silicone emulsion. ..
Then, an aqueous solution containing 0.4 parts by mass of 1-hydroxyethane-1,1-diphosphonic acid was added to the composition for preparing a silicone emulsion to obtain a silicone emulsion composition. The prescriptions are shown in Table 1. The obtained silicone emulsion composition was a macroemulsion having a white appearance.
Also in Example 2, a silicone emulsion adjusting composition was obtained by emulsification, and then a polyvalent acid, 1-hydroxyethane-1, 1-diphosphonic acid, was added to obtain a silicone emulsion composition. The particle size of the emulsion particles was less than 1 μm, there was no creaming or sedimentation separation, and the stability over time was excellent.
Since the compounding ratio of the surfactant to the amino-modified silicone was 11%, which was lower than that of Example 1, the particle size was 350 nm, and the appearance was a white silicone emulsion composition, the transmittance was not measured. ..

<Comparative Example 1>
An aqueous solution containing 11.3 parts by mass of polyoxyethylene cetyl ether having an added number of 13 mol of ethylene oxide and 0.1 part by mass of 1-hydroxyethane-1,1-diphosphonic acid was added into an oily mixture without phase separation. An attempt was made to prepare a composition for preparing a silicone emulsion in the same manner as in Example 1 except that it was added, but the amino-modified silicone and 1-hydroxyethane-1,1-diphosphonic acid aggregated and could not be emulsified. rice field. The prescriptions are shown in Table 1.
In Comparative Example 1, since the polyvalent acids 1-hydroxyethane-1, 1-diphosphonic acid were blended before emulsification, a network with the amino-modified silicone was formed, and aggregation of the amino-modified silicone and the like occurred. As a result, it is considered that creaming and sedimentation separation occurred and emulsification could not be performed.

<Comparative Example 2>
A composition for preparing a silicone emulsion was prepared in the same manner as in Example 2 except that an aqueous solution containing 0.1 part by mass of 1-hydroxyethane-1,1-diphosphonic acid was added to an oily mixture without phase separation. Attempts were made, but amino-modified silicone and 1-hydroxyethane-1,1-diphosphonic acid aggregated and could not be emulsified.
Also in Comparative Example 2, since the polyvalent acids 1-hydroxyethane-1, 1-diphosphonic acid were blended before emulsification, a network with the amino-modified silicone was formed, and aggregation of the amino-modified silicone and the like occurred. As a result, it is probable that creaming and sedimentation separation occurred and emulsification could not be performed.
Table 1 shows the above prescription and evaluation results.

<Silicone emulsion composition formulation and its evaluation results>

In Table 1, a comparison between Examples and Comparative Examples shows a silicone emulsion composition containing a polyvalent acid according to the present invention and having excellent stability over time.

Claims (9)

(a) Surfactants and
(b) Amino-modified silicone and
(c) Containing at least one compound selected from polyvalent acids or salts thereof,
The blending amount of the amino-modified silicone is 5% by mass or more, and
The blending amount of at least one compound selected from the polyvalent acid or a salt thereof is 0.1% by mass or more.
A silicone emulsion composition in which the particle size of the emulsion particles is less than 1 μm. The silicone emulsion composition according to claim 1, wherein the particle size is less than 150 nm. The silicone emulsion composition according to claim 1 or 2, which has a transmittance of 75% or more at a wavelength of 550 nm after storage at 40 ° C. for 1 month. (B) Any one of claims 1 to 3, wherein the product of the number of amines (milli equivalent / g) of the amino-modified silicone and the blending amount (mass%) of the amino-modified silicone is 2 or more. The silicone emulsion composition according to. The silicone emulsion composition according to any one of claims 1 to 4, wherein the (a) surfactant is contained in an amount of 45% by mass or more and 90% by mass or less with respect to the (b) amino-modified silicone. .. (d) The silicone emulsion composition according to claim 1 to 5, further comprising a monovalent acid. A method for producing a silicone emulsion composition.
An emulsification step of emulsifying a mixture of amino-modified silicone and a surfactant and water to obtain a composition for preparing a silicone emulsion.
The composition for preparing a silicone emulsion obtained in the emulsification step comprises an acid blending step of blending an aqueous solution containing at least one compound selected from a polyvalent acid or a salt thereof.
A silicone emulsion composition in which the blending amount of the amino-modified silicone is 5% by mass or more, and the blending amount of at least one compound selected from the polyvalent acid or a salt thereof is 0.1% by mass or more. How to make things. A method for stabilizing a silicone emulsion composition.
A step of blending an aqueous solution containing at least one compound selected from a polyvalent acid or a salt thereof into a composition for preparing a silicone emulsion obtained by emulsifying a mixture of an amino-modified silicone and a surfactant and water is included. ,
The blending amount of the amino-modified silicone in the obtained emulsion composition is 5% by mass or more, and the blending amount of at least one compound selected from the polyvalent acid or a salt thereof is 0.1% by mass. A method for stabilizing a silicone emulsion composition, which comprises the above-mentioned aqueous solution. A cosmetic and / or a softener / fiber treatment agent containing the silicone emulsion composition according to any one of claims 1 to 4.