JP7591874B2 - Polyvalent acid-containing silicone emulsion composition, its production method and stabilization method for said composition - Google Patents

Description

The present invention relates to a silicone emulsion composition containing a polyacid and an amino-modified silicone, a method for producing the composition, a method for stabilizing the composition, and a cosmetic, a fabric softener, and a fabric treatment agent that contain the composition.

Amino-modified silicones are widely used in textile treatments, fabric softeners, cosmetics, etc., because they exhibit excellent conditioning effects. When blending amino-modified silicones, they can be blended in an oil state, but blending them in an emulsion state is more preferable and common. Blending amino-modified silicones in an emulsion state has a lower viscosity and is easier to work with, and can be more easily blended into aqueous emulsion products such as cosmetics than blending them in an oil state.
On the other hand, amino-modified silicone deteriorates and discolors over time due to the action of ultraviolet light, heat, and other components, so it is often mixed together with antioxidants and radical inhibitors.For example, Patent Document 1 and Patent Document 2 disclose a method of suppressing discoloration by adding polyvalent acid such as hydroxyethanediphosphonic acid to emulsion-type cosmetic compositions and textile product treatment compositions containing amino-modified silicone.However, the amount of amino-modified silicone mixed in the above-mentioned applications is less than 10% at most, and in applications where the amount of amino-modified silicone mixed is desired to be 10% or more, such as silicone emulsion compositions containing amino-modified silicone as the main component, it is difficult to prepare a composition with excellent stability over time due to the aggregation and networking of amino-modified silicone and polyvalent acid.
For this reason, in silicone emulsion compositions that contain amino-modified silicone as a main component and are incorporated into cosmetics and the like, an acid component is often incorporated in order to obtain a stable emulsion with a small particle size, as described in Patent Document 3. However, monovalent acids are mainly used, and it has been difficult to incorporate polyvalent acids.

JP 2008-143817 A JP 2006-249604 A JP 2011-1419 A

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 with amino-modified silicone and form a network, causing instability, especially in the presence of high concentrations of amino-modified silicone. The above problems are unlikely to occur with monovalent acids. Polyvalent acids have multiple reaction points with amino-modified silicone, so they act like crosslinkers, causing aggregation and precipitation of amino-modified silicone, often causing instability. Furthermore, the tendency was greater the greater the amount of polyvalent acid and amino-modified silicone blended.
Therefore, it has been difficult to combine these in silicone emulsion compositions that contain amino-modified silicone as a main component. Therefore, polyvalent acids such as hydroxyethanediphosphonic acid and citric acid have not been used in silicone emulsion compositions that contain amino-modified silicone as a main component and are incorporated into cosmetics, etc., and monovalent acids such as acetic acid and lactic acid have mainly been used.
In the field of textile treatment agents, fabric softeners and cosmetics, there are many stable formulations that combine amino-modified silicone with hydroxyethanediphosphonic acid or citric acid, but for the reasons mentioned above, there are limitations on the amounts of amino-modified silicone and polyvalent acid that can be mixed.

The object of the present invention is therefore to provide a silicone emulsion composition that contains a certain amount or more of amino-modified silicone as the main component and contains a polyvalent acid, which has been difficult to achieve stability over time in the past.

The present inventors have found that when preparing a silicone emulsion composition containing at least a certain amount of amino-modified silicone as a main component, depending on the timing of adding a polyvalent acid, the stability over time of the silicone emulsion composition containing at least a certain amount of amino-modified silicone as a main component and containing a polyvalent acid can be dramatically improved. The present invention is based on this finding.

The present invention relates to
(a) a surfactant;
(b) amino-modified silicone;
(c) at least one compound selected from a polyvalent acid or a salt thereof;
The amount of the amino-modified silicone is 10% by mass or more, and
The present invention provides a silicone emulsion composition in which the blending amount of at least one compound selected from the group consisting of polyvalent acids and salts thereof is 0.1 mass % or more.

The present invention provides a silicone emulsion composition that contains a certain amount or more of amino-modified silicone as the main component and is blended with a polyacid, and has excellent stability over time.

The silicone emulsion composition according to the present invention, its manufacturing method, and the method for stabilizing the silicone emulsion are described in detail below.

The silicone emulsion composition of the present invention comprises:
(a) a surfactant;
(b) amino-modified silicone;
(c) at least one compound selected from a polyvalent acid or a salt thereof;
The amount of the amino-modified silicone is 10% by mass or more, and
The silicone emulsion composition contains at least one compound selected from the group consisting of polyvalent acids and salts thereof in an amount of 0.1% by mass or more.

The method for producing the silicone emulsion composition of the present invention comprises the steps of:
an emulsification step of emulsifying a mixture of an amino-modified silicone and a surfactant with water to obtain a composition for preparing a silicone emulsion;
an acid blending step of blending an aqueous solution containing at least one compound selected from a polyvalent acid or a salt thereof with the silicone emulsion preparation composition obtained in the emulsification step,
The method for producing a silicone emulsion composition is characterized in that the blending amount of the amino-modified silicone is 10% by mass or more, and the blending amount of the at least one compound selected from the polyvalent acid or a salt thereof is 0.1% by mass or more.

The method for stabilizing a silicone emulsion composition of the present invention comprises the steps of:
The method includes a step of blending an aqueous solution containing at least one compound selected from a polyvalent acid or a salt thereof with a silicone emulsion preparation composition obtained by emulsifying a mixture of an amino-modified silicone and a surfactant with water,
The method for stabilizing a silicone emulsion composition is one in which the blending amount of the amino-modified silicone is 10% by mass or more, and the blending amount of the at least one compound selected from the group consisting of polyvalent acids and salts thereof is 0.1% by mass or more.

The present invention includes a step of emulsifying the amino-modified silicone with any surfactant and then adding a polybasic acid. It is believed that the presence of the surfactant between the amino-modified silicone and the polybasic acid prevents the formation of a network between the amino-modified silicone and the polybasic acid even in a range where it has been difficult to obtain stability over time in the past, and allows the polybasic acid and the amino-modified silicone to coexist stably.
The above-mentioned manufacturing method can provide a silicone emulsion composition with excellent stability over time, even if the composition contains 10% by mass or more of amino-modified silicone and 0.1% by mass or more of at least one compound selected from polyvalent acids or their salts. In this specification, "excellent stability over time" means that there is no creaming or sedimentation at the initial stage (24 hours after preparation) or after one month of storage at 40°C.

Even if the product of the amine number (milli-equivalents/g) of the amino-modified silicone and the blending amount (mass%) of the amino-modified silicone is less than 2, a silicone emulsion composition with excellent stability over time can be produced. However, even if the product is 2 or more, which is considered to be an inability to obtain a stable silicone emulsion composition, according to the present invention, a silicone emulsion composition with excellent stability over time can be obtained.

The silicone emulsion composition produced as described above can have an emulsion particle size of less than 1 μm. In this specification, the particle size of the emulsion particles means the z-average value measured by dynamic light scattering. For example, the particle size of the emulsion particles can be measured using a Malvern Nano-ZS90 model machine. The preferred particle size of the emulsion particles is 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 are unlikely to occur, especially over time. When the particle size is 150 nm or less, not only is the composition stable over time, but it also has a translucent to transparent appearance, making it suitable for use in transparent cosmetics.

The emulsification process for the silicone emulsion preparation composition of the present invention can be carried out using a suitable commonly used mixer, such as a homogenizer, colloid mill, homomixer, or high-speed stator rotor agitator.

Known emulsification methods include a liquid crystal emulsification method, a phase inversion emulsification method, a phase inversion temperature emulsification method, and a D phase emulsification method.
The liquid crystal emulsification method is a technique for producing fine emulsion particles that disperse and hold a dispersed phase (oil phase in an O/W emulsion) in liquid crystal formed by a surfactant.
The phase inversion emulsification method is a method for producing an O/W emulsion by dissolving a surfactant in an oil phase, then adding an aqueous phase while stirring, and inverting the continuous phase from the oil phase to the aqueous phase.
The phase inversion temperature emulsification method is an emulsification method that utilizes the phase inversion temperature in a three-component system of nonionic surfactant, oil, and water, in which, at a certain temperature, the nonionic surfactant associates infinitely and separates into a macroscopic phase containing a large amount of oil and water, and when the temperature is further increased, the nonionic surfactant dissolves in the oil phase, forming reverse micelles and solubilizing the water.
The D-phase emulsification method is a method in which a polyhydric alcohol is added as a fourth component to a surfactant, oil, and water to produce a fine O/W emulsion.

The concentration of amino-modified silicone in the silicone emulsion composition obtained by the manufacturing method of the present invention is 10% by mass or more, and there is no upper limit as long as the emulsion composition is stable, but the concentration of amino-modified silicone is, for example, 10 to 60% by mass, and preferably 15 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 (dilution water) to the emulsion and mixing it.

The surfactant used in the silicone emulsion composition of the present invention is not particularly limited as long as it disperses the amino-modified silicone or the amino-modified silicone and other oil components uniformly in water. A general surfactant is usually used, and in addition to cationic, anionic, or nonionic surfactants or amphiphilic surfactants, silica particles that act as surface active agents can also be included. Nonionic surfactants are preferred because they do not deteriorate the environment and are less irritating to the human body. Examples of such surfactants include polyoxyalkylene alkyl ethers such as polyoxyethylene alkyl ethers and polyoxyethylene polyoxypropylene alkyl ethers; polyoxyethylene alkyl phenyl ethers; polyoxyethylene alkyl esters; polyoxyethylene sorbitan esters; polyhydric alcohol fatty acid esters such as glycerin esters, sorbitan fatty acid esters, and sucrose fatty acid esters; ethoxylated fatty acids; and ethoxylated fatty acid amides. Among these, polyoxyethylene alkyl ethers and polyoxyethylene polyoxypropylene alkyl ethers are preferred. The total HLB (hydrophilic group/lipophilic group balance) of the nonionic surfactants used is preferably within the range of 8 to 17, and more preferably within the range of 10 to 16.

The surfactant content is not limited, but when preparing a transparent to translucent amino microemulsion having a transmittance of 75% or more at a wavelength of 550 nm after one month of storage at 40°C in the emulsion composition of the present invention, a surfactant content of 30% by mass or more of the amino-modified silicone provides particularly excellent stability over time, and a surfactant content of 45% by mass or more provides even better stability over time. On the other hand, if the surfactant content exceeds 90% by mass, the viscosity of the silicone emulsion composition increases, making it difficult to handle. A more preferred 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 terms of its structure or properties, but is usually an amino-modified organopolysiloxane having an average composition represented by the general formula (1). This amino-modified organopolysiloxane is a component in the aqueous emulsion that provides cosmetic functions, in particular imparting a smooth feel and ease of passing hair.
R ¹ _a R ² _b SiO _(4-ab)/2 (1)
In general formula (1), R ¹ may be the same or different within a molecule and is selected from an unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a hydroxyl group. Examples of unsubstituted monovalent hydrocarbon groups include a methyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; an aryl group such as a phenyl group; and an aralkyl group such as 2-phenylethyl or 2-phenylpropyl. Of these, a methyl group and/or a phenyl group is preferred, and it is particularly preferred that 50 mol % or more of the methyl group is present. ^{R 1} may partially contain an alkoxy group having 1 to 3 carbon atoms.

^R2 in general formula (1) is a hydrocarbon group containing one or more amino groups, and is represented by the following general formula (2).
-R ³ -[(NR ⁴ )-R ⁵ ] _t NR ⁶ R ⁷ (2)
In general formula (2), R ³ and R ⁵ each represent a divalent C1 to C18 hydrocarbon residue, R ⁴ , R ⁶ and R ⁷ each represent a hydrogen atom or an unsubstituted C1 to C10 alkyl group, and t represents 0 or an integer of 1 to 6.

Examples of divalent C1-C18 hydrocarbon residues R ³ and R ⁵ are methylene, ethylene, n-propylene, iso-propylene, n-butylene, iso-butylene, t-butylene, n-pentylene, iso-pentylene, hexylene, such as n-hexylene, heptylene, such as n-heptylene, octylene, such as n-octylene and iso-octylene, such as 2,2,4-trimethylpentylene, nonylene, such as n-nonylene, decylene, dodecylene, such as n-dodecylene, octadecylene. Examples of alkyl groups R ⁴ , R ⁶ and R ⁷ are the alkyl groups up to C10 mentioned for R ¹ .

Examples of R ² groups include -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( _CH3 ), _-CH2 - _CH2 - _CH2 -N( _CH3 ) ₂ - _CH2 - _CH2 -NH- _CH2 - _CH2 -NH2- _CH2 - _{CH2 - CH2-} 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} - _CH2 - _{CH2 -} NH( _CH2CH3 ), _-CH2 - _CH2 -CH2-NH- _CH2 - _CH2 -N( _CH2CH3 ) ₂ , _{-CH2 - CH2} An example is _--CH.sub.2-- NH-- _CH.sub.2 -- _CH.sub.2 -- _NH (cyclo- _{C.sub.6H.sub.11} ).
In amino-modified silicones suitable for use in cosmetics, R ² is -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 ₂ —CH ₂ —NH ₂ are preferred, and —CH ₂ —CH ₂ —CH _2- NH- _CH2 - _CH2 - _NH2 .

In the general formula (1), a and b are natural numbers indicating the average number of the substituents R ¹ and R ² bonded to the silicon of the amino-modified polyorganosiloxane, and a+b is 1.8 to 2.2. The molecular structure of the organopolysiloxane may be not only linear but also branched, but preferably has a linear structure.

The amino-modified silicone used in the silicone emulsion composition of the present invention may be any silicone that can form a silicone emulsion composition, and although there are no limitations on its form, it is preferably oil-like. It may also be a single-component polymer or a mixture of multiple polymers. Although some of the components may be solids such as resins, it is preferable that the overall composition exhibits oil-like fluidity.

The oil component is not limited to amino-modified silicone, and other components may be used in combination. Any modified oil, including dimethylpolysiloxane, may be used. Also, a resin component may be included. Also, the type of these oils or resins may be one type or multiple types.
There is no limitation on the ratio of the amino-modified silicone to these oils and/or resins. It is sufficient that the desired properties of the amino-modified silicone are exhibited as an emulsion. However, it is preferable that the amino-modified silicone and the oil and/or 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 amino-modified organopolysiloxane oil, and can be produced by methods known to those skilled in the art. A typical synthesis method for amino-modified organopolysiloxane oil is as follows. That is, the introduction of an aminoalkyl group to a silicon atom is usually carried out at the silane stage, and an aminoalkylsilane is first produced. The aminoalkylsilane is hydrolyzed to produce an amino-group-containing siloxane oligomer or an amino-group-containing disiloxane, which is then subjected to a re-equilibration reaction of the Si-O bond with a linear oligomer or cyclic oligomer of dimethylsiloxane in the presence of an alkali catalyst to produce an amino-modified organopolysiloxane oil. If hexamethyldisiloxane is used in the re-equilibration reaction, a terminal trimethylsilyl type amino-modified organopolysiloxane oil can be obtained. By adjusting the ratio of the oligomers or disiloxane used in the production, an amino-modified organopolysiloxane oil having a specific kinetic viscosity and amine number 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 having one or more amino groups is preferably 15 to 600. The ratio a/b is a measure of the ratio of siloxane units having no amino group to siloxane units having amino groups. The amine number, which is expressed as the volume (mL) of 1 N hydrochloric acid required to neutralize 1 g of the siloxane, is also used to indicate the total amount of amino groups in the amino-modified organopolysiloxane.
This amine number will vary depending on the number of amino groups in one molecule of the amino-modified silicone and the molecular weight. The amine number of the amino-modified organopolysiloxane of the present invention is not particularly limited, but is preferably 0.1 to 3.0, and more preferably 0.15 to 2.0. If the amine number is less than 0.1, the ability to adsorb to the hair surface will be weak, and if the amine number exceeds 3.0, the number of hydrophilic amino groups will be too large, making it difficult to adsorb to hair.
The structural factors of the amino-modified silicone are preferably within the above ranges when applied to cosmetics and the like, but the present invention is not limited thereto.

There is no particular limit to the lower limit of the product of the number of amines (milli-equivalents/g) and the amount blended (mass%), but it is particularly effective when it is 2 or more. The upper limit of the product is preferably 180 or less, and more preferably 120 or less.

The at least one compound selected from the polyvalent acids or salts thereof of the present invention is not particularly limited, and examples thereof include 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri(methylenephosphonic acid), ethylenediaminetetra(methylenephosphonic acid), triethylenetetraminehexaacetic acid, ethylenediaminediacetic acid, ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, ethylenediethyltriamine-N,N,N',N'',N'''-pentaacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminetetrakis(methylenephosphonic acid), nitrilotris(methylenephosphonic acid), phosphoric acid, pyrophosphoric acid, metaphosphoric acid, polyphosphoric acid, citric acid, succinic acid, malic acid, tartaric acid, phthalic acid, and salts thereof. Among these, citric acid, succinic acid, phthalic acid, phosphoric acid, pyrophosphoric acid, polyphosphoric acid, EDTA, EHDP, and salts thereof are preferred, and pyrophosphoric acid, polyphosphoric acid, EDTA, HEDP, and salts thereof are more preferred.

Examples of the monovalent acid of the present invention include formic acid, lactic acid, acetic acid, propionic acid, and hydrochloric acid, among which lactic acid and acetic acid are preferred, and more preferred than lactic acid.

The silicone emulsion composition of the present invention may further contain a monovalent acid in addition to the polyvalent acid or its salt. The process for adding the monovalent acid is not particularly limited, but when the monovalent acid is added to the composition for preparing the silicone emulsion (i.e., when added in the emulsification process), silicone emulsion particles with a smaller particle size can be formed, and as a result, a silicone emulsion composition with even better stability over time can be produced.

The silicone emulsion composition of the present invention may contain water. There are no limitations on the water that can be used, but it is preferable to use ion-exchanged water, preferably with a pH of 2 to 12, and particularly preferably with a pH of 4 to 10. It is not recommended to use mineral water, but when used, it is desirable to use it together with a metal deactivator or the like. The amount of water added during emulsification is an amount equivalent to 40 to 90% by mass, preferably 40 to 60% by mass, of the emulsion composition of the present invention. The emulsion composition of the present invention is stable against dilution with water, and further dilution is possible after preparation of the emulsion, and there is no particular limitation on the amount of water in the diluted emulsion.

The emulsion composition of the present invention may contain other components that are acceptable depending on the purpose, as long as they do not impair the purpose of the present invention. For example, other components that are acceptable as blending components include preservatives such as quaternary ammonium-containing compounds, sodium benzoate, phenoxyethanol, methylparaben, propylparaben, salicylic acid, glycerin, butylene glycol, propylene glycol, and isopropanol, amino acid-based active agents, various surfactants, thickeners such as guar gum and xanthan gum, and fragrances.

When the emulsion of the silicone emulsion composition of the present invention is blended into cosmetics, it is possible to suppress changes in the color tone of the cosmetics, particularly yellowing, and this effect is particularly pronounced when it is blended into cosmetics such as conditioners, shampoos, and rinses, in which amino-modified silicones are often used.
When the silicone emulsion composition of the present invention is incorporated into a textile treatment agent, it is possible to suppress discoloration of the textile.

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

Next, the present invention will be described with reference to examples. However, the present invention is not limited to these examples. The silicone emulsion composition of the present invention in the examples was evaluated as follows. All viscosity values are at a temperature of 25°C.

When the silicone emulsion composition is a transparent to translucent amino microemulsion, for example, when the silicone emulsion particles have a particle size of 150 nm or less, the temporal stability and transparency are evaluated.When the silicone emulsion composition is a white macroemulsion, for example, when the silicone emulsion particles have a particle size of more than 150 nm, only the temporal stability is evaluated.
<Method of measuring particle size>
The particle size of the silicone emulsion particles in the emulsion composition was determined as the z-average value measured using a Nano-ZS90 model machine manufactured by Malvern Instruments.
<Method for evaluating stability over time>
80 g of the prepared silicone emulsion composition was placed in a 100 ml PP bottle and the bottle was visually inspected for changes over time, such as the presence or absence of creaming and settling, initially (24 hours after preparation) and after one month of storage at 40°C.
Evaluation criteria:
: No creaming or sedimentation at all ◯: Almost no creaming or sedimentation Δ: Tendency of creaming or sedimentation ×: Creaming or sedimentation occurs Visual observation of ◯ or ◯ is considered to be acceptable regardless of transmittance. For transparent to translucent silicone emulsion compositions, 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 stored at 40° C. for one month, after which the change over time in transmittance at a wavelength of 550 nm was checked.

Example 1
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 as the amino-modified silicone was mixed with 6.4, 8.0, 9.6, and 11.3 parts by mass of polyoxyethylene cetyl ether having an ethylene oxide addition number of 13 moles as the surfactant, 0.5 parts by mass of lactic acid as the monovalent acid, and 1.3 parts by mass of phenoxyethanol and 10 parts by mass of glycerin as optional components to obtain an oily mixture without phase separation (three types having different contents of polyoxyethylene cetyl ether having an ethylene oxide addition number of 13 moles).
Purified water was then added to each oily mixture, and the mixture was stirred at 3,000 rpm at room temperature for 20 minutes using an IKA Ultra Turrax T50 Basic Shaft Generator G45G, to obtain a composition for preparing a silicone emulsion.
Next, 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 silicone emulsion preparing composition to obtain a silicone emulsion composition, the formulation of which is shown in Table 1. The obtained silicone emulsion composition was a microemulsion with a translucent to transparent appearance, and all of the compositions had a light transmittance of 95% or more at a wavelength of 550 nm.
In Example 1, four types of silicone emulsion compositions were obtained, each with a different surfactant content. All four types were obtained by first obtaining a silicone emulsion adjusting composition by emulsification, and then blending the polyacid 1-hydroxyethane-1,1-diphosphonic acid. The blended amount of the amino-modified silicone was 20% by mass, and all of them showed no or almost no creaming or sedimentation, and had excellent stability over time.
When the surfactant to amino-modified silicone ratio was relatively high at 48% or 57%, the particle size was smaller (25 nm and 20 nm, respectively), and a highly transparent silicone emulsion composition was obtained that had a higher transmittance after storage at 40° C. for one month.

Example 2
As the amino-modified silicone, 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 was mixed with 4.0 parts by mass of polyoxyethylene dodecyl ether having an ethylene oxide addition number of 10 moles and a propylene oxide addition number of 4 moles as a surfactant 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 Ultra Turrax T50 Basic Shaft Generator G45G manufactured by IKA to obtain a silicone emulsion preparation composition.
Next, an aqueous solution containing 0.4 parts by mass of 1-hydroxyethane-1,1-diphosphonic acid was added to the silicone emulsion preparing composition to obtain a silicone emulsion composition, the formulation of which is shown in Table 1. The obtained silicone emulsion composition had a white appearance and was a macroemulsion.
In Example 2, a silicone emulsion composition was obtained by emulsification, and then the polyacid 1-hydroxyethane-1,1-diphosphonic acid was added to obtain a silicone emulsion composition. The amount of amino-modified silicone added was 36% by mass, and there was no creaming or settling, showing excellent stability over time.
The surfactant blending ratio to the amino-modified silicone was 11%, which was lower than in Example 1, and the particle size was 350 nm. The silicone emulsion composition had a white appearance, so transmittance measurements were not performed.

<Comparative Example 1>
An attempt was made to prepare a composition for preparing a silicone emulsion in the same manner as in Example 1, except that an aqueous solution containing 11.3 parts by mass of polyoxyethylene cetyl ether with an ethylene oxide addition number of 13 moles and 0.1 parts by mass of 1-hydroxyethane-1,1-diphosphonic acid was added to an oily mixture without phase separation, but the amino-modified silicone and 1-hydroxyethane-1,1-diphosphonic acid aggregated and emulsification was not possible. The formulation is shown in Table 1.
In Comparative Example 1, the polyvalent acid 1-hydroxyethane-1,1-diphosphonic acid was blended before emulsification, which caused the formation of a network with the amino-modified silicone, resulting in aggregation of the amino-modified silicone. As a result, creaming and sedimentation occurred and emulsification was not possible, even though the blended amount of amino-modified silicone was the same as in Example 1.

<Comparative Example 2>
An attempt was made to prepare a composition for preparing a silicone emulsion in the same manner as in Example 2, except that an aqueous solution containing 0.1 parts by mass of 1-hydroxyethane-1,1-diphosphonic acid was added to an oily mixture without phase separation, but the amino-modified silicone and 1-hydroxyethane-1,1-diphosphonic acid aggregated and emulsification was not possible. The formulation is shown in Table 1.
In Comparative Example 2 as well, the polyvalent acid 1-hydroxyethane-1,1-diphosphonic acid was blended before emulsification, which caused a network to be formed with the amino-modified silicone, resulting in aggregation of the amino-modified silicone. As a result, creaming and sedimentation occurred and emulsification was not possible, even though the blended amount of amino-modified silicone was the same as in Example 2.
The above formulations and evaluation results are shown in Table 1.

<Silicone emulsion composition formulation and evaluation results>

In Table 1, a comparison between the Examples and Comparative Examples shows that the silicone emulsion compositions according to the present invention, which contain a polyvalent acid, have excellent stability over time.

Claims (9)

(a) a nonionic surfactant having a sum of HLB of 10 to 16;
(b) an amino-modified silicone;
(c) at least one compound selected from 1-hydroxyethane-1,1-diphosphonic acid or a salt thereof;
(d) a monovalent acid;
The amount of the amino-modified silicone is 15 to 50% by mass,
The (a) nonionic surfactant having a total HLB of 10 to 16 is contained in an amount of 45% by mass or more and 90% by mass or less relative to the (b) amino-modified silicone, and
A silicone emulsion composition in which the blending amount of at least one compound selected from the 1-hydroxyethane-1,1-diphosphonic acid or a salt thereof is 0.1 mass% or more (however, excluding those containing an ethylene glycol monoalkyl ether having an alkyl group having 6 to 12 carbon atoms and those containing glycol ether). The composition according to claim 1, wherein the (a) nonionic surfactant having a total HLB of 10 to 16 is a polyoxyethylene alkyl ether or polyoxyethylene polyoxypropylene alkyl ether having a total HLB of 10 to 16. The composition according to claim 1, wherein the (a) nonionic surfactant having a total HLB of 10 to 16 is polyoxyethylene cetyl ether having 13 moles of ethylene oxide added, or polyoxyethylene dodecyl ether having 10 moles of ethylene oxide added and 4 moles of propylene oxide added. The silicone emulsion composition according to any one of claims 1 to 3, which has a transmittance of 75% or more at a wavelength of 550 nm after storage at 40°C for one month. 5. The silicone emulsion composition according to claim 1, wherein the product of the amine number (milliequivalents/g) of the amino-modified silicone (b) and the blending amount (mass%) of the amino-modified silicone (b) is 2 or greater . The silicone emulsion composition according to any one of claims 1 to 5 , wherein ( d) the monovalent acid is lactic acid . 1. A method for producing a silicone emulsion composition, comprising:
an emulsification step of emulsifying a mixture containing an amino-modified silicone , a nonionic surfactant having a total HLB of 10 to 16, and a monovalent acid with water to obtain a composition for preparing a silicone emulsion;
an acid blending step of blending an aqueous solution containing at least one compound selected from 1-hydroxyethane-1,1-diphosphonic acid or a salt thereof with the silicone emulsion preparation composition obtained in the emulsification step,
The method for producing a silicone emulsion composition (excluding those containing ethylene glycol monoalkyl ether having an alkyl group having 6 to 12 carbon atoms and those containing glycol ether), wherein the blending amount of the amino-modified silicone is 15 to 50 mass %, the nonionic surfactant having a total HLB of 10 to 16 is contained in an amount of 45 mass % or more and 90 mass % or less relative to the amino-modified silicone, and the blending amount of at least one compound selected from 1-hydroxyethane-1,1-diphosphonic acid or a salt thereof is 0.1 mass % or more. A method for stabilizing a silicone emulsion composition, comprising the steps of:
The method includes a step of blending an aqueous solution containing at least one compound selected from 1-hydroxyethane-1,1-diphosphonic acid or a salt thereof with a composition for preparing a silicone emulsion, the composition being prepared by emulsifying a mixture containing an amino-modified silicone, a nonionic surfactant having a total HLB of 10 to 16, and a monovalent acid with water;
The method for stabilizing a silicone emulsion composition (excluding those containing ethylene glycol monoalkyl ether having an alkyl group having 6 to 12 carbon atoms and those containing glycol ether), wherein the blending amount of the amino-modified silicone is 15 to 50 mass %, the nonionic surfactant having a total HLB of 10 to 16 is contained in an amount of 45 mass % or more and 90 mass % or less relative to the amino-modified silicone, and the blending amount of at least one compound selected from 1-hydroxyethane-1,1-diphosphonic acid or a salt thereof is 0.1 mass % or more. A cosmetic and/or a fabric softener/fabric treatment agent, comprising the silicone emulsion composition according to any one of claims 1 to 6 .