JP5063946B2 - Oil-in-water emulsion composition - Google Patents

Description

  The present invention relates to a stable oil-in-water emulsion composition comprising a polymer emulsifier, an oil component, and water.

  It is known that a nonionic emulsifier / oil / water emulsion composition forms a solubilized state in which the oil is apparently dissolved in the aqueous phase at a solubility higher than the solubility in a limited temperature range below the cloud point. ing. For this reason, it has been known that when the system is kept in a solubilized state for a certain period of time and then cooled, an emulsion composition having a high oil component content and a fine average particle diameter of oil droplets can be obtained ( Non-patent document 1).

  However, depending on the type of the oil component, there has been a problem that the average particle size of the oil droplets increases with time and the emulsion composition becomes unstable.

On the other hand, in recent years, amphiphilic polymers having a hydrophilic group and a lipophilic group have been proposed, and their specific surface activity has attracted attention. Among them, amphiphilic polymers having nonionic hydrophilic groups and hydrophobic groups have also been proposed, but only examples used as water-soluble polymers having film-forming properties are disclosed, and as emulsifiers Thus, it cannot be said that the emulsifying performance of the amphiphilic polymer is fully utilized (Patent Document 1).
Hideo Nakajima, Surface, 36, 39-50, 1998 JP 2001-316422 A

  An object of the present invention is to provide an oil-in-water emulsified composition containing a polymer emulsifier, having a fine average particle diameter of oil droplets, and having good stability.

  The present invention allows a system in which a polymer emulsifier (A) containing a nonionic hydrophilic structural unit (a) and a hydrophobic structural unit (b), an oil component (B), and water (C) are mixed. An oil-in-water emulsified composition obtained by cooling to 40 ° C. or lower after being in a solution state is provided.

  According to the present invention, it is possible to obtain an emulsion composition in which the average particle size of oil droplets is fine and the stability is good.

[Polymer emulsifier (A)]
The polymer emulsifier (A) of the present invention comprises a nonionic hydrophilic structural unit (a) and a hydrophobic structural unit (b).

  Here, the hydrophilicity in the hydrophilic structural unit means that the monomer forming the structural unit has a solubility in distilled water at 20 ° C. (g / 100 g water) of 8 or more. Means that the monomer forming the structural unit has a solubility (g / 100 g water) in distilled water at 20 ° C. of less than 8.

  Examples of the nonionic hydrophilic structural unit (a) include a structural unit derived from a nonionic hydrophilic monomer (hereinafter referred to as nonionic hydrophilic monomer (a)), and a hydrophilic group to which a nonionic hydrophilic group is added after polymerization. Sex structural units and the like.

  Examples of the nonionic hydrophilic monomer (a) include methoxypolyethylene glycol (meth) acrylate, methoxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate, ethoxypoly (ethylene glycol / propylene glycol) mono (meth) acrylate, polyethylene Examples include glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate.

  Among these, a nonionic hydrophilic monomer represented by the general formula (3) is preferable, and a methoxypolyethylene glycol (meth) acrylate having a polyethylene oxide chain polymerization degree of 1 to 30, particularly 1 to 9, is more preferable. .

Wherein R ¹ , R ² and R ³ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ⁴ represents a linear or branched alkylene group having 1 to ⁴ carbon atoms. R ⁵ represents an alkyl group having 1 to 2 carbon atoms, X ¹ represents an oxygen atom or NH, and n represents a number of 1 to 30.)
In general formula (3), R ¹ and R ² are preferably hydrogen atoms. R ⁴ is preferably an ethylene group or a propylene group, and more preferably an ethylene group. X ¹ is preferably an oxygen atom. n is preferably 1-9.

  Examples of the hydrophobic structural unit (b) include a structural unit derived from a hydrophobic monomer (hereinafter referred to as hydrophobic monomer (b)), a hydrophobic structural unit to which a hydrophobic group is added after polymerization, and the like.

  As the hydrophobic monomer (b), a hydrophobic monomer represented by the general formula (4) is preferable.

(Wherein R ⁶ , R ⁷ and R ⁸ are the same or different and each represents a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and R ⁹ is a linear or branched alkyl group having 1 to 30 carbon atoms or Represents an alkenyl group, and X ² represents an oxygen atom or NH.)
In the general formula (4), R ⁶ and R ⁷ are preferably hydrogen atoms. R ⁹ is preferably an alkyl group or an alkenyl group having 8 to 22 carbon atoms, particularly 12 to 22 carbon atoms, from the viewpoint of emulsion stability. Specific examples include octyl group, 2-ethylhexyl group, decyl group, lauryl group, myristyl group, cetyl group, stearyl group, oleyl group, and behenyl group. X ² is preferably an oxygen atom.

  Specific examples of the hydrophobic monomer (b) include butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, butyl (meth) acrylamide, octyl ( Examples include meth) acrylamide, lauryl (meth) acrylamide, stearyl (meth) acrylamide, and behenyl (meth) acrylamide. Of these, lauryl (meth) acrylate and stearyl (meth) acrylate are preferred.

  The arrangement of the nonionic hydrophilic structural unit (a) and the hydrophobic structural unit (b) may be random, block, or graft. Moreover, structural units other than these structural units may be included.

  From the viewpoint of setting the cloud point of the polymer emulsifier (A) to 50 to 90 ° C., the proportion of the nonionic hydrophilic structural unit (a) in all the structural units constituting the polymer emulsifier (A) of the present invention is as follows. 30 weight% or more is preferable and 40 to 80 weight% is more preferable. In addition, the proportion of the hydrophobic structural unit (b) in all the structural units is preferably 10% by weight or more, more preferably 20 to 60% by weight from the viewpoint of obtaining sufficient emulsification performance.

  Particularly preferred as the polymer emulsifier (A) of the present invention is one having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , X ¹ , X ² and n have the above-mentioned meanings.)
The polymer emulsifier (A) can be obtained by a known synthesis method. For example, it can be obtained by polymerizing a monomer component containing a nonionic hydrophilic monomer (a) and a hydrophobic monomer (b) by a solution polymerization method.

  Examples of the solvent used for the solution polymerization include organic solvents such as aromatic hydrocarbons (toluene, xylene, etc.), lower alcohols (ethanol, isopropanol, etc.), ketones (acetone, methyl ethyl ketone), tetrahydrofuran, diethylene glycol dimethyl ether, etc. can do. The amount of solvent (weight basis) is preferably 0.5 to 10 times the total amount of monomers.

As the polymerization initiator, known radical polymerization initiators can be used, and examples thereof include azo polymerization initiators, hydroperoxides, dialkyl peroxides, diacyl peroxides, and ketone peroxides. The amount of the polymerization initiator is preferably from 0.01 to 5 mol%, more preferably from 0.01 to 3 mol%, particularly preferably from 0.01 to 1 mol%, based on the total amount of the monomer components.
The polymerization reaction is preferably performed in a temperature range of 60 to 180 ° C. under a nitrogen stream, and the reaction time is preferably 0.5 to 20 hours.

  The emulsified composition of the polymer emulsifier (A) / oil / water system forms a solubilized state in a limited temperature range below the cloud point of the polymer emulsifier (A). From the viewpoint of obtaining an emulsified composition having a fine average particle diameter of droplets, the cloud point of the polymer emulsifier (A) used in the present invention is preferably higher than room temperature (25 ° C.) and lower than the boiling point of water. The thing of 50-90 degreeC is more preferable, and the thing of 50-70 degreeC is still more preferable.

  Here, the cloud point is a temperature at which the polymer starts to insolubilize from the solution when the temperature of the aqueous solution of the polymer emulsifier (A) is raised, and details of the cloud point measurement conditions are as shown in the Examples. It is.

  The weight average molecular weight of the polymer emulsifier (A) is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 200,000, from the viewpoints of irritation to skin and emulsification performance. The weight average molecular weight is a value measured by GPC (gel permeation chromatography), and details of the measurement conditions are as shown in the examples.

[Oil component (B)]
The oily component (B) used in the present invention may be either volatile or non-volatile, and the form at normal temperature may be any of solid, paste, and liquid. For example, hydrocarbons such as solid or liquid paraffin, petrolatum, ceresin, ozokerite, montan wax, squalane, squalene; eucalyptus oil, mint oil, camellia oil, macadamia nut oil, avocado oil, beef fat, lard, horse oil, egg yolk oil Oils such as olive oil, carnauba wax, lanolin, jojoba oil; glycerol monostearate, glycerol distearate, glycerol monooleate, isopropyl palmitate, isopropyl stearate, butyl stearate, isopropyl myristate, neocapric acid neo Pentyl glycol, diethyl phthalate, myristyl lactate, diisostearyl malate, diisopropyl adipate, cetyl myristate, cetyl lactate, 1-isostearoyl-3-myristoyl glycol Roll, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, 2-octyldodecyl myristate, neopentyl glycol di-2-ethylhexanoate, 2-octyldodecyl oleate, glycerol triisostearate, glycerol tricaprate, diparamethoxy Ester oils such as glyceryl cinnamate mono-2-ethylhexanoate; higher fatty acids such as stearic acid, palmitic acid and oleic acid; higher alcohols such as stearyl alcohol and cetyl alcohol; natural essential oils such as rosemary, rooibos, royal jelly, and hamelis; Lignans, vitamin E, oil-soluble vitamin C, vitamin A derivatives, ceramides, ceramide-like structural substances (for example, N- (3-hexadecyloxy-2-hydroxypropyl) -N-2-hydroxyeth Hekisadekanamido; see JP 62-228048 JP), oil-soluble ultraviolet absorber, in addition to such functional oil substances such as perfumes, silicones, and fluorine-based oil and the like.

  Among these oily components (B), in combination with the polymer emulsifier (A), from the viewpoint of providing an emulsified composition having significantly superior storage stability over time than the existing nonionic emulsifier, an organic concept Oily component of 0 ≦ inorganicity ≦ 100 and organicity of 500 or less, 100 <inorganicity ≦ 200 and organicity of 600 or less on the diagram (Organic Conceptual Diagram, Yoshio Koda, Sankyo Publishing, 1984) 200 <inorganicity ≦ 300 and organic component having an organic component of 700 or less, 300 <inorganic component and at least one selected from organic components having an organic property of 800 or less are preferable.

  Examples of oily components having 0 ≦ inorganic ≦ 100 and organic property of 500 or less include liquid paraffin such as decane, isopropyl palmitate, isopropyl stearate, butyl stearate, isopropyl myristate, cetyl 2-ethylhexanoate, palmitic Examples include acid 2-ethylhexyl, stearyl alcohol, cetyl alcohol and the like.

  Oily components with 100 <inorganic ≦ 200 and organicity of 600 or less include neopentyl glycol dicaprate, diethyl phthalate, myristyl lactate, diisopropyl adipate, cetyl lactate, neopentyl glycol di-2-ethylhexanoate, Examples include stearic acid and palmitic acid.

  Examples of the oil component with 200 <inorganic ≦ 300 and organic property of 700 or less include glycerin monostearate, glycerin monooleate, diisostearyl malate, and glycerol tricaprate.

  300 <Inorganic and organic components having an organic property of 800 or less include diglyceryl monoisostearate and the like.

[Oil-in-water emulsion composition and production method thereof]
The oil-in-water emulsion composition of the present invention is obtained by solubilizing a system in which a polymer emulsifier (A), an oil component (B), and water (C) are mixed, and then cooling to 40 ° C. or lower. It is done.

  Here, the solubilized state is a state in which the oil component is dissolved in the emulsifier aqueous solution at a level higher than its solubility in water. The details of the conditions for confirming that the system is in a solubilized state are as shown in the examples.

  The polymer emulsifier (A) can be used singly or in combination of two or more, and can be optionally blended, but the content of the polymer emulsifier (A) in the emulsion composition of the present invention is excellent in emulsion stability. From the viewpoint of obtaining, preferably 0.01 to 10% by weight, more preferably 0.1 to 10% by weight.

  The oil component (B) can be used singly or in combination of two or more, and the oil component (B) in the emulsified composition of the present invention provides excellent emulsion stability. From the viewpoint, it is preferably 0.01 to 10% by weight, more preferably 0.1 to 5% by weight.

  Although water (C) can be arbitrarily mixed, the content of water (C) in the emulsion composition of the present invention is preferably 50 to 99% by weight, more preferably 60%, from the viewpoint of obtaining excellent emulsion stability. ~ 99% by weight.

  Further, the weight ratio ((A) / (B)) of the polymer emulsifier (A) and the oil component (B) is preferably 1 / 0.2 to 1/10 from the viewpoint of obtaining excellent emulsion stability. More preferably, it is 1 / 0.2 to 1/5, and particularly preferably 1 / 0.5 to 1/5.

  The emulsion composition of the present invention can further contain a water-soluble organic solvent. Examples of the water-soluble organic solvent include lower alcohols such as ethanol and isopropanol; glycols such as ethylene glycol, propylene glycol, dipropylene glycol, isoprene glycol, 1,3-butylene glycol, and polyethylene glycol (average molecular weight 200 to 1540). Polyhydric alcohols such as polyoxyethylene methyl glucoside, glycerin and diglycerin; tris (2- (2-ethoxyethoxy) ethyl) phosphate and the like, and one or more of them can be used. The content of the water-soluble organic solvent in the emulsion composition of the present invention is preferably 30% by weight or less, more preferably 20% by weight or less, from the viewpoint of obtaining excellent emulsion stability.

  In the oil-in-water emulsion composition of the present invention, for example, the polymer emulsifier (A), the oil component (B), and water (C) are mixed and heated with stirring to a solubilized state. After being kept for a certain time, preferably 10 minutes or more, it is prepared by cooling to 40 ° C. or lower, preferably 30 ° C. or lower, more preferably 0 to 30 ° C.

  In order to obtain an emulsified composition having a large content of the oil component (B) and a fine average particle diameter of oil droplets, the polymer emulsifier (A) is at a certain concentration or more, particularly 5% by weight in the step before cooling. It is preferable to use the above. The emulsion composition after cooling can be diluted with water as necessary. Moreover, a water-soluble organic solvent can also be added in all processes.

  In the present invention, each component may be added and mixed by stirring and mixing by an ordinary method. For example, a homogenizer, an ultrasonic emulsifier, a high-pressure emulsifier or the like can be used.

  In the present invention, the average particle diameter of the oil droplets can be controlled by selecting the ratio of the polymer emulsifier (A) and the oil component (B) and the type and amount of the water-soluble organic solvent. The average particle diameter of the oil droplets in the oil-in-water emulsion composition of the present invention is preferably 1 to 200 nm, more preferably 1 to 100 nm.

  In the present invention, the average particle diameter of the oil droplets is the arithmetic average diameter (volume average) obtained from the scattered light intensity measured using a dynamic light scattering particle size distribution measuring device Microtrac UPA (manufactured by HONEYWELL). Use. These particle size measurements are performed at 25 ° C.

  The measurement conditions for each physical property in the following synthesis examples and examples are summarized below.

<Weight average molecular weight measurement conditions>
The weight average molecular weight of the polymer emulsifier is a polystyrene equivalent weight average molecular weight obtained by measuring a 0.5 wt% solution of the polymer emulsifier in chloroform under the following conditions by GPC.

GPC measurement conditions Column: KF-804L 2 manufactured by Showa Denko KK, eluent: 1 mmol / L Farmin DM20 (manufactured by Kao Corporation) / CHCl ₃ , flow rate: 1.0 mL / min, column temperature: 40 ° C. , Detector: Differential refractometer <NMR measurement conditions>
The proportion of each constituent unit in all constituent units of the polymer emulsifier was determined by measuring a 1% by weight solution of the polymer emulsifier dissolved in deuterium-substituted dimethyl sulfoxide by proton nuclear magnetic resonance spectrum.

<Cloud point measurement conditions>
The cloud point was confirmed according to the following method in accordance with the book written by Shinsei Surfactant, Takehiko Fujimoto, Sanyo Chemical Industries, 1992). That is, a 5% by weight aqueous solution of a polymer emulsifier is held at a constant temperature for 30 minutes, and it is observed whether the polymer emulsifier is insolubilized from the solution. The temperature at which the polymer emulsifier began to become insoluble when the temperature was raised was taken as the cloud point.

<Solubilization condition confirmation conditions>
It was confirmed according to the following method that the system was in a solubilized state. That is, a mixed solution of a polymer emulsifier, an oil component, and water is held at a constant temperature for 10 minutes to observe whether the turbidity of the solution changes. Since the turbidity of the solution increases when the system is not in the solubilized state, the system is said to be in the solubilized state when the turbidity of the solution does not change.

Synthesis Example 1 (Synthesis of polymer emulsifier (A-1))
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 60 g of methoxypolyethylene glycol (9 mol) methacrylate, 40 g of lauryl methacrylate, and 100 g of polymerization solvent methyl ethyl ketone, initiator V-65 (Wako Pure Chemical ( 1.0 g) was prepared, and a polymerization reaction was carried out at 65 ° C. for 6 hours. Thereafter, drying was performed to obtain a polymer emulsifier (A-1). The weight average molecular weight of the obtained polymer emulsifier (A-1) was 73,000. The proportion of structural units derived from methoxypolyethylene glycol (9 mol) methacrylate in all the structural units of the obtained polymer emulsifier (A-1) was 63% by weight, and the proportion of structural units derived from lauryl methacrylate was 37% by weight. It was. The cloud point of the polymer emulsifier (A-1) was 60 ° C.

Synthesis Example 2 (Synthesis of polymer emulsifier (A-2))
A polymer emulsifier (A-2) having a weight average molecular weight of 69,000 was obtained by synthesizing under the same conditions as in Synthesis Example 1 except that 40 g of stearyl methacrylate was used instead of 40 g of lauryl methacrylate. The proportion of the structural unit derived from methoxypolyethylene glycol (9 mol) methacrylate in all the structural units of the obtained polymer emulsifier (A-2) was 60% by weight, and the proportion of the structural unit derived from stearyl methacrylate was 40% by weight. It was. The cloud point of the polymer emulsifier (A-2) was 60 ° C.

Example 1
After mixing 1 g of polymer emulsifier (A-1), 1 g of decane (inorganic = 0 on the organic conceptual diagram = 0 and organic is 200), and 9 g of water, the mixture was kept at 60 ° C. for 10 minutes with stirring. Cooled to 25 ° C. Thereafter, 89 g of water was added to prepare an oil-in-water emulsion composition. The system was solubilized at 60 ° C.

Example 2
In the same manner as in Example 1, except that 1 g of decane was used instead of dipentaglycol neopentyl glycol (Esthemol N-01, manufactured by Nisshin Oil Co., Ltd., inorganicity on organic conceptual diagram = 179 and organic 480) An oil-in-water emulsion composition was prepared using 1 g. The system was solubilized at 60 ° C.

Examples 3 and 4
In the same manner as in Example 1, except that the polymer emulsifier (A-2) instead of the polymer emulsifier (A-1) and 1 g of decane, respectively, squalane (manufactured by Tokyo Chemical Industry Co., Ltd., organic conceptual diagram) 0.5 g of inorganicity at 0 and organicity of 540), 0.5 g of olive oil (Cropure OL, made by Croda Japan Co., Ltd., inorganicity on organic conceptual diagram = 765 and organicity of 1140) An oil-in-water emulsion composition was prepared using the composition. The system was solubilized at 60 ° C.

Comparative Example 1
An oil-in-water emulsion composition was prepared in the same manner as in Example 2, except that polyoxyethylene (7 mol) dodecyl ether was used instead of the polymer emulsifier (A-1). The system was solubilized at 60 ° C.

Comparative Example 2
In the same manner as in Example 1, except that the mixture of the polymer emulsifier (A-1), decane and water was heated to 50 ° C. and held for 10 minutes, and then cooled to 25 ° C. Two-layer separation of the system occurred, and a good emulsion was not obtained. At 50 ° C. the system was not solubilized.

  About the oil-in-water type emulsion composition obtained in Examples 1-4 and Comparative Examples 1-2, the compounding composition of each component, and the average particle diameter of the emulsified oil droplets in the obtained emulsion composition and at 25 ° C Table 1 also shows the average particle diameter of the emulsified oil droplets after storage for 1 hour or after storage at 25 ° C. for 3 months. All the emulsified compositions were confirmed to be oil-in-water by electric conductivity.

As is apparent from the results in Table 1, the oil-in-water emulsion compositions obtained in the examples had small oil droplet average particle sizes and good storage stability. On the other hand, the oil-in-water emulsion composition obtained in Comparative Example 1 was poor in storage stability. In Comparative Example 2, a good emulsion was not obtained.

Claims (6)

A polymer emulsifier having a cloud point of 50 to 90 ° C. comprising a nonionic hydrophilic structural unit (a) represented by the general formula (1) and a hydrophobic structural unit (b) represented by the general formula (2) (A), an oily component (B), and an oil-in-water emulsion composition obtained by cooling to 40 ° C. or lower after making a system in which water (C) is mixed solubilized ,
The oil component (B) is 0 ≦ inorganic ≦ 100 and the organic property is 500 or less on the organic conceptual diagram, 100 <inorganic property ≦ 200 and the organic property is 600 or less, 200 <inorganic property ≦ 300 and containing at least one selected from oily components having an organic property of 700 or less, 300 <inorganic and organic components having an organic property of 800 or less,
The average particle size of the oil droplets is 1 to 200 nm,
Oil-in-water emulsion composition.

(Wherein R ¹ , R ² , R ⁶ and R ⁷ represent a hydrogen atom, R ³ and R ⁸ are the same or different, represent a hydrogen atom or a methyl group, R ⁴ represents an ethylene group, and R ⁵ Represents a methyl group, R ⁹ represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, X ¹ and X ² are the same or different and represent an oxygen atom or NH, and n represents The number of 1-30 is shown.)   The ratio of the nonionic hydrophilic structural unit (a) in the total structural units constituting the polymer emulsifier (A) is 40 to 80% by weight, and the ratio of the hydrophobic structural unit (b) in the total structural units is The oil-in-water emulsion composition according to claim 1, which is 20 to 60% by weight. The oil-in-water solution according to claim 1 or 2 , wherein the blending ratio of the polymer emulsifier (A) and the oil component (B) is (A) / (B) (weight ratio) = 1 / 0.2 to 1/10. Type emulsified composition. A polymer emulsifier having a cloud point of 50 to 90 ° C. comprising a nonionic hydrophilic structural unit (a) represented by the general formula (1) and a hydrophobic structural unit (b) represented by the general formula (2) An oil-in-water type in which the average particle size of oil droplets is 1 to 200 nm, after the system in which (A), the oil component (B), and water (C) are mixed is solubilized and then cooled to 40 ° C. or lower. A method for producing an emulsified composition comprising:
The oil component (B) is 0 ≦ inorganic ≦ 100 and the organic property is 500 or less on the organic conceptual diagram, 100 <inorganic property ≦ 200 and the organic property is 600 or less, 200 <inorganic property ≦ 300 and contains at least one selected from oily components having organicity of 700 or less, 300 <inorganic and organic components having 800 or less organicity,
A method for producing an oil-in-water emulsion composition.

(Wherein R ¹ , R ² , R ⁶ And R ⁷ Represents a hydrogen atom, R ³ And R ⁸ Are the same or different and each represents a hydrogen atom or a methyl group; ⁴ Represents an ethylene group, R ⁵ Represents a methyl group, R ⁹ Represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, and X ¹ And X ² Are the same or different and each represents an oxygen atom or NH, and n represents a number of 1 to 30. ) The ratio of the nonionic hydrophilic structural unit (a) in the total structural units constituting the polymer emulsifier (A) is 40 to 80% by weight, and the ratio of the hydrophobic structural unit (b) in the total structural units is The manufacturing method of the oil-in-water type emulsion composition of Claim 4 which is 20 to 60 weight%. The oil-in-water oil according to claim 4 or 5, wherein the blending ratio of the polymer emulsifier (A) and the oil component (B) is (A) / (B) (weight ratio) = 1 / 0.2 to 1/10. A method for producing a mold emulsion composition.