JP2015224301A - Manufacturing method of polyisobutylene emulsion and o/w type polyisobutylene emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of high molecular weight polyisobutylene emulsion excellent in stability.SOLUTION: The manufacturing method of polyisobutylene is a manufacturing method of an O/W type polyisobutylene emulsion containing polyisobutylene (A), an emulsifier (B) and water (C) and having a solid content concentration of 1 to 75 mass%, including a mixing process of heating and mixing a mixture by mixing the polyisobutylene (A) and the emulsifier (B), an inversion process of phase inversion from a W/O type emulsion to an O/W type emulsion by gradually adding the water (C) to the heated and mixed mixture of the polyisobutylene (A) and the emulsifier (B) in the mixing process, and the emulsifier (B) is 2 or more mixtures.

Description

  The present invention relates to a method for producing a polyisobutylene emulsion and an O / W type polyisobutylene emulsion.

  Polyisobutylene is regarded as a sanitary safe compound, and in particular, polyisobutylene having a viscosity average molecular weight of 30,000 to 70,000 is a cosmetic, for example, a hair styling agent, a base polymer for lotion cream, a medical product, for example, a haptic agent. It is used for adhesive base polymer. When used in such applications, polyisobutylene having a viscosity average molecular weight of 30,000 to 70,000 is semi-solid, so when applying polyisobutylene to a base material such as a haptic agent, an emulsion is used. It is easier to operate.

  Conventionally, as emulsions of high molecular weight polyisobutylene, emulsions using sucrose fatty acid ester and polyalkylene glycol monoalkyl (or alkenyl) ether as an emulsifier (see, for example, Patent Document 1), sucrose fatty acid ester and polyoxy There have been proposed those using a combination of a sucrose fatty acid ester and various emulsifiers such as an emulsion using ethylene sorbitan monofatty acid ester or branched dodecylbenzenesulfonate (see, for example, Patent Document 2).

  In addition, a polyisobutylene emulsion using a polyoxyethylene polyoxypropylene block polymer having a number average molecular weight of 1,500 to 80,000 and a sucrose fatty acid ester as an emulsifier (for example, Patent Document 3), and a number average molecular weight of 1, A polyisobutylene emulsion in which a polyoxyethylene polyoxypropylene block polymer of 500 to 80,000 and a polyoxyethylene alkyl ether sulfate are used in combination (for example, Patent Document 4), having a number average molecular weight of 1,500 to 80,000 as an emulsifier A polyisobutylene emulsion in which a polyoxyethylene polyoxypropylene block polymer and a polyoxyethylene alkyl ether phosphate ester are used in combination (for example, Patent Document 5) has been proposed.

  Furthermore, a polyisobutylene emulsion using a (meth) acrylic acid ester- (meth) acrylic acid copolymer, a styrene- (meth) acrylic acid copolymer, or polyvinyl alcohol as an emulsifier (for example, Patent Document 6), A polyisobutylene emulsion using, for example, polyisobutylene having an amino group or a carbonyl group introduced at the terminal as an emulsification aid has been proposed (for example, Patent Document 7).

JP 58-208341 A JP 59-122534 A JP-A-7-173346 JP-A-10-204234 JP-A-10-204235 JP 2013-129748 A JP 2013-155372 A

  Cited Document 6 describes that when the average particle size is larger than 10 μm, the creaming of the emulsion is severe and the stability of the emulsion may be significantly impaired. Further, although cited documents 4, 5 and 6 describe the average particle size of the emulsion, no consideration has been given to the problem of reducing the large particle size emulsion which affects the performance of the emulsion.

  The present invention has been made in view of the above, and relates to the production of an emulsion using a high molecular weight polyisobutylene in which it is difficult to produce an emulsion. The present invention focuses not only on the average particle size of the emulsion but also on the particle size distribution of the emulsion. An object of the present invention is to provide a novel method for producing an emulsion that makes it possible to control the particle size distribution of the emulsion. It is another object of the present invention to provide an emulsion having excellent performance with a controlled particle size distribution.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research. As a result, an appropriate amount of warm water was added to a mixture of polyisobutylene and an emulsifier to form a W / O emulsion, and water was further added. In addition, by reversing the phase to an O / W emulsion, it was found that not only the average particle size of the emulsion is small, but also the particle size distribution can be controlled within a narrow range, and the present invention has been completed.

  That is, the method for producing a polyisobutylene emulsion of the present invention comprises polyisobutylene (A) having a viscosity average molecular weight of 30,000 to 70,000, an emulsifier (B), and water (C), and has a solid content concentration of 1 to 1. A method for producing an O / W type polyisobutylene emulsion of 75% by mass, wherein the polyisobutylene (A) and the emulsifier (B) are added to the emulsifier (B) with respect to 100 parts by mass of the polyisobutylene (A). ) The water (C) is added to the mixture of the polyisobutylene (A) and the emulsifier (B) heated and mixed in the mixing step, and the mixing step of heating and mixing the mixture mixed at a ratio of 1 to 35 parts by mass. An inversion step of phase inversion from W / O emulsion to O / W emulsion by gradually adding, and the emulsifier (B) has a number average molecular weight of 1,500-80 000 polyoxyethylene polyoxypropylene block polymer (B1), polyoxyethylene alkyl ether sulfate ester (B2), polyoxyethylene alkyl ether phosphate ester (B3), and sucrose fatty acid ester (B4) It is characterized by being a mixture of two or more.

  The polyisobutylene emulsion of the present invention comprises a polyisobutylene (A) having a viscosity average molecular weight of 60,000 to 70,000 and a polyoxyethylene polyoxypropylene block polymer (B1) having a number average molecular weight of 1,500 to 80,000. ), Two or more emulsifiers (B) selected from the group consisting of polyoxyethylene alkyl ether sulfate (B2), polyoxyethylene alkyl ether phosphate (B3), and sucrose fatty acid ester (B4), and water (C) and an O / W type polyisobutylene emulsion having a solid content concentration of 1 to 75% by mass, wherein the emulsifier (B) is 1 to 35 with respect to 100 parts by mass of the polyisobutylene (A). In addition to being blended at a ratio of part by mass, the number average particle size of the emulsion is 3.0 μm or less, and the number average particle size Wherein the volume ratio of the average particle size of 3.0 or less with respect to.

  According to the present invention, after once forming a W / O type emulsion containing a high molecular weight polyisobutylene, the average particle size is reduced to 3.0 μm or less by phase inversion to the O / W type emulsion. The distribution is narrow and the proportion of emulsions with large particle sizes can be reduced. According to the present invention, it is possible to effectively use a polyisobutylene dispersed phase, and it is possible to easily produce an emulsion that does not cause a problem of foreign matters and nonuniformity due to a large particle size emulsion.

  Hereinafter, the polyisobutylene emulsion and the method for producing the polyisobutylene emulsion according to the present invention will be described.

Polyisobutylene (A) according to the present invention, the isobutylene and in a solvent such as hexane, FCC (fluid catalytic cracking, Fluid Catalytic Cracking) in petroleum refining containing isobutylene C ₄ fraction from, C ₄ fraction from naphtha crackers A copolymer with butene-1 or the like can be used as long as it is obtained by polymerizing the content with a Friedel-Crafts catalyst such as aluminum chloride or boron fluoride and is mainly composed of isobutylene. .

  The polyisobutylene (A) used in the present invention has a viscosity average molecular weight in the range of 30,000 to 70,000. If the viscosity average molecular weight exceeds 70,000, it is difficult to make an emulsion. By using polyisobutylene (A) having a viscosity average molecular weight of 30,000 to 70,000, a smaller amount of emulsion can be used to increase the viscosity. It becomes possible to obtain the base material. Even when polyisobutylene having a viscosity average molecular weight of less than 30,000 is used, an emulsion having a small average particle size and a narrow particle size distribution can be produced by the production method of the present invention. It is particularly effective when polyisobutylene (A) having a molecular weight of 000 to 70,000 is used, and is particularly preferable for polyisobutylene (A1) having a viscosity average molecular weight of 60,000 to 70,000.

  As long as the polyisobutylene (A) used in the present invention is a viscous semi-solid and the viscosity average molecular weight is within the above range, it is composed of a normal temperature solid rubber-like polyisobutylene and a low molecular weight polyisobutylene or butene-1. Mixtures with low molecular weight polybutenes and the like can also be used. The polyisobutylene (A) preferably has a low chlorine concentration from the viewpoint of stability when it is made into an emulsion. The chlorine concentration is preferably 100 ppm or less, and particularly preferably 10 ppm or less.

  The emulsifier (B) according to the present invention comprises a polyoxyethylene polyoxypropylene block polymer (B1) having a number average molecular weight of 1,500 to 80,000, a polyoxyethylene alkyl ether sulfate (B2), and a polyoxyethylene alkyl ether phosphorus. It is a mixture of two or more selected from the group consisting of acid ester (B3) and sucrose fatty acid ester (B4).

  The polyoxyethylene polyoxypropylene block polymer (B1) is a block polymer having an ethylene oxide polymer block portion and a propylene oxide polymer block portion in at least one molecule. For example, the following general formula ( Examples thereof include polymers as shown in 1).

  In the formula (1), a, b and c are each independently an integer of 1 to 700, preferably a is 5 to 450, b is 15 to 700, and c is 5 to 40.

  The number average molecular weight of the polyoxyethylene polyoxypropylene block polymer (B1) is 1,500 to 80,000, preferably 10,000 to 30,000. Outside this range, that is, when the number average molecular weight is less than 1,500 or more than 80,000, it is not preferable because sufficient emulsion stability cannot be obtained.

  The polyoxyethylene alkyl ether sulfate (B2) is obtained by sulfating an ethylene oxide adduct such as an alkylphenol such as nonylphenol or a higher alcohol such as lauryl alcohol. In the present invention, a salt of polyoxyethylene alkyl ether sulfate (B2) is preferably used. Examples of the salt of polyoxyethylene alkyl ether sulfate (B2) include alkali metal salts such as sodium and ammonium salts. The number of moles of ethylene oxide added to the polyoxyethylene alkyl ether sulfate (B2) is not particularly limited, but those in the range of 1 to 20 are preferably used.

  As an example of the polyoxyethylene alkyl ether sulfate (B2), a polyoxyethylene alkyl ether sulfate ammonium salt represented by the following general formula (2) can be exemplified as a more preferable example.

式（２）中、Ｒ^１は炭素数１０〜１８のアルキル基、またはアリール基である。

In formula (2), R ¹ is an alkyl group having 10 to 18 carbon atoms or an aryl group.

In Formula (2), R ¹ is particularly preferably an aryl group, and specific examples include polyoxyethylene alkylphenyl ether sulfate ammonium salt.

  As described above, the polyoxyethylene alkyl ether sulfate (B2) salt is obtained by sulfating an ethylene oxide adduct such as an alkylphenol such as nonylphenol or a higher alcohol such as lauryl alcohol by a conventional method, and then converting it to a sulfate ester salt. Can be manufactured. For the sulfation, sulfuric acid, fuming sulfuric acid, chlorosulfonic acid, sulfuric anhydride and the like are used. The obtained sulfate ester can be neutralized with a metal hydroxide such as sodium hydroxide, aqueous ammonia or the like by a conventional method to form a salt. An ammonium salt can be produced directly by reacting sulfamic acid or the like.

  The polyoxyethylene alkyl ether phosphate ester (B3) is a phosphate ester of a higher alcohol ethylene oxide adduct such as lauryl alcohol. Polyoxyethylene alkyl ether phosphate ester (B3) is an anionic or nonionic interface produced by reacting a higher alcohol ethylene oxide adduct such as lauryl alcohol with a phosphoric acid agent such as anhydrous phosphoric acid or phosphorus oxychloride. It is an activator. The number of moles of ethylene oxide added is not particularly limited, but those in the range of 1 to 20 are preferably used. As polyoxyethylene alkyl ether phosphate (B3), a salt can also be used suitably.

  Specific examples of the polyoxyethylene alkyl ether phosphate (B3) include any of the following general formula (3), general formula (4), and general formula (5), or a mixture thereof.

In Formula (3), X ¹ and X ² are each independently a substituent represented by hydrogen, K, Na, Li, NH ₂ , NHR ′, NR ′ ₂ , or NHOH. R ² is an alkyl group having 8 to 14 carbon atoms, and n2 is an integer of 1 to 20. R ′ is an alkyl group having 1 to 5 carbon atoms.

In formula (4), X ³ is a substituent represented by hydrogen, K, Na, Li, NH ₂ , NHR ′, NR ′ ₂ , or NHOH. R ³ and R ⁴ are each independently an alkyl group having 8 to 14 carbon atoms, and n3 and n4 are each independently an integer of 1 to 20. R ′ is an alkyl group having 1 to 5 carbon atoms.

In the formula (5), R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 8 to 14 carbon atoms, and n5, n6 and n7 are each independently an integer of 1 to 20. .

  As the polyoxyethylene alkyl ether phosphate ester (B3), those having 14 or more HLB (Hydrophil Lipophil Balance) are preferably used.

  Sucrose fatty acid ester (B4) is an ester of sucrose with fatty acids such as stearic acid, palmitic acid, oleic acid and the like, for example, higher fatty acids obtained from hardened beef tallow, and lower fatty acids such as acetic acid and isobutyric acid The sucrose part is a nonionic surfactant having a hydrophilic group and a fatty acid part having a hydrophobic group. As the sucrose fatty acid ester (B4), those having an HLB of 15 or more are preferably used.

  The isobutylene emulsion concerning this invention is mix | blended so that emulsification solid content, ie, the total amount of the said polyisobutylene (A) and the said emulsifier (B) may be 1-75 mass%.

  In the polyisobutylene emulsion according to the present invention, the blending amount of the emulsifier (B) is used in the range of 1 to 35 parts by mass with respect to 100 parts by mass of the polyisobutylene (A). Here, the blending amount of the emulsifier (B) is as follows: polyoxyethylene polyoxypropylene block polymer (B1), polyoxyethylene alkyl ether sulfate (B2), polyoxyethylene alkyl ether phosphate (B3), and sucrose It means the blending amount of two or more mixtures selected from the group consisting of fatty acid esters (B4).

  The emulsifier (B) is composed of a polyoxyethylene polyoxypropylene block polymer (B1), a polyoxyethylene alkyl ether sulfate ester (B2), a polyoxyethylene alkyl ether phosphate ester (B3), or a sucrose fatty acid ester ( B4) is preferably used as a mixture.

  As an emulsifier (B), polyoxyethylene polyoxypropylene block polymer (B1), polyoxyethylene alkyl ether sulfate (B2), polyoxyethylene alkyl ether phosphate (B3), or sucrose fatty acid ester (B4) 1 to 30 parts by weight of polyoxyethylene polyoxypropylene block polymer (B1) and 0.1 to 5 other emulsifiers with respect to 100 parts by weight of polyisobutylene (A). It is preferable to mix and use at a ratio of parts by mass. If the ratio of the polyoxyethylene polyoxypropylene block polymer (B1) is less than 1 part by mass or more than 30 parts by mass with respect to 100 parts by mass of the polyisobutylene (A), it is preferable because sufficient emulsion stability cannot be obtained. Absent. Further, the ratio of polyoxyethylene alkyl ether sulfate (B2), polyoxyethylene alkyl ether phosphate (B3), or sucrose fatty acid ester (B4) to 0.1 parts by mass of polyisobutylene (A) is 0.00. Less than 1 part by mass or more than 5 parts by mass is not preferable because sufficient emulsion stability cannot be obtained.

  The polyisobutylene emulsion according to the present invention may be used in combination with an emulsion stabilizer in addition to the components (A) to (C) described above. By adding an emulsion stabilizer, it is possible to obtain an emulsion in which the emulsification performance does not deteriorate even under acidic conditions or high temperature conditions.

  The emulsion stabilizer itself usually does not exhibit emulsification performance, but the emulsion stability is increased by adding the emulsion stabilizer, and specific examples thereof include polysaccharides such as xanthan gum. This xanthan gum is the name of a polysaccharide produced by Xanthomonas Compestris separated from cabbage, and is used in food additives, medicines, thickeners, dispersants, suspensions, emulsion stabilizers and the like.

  In the case of using an emulsion stabilizer such as xanthan gum in the polyisobutylene emulsion according to the present invention, for example, xanthan gum may be used at a ratio of 0.1 to 2 parts by mass with respect to 100 parts by mass of polyisobutylene (A). it can. When the amount of xanthan gum exceeds 2 parts by mass with respect to 100 parts by mass of polyisobutylene (A), it is not preferable because sufficient emulsion stability cannot be obtained.

  In addition, polyisobutylene emulsions may contain preservatives, antibacterial agents, antibacterial agents, etc. as compounding agents depending on the application, and some of these may have reduced medicinal effects unless under acidic conditions. There is. In such a case, a pH adjuster is added to the polyisobutylene emulsion.

  In the present specification, the pH adjuster means an additive added to make the polyisobutylene emulsion according to the present invention acidic, or the emulsion of the present invention as a result of being blended into the emulsion to be acidic in itself. Means an additive that makes it acidic, "Commentary on Standards for Cosmetic Raw Materials 2nd Edition (edited by the Japan Standards Association, Yakuho Nippo Inc.)", "Japanese Pharmacopoeia Commentary (edited by the Japan Standards Association) , Yodogawa Shoten Co., Ltd.) ”.

  The pH adjusting agent used in the present invention is, for example, citric acid, anhydrous citric acid, benzoic acid, salicylic acid, sorbic acid, dehydroacetic acid, ascorbic acid, aspartic acid, isostearic acid, isosylaminocaproic acid, undecylenic acid, erythorbine Acid, oleic acid, glycyrrhizic acid, β-glycyrrhizic acid, succinic acid, tartaric acid, stearic acid, sorbic acid, lactic acid, palmitic acid, glacial acetic acid, behenic acid, myristic acid, silicic anhydride, phosphoric acid, boric acid, hydrochloric acid, etc. Can be mentioned.

  The blending amount of the pH adjusting agent is not particularly limited because it varies depending on the purpose of use or application, and an amount sufficient to exert its function is used. However, in general, the emulsion composition is used in an amount of about 0.01 to 5% by mass, preferably 0.05 to 1% by mass. These pH adjusters can be used alone or in combination as appropriate, and are used for emulsions whose pH is adjusted in the range of 3 to 5.

In the present invention, the polyisobutylene emulsion is
A mixing step (I) of heating and mixing a mixture of polyisobutylene (A) and emulsifier (B) in a proportion of 1 to 35 parts by weight of the emulsifier (B) with respect to 100 parts by weight of the polyisobutylene (A);
Inversion step of phase inversion from W / O type emulsion to O / W type emulsion by gradually adding water (C) to the mixture of polyisobutylene (A) and emulsifier (B) heated and mixed in the mixing step ( II).

The heating temperature in the mixing step (I) is, for example, any temperature in the range of 40 ° C. to 70 ° C., and preferably in the range of 45 ° C. to 65 ° C.
In the mixing step (I), a predetermined amount of polyisobutylene (A) and a mixture of two or more emulsifiers (B) are charged into a container heated to a specific temperature, and mixed by heating and stirring. In the container, after the polyisobutylene (A) is charged, the emulsifier (B) may be charged, or after the emulsifier (B) is charged, the polyisobutylene (A) may be charged. In order to shorten the mixing time, the emulsifier (B) is dissolved in a small amount of water (C1) in advance and then charged into the container, or a small amount of water (C1) and the emulsifier (B) are charged into the container. After dissolving, it is preferable to mix with polyisobutylene (A). When the emulsifier (B) is dissolved in water (C1) in advance, 10 parts by mass to 1000 parts by mass of water (C1) may be used with respect to 100 parts by mass of the emulsifier (B). Two or more emulsifiers (B) may be blended separately or simultaneously.

  After the mixing step (I), the mixture in the container, that is, a mixture of polyisobutylene (A) and emulsifier (B), or polyisobutylene (A) and emulsifier (B) and a small amount of water (C1) The emulsion of the present invention can be obtained by gradually adding water (C) or the remaining water (C2) while stirring the mixture.

  By gradually adding water (C) or the remaining water (C2) into the mixture in the container, the W / O emulsion can be inverted to the O / W emulsion. The addition of water (C) or the remaining water (C2) to the mixture in the container is preferably carried out in several steps, although it depends on the amount of emulsion charged.

In order to prepare a polyisobutylene emulsion having a small average particle size and a narrow particle size distribution, the inversion step (II) is preferably
A first emulsification step (IIa) in which water (C) or part of remaining water (C2) (C3) is heated and then added to the mixture in the container to form a W / O type emulsion;
A second emulsification step (IIb) in which the remaining water (C4) is gradually added to the W / O type emulsion formed in the first emulsification step (IIa) to reverse the O / W type emulsion;
Is preferably performed.

  In the first emulsification step (IIa), water (C3) that is a part of water (C) or the remaining water (C2) is heated to the same temperature as the temperature of the mixture in the container. preferable. In addition, in the first emulsification step (IIa), water (C3) added to the container or water (C3) which is a part of the remaining water (C2) is added to 100 parts by mass of polyisobutylene (A). It is preferable to add 10 to 50 parts by mass.

  In the second emulsification step (IIb), the remaining water (C4) added to the mixture in the container is from the temperature of the water (C3) added in the vessel in the first emulsification step (IIa). It is preferable that it is a low temperature, and it is preferable that it is 0 degreeC-20 degreeC. Moreover, it is preferable that water (C4) which is the remainder added in the mixture in a container is added in several steps preferably.

  In the present invention, the emulsion stabilizer and additives may be added before or after the formation of the emulsion. In addition, an emulsion stabilizer or additive may be mixed with water (C) in advance, or the emulsion stabilizer or additive may be added to the container as it is.

  In the production method of the polyisobutylene emulsion of the present invention, if necessary, not only a simple stirrer but also a planetary stirrer, a universal turbine mixer, a colloid mill, a homogenizer and the like can be used.

  The number average particle size of the polyisobutylene emulsion produced by the method of the present invention is 3.0 μm or less, preferably 2.0 μm or less. In addition, the polyisobutylene emulsion produced by the method of the present invention has a small variation in particle size, and the ratio of the volume average particle size to the number average particle size showing the particle size distribution is preferably 3.0 or less.

  The particle size and average particle size of polyisobutylene emulsion can be measured by analytical methods such as centrifugal sedimentation, light diffraction stirring method, electrical resistance method, photon correlation method, etc. It can be easily measured with a counter.

  The number average particle size and volume average particle size of the polyisobutylene emulsion can be determined by measuring the particle size distribution using, for example, a Coulter counter.

  Since the emulsion of the present invention has a sufficiently small number average particle size and a narrow particle size distribution, the content of large particle size emulsion particles is small. Therefore, since the polyisobutylene emulsion has a large surface area, the polyisobutylene component can be used effectively. Further, for example, problems such as foreign matter and non-uniformity due to large-sized emulsion particles do not occur in the blended product.

More specifically, since the polyisobutene emulsion of the present invention has a sufficiently small particle size and a narrow particle size distribution, a thin and uniform pressure-sensitive adhesive layer can be easily formed. When used, it can exhibit excellent adhesive performance in a small amount.
Further, when the polyisobutene emulsion of the present invention has a sufficiently small particle size and a narrow particle size distribution, when blended into a coating film or the like, a thin, uniform coating film with few defects can be easily formed.

  The polyisobutylene emulsion prepared by the method of the present invention can be used in cosmetics such as spray-type hair styling agents, mousse-type hair styling agents, creams, lotions, shampoos and the like. Since the polyisobutene emulsion of the present invention has a sufficiently small particle size and a narrow particle size distribution, an excellent texture can be expected when used as a treatment, for example.

  When the polyisobutylene emulsion according to the present invention is used as a hair styling agent, a cationic polymer, a volatile or non-volatile silicone, a silicone tetrachloride (for example, trade name: “ABIL (registered trademark)”-QUAT, manufactured by Th. Goldschmidt) Hair conditioning agents such as perfluoropolyethers (eg trade name: “FOMBLIN®”, manufactured by Montefluos), protein hydrolysates and tetrachloride protein hydrolysates; antibacterial agents; zinc pyridinethione or Octopirox Anti-dandruff agent; Foam enhancer; Pearlescent agent; Perfume; Dye; Colorant; Preservative; Viscosity modifier; Protein; Buffer agent; Lubricant such as polyol; Tea tree, Ylang Ylang, Jasmine, Rose, Sandal Herbal extracts such as wood; Min It can be blended components such as; oil; honey. The hair styling agent obtained using the polyisobutylene emulsion according to the present invention can impart elasticity and styling ease to the hair.

  Moreover, when using the polyisobutylene emulsion concerning this invention for cosmetics, such as a cream and a lotion, you may contain protein, a silicone oil, squalane, a fragrance | flavor, etc.

  The polyisobutylene emulsion prepared by the method of the present invention can be used in a medical product, for example, a haptic agent. When the polyisobutylene emulsion according to the present invention is used as a haptic agent, a polymer solution such as gelatin, gum arabic, polyvinyl alcohol or methyl cellulose; an endothermic agent such as kaolin or bentonite; a bactericidal agent such as boric acid; a rosin or an ester gum Etc. can be blended. When the polyisobutylene emulsion according to the present invention is used as a haptic agent, a haptic agent having appropriate adhesion to the skin, little sagging, improved moisture prevention and water retention can be obtained.

  The emulsion of the present invention has excellent stability because the particle size is sufficiently small and the particle size distribution is narrow.

The stability of the emulsion of the present invention can be evaluated by, for example, a centrifugal test (acceleration test).
More specifically, using a centrifuge, put 10 ml of a sample in a 50 ml container, centrifuge at 15 ° C. × 1500 rpm for 30 minutes, visually confirm the presence or absence of separation of the emulsion, and the volume of the separated aqueous phase Stability can be evaluated by the ratio.

  The emulsion of the present invention preferably has a value of the above centrifugation test of 5% or less, more preferably 3% or less. When the value of the centrifuge test is 3% or less, the emulsion and the applied product have high stability and excellent workability including dynamic environments such as pipe transportation, stirring, and mixing during production.

  Embodiments of the present invention are illustrated below by examples, but the present invention is not limited to these examples.

Example 1
1000 g of polyisobutylene having a viscosity average molecular weight of 65,000 and a chlorine concentration of 8 ppm in a 5 l kneader, 150 g of polyoxyethylene polyoxypropylene block polymer ("Epan" U-108 (registered trademark), Daiichi Kogyo Seiyaku Co., Ltd.) A polyisobutylene emulsion was prepared from 30 g of sucrose fatty acid ester (“DK ester” F-160 (registered trademark), Daiichi Kogyo Seiyaku Co., Ltd.), 2.5 g of citric acid, and 1302.5 g of water.

  First, 32% by mass of the total polyisobutylene (A) was charged into a kneader maintained at 60 ° C., stirred for 30 minutes, 3% by mass of water (C1) of the total charged water, and polyoxyethylene polyoxy The total amount of the propylene block polymer (B1) and sucrose fatty acid ester (B4) was stirred and mixed for 10 minutes, then charged into the kneader, stirred for 30 minutes and dissolved in the polyisobutylene (A). Thereafter, the remaining amount of polyisobutylene (A) was added and stirred for 60 minutes (mixing step).

  Subsequently, 5% by mass of water (C3) was added to the kneader and stirred at 60 ° C. for 30 minutes to form a W / O type emulsion (first emulsification step).

  Thereafter, 92% by mass of water (C4) was added gradually, and the mixture was stirred for 175 minutes to reverse the phase of the O / W emulsion (second emulsification step). The temperature of water (C4) used in the second emulsification step was 10 ° C., and the heating in the kneader was stopped. Citric acid was finally charged into the kneader. The number average particle diameter of the obtained polyisobutylene emulsion was 1.2 μm, and the ratio of the volume average particle diameter to the number average particle diameter was 2.8. Moreover, the result of the centrifugation test was 2%.

(Example 2)
A polyisobutylene emulsion was produced in the same procedure as in Example 1 except that the temperature of water (C4) charged in Step 6 was changed from 10 ° C to 15 ° C.
The number average particle size of the obtained polyisobutylene emulsion was 1.7 μm, and the ratio of the volume average particle size to the number average particle size was 2.5. Moreover, the result of the centrifugation test was 2%.

(Example 3)
A polyisobutylene emulsion was produced in the same procedure as in Example 1 except that the temperature of water charged in Step 6 was changed from 10 ° C to 60 ° C.
The number average particle diameter of the obtained polyisobutylene emulsion was 1.2 μm, and the ratio of the volume average particle diameter to the number average particle diameter was 2.8.

(Comparative Example 1)
A polyisobutylene emulsion was prepared by the following steps with the same formulation as in the examples.

  Polyisobutylene (A) was charged into a kneader maintained at 60 ° C. and stirred for 60 minutes, and then 3% by mass of water (C1) of the total charged water, polyoxyethylene polyoxypropylene block polymer (B1), The total amount of sucrose fatty acid ester (B4) was stirred for 10 minutes and mixed, then charged into a kneader, stirred for 90 minutes and dissolved in polyisobutylene (A).

  Subsequently, 97% by mass of water (C2), which is the balance of the input water, was charged into the kneader and stirred for 180 minutes to form an O / W emulsion. The temperature of water (C2) used for forming the O / W type emulsion was 10 ° C., and heating was stopped in the kneader. Citric acid was finally charged into the kneader. The average particle diameter of the obtained polyisobutylene emulsion was 1.8 μm, and the ratio of the volume average particle diameter to the number average particle diameter was 3.5. Moreover, the result of the centrifugation test was 7%.

  As described above, the method for producing a polyisobutylene emulsion according to the present invention is useful for producing a polyisobutylene emulsion having excellent stability and is suitable for a polyisobutylene emulsion for cosmetics and medical use.

Claims (4)

An O / W type polyisobutylene emulsion comprising a polyisobutylene (A) having a viscosity average molecular weight of 30,000 to 70,000, an emulsifier (B), and water (C) and having a solid content concentration of 1 to 75% by mass. A manufacturing method comprising:
A mixing step of heating and mixing a mixture obtained by mixing the polyisobutylene (A) and the emulsifier (B) at a ratio of 1 to 35 parts by mass of the emulsifier (B) with respect to 100 parts by mass of the polyisobutylene (A); ,
Phase inversion from a W / O emulsion to an O / W emulsion by gradually adding the water (C) to the mixture of the polyisobutylene (A) and the emulsifier (B) heated and mixed in the mixing step. Reversing process to
Including
The emulsifier (B) is a polyoxyethylene polyoxypropylene block polymer (B1) having a number average molecular weight of 1,500 to 80,000, a polyoxyethylene alkyl ether sulfate ester (B2), a polyoxyethylene alkyl ether phosphate ester ( A process for producing a polyisobutylene emulsion, which is a mixture of two or more selected from the group consisting of B3) and a sucrose fatty acid ester (B4). The inversion step includes
A first emulsification step of heating a part of the water (C) and then adding to the mixture to form a W / O type emulsion;
A second emulsification step of gradually adding the remainder of the water (C) to the W / O emulsion to invert the O / W emulsion;
The method for producing a polyisobutylene emulsion according to claim 1, comprising:   The emulsifier (B) is 1 to 30 parts by mass of a polyoxyethylene polyoxypropylene block polymer (B1) per 100 parts by mass of the polyisobutylene (A), polyoxyethylene alkyl ether sulfate (B2), polyoxyethylene. The method for producing a polyisobutylene emulsion according to claim 1 or 2, wherein the mixture is a mixture obtained by mixing 0.1 to 5 parts by mass of an alkyl ether phosphate (B3) or a sucrose fatty acid ester (B4). A polyisobutylene (A) having a viscosity average molecular weight of 60,000 to 70,000,
Polyoxyethylene polyoxypropylene block polymer (B1), polyoxyethylene alkyl ether sulfate ester (B2), polyoxyethylene alkyl ether phosphate ester (B3), and sucrose fatty acid having a number average molecular weight of 1,500 to 80,000 An O / W type polyisobutylene emulsion having a solid content concentration of 1 to 75% by mass, comprising two or more emulsifiers (B) selected from the group consisting of esters (B4) and water (C),
The emulsifier (B) is blended at a ratio of 1 to 35 parts by mass with respect to 100 parts by mass of the polyisobutylene (A), and the emulsion has a number average particle size of 3.0 μm or less and a volume average with respect to the number average particle size. An O / W type polyisobutylene emulsion characterized by having a particle size ratio of 3.0 or less.