Microcapsule water dispersion

By using polysaccharides with cationically modified branched chain structure in the aqueous dispersion of microcapsules, the problems of decreasing fluidity and uneven particle size after long-term storage of microcapsules are solved, and the effects of high dispersion stability and good particle size uniformity are achieved.

JP7658679B2Active Publication Date: 2025-04-08KAO CORP
View PDF 6 Cites 0 Cited by

Patent Information

Application Number
JP2022105138
Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Priority Date
2021-06-30
Filing Date
2022-06-29
Publication Date
2025-04-08
Estimated Expiration
2042-06-29

AI Technical Summary

Technical Problem

After long-term storage of existing microcapsule aqueous dispersions, the fluidity of existing microcapsules decreases and aggregates to form a gel, resulting in insufficient dispersion stability and uneven particle size.

Method used

Microcapsules with silicate shells containing one or more organic compounds are used, and polysaccharides with cationically modified branched chain structure are added to the aqueous dispersion.

Benefits of technology

The dispersion stability of the microcapsule aqueous dispersion is significantly improved, the fluidity after long-term storage is maintained, the particle size variation is reduced, and the particle size uniformity is improved.

✦ Generated by Eureka AI based on patent content.

Smart Images

  • Figure 0007658679000001
    Figure 0007658679000001
  • Figure 0007658679000002
    Figure 0007658679000002
  • Figure 0007658679000003
    Figure 0007658679000003
Patent Text Reader

Abstract

To provide an aqueous microcapsule dispersion that shows stable dispersion even after long-term storage, with its microcapsules having excellent particle size: namely, small variations in particle size and high uniformity of particle size.SOLUTION: The present invention relates to an aqueous microcapsule dispersion containing component (A) and component (B). Component (A) is a microcapsule having a shell containing an inorganic substance as a constituent, and a core containing at least one organic compound inside the shell. Component (B) is a polysaccharide containing a cation-modified branched chain structure.SELECTED DRAWING: None
Need to check novelty before this filing date? Find Prior Art

Description

[Technical field]

[0001] The present invention relates to an aqueous dispersion of microcapsules. [Background technology]

[0002] Various microcapsules encapsulating fragrances and bioactive substances have been developed and used in a wide range of business fields, such as cosmetics, pharmaceuticals, general household products, and printing. As a method for producing such microcapsules, chemical methods such as suspension polymerization, mini-emulsion polymerization, emulsion polymerization, precipitation polymerization, dispersion polymerization, interfacial polycondensation, and liquid curing methods; physicochemical methods such as liquid drying, phase inversion emulsification, and coacervation methods; and mechanical methods such as spray drying and heterocoagulation methods are used. In many of the methods for producing the microcapsules, an aqueous dispersion in which the microcapsules are dispersed in an aqueous medium is obtained, and from an industrial point of view, it is desirable to use the obtained aqueous dispersion of microcapsules as it is without performing isolation operations such as filtration and drying. For this reason, various studies have been conducted on aqueous dispersions of microcapsules.

[0003] Patent Document 1 describes a fluid and stable silica capsule composition that is composed of a silica capsule suspension and an adjuvant, and uses a cationic polymer such as a vinylpyrrolidone / dimethylaminoethyl methacrylate copolymer as the adjuvant. Patent Document 2 describes a microcapsule composition containing microcapsules dispersed in an aqueous phase and a viscosity modifier for the purpose of increasing the dispersion stability of the microcapsule composition by the viscosity modifier, and describes that the viscosity modifier is an acrylate copolymer, a cationic acrylamide copolymer, or a polysaccharide. Patent Document 3 describes an aqueous suspension of microcapsules having a silicate shell in which an organofunctional silane is used as a colloidal silicate blocking agent in order to improve the stability of the aqueous suspension of microcapsules having a silicate shell. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] European Patent Application Publication No. 2862597 [Patent Document 2] International Publication No. 2018 / 053356 [Patent Document 3] Special Publication No. 2012-501849 Summary of the Invention [Problem to be solved by the invention]

[0005] Here, the aqueous dispersion of microcapsules has a problem that the fluidity decreases depending on the difference in specific gravity between the microcapsules and the aqueous medium, the viscosity of the aqueous medium, and the particle size and shape of the microcapsules. For example, if the specific gravity of the microcapsules is relatively small compared to the aqueous medium, creaming occurs over time and fluidity is lost, and if the specific gravity of the microcapsules is relatively large, sedimentation occurs over time and fluidity is lost. Furthermore, aqueous dispersions of microcapsules can suffer from the problem of gelation or the formation of aggregates due to physical or chemical changes in the surface of the shell constituting the microcapsules or in the components contained in the aqueous medium, causing the aqueous dispersion to lose its fluidity. However, the techniques of Patent Documents 1 to 3 have insufficient dispersion stability of microcapsules in aqueous dispersions. Although microcapsules are used in a wide range of business fields, there are no fully satisfactory microcapsules in terms of ease of handling as aqueous dispersions. Therefore, there is a demand for an aqueous dispersion of microcapsules that has excellent dispersion stability, in which the formation of microcapsule aggregates is suppressed even when stored for a long period of time, and the decrease in fluidity is suppressed. Furthermore, from the viewpoint of controlling the sustained release of organic compounds encapsulated in microcapsules, there is a demand for an aqueous dispersion of microcapsules in which the microcapsules have a good particle size, little particle size variation, and excellent particle size uniformity, even after long-term storage of the aqueous dispersion of microcapsules. An object of the present invention is to provide an aqueous dispersion of microcapsules which has excellent dispersion stability, in which the microcapsules have a good particle size, and in which there is little variation in particle size and which has excellent particle size uniformity, even after long-term storage. [Means for solving the problem]

[0006] The present inventors have found that the above-mentioned problems can be solved by containing a polysaccharide having a cationically modified branched chain structure in an aqueous dispersion of microcapsules having a shell containing an inorganic substance as a constituent component and a core containing one or more organic compounds inside the shell. That is, the present invention provides an aqueous microcapsule dispersion containing the following components (A) and (B): Component (A): a microcapsule having a shell containing an inorganic substance as a constituent component and a core containing one or more organic compounds inside the shell. (B) Component: Polysaccharide containing a cationically modified branched chain structure Effect of the Invention

[0007] According to the present invention, it is possible to provide an aqueous dispersion of microcapsules which has excellent dispersion stability even after long-term storage, in which the microcapsules have a good particle size, with little particle size variation and excellent particle size uniformity. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] [Microcapsule water dispersion] The microcapsule aqueous dispersion of the present invention (hereinafter, simply referred to as "aqueous dispersion") contains the following components (A) and (B). Component (A): a microcapsule having a shell containing an inorganic substance as a constituent component and a core containing one or more organic compounds inside the shell. (B) Component: Polysaccharide containing a cationically modified branched chain structure Hereinafter, in this specification, the uniformity of particle size, i.e., the small variation in particle size of microcapsules after long-term storage, will also be referred to simply as "uniformity of particle size".

[0009] In the present invention, the term "polysaccharide containing a cationically modified branched chain structure" means a polysaccharide in which at least one of the components of the cationically modified polysaccharide has a cationically modified branched chain structure. In other words, in the present invention, the term "polysaccharide having a cationically modified branched chain structure" is a concept that includes a polysaccharide consisting only of a polysaccharide having a cationically modified branched chain structure, and a mixture containing a polysaccharide having a cationically modified branched chain structure and a polysaccharide having a cationically modified linear structure. In the present invention, the term "cationically modified polysaccharide having a branched chain structure" refers to a modified polysaccharide in which a cationic group has been introduced into the backbone of a polysaccharide in which three or more types of monosaccharides are linked together, and the structure of the modified polysaccharide is a branched chain structure in which at least one monosaccharide molecule has three or more bonding sites with adjacent monosaccharide molecules. In contrast, a "cationically modified polysaccharide having a linear structure" refers to a modified polysaccharide in which a cationic group has been introduced into the backbone of a polysaccharide in which three or more types of monosaccharides are linked together, and the structure of the modified polysaccharide is a linear structure in which each monosaccharide molecule has two bonding sites with adjacent monosaccharide molecules. Here, the cationic group refers to a cationic group or a group that can be ionized to become a cationic group, such as a quaternary ammonium group or a group that can become a cation by adding a proton. In this specification, the "polysaccharide containing a cationically modified branched chain structure" is also simply referred to as a "cationized branched polysaccharide."

[0010] The microcapsule aqueous dispersion of the present invention comprises microcapsules, which are component (A), dispersed in an aqueous medium. In this specification, the term "aqueous medium" refers to a liquid containing at least water, and preferably a medium in which water accounts for the largest proportion. Examples of components other than water that may be contained in the aqueous medium include aliphatic alcohols having 1 to 4 carbon atoms, ketones having 3 to 8 carbon atoms, ethers such as ethyl ether and tetrahydrofuran, and esters such as methyl acetate. The content of water in the aqueous medium is preferably 80% by mass or more, more preferably 90% by mass or more, and 100% by mass or less, and even more preferably 100% by mass, from the viewpoint of improving the dispersion stability of the microcapsules, and from the viewpoint of improving the particle size and uniformity of the particle size of the microcapsules. As the water, ion-exchanged water, deionized water, or distilled water is preferably used. In the present invention, "containing the component (A) and the component (B)" also means "formed by blending the component (A) and the component (B)".

[0011] In the present invention, the microcapsules which are the component (A) in the aqueous dispersion may form flocs. In this specification, the term "floc" refers to a state in which microcapsules dispersed in an aqueous dispersion form aggregates in the aqueous dispersion upon standing still or the like. In the present invention, even after the microcapsules form flocs in the aqueous dispersion, the microcapsules can be returned to the original dispersed state in the aqueous dispersion by stirring or shaking. From this viewpoint, "floc" in this specification means a reversible phenomenon. In contrast, "aggregation" in this specification means a state in which the microcapsules dispersed in the aqueous dispersion form aggregates in the aqueous dispersion by standing still or the like. This aggregate cannot return to the original dispersed state in the aqueous dispersion even if it is stirred or shaken. The aggregate may be redispersed by disintegration, which is a method of disintegrating the aggregates by applying a physical force to the aggregates, but a state in which the aggregates cannot be redispersed by stirring or shaking is called "aggregation". From this viewpoint, "aggregation" in this specification means a phenomenon that is irreversible by dispersion means such as stirring or shaking. In this specification, "stirring" and "shaking" when redispersing microcapsules refer to an operation for applying an external physical force to the aqueous dispersion so as to cause as little damage as possible to the microcapsules, thereby returning the system to a uniformly dispersed state.

[0012] The reason why the present invention has an effect is not clear, but is thought to be as follows. In the present invention, the polysaccharide containing a cationically modified branched chain structure (cationized branched polysaccharide) has a plurality of hydroxyl groups and cationic groups. Therefore, in an aqueous dispersion, the hydroxyl groups of the cationic branched polysaccharide are adsorbed to the surface of the microcapsule, while the cationic groups of the cationic branched polysaccharide are electrostatically repelled by the positive charge of the microcapsule surface, so that the polymer chain of the cationic branched polysaccharide spreads in the aqueous medium, and the steric repulsive force and the electrostatic repulsive force act synergistically between the microcapsules to suppress the formation of microcapsule aggregates. Furthermore, in the present invention, since the cationic branched polysaccharide has a branched chain structure, the phenomenon in which one polymer chain is simultaneously adsorbed to the surfaces of multiple microcapsules to cause the microcapsules to aggregate, that is, the so-called cross-linking aggregation, is unlikely to occur, and the steric repulsive force and the electrostatic repulsive force between the microcapsules described above act more effectively to suppress the formation of microcapsule aggregates, which is considered to result in improved dispersion stability of the microcapsules, improved particle size of the microcapsules, and improved particle size uniformity.

[0013] <Component (A)> The microcapsule aqueous dispersion of the present invention contains, as component (A), microcapsules having a shell containing an inorganic substance as a constituent component and a core containing one or more organic compounds inside the shell. The inorganic material constituting the shell of component (A) is preferably a metal oxide containing a metal element or a metalloid element, and more preferably an inorganic polymer formed by a sol-gel reaction using a metal alkoxide [M(OR)x] as a shell precursor. Here, M is a metal or metalloid element, and R is a hydrocarbon group. Examples of the metal or metalloid element constituting the metal alkoxide include silicon, aluminum, titanium, zirconium, and zinc. From the viewpoints of improving the dispersion stability of the microcapsules, improving the particle size and particle size uniformity of the microcapsules, and reducing the environmental load when released to the external environment, the inorganic material is more preferably an inorganic polymer formed by a sol-gel reaction using one or more metal alkoxides selected from silicon, aluminum, and titanium as the shell precursor, and even more preferably silica formed by a sol-gel reaction using an alkoxysilane as the shell precursor. That is, the (A) component is preferably a microcapsule (silica microcapsule) (hereinafter also referred to as "silica capsule") having a shell containing silica as a constituent component and a core containing one or more organic compounds inside the shell.

[0014] The alkoxysilane is preferably a tetraalkoxysilane from the viewpoints of improving the dispersion stability of the microcapsules, and of improving the particle size and uniformity of the microcapsules. From the same viewpoint as above, the tetraalkoxysilane is preferably one having an alkoxy group having 1 to 4 carbon atoms, more preferably one or more selected from tetramethoxysilane, tetraethoxysilane, and tetraisopropoxysilane, even more preferably one or more selected from tetramethoxysilane and tetraethoxysilane, and still more preferably tetraethoxysilane.

[0015] The organic compound contained in the core of component (A) is preferably one or more selected from fragrances; fragrance precursors; oils; antioxidants; antibacterial agents; fertilizers; surface modifiers for fibers, skin, hair, etc.; cooling agents; dyes; pigments; silicones; solvents; and oil-soluble polymers, more preferably one or more selected from fragrances, fragrance precursors, oils, antioxidants, antibacterial agents, fertilizers, surface modifiers, and solvents, even more preferably one or more selected from fragrances, fragrance precursors, oils, antioxidants, and solvents, still more preferably one or more selected from fragrances, fragrance precursors, and oils, and even more preferably one or more selected from fragrances and fragrance precursors. The organic compounds can be appropriately combined depending on the application of the microcapsules.

[0016] Examples of the fragrance precursor include a compound that reacts with water to release a fragrance component, and a compound that reacts with light to release a fragrance component. Examples of compounds that release fragrance components in reaction with water include silicate ester compounds having an alkoxy component derived from a fragrance alcohol, fatty acid ester compounds having an alkoxy component derived from a fragrance alcohol, acetal compounds or hemiacetal compounds obtained by reacting a carbonyl component derived from a fragrance aldehyde or fragrance ketone with an alcohol compound, Schiff base compounds obtained by reacting a carbonyl component derived from a fragrance aldehyde or fragrance ketone with a primary amine compound, and hemiaminal compounds or hydrazone compounds obtained by reacting a carbonyl component derived from a fragrance aldehyde or fragrance ketone with a hydrazine compound. Examples of compounds that release fragrance components in response to light include 2-nitrobenzyl ether compounds having an alkoxy component derived from a fragrance alcohol, α-ketoester compounds having a carbonyl component derived from a fragrance aldehyde or fragrance ketone, coumaric acid ester compounds having an alkoxy component derived from a fragrance alcohol, etc. These fragrance precursors may be used as polymers, such as the reaction product of some carboxy groups of polyacrylic acid with a fragrance alcohol.

[0017] From the viewpoint of retention of the organic compound, it is preferable that the organic compound has a suitable hydrophobicity. As an index representing the hydrophilicity or hydrophobicity of the organic compound, a cLogP value, which is a calculated value of the common logarithm "logP" of the partition coefficient P (n-octanol / water) between n-octanol and water, can be used. The cLogP value is "LogP (cLogP)" calculated by the method described in A.Leo Comprehensive Medicinal Chemistry, Vol.4 C.Hansch, P.G.Sammens, JB Taylor and CARamsden, Eds., P.295, Pergamon Press, 1990, and is a cLogP value calculated by the program CLOGP v4.01. When the organic compound is composed of a plurality of components, the cLogP value of the organic compound can be calculated by multiplying the cLogP value of each component by the volume ratio of each component and calculating the sum of the results. The cLogP value of the organic compound is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, still more preferably 4 or more, and is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less.

[0018] The shell of the silica capsule encapsulates the core, contains silica as a constituent, and preferably has an average thickness of 5 nm or more and 20 nm or less. From the viewpoint of improving the dispersion stability of microcapsules and the viewpoint of the retention of organic compounds, the shell of the silica capsule is preferably a multi-layer shell having an inner shell that contains silica, which is hydrolysis polycondensation product of alkoxysilane, as a component, and an outer shell that further contains silica, which is hydrolysis polycondensation product of alkoxysilane, as a component, on the outside of the inner shell.A specific example of such silica capsule can be, for example, the silica capsule described in JP 2015-128762 A. When the shell of the silica capsule is a multilayer shell having an inner shell and an outer shell, the inner shell encapsulates the core, contains silica as a constituent component, and preferably has an average thickness of 5 nm or more and 20 nm or less, and the outer shell encapsulates the inner shell, contains silica as a constituent component, and preferably has an average thickness of 10 nm or more and 100 nm or less. The average thickness of the shell of the silica capsule and the average thickness of the inner and outer shells of the silica capsule can be measured by observation with a transmission electron microscope (TEM). Specifically, the thickness of the shell or the inner and outer shells is measured on a photograph under a transmission electron microscope. This operation is performed by changing the field of view five times. The distribution of the average thickness of the shell or the inner and outer shells is obtained from the obtained data. The magnification of the transmission electron microscope is approximately 10,000 times or more and 100,000 times or less, but is appropriately adjusted depending on the size of the silica capsule. Here, as the transmission electron microscope (TEM), for example, the product name "JEM-2100" (manufactured by JEOL Ltd.) can be used.

[0019] The component (A) can be an appropriately synthesized product. When the component (A) is a silica capsule, for example, a suitable production method for the silica capsule can be one produced by a method including the following step I. Step I: A step of subjecting an emulsion obtained by emulsifying an aqueous phase component containing a cationic surfactant with an oil phase component containing an organic compound and a tetraalkoxysilane to a sol-gel reaction under acidic conditions to form silica capsules having a core and a shell composed of silica, and obtaining an aqueous dispersion containing the silica capsules.

[0020] Examples of the cationic surfactant used in step I include alkylamine salts, alkyl quaternary ammonium salts, etc. The number of carbon atoms in the alkyl group of the alkylamine salts and alkyl quaternary ammonium salts is preferably 10 or more and 22 or less. In step I, the content of the cationic surfactant in the aqueous phase component is preferably from 0.05% by mass to 10% by mass, from the viewpoint of dispersion stability of the emulsion droplets. The amount of tetraalkoxysilane used in step I is preferably 10 parts by mass or more relative to 100 parts by mass of the organic compound used in step I, from the viewpoint of promoting the sol-gel reaction and forming a sufficiently dense shell, and is preferably 60 parts by mass or less, from the viewpoint of preventing excess tetraalkoxysilane from remaining in the organic compound. The amount of the oil phase component in the total amount of the emulsion used in step I is preferably 5% by mass or more and 50% by mass or less, from the viewpoint of production efficiency. The stirring means used in preparing the emulsion is not particularly limited, but a homogenizer, a high-pressure disperser, an ultrasonic disperser, or the like having a strong shearing force can be used. The temperature during mixing and emulsification of the aqueous phase component and the oil phase component is preferably 5° C. or higher and 50° C. or lower, from the viewpoint of production stability. The rotation speed of the stirring means and the time for mixing and emulsifying the aqueous phase component and the oil phase component are determined based on the median diameter D of the emulsion droplets. 50 It is preferable to appropriately adjust the amount of the saturation so that the amount of the saturation falls within the range described below. Median diameter D of the emulsion droplets in the emulsion of step I 50 is preferably 0.1 μm or more from the viewpoint of reducing the specific surface area relative to the environment outside the silica capsule and enhancing the retention of organic compounds, and is preferably 50 μm or less from the viewpoint of reducing the particle size of the silica capsule and the physical strength of the silica capsule. Median diameter of emulsion droplets D 50 can be measured by the method described in the Examples.

[0021] The initial pH of the sol-gel reaction in step I is preferably 3.0 or more from the viewpoint of maintaining a balance between the hydrolysis reaction and the condensation reaction of the tetraalkoxysilane, and from the viewpoint of suppressing the production of a highly hydrophilic sol and promoting the progress of encapsulation, and is preferably 4.5 or less from the viewpoint of suppressing the simultaneous formation of a silica shell and the aggregation of emulsion droplets and obtaining silica capsules having a dense shell. In order to adjust the initial pH to a desired level depending on the strength of acidity or alkalinity of the oil phase component containing the organic compound, the pH of the emulsion may be adjusted using a pH adjuster. Examples of acidic pH adjusters include inorganic acids such as hydrochloric acid, nitric acid, and sulfuric acid, organic acids such as acetic acid and citric acid, and liquids in which cation exchange resins or the like have been added to water or ethanol, and preferably at least one selected from hydrochloric acid, sulfuric acid, nitric acid, and citric acid. Examples of alkaline pH adjusters include sodium hydroxide, sodium hydrogen carbonate, potassium hydroxide, ammonium hydroxide, diethanolamine, triethanolamine, trishydroxymethylaminomethane, and the like, and preferably one or more selected from sodium hydroxide and ammonium hydroxide. The pH of the emulsion may be lower than the desired value, in which case it is preferable to adjust it using the alkaline pH adjuster described above.

[0022] The reaction temperature of the sol-gel reaction in step I can be any value as long as it is equal to or higher than the melting point and equal to or lower than the boiling point of water contained as the aqueous phase, but it is preferable to set the temperature within a certain range from the viewpoint of controlling the balance between the hydrolysis reaction and the condensation reaction in the sol-gel reaction and forming a dense shell, preferably from the viewpoint of setting the temperature within a range of 5°C to 60°C, more preferably from 10°C to 50°C. The reaction time of the sol-gel reaction in step I is preferably 0.5 hours or more and 50 hours or less, when the start of the reaction is defined as when the reaction system reaches a predetermined reaction temperature.

[0023] In addition, when the shell of the silica capsule is the above-mentioned multi-layer shell, a specific example of such silica capsule is preferably a silica capsule obtained by adding tetraalkoxysilane as a silica precursor to an aqueous dispersion containing the silica capsule obtained in step I (hereinafter referred to as silica capsule (1)), and carrying out a sol-gel reaction in two stages to form silica as a constituent. That is, the silica capsule in this case is preferably produced by a method including the following steps 1 and 2. Step 1: A step of subjecting an emulsion obtained by emulsifying an aqueous phase component containing a cationic surfactant and an oil phase component containing an organic compound and a tetraalkoxysilane to a sol-gel reaction under acidic conditions to form silica capsules (1) having a core and a first shell composed of silica, and obtaining an aqueous dispersion containing the silica capsules (1). Step 2: A step of adding tetraalkoxysilane to the aqueous dispersion containing the silica capsules (1) obtained in step 1 to carry out a sol-gel reaction to form silica capsules having a second shell that encapsulates the first shell.

[0024] In this specification, when carrying out steps 1 and 2, "encapsulating a first shell" means encapsulating the first shell of the silica capsule (1) formed in step 1, and also includes encapsulating the silica capsule (1). By step 2, a shell is further formed on the silica capsule formed in step 1, and it is considered that the silica capsule obtained in step 2 has an increased shell thickness overall, and has a shell with the shell formed in step 1 as the inner shell and the shell formed in step 2 as the outer shell.

[0025] Step 1 can be carried out in the same manner as in step I described above. The amount of tetraalkoxysilane used in step 2 is preferably 7 parts by mass or more relative to 100 parts by mass of the organic compound used in step 1, from the viewpoint of forming a second shell that encapsulates the first shell, and is preferably 200 parts by mass or less, from the viewpoint of suppressing the production of silica sol that disperses in the aqueous phase and improving the dispersion stability of the silica capsules, and from the viewpoint of achieving a good particle size of the microcapsules and improving particle size uniformity. The total amount of tetraalkoxysilane used when steps 1 and 2 are included, i.e., the total amount of tetraalkoxysilane used in steps 1 and 2, is preferably 30 parts by mass or more and preferably 250 parts by mass or less relative to 100 parts by mass of the organic compound used in step 1.

[0026] (A) Median diameter D of the microcapsules of the component 50 is preferably 100 μm or less, more preferably 75 μm or less, even more preferably 50 μm or less, even more preferably 30 μm or less, and even more preferably 10 μm or less, from the viewpoint of improving the dispersion stability of the microcapsules based on Stokes' equation. From the viewpoint of reducing the specific surface area of ​​the microcapsules and improving the retention of the organic compound, and from the viewpoint of improving the particle size of the microcapsules and improving the particle size uniformity, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.07 μm or more, even more preferably 0.1 μm or more, even more preferably 0.5 μm or more, and even more preferably 1 μm or more. The median diameter D of component (A) 50 can be measured by the method described in the Examples.

[0027] From the viewpoint of improving the dispersion stability of the microcapsules and suppressing a decrease in the fluidity of the microcapsule aqueous dispersion over time, and from the viewpoint of improving the particle size of the microcapsules and improving the particle size uniformity, the difference in specific gravity between the (A) component and the aqueous medium is preferably less than 0.30, more preferably less than 0.20, even more preferably less than 0.15, even more preferably less than 0.10, even more preferably less than 0.05, even more preferably less than 0.01, and even more preferably there is no difference in specific gravity. The specific gravity of component (A) is determined by the specific gravity of the shell and core that constitute component (A), and the mass ratio of the shell to the core.

[0028] <(B) component> The microcapsule aqueous dispersion of the present invention contains, as component (B), a polysaccharide containing a cationically modified branched chain structure (cationized branched polysaccharide), from the viewpoint of improving the dispersion stability of the microcapsules, improving the particle size of the microcapsules, and improving the particle size uniformity. As component (B), the cationic branched polysaccharide may be used alone or in combination of two or more kinds.

[0029] The cationic charge density of component (B), from the viewpoint of improving the dispersion stability of the microcapsules and from the viewpoint of improving the particle size and uniformity of the microcapsules, is preferably 0.3 meq / g or more, more preferably 0.5 meq / g or more, even more preferably 0.7 meq / g or more, and is preferably 3.0 meq / g or less, more preferably 2.5 meq / g or less, even more preferably 2.0 meq / g or less, even more preferably 1.7 meq / g or less, and even more preferably 1.5 meq / g or less. In the present invention, the cationic charge density can be calculated by the following formula (1). Cation charge density (meq / g) = nitrogen content (mass%) ÷ 14 × 10 (1) The nitrogen content in component (B) can be measured by the Kjeldahl method. When two or more cationic branched polysaccharides are used as the component (B), the cationic charge density is determined by calculating a weighted average from the cationic charge density and the blending amount of each cationic branched polysaccharide.

[0030] The polymer backbone of component (B) is preferably a polysaccharide containing linked hexose residues, at least one of which has three or more bonding sites selected from 1,2 bonds, 1,3 bonds, 1,4 bonds, and 1,6 bonds as bonding sites for adjacent hexose residues, more preferably a polysaccharide containing linked hexose residues, at least one of which has three bonding sites selected from 1,2 bonds, 1,3 bonds, 1,4 bonds, and 1,6 bonds as bonding sites for adjacent hexose residues, and even more preferably a polysaccharide having a main chain of hexose residues linked by 1,4 bonds and having a branched chain of hexose residues branched by 1,6 bonds to the hexose residues of the main chain. The number of hexose residues per branched chain may be one or two or more. The hexose constituting the polymer backbone of component (B) is preferably one or more types selected from mannose, galactose, glucose, and xylose.

[0031] Preferred examples of the polymer backbone of component (B) include one or more polysaccharides selected from the group consisting of polysaccharides having a main chain of mannose residues linked through β-1,4 bonds and having branched chains of galactose residues branched through α-1,6 bonds to the mannose residues in the main chain, and polysaccharides having a main chain of glucose residues linked through α-1,4 bonds and having branched chains of glucose residues branched through α-1,6 bonds to the glucose residues in the main chain. When component (B) is a mixture containing a polysaccharide having a cationically modified branched chain structure and a polysaccharide having a cationically modified linear structure, the polysaccharide having a cationically modified branched chain structure contained as a constituent of component (B) may have the above-mentioned polymer skeleton.

[0032] Specific examples of component (B) include cationic galactomannans such as cationic guar gum, cationic tara gum, cationic fenugreek gum, and cationic locust bean gum; cationic starch; and tamarind seed gum. Among these, from the viewpoints of improving the dispersion stability of the microcapsules, of improving the particle size and particle size uniformity of the microcapsules, and of being able to increase the dispersion stability of the microcapsules even in small amounts, component (B) is preferably one or more selected from cationized galactomannan and cationized starch, and more preferably cationized galactomannan.

[0033] Cationic galactomannan is a modified polysaccharide in which a quaternary ammonium group is introduced into galactomannan having a main chain with mannose as a structural unit and a side chain with galactose as a structural unit. Galactomannan can be obtained, for example, from the endosperm of the seeds of legumes. Since cationized galactomannan has multiple hydroxyl groups and cationic groups, and also has a branched chain structure, the three-dimensional repulsive forces and electrostatic repulsive forces between the microcapsules described above act more effectively, suppressing the formation of microcapsule aggregates. As a result, it is believed that the dispersion stability of the microcapsules can be improved, the particle size of the microcapsules can be improved, and the particle size uniformity can be improved. From this viewpoint, the component (B) is more preferably one or more selected from cationized guar gum, cationized tara gum, cationized fenugreek gum, and cationized locust bean gum, even more preferably one or more selected from cationized guar gum and cationized tara gum, even more preferably cationized guar gum, and even more preferably one or more selected from O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride (display name: guar hydroxypropyltrimonium chloride) and a hydroxypropyl derivative of O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride (display name: hydroxypropyl guar hydroxypropyltrimonium chloride).

[0034] Examples of commercially available component (B) include cationized guar gums such as the Jaguar series manufactured by Solvay and the Labolgum series manufactured by DSP Gokyo Food & Chemical Co., Ltd.; cationized tara gums such as "Catinal CTR-100" manufactured by Toho Chemical Industry Co., Ltd.; cationized locust bean gums such as "Catinal CLB-100" manufactured by Toho Chemical Industry Co., Ltd.; and cationized starches such as the EXCELL series manufactured by Nippon Starch Chemical Co., Ltd.

[0035] The microcapsule aqueous dispersion of the present invention may contain other components in addition to the components (A) and (B) as necessary, such as a pH adjuster, a dye, a preservative, an antioxidant, an ultraviolet absorber, a shell surface modifier, an inorganic salt, a thickener, a deposition aid, a rheology adjuster, etc.

[0036] In order to incorporate the microcapsule aqueous dispersion of the present invention into various preparations, the microcapsule aqueous dispersion of the present invention may previously contain, as necessary, fabric softeners, fabric freshening agents, fabric strengthening agents, enzymes, builders, hair conditioning agents, skin conditioning agents, fragrances, clays, zeolites, silicones, and the like, other than the components (A) and (B).

[0037] (Production of microcapsule aqueous dispersion) The method for producing the microcapsule aqueous dispersion of the present invention is not particularly limited. For example, the microcapsule aqueous dispersion of the present invention can be produced by a method including a step of mixing the (A) component, the (B) component, and the other components described above, which have been produced in advance by a known method, using a known stirring device or the like. Among them, the method for producing the microcapsule aqueous dispersion of the present invention is preferably a method including a step of mixing an aqueous dispersion containing the (A) component, the (B) component, and the other components described above, if necessary, from the viewpoint of ease of production. When the component (A) is silica capsules, the method for producing the microcapsule aqueous dispersion of the present invention is preferably a method including a step of mixing an aqueous dispersion containing silica capsules as the component (A), the component (B), and, if necessary, the other components described above. The aqueous dispersion containing silica capsules can be obtained by the above-mentioned method. In the present invention, from the viewpoint of ease of production, the method for mixing the aqueous dispersion containing the component (A) with the component (B) is not particularly limited, but it is preferable to include a step of adding the component (B) to the aqueous dispersion containing the component (A) and mixing them. From the viewpoint of ease of blending, the component (B) may be used as an aqueous solution. The aqueous solution of the component (B) may be prepared by dissolving the component (B) in water and adjusting the pH according to the solubility of the component (B) in water. From the viewpoint of dispersion stability of the microcapsules, the mixing temperature of the aqueous dispersion containing the component (A), the component (B), and, if necessary, the other components described above, is preferably 15°C or higher, more preferably 20°C or higher, and is preferably 35°C or lower, more preferably 30°C or lower. The components can be mixed using a known stirring device or the like.

[0038] (Composition of microcapsule aqueous dispersion) The content or blending amount of component (A) in the microcapsule aqueous dispersion of the present invention is, from the viewpoints of reducing the viscosity of the aqueous dispersion and improving handleability, improving the dispersion stability of the microcapsules, and improving the particle size and uniformity of the microcapsules, preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and even more preferably 25% by mass or less, and from the viewpoints of facilitating the preparation of a liquid composition or product using the aqueous dispersion, preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, even more preferably 15% by mass or more, even more preferably 18% by mass or more, and even more preferably 20% by mass or more.

[0039] The content or blending amount of the (B) component in the microcapsule aqueous dispersion of the present invention is, from the viewpoint of dispersion stability of the microcapsules, and from the viewpoint of improving the particle size of the microcapsules and improving the particle size uniformity, preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, still more preferably 0.03% by mass or more, and still more preferably 0.05% by mass or more. From the viewpoint of suppressing the formation of aggregates of the microcapsules in the aqueous dispersion and improving the dispersion stability of the microcapsules, from the viewpoint of improving the particle size of the microcapsules and improving the particle size uniformity, and from the viewpoint of reducing the viscosity of the aqueous dispersion and improving the handleability, the content or blending amount of the (B) component in the microcapsule aqueous dispersion is preferably 1.5% by mass or less, more preferably 1% by mass or less, even more preferably 0.7% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, still more preferably 0.2% by mass or less, still more preferably 0.15% by mass or less, still more preferably 0.13% by mass or less, and still more preferably 0.1% by mass or less.

[0040] The content or blending amount of the (B) component in the microcapsule aqueous dispersion of the present invention relative to 100 parts by mass of the (A) component is, from the viewpoint of the dispersion stability of the microcapsules, and from the viewpoint of improving the particle size of the microcapsules and improving the particle size uniformity, preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, still more preferably 0.15 parts by mass or more, and still more preferably 0.2 parts by mass or more. From the viewpoint of suppressing the formation of aggregates of the microcapsules in the aqueous dispersion and improving the dispersion stability of the microcapsules, from the viewpoint of improving the particle size of the microcapsules and improving the particle size uniformity, and from the viewpoint of reducing the viscosity of the aqueous dispersion and improving the handleability, the content or blending amount of the (B) component relative to 100 parts by mass of the (A) component is, from the viewpoint of the dispersion stability of the microcapsules, and from the viewpoint of improving the particle size of the microcapsules, and improving the particle size uniformity, the content or blending amount of the (B) component relative to 100 parts by mass of the (A) component is, from the viewpoint of the dispersion stability of the microcapsules, and from the viewpoint of reducing the viscosity of the aqueous dispersion and improving the handleability, the content or blending amount of the (B) component is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, even more preferably 1 part by mass or less, still more preferably 0.8 parts by mass or less, and still more preferably 0.6 parts by mass or less.

[0041] The water content or blending amount in the microcapsule aqueous dispersion of the present invention, from the viewpoint of dispersion stability of the microcapsules and of improving the particle size uniformity of the microcapsules, is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 75% by mass or more, and is preferably 97% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, and still more preferably 85% by mass or less.

[0042] The viscosity of the microcapsule aqueous dispersion of the present invention at 25°C is preferably 1 mPa·s or more, more preferably 3 mPa·s or more, even more preferably 5 mPa·s or more, still more preferably 10 mPa·s or more, and preferably 4,000 mPa·s or less, more preferably 2,000 mPa·s or less, even more preferably 1,000 mPa·s or less, still more preferably 500 mPa·s or less, still more preferably 100 mPa·s or less, still more preferably 50 mPa·s or less, still more preferably 30 mPa·s or less, and still more preferably 20 mPa·s or less. The viscosity of the microcapsule aqueous dispersion of the present invention at 25°C can be measured using a B-type viscometer (model: TVB-10, manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 60 rpm or 6 rpm and a measurement temperature of 25°C, as described in the Examples.

[0043] The microcapsule aqueous dispersion of the present invention has excellent dispersion stability of the microcapsules, good particle size of the microcapsules, excellent particle size uniformity, and excellent handling properties, and can be used for various applications. Examples of applications include cosmetics such as milky lotions, cosmetic liquids, lotions, beauty essences, creams, gel preparations, hair treatment agents, and quasi-drugs; fiber treatment agents such as detergents, fabric softeners, and anti-wrinkle sprays; sanitary products such as paper diapers; and fragrances, and can be suitably used in the production of these applications.

[0044] The microcapsule aqueous dispersion of the present invention is preferably used by being contained in or blended with a liquid composition such as a detergent composition, a fabric treatment composition, a cosmetic composition, an aroma composition, a deodorant composition, etc. The composition is preferably one or more selected from detergent compositions such as a powder detergent composition and a liquid detergent composition; fabric treatment compositions such as a softener composition, etc., more preferably a fabric treatment composition, and even more preferably a softener composition.

[0045] In relation to the above-mentioned embodiment, the present invention further discloses the following aqueous microcapsule dispersion and a method for producing the aqueous microcapsule dispersion. <1> An aqueous dispersion of microcapsules comprising the following components (A) and (B): Component (A): a microcapsule having a shell containing an inorganic substance as a constituent component and a core containing one or more organic compounds inside the shell. (B) Component: Polysaccharide containing a cationically modified branched chain structure

[0046] <2> The cationic charge density of the (B) component is preferably 0.3 meq / g or more, more preferably 0.5 meq / g or more, even more preferably 0.7 meq / g or more, and is preferably 3.0 meq / g or less, more preferably 2.5 meq / g or less, even more preferably 2.0 meq / g or less, still more preferably 1.7 meq / g or less, even more preferably 1.5 meq / g or less. <1> The microcapsule aqueous dispersion according to claim 1. <3> The component (B) is preferably at least one selected from cationic galactomannan and cationic starch, more preferably cationic galactomannan, even more preferably cationic guar gum, and even more preferably at least one selected from O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride (display name: guar hydroxypropyltrimonium chloride) and a hydroxypropyl derivative of O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride (display name: hydroxypropyl guar hydroxypropyltrimonium chloride). <1> or <2> The microcapsule aqueous dispersion according to claim 1.

[0047] <4> The inorganic substance constituting the shell of the component (A) is preferably a metal oxide containing a metal element or a metalloid element, more preferably an inorganic polymer formed by a sol-gel reaction using a metal alkoxide [M(OR)x] as a shell precursor, even more preferably an inorganic polymer formed by a sol-gel reaction using one or more metal alkoxides selected from silicon, aluminum, and titanium as a shell precursor, and even more preferably silica formed by a sol-gel reaction using an alkoxysilane as a shell precursor. <1> ~ <3> 2. The microcapsule aqueous dispersion according to claim 1 . <5> The alkoxysilane is preferably a tetraalkoxysilane. <4> The microcapsule aqueous dispersion according to claim 1. <6> The component (A) is a microcapsule having a shell containing silica as a constituent component and a core containing one or more organic compounds inside the shell. <1> ~ <3> 2. The microcapsule aqueous dispersion according to claim 1 . <7> The shell is a multi-layer shell having an inner shell containing silica, which is a hydrolysis and polycondensation product of alkoxysilane, as a constituent, and an outer shell further containing silica, which is a hydrolysis and polycondensation product of alkoxysilane, as a constituent, outside the inner shell. <6> The microcapsule aqueous dispersion according to claim 1.

[0048] <8> The organic compound is preferably one or more selected from fragrances; fragrance precursors; oils; antioxidants; antibacterial agents; fertilizers; surface modifiers for fibers, skin, hair, and the like; cooling agents; dyes; pigments; silicones; solvents; and oil-soluble polymers, more preferably one or more selected from fragrances, fragrance precursors, oils, antioxidants, antibacterial agents, fertilizers, surface modifiers, and solvents, even more preferably one or more selected from fragrances, fragrance precursors, oils, antioxidants, and solvents, even more preferably one or more selected from fragrances, fragrance precursors, and oils, and even more preferably one or more selected from fragrances and fragrance precursors. <1> ~ <7> 2. The microcapsule aqueous dispersion according to claim 1 . <9> The cLogP value of the organic compound is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, even more preferably 4 or more, and is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less. <1> ~ <8> 2. The microcapsule aqueous dispersion according to claim 1 . <10> (A) Median diameter D of the microcapsules of the component 50 is preferably 100 μm or less, more preferably 75 μm or less, even more preferably 50 μm or less, still more preferably 30 μm or less, even more preferably 10 μm or less, and is preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.07 μm or more, still more preferably 0.1 μm or more, still more preferably 0.5 μm or more, and still more preferably 1 μm or more. <1> ~ <9> 2. The microcapsule aqueous dispersion according to claim 1 .

[0049] <11> An aqueous dispersion of microcapsules comprising the following components (A) and (B): Component (A): A microcapsule having a shell containing silica as a constituent component and a core containing one or more organic compounds inside the shell. Component (B): one or more selected from cationic galactomannan and cationic starch <12> The cationic charge density of the (B) component is preferably 0.3 meq / g or more, more preferably 0.5 meq / g or more, even more preferably 0.7 meq / g or more, and is preferably 3.0 meq / g or less, more preferably 2.5 meq / g or less, even more preferably 2.0 meq / g or less, still more preferably 1.7 meq / g or less, even more preferably 1.5 meq / g or less. <11> The microcapsule aqueous dispersion according to claim 1. <13> The component (B) is preferably a cationized galactomannan, more preferably one or more selected from cationized guar gum, cationized tara gum, cationized fenugreek gum, and cationized locust bean gum, even more preferably one or more selected from cationized guar gum and cationized tara gum, still more preferably cationized guar gum, and even more preferably O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride (display name: guar hydroxypropyltrimonium chloride) and a hydroxypropyl derivative of O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride (display name: hydroxypropyl guar hydroxypropyltrimonium chloride). <11> or <12> The microcapsule aqueous dispersion according to claim 1.

[0050] <14> The content or blending amount of the (A) component in the microcapsule aqueous dispersion is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, still more preferably 25% by mass or less, and is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 18% by mass or more, still more preferably 20% by mass or more. <1> ~ <13> 2. The microcapsule aqueous dispersion according to claim 1 . <15> the content or blending amount of the (B) component in the microcapsule aqueous dispersion is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, still more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, and is preferably 1.5% by mass or less, more preferably 1% by mass or less, even more preferably 0.7% by mass or less, still more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, still more preferably 0.2% by mass or less, still more preferably 0.15% by mass or less, still more preferably 0.13% by mass or less, still more preferably 0.1% by mass or less; <1> ~ <14> 2. The microcapsule aqueous dispersion according to claim 1 . <16> The content or blending amount of the (B) component relative to 100 parts by mass of the (A) component in the microcapsule aqueous dispersion is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.1 parts by mass or more, still more preferably 0.15 parts by mass or more, still more preferably 0.2 parts by mass or more, and is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, still more preferably 1 part by mass or less, still more preferably 0.8 parts by mass or less, and still more preferably 0.6 parts by mass or less. <1> ~ <15> 2. The microcapsule aqueous dispersion according to claim 1 . <17> The method includes a step of mixing an aqueous dispersion containing the component (A) with the component (B). <1> ~ <16> 13. A method for producing the microcapsule aqueous dispersion according to any one of claims 1 to 12. EXAMPLES

[0051] Various measurements in the examples and comparative examples were carried out by the following methods. [Median diameter D 50 〕 Median diameter of emulsion droplets D 50 and the median diameter of the microcapsules D 50 was measured using a laser diffraction / scattering particle size distribution analyzer "LA-960" (product name, manufactured by Horiba, Ltd.). A flow cell was used for the measurement, the medium was water, and the refractive index of the dispersoid was set to 1.45-0i. An emulsion or a water dispersion containing microcapsules was added to the flow cell, and measurements were performed at a concentration that showed a transmittance of approximately 90%, and the median diameter D 50 asked for.

[0052] <Model Fragrance> As the organic compound to be encapsulated in the microcapsules, model fragrance A (volume average cLogP: 3.8, specific gravity: 0.88) having the composition shown in Table 1 was used. The volume average cLogP value of the model fragrance was calculated as the sum of the cLogP values ​​of all fragrance components contained in the model fragrance multiplied by their volume ratios in the model fragrance.

[0053] [Table 1]

[0054] (Synthesis of component (A)) Synthesis Example 1 (Process 1) 3.00 g of Coatamin 60W (trade name, manufactured by Kao Corporation, cetyltrimethylammonium chloride, active content 30% by mass) was diluted with 747.00 g of ion-exchanged water to obtain an aqueous phase component. An oil phase component prepared by mixing 200.70 g of model fragrance A and 50.08 g of tetraethoxysilane (hereinafter also referred to as "TEOS") was added to this aqueous phase component, and the mixture was emulsified for 15 minutes at room temperature (about 25°C) using a homomixer (manufactured by HsiangTai Co., Ltd., model: HM-310) set at a rotation speed of 8,500 rpm for 15 minutes to obtain an emulsion. The median diameter D of the emulsified droplets at this time was 50 was 1.1 μm. The pH of the resulting emulsion was then adjusted to 3.8 using a 1% by mass aqueous sulfuric acid solution, and the emulsion was then transferred to a separable flask equipped with a stirring blade and a cooler. The liquid was stirred at 200 rpm for 24 hours while maintaining the liquid temperature at 30°C, yielding an aqueous dispersion containing silica capsules having a core made of model fragrance A and a first shell. (Process 2) Next, 32.8 g of TEOS was added dropwise to 973.24 g of the aqueous dispersion obtained in step 1 over 420 minutes. After the addition, the mixture was stirred for an additional 17 hours to form a second shell encapsulating the first shell, and an aqueous dispersion was obtained containing 21.7 mass% of silica capsules (A-1) in which the model fragrance A was encapsulated in a multi-layer shell having an inner shell containing silica, which is a hydrolysis polycondensate of alkoxysilane, as a constituent, and an outer shell further containing silica, which is a hydrolysis polycondensate of alkoxysilane, as a constituent, on the outside of the inner shell. The median diameter D of the silica capsules (A-1) was 1.0 mm. 50 The content of the silica capsules (A-1) in the water dispersion was a calculated value based on the composition at the time of synthesizing the silica capsules.

[0055] (Production of microcapsule aqueous dispersion) Examples 1-2 and Comparative Examples 1-3 The aqueous dispersion containing component (A) obtained in Synthesis Example 1 and an aqueous solution of component (B) were mixed at room temperature (about 25°C) so that the contents of component (A) and component (B) in the aqueous dispersion were as shown in Table 2 below, to prepare an aqueous microcapsule dispersion. The aqueous solution of component (B) was prepared by dissolving the powder of component (B) in ion-exchanged water to a predetermined concentration as required. In Examples 1 and 2, the aqueous solution of component (B) was adjusted to pH 4 to 5 using a 1% by mass aqueous solution of sulfuric acid. In Comparative Example 1, the component (B) was not added, and the aqueous dispersion containing the silica capsules (A-1) obtained in Synthesis Example 1 was used as it was for evaluating the dispersion stability.

[0056] The cationic branched polysaccharides and polymer dispersants used in the examples and comparative examples in Table 2 are shown below. Hydroxypropyl guar hydroxypropyltrimonium chloride: Jaguar C-162 (cationized guar gum (hydroxypropyl derivative of O-[2-hydroxy-3-(trimethylammonio)propyl] guar gum chloride), cationic charge density 0.93 meq / g, manufactured by Solvay, appearance: powder) Guar hydroxypropyltrimonium chloride: Jaguar C-17K (cationized guar gum (O-[2-hydroxy-3-(trimethylammonio)propyl] guar gum chloride), cationic charge density 1.07 - 1.50 meq / g, manufactured by Solvay, appearance: powder) Hydroxyethyl cellulose: Natrosol 250HHR PC (manufactured by Ashland, appearance: powder) Dimethyldiallylammonium chloride / acrylamide copolymer: Mercote 550 (active ingredient 9%) (manufactured by Nippon Lubrizol Corporation) In addition, the content of component (A) in Table 2 is a calculated value based on the blending amount of the aqueous dispersion containing component (A) obtained in Synthesis Example 1 and the content of component (A) in the aqueous dispersion, as well as the blending amount of the aqueous solution of component (B) and the content of component (B) in the aqueous solution.

[0057] [Evaluation of the dispersion stability of microcapsules] The microcapsule aqueous dispersions obtained in Examples 1 - 2 and Comparative Examples 1 - 3 were stored statically at room temperature (about 25°C), and the dispersion stability of the microcapsules in the aqueous dispersion was evaluated by visually observing the decrease in fluidity (caking) and the presence or absence of aggregation of the aqueous dispersion. In Table 2, when it is described as ">X days", it indicates that neither the decrease in fluidity nor the aggregation of the microcapsules was confirmed for at least X days, and when it is described as "<X days", it indicates that the decrease in fluidity or aggregation of the microcapsules was confirmed on the Xth day. The longer the number of days without confirming either the decrease in fluidity or the aggregation of the microcapsules, the better the dispersion stability of the microcapsules in the aqueous dispersion. In addition, for Examples 1 - 2, a turbid phase was confirmed and gradually separated into a turbid phase and a transparent phase, but no solidified phase was confirmed, and it was confirmed that the fluidity could be maintained even after storage. 30 mL of the microcapsule aqueous dispersion after static storage in Examples 1 and 2 was sealed in a glass vial (capacity 50 mL) and stirred with a magnetic stirrer at room temperature (25°C) for about 5 minutes, and the cloudy white phase was able to return to its original dispersed state by the stirring, and no decrease in fluidity or aggregation was confirmed by visual observation after the stirring. In addition, 30 mL of the microcapsule aqueous dispersion after static storage in Examples 1 and 2 was sealed in a glass vial (capacity 50 mL) and strongly shaken by hand about 20 times, and the cloudy white phase was able to return to its original dispersed state, and no decrease in fluidity or aggregation was confirmed by visual observation after the shaking. From this, it is presumed that the microcapsule aqueous dispersion obtained in Examples 1 and 2 is a floc of microcapsules, since it can be returned to its original dispersed state by stirring or shaking even after storage, and no decrease in fluidity or aggregation was confirmed by visual observation after the stirring or shaking.

[0058] [Table 2]

[0059] It can be seen from Table 2 that the microcapsule aqueous dispersions of the Examples are superior in dispersion stability to those of the Comparative Examples. Note that Comparative Example 3 contained a synthetic polymer having a cationic group, but did not provide good dispersion stability. Therefore, according to the present invention, it is possible to improve the dispersion stability of the microcapsules in the aqueous dispersion.

[0060] (Production of microcapsule aqueous dispersion) Examples 3 to 5 and Comparative Example 4 The aqueous dispersion containing component (A) obtained in Synthesis Example 1 and an aqueous solution of component (B) were mixed at room temperature (about 25°C) so that the contents of component (A) and component (B) in the aqueous dispersion were as shown in Table 3 below, to prepare an aqueous microcapsule dispersion. In addition, as the aqueous solution of component (B), a solution prepared by dissolving the powder of component (B) in ion-exchanged water to a predetermined concentration was used as necessary. In Example 3, as the aqueous solution of component (B), a solution adjusted to pH 4 to 5 using a 1 mass% sulfuric acid aqueous solution was used.

[0061] The cation-modified polysaccharides used in Examples 3 to 5 and Comparative Example 4 in Table 3 are shown below. Hydroxypropyl guar hydroxypropyltrimonium chloride: Jaguar C-162 (cationized guar gum (hydroxypropyl derivative of O-[2-hydroxy-3-(trimethylammonio)propyl]guar gum chloride), cation charge density 0.93 meq / g, manufactured by Solvay, appearance: powder) Cationized tara gum: Katinal CTR-100 (manufactured by Toho Chemical Industry Co., Ltd., appearance: powder) Cationized starch: EXCELL DH (manufactured by Nippon Starch Chemical Co., Ltd., appearance: powder) Cationized HEC: Poise C-60H (polyquaternium-10, O-[2-hydroxy-3-(trimethylammonio)propyl]hydroxyethyl cellulose chloride, cation charge density 1.1 to 1.8 meq / g, manufactured by Kao Corporation, appearance: powder (active ingredient 90%)) In addition, the content of component (A) in Table 3 is a calculated value based on the blending amount of the aqueous dispersion containing component (A) obtained in Synthesis Example 1 and the content of component (A) in the aqueous dispersion, as well as the blending amount of the aqueous solution of component (B) and the content of component (B) in the aqueous solution.

[0062] 〔Evaluation of dispersion stability of microcapsules〕 The microcapsule aqueous dispersions obtained in Examples 3 to 5 and Comparative Example 4 were stored at room temperature (about 25°C) while standing, and the dispersion stability of the microcapsules in the aqueous dispersion was evaluated by visually observing the decrease in fluidity (caking) and the presence or absence of aggregation of the aqueous dispersion. In Table 3, when described as ">X days", it indicates that neither a decrease in fluidity nor aggregation of the microcapsules was confirmed for at least X days, and when described as "<X days", it indicates that a decrease in fluidity or aggregation of the microcapsules was confirmed on the Xth day. The longer the number of days during which neither a decrease in fluidity nor aggregation of the microcapsules is observed, the more excellent the dispersion stability of the microcapsules in the aqueous dispersion.

[0063] [Evaluation of particle size uniformity of microcapsules] The microcapsule aqueous dispersions obtained in Examples 2 to 5 and Comparative Example 4 were allowed to stand for 14 days at room temperature (about 25° C.), and then the median diameter D of the microcapsules was measured using a laser diffraction / scattering type particle size distribution analyzer “LA-960” (product name, manufactured by Horiba, Ltd.). 50 Using the same method as in the measurement of the volumetric median diameter D of the microcapsules contained in the aqueous dispersion after storage, 50 The results are shown in Table 3. The coefficient of variation CV was calculated from the standard deviation and average value in the volumetric particle size distribution obtained for the microcapsules contained in the aqueous dispersion after storage using the laser diffraction / scattering particle size distribution analyzer, according to the following formula. The results are shown in Table 3. The smaller the coefficient of variation CV, the better the particle size uniformity. Coefficient of variation CV(%)=(standard deviation / mean value)×100

[0064] [Viscosity of microcapsule aqueous dispersion after storage] The microcapsule aqueous dispersions obtained in Examples 2 to 5 and Comparative Example 4 were stored at room temperature (about 25° C.) for 14 days, and then the viscosity of the stored microcapsule aqueous dispersions at 25° C. was measured using a B-type viscometer (model: TVB-10, manufactured by Toki Sangyo Co., Ltd.) with a spindle of M3 or M4 at a rotation speed of 60 rpm or 6 rpm at a measurement temperature of 25° C. The results are shown in Table 3. [Table 3]

[0065] From Table 3, it can be seen that the microcapsule aqueous dispersion of the Example has excellent dispersion stability, and the particle size of the microcapsule and the viscosity of the microcapsule aqueous dispersion are good even after storage. In addition, the microcapsule aqueous dispersion of the Example has a smaller coefficient of variation CV value than that of the Comparative Example, and therefore has less variation in particle size and excellent particle size uniformity. From this, it is presumed that the microcapsule aqueous dispersion of the Example contains a cationic branched polysaccharide containing a branched chain structure as component (B), so that cross-linking aggregation is unlikely to occur and the formation of microcapsule aggregates can be suppressed, and as a result, the particle size uniformity is excellent even after storage. On the other hand, it is presumed that the structure of the cationic polysaccharide contained in the microcapsule aqueous dispersion of the Comparative Example is a straight-chain structure, so that cross-linking aggregation is likely to occur, the formation of microcapsule aggregates cannot be suppressed, and the particle size uniformity is poor. Therefore, according to the present invention, it is possible to improve the dispersion stability of the microcapsules in the aqueous dispersion, to improve the particle size of the microcapsules, and to improve the particle size uniformity. [Industrial Applicability]

[0066] The microcapsule aqueous dispersion of the present invention can be stored in a state where the dispersion stability of the microcapsules is well maintained, and furthermore, even after long-term storage, the microcapsules have a good particle size and excellent particle size uniformity. Therefore, the microcapsule aqueous dispersion of the present invention is easy to handle without causing thickening due to gelation or formation of aggregates, and can be widely used in imparting various functionalities, including fragrance, to various products such as laundry products, personal care products, cosmetics, and household liquid products.

Claims

1. Contains the following components (A) and (B), The content of the component (A) in the microcapsule aqueous dispersion is 10% by mass or more and 50% by mass or less, The content of the (B) component relative to 100 parts by mass of the (A) component in the microcapsule aqueous dispersion is 0.03 parts by mass or more and 3 parts by mass or less. Microcapsule water dispersion. Component (A): a microcapsule having a shell containing an inorganic substance as a constituent component and a core containing one or more organic compounds inside the shell. Component (B): Polysaccharide containing a cationically modified branched chain structure

2. A microcapsule aqueous dispersion as described in claim 1, wherein the content of the (B) component in the microcapsule aqueous dispersion is 0.001 mass% or more and 1.5 mass% or less.

3. The microcapsule aqueous dispersion according to claim 1, wherein the cationic charge density of the component (B) is 0.3 meq / g or more and 3.0 meq / g or less.

4. The microcapsule aqueous dispersion according to claim 1 , wherein the component (B) is a cationized galactomannan.

5. The microcapsule aqueous dispersion according to claim 1 , wherein the component (B) is a cationic guar gum.

6. The microcapsule aqueous dispersion according to any one of claims 1 to 5, wherein the component (A) is a microcapsule having a shell containing silica as a constituent component and a core containing one or more organic compounds inside the shell.

7. The median diameter D of the microcapsules of the component (A) 50 The microcapsule aqueous dispersion according to any one of claims 1 to 5, wherein the average particle size is 0.1 µm or more and 50 µm or less.

8. The microcapsule aqueous dispersion according to any one of claims 1 to 5, wherein the organic compound is at least one selected from the group consisting of fragrances, fragrance precursors, oils, antioxidants, and solvents.

9. 6. A method for producing a microcapsule aqueous dispersion according to claim 1, comprising the step of mixing an aqueous dispersion containing the component (A) with the component (B).

Citation Information

Patent Citations

  • Stable, flowable silica capsule formulation

    EP2862597A1

  • Deposition of lipophilic active materials in compositions containing surfactants

    JP2011517323A

  • Suspension of silicate shell microcapsules

    JP2012501849A

  • Hybrid Microcapsules

    JP2019534139A

  • Method for manufacturing microcapsules

    WO2015083836A1