JP4562050B2 - Encapsulated microcapsule and method for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an encapsulated microcapsule and a method for producing the same. More specifically, the present invention relates to an organopolysiloxane obtained by condensation polymerization of specific hydroxysilane as a wall film, and has thermal, mechanical stability, light resistance, The present invention relates to an active encapsulated microcapsule and a method for producing the same. Such encapsulated microcapsules of the present invention include, for example, pharmaceuticals, liquid crystals, chemical products, recording materials, cosmetics, fragrances, enzymes, agriculture, adhesives, fibers, foods, catalysts, detergents, dyes, paints, rust inhibitors, Applied to solvent applications. Specifically, for example, aspirin-containing capsules, vitamin-containing capsules, liquid crystal-containing capsules, pressure-sensitive copying paper, ultraviolet absorber-containing capsules, dye-containing capsules, pigment-containing capsules, fragrance-containing capsules, menthol-containing capsules, insecticide-containing capsules It is applied to adhesive capsules, capsules with rust preventives for rivets, etc., but it is not limited to them.
[0002]
[Prior art]
Organopolysiloxanes have excellent properties such as thermal, mechanical stability and light resistance as well as biological inertness as general basic properties, and are expected to be applied in a wide range of fields. Also in the field of microcapsules such as capsules, attempts have been made to produce microcapsules using polysiloxane or a similar material as a wall film.
[0003]
For example, US Pat. No. 3,257,330 discloses a method for producing colored gel particles using an organopolysiloxane as a matrix (interstitial material). However, the alkoxysilane having a hydrophobic organic group such as methyltriethoxysilane, which is the starting material of the matrix, is polymerized in a short time when it is neutralized after being hydrolyzed acidic or basic in an aqueous solution. Since it precipitates out of the aqueous solution, it was difficult to produce microcapsules by incorporating the hydrophobic core substance while polymerizing the hydrolyzate of alkoxysilane in the aqueous solution.
[0004]
On the other hand, in US Pat. No. 3,551,346, a polysiloxane is synthesized from trialkoxysilane when producing a microcapsule. The role of this polysiloxane is merely to separate an inner phase from an outer phase. In the above U.S. patent specification, it is recognized that the film does not have sufficient strength as a wall film. Therefore, a wall film by a conventional coacervation method is simultaneously produced to make the wall film a two-layer structure. A method for producing microcapsules is disclosed. That is, the wall film of the microcapsule is not produced solely by the condensation polymer of the alkoxysilane hydrolyzate. In addition, because of the polysiloxane wall film function that prevents the inner and outer phases from reacting with each other, which is the target of this method, trialkoxysilane confined in the inner phase can contribute to the wall film construction more than a certain amount. The method for producing the microcapsules of the wall membrane made of the hydrolyzate polycondensate of alkoxysilane is limited, and is not considered to be versatile.
[0005]
Further, as an example of producing a microcapsule wall film by crosslinking a polysiloxane having a functional group involved in crosslinking or polymerization as a component for constructing a microcapsule wall film, Japanese Patent Publication No. 60-25185, Japanese Patent Publication No. 3-10309, Japanese Patent Publication No. 5-70496, Japanese Patent Publication No. 7-62109, and the like. However, these do not produce a wall film by polycondensation of hydroxysilane, and require special organopolysiloxanes having functional groups involved in cross-linking and polymerization, and are difficult to handle except by silicone manufacturers.
[0006]
[Problems to be solved by the invention]
As described above, in the prior art, it has been difficult to easily produce microcapsules having organopolysiloxane as a wall film in a state of versatility.
[0007]
However, if microcapsules having an organopolysiloxane wall film that directly utilizes the excellent properties of organopolysiloxane can be directly produced from various hydroxysilane precursors, it is advantageous in terms of cost, and various hydroxysilane precursors can be produced. By combining the body, it is flexible in designing microcapsules suitable for the purpose, wall membrane with dense network or wall membrane with appropriate substance permeability, high strength wall membrane or moderately soft It is expected that a microcapsule having characteristics that could not be obtained with a microcapsule having a wall film made of a conventional material can be produced, and is very useful. However, it has been difficult to produce microcapsules while controlling conditions such as polymerization rate and solubility only with low-molecular hydroxysilane.
[0008]
Accordingly, an object of the present invention is to easily produce a microcapsule having an organopolysiloxane as a wall film from a silicon compound which is generally distributed while examining various conditions with high productivity.
[0009]
[Means for Solving the Problems]
  In order to solve the above problems, the present inventors have conducted extensive research on a method for directly producing a microcapsule having an organopolysiloxane as a wall film. As a result, the following general structural formula (I)
RnSiX (4-n) (I)
[Where n is1And R is an organic group in which a carbon atom is directly bonded to a silicon atom, and the n Rs may be the same or different. (4-n) X is at least one group selected from the group consisting of a hydroxyl group, hydrogen, an alkoxy group, a halogen group, a carboxy group, an amino group, and a siloxy group.
A hydrolyzate of one or several compounds (A) selected from the group of compounds (A) represented by the following general formula (II)
RnSi (OH) mY (4-mn) (II)
[Where m is from 13Integer, n is1To an integer of 3 and m + n ≦ 4, R is an organic group in which a carbon atom is directly bonded to a silicon atom, and the n Rs may be the same or different. (4-mn) Y is at least one group selected from the group consisting of an alkoxy group, hydrogen and a siloxy group.
In the case of using one or several kinds of compounds (B) selected from the group of compounds (B) represented by the formula (B), at least one of them is(1)m = 2 or 3, and(2)When synthesizing an organopolysiloxane to be a wall film by directly polycondensing a compound (B) having at least one R that is amphiphilic in at least one of a continuous phase or a dispersed phase, the above-mentioned problem can be solved. The headline and the present invention were completed. In the general structural formulas (I) and (II), n, (4-n), m, and (4-mn) are all subscripts.
[0010]
That is, according to the present invention, it is possible to directly synthesize an organopolysiloxane that becomes a wall film of a microcapsule from a compound (B) belonging to a so-called hydroxysilane, and the organopolysiloxane alone is contained in a microcapsule. The wall film required for the capsule can be formed, and it is not necessary to prepare the wall film by the coacervation method as in the prior art.
[0011]
  However, in the present invention, the compound (B) may be any compound in which a hydroxyl group is bonded to a silicon atom. For example, methyltriethoxysilane corresponding to the compound (A)NA partially hydrolyzed product in which an ethoxy group remains bonded to a silicon atom is also included in the compound (B) of the present invention.
[0012]
In addition, when the present inventors directly produce an encapsulated microcapsule having an organopolysiloxane as a wall film as described above, one or several compounds (B) selected from the compound (B) group are used. When an aqueous solvent is used for the continuous phase or the dispersed phase, (1) m = 2 or 3, and (2) at least one compound (B) having at least one hydrophilic R It has been found that it is preferable to contain.
[0013]
Furthermore, when the present inventors directly produce encapsulated microcapsules having organopolysiloxane as a wall film as described above, one or several compounds (B) selected from the compound (B) group are used. When an aqueous solvent is used for the continuous phase or the dispersed phase, (1) m = 2 or 3, and (2) at least one R is a polypeptide or number having a number average molecular weight of 100 to 50,000. It has been found that it is preferable to contain at least one compound (B) having polyoxyethylene having an average degree of polymerization of 1 to 2000.
[0014]
In addition, the present inventors preferably manufacture the encapsulated microcapsules in a medium having a viscosity of 10 to 2000 mPa · s before adding the silicon compound for constructing the wall film of the encapsulated microcapsules. I found.
[0015]
Furthermore, the present inventors preferably manufacture the encapsulated microcapsules in an aqueous gelatin solution having a viscosity of 10 to 2000 mPa · s before adding the silicon compound that constructs the wall film of the encapsulated microcapsules. I found out.
[0016]
In addition, in the method for producing an encapsulated microcapsule having an organopolysiloxane as a wall membrane, the present inventors preferably go through a step of preparing a prepolymer by condensation polymerization of the compound (B) in an aqueous solvent. After the step of preparing an emulsion by mixing this prepolymer with a hydrophobic substance and / or a non-aqueous solvent in an aqueous solvent, the emulsion is reduced by dehydration over time or by heating, dehydration outside the reaction system, etc. The present inventors have found a method for producing an encapsulated microcapsule having an organopolysiloxane as a wall film by further proceeding a polymerization reaction.
[0017]
Furthermore, the inventors of the present invention provide a method for producing a microcapsule containing at least one selected from the group consisting of a hydrophobic substance, a hydrophilic substance, a mixture thereof, and a fluorocarbon substance in the method for producing an encapsulated microcapsule. I found.
[0018]
In the present invention, the microcapsule refers to a capsule such as a microcapsule or a nanocapsule, and the encapsulated microcapsule refers to a microcapsule in which a core substance is encapsulated in a space formed by a wall film. In the present invention, the condensation of the compound (B) refers to SiOH + SiL → SiOSi + HL, and the compound (B) is polymerized by the condensation reaction to produce an organopolysiloxane that becomes a wall film. L in the above reaction formula is a leaving group such as a hydroxyl group, an alkoxy group, a halogen group, a carboxy group, and an amino group.
[0019]
In the present invention, the organopolysiloxane is one or several compounds (B), of whichofAt least one kind refers to a polycondensation product obtained by condensation polymerization of the compound (B) where m = 2 or 3, and an alkoxy group or a hydroxyl group may partially remain on the silicon atom of the condensation polymerization product, Furthermore, after polycondensation with the compound (B) in which m = 1, an alkoxy group or a hydroxyl group may partially remain on the silicon atom of the polycondensation product, or an alkoxy group or a hydroxyl group may remain. Not at all.
[0020]
DETAILED DESCRIPTION OF THE INVENTION
When the outline of the production method of the present invention is shown in the order of processes, it becomes "mixing / emulsification-curing treatment with the core material and / or the second liquid phase by hydrolysis-neutralization of the compound (A)-", Furthermore, “treatment with the compound (A) for surface treatment” is added before “curing treatment” as necessary.
[0021]
In the present invention, the compound (A) is hydrolyzed, and until the step of preparing a prepolymer by polycondensation by neutralization before mixing this with a hydrophobic substance and / or a non-aqueous solvent, the compound ( It is preferable to prepare a prepolymer in advance by production of compound (B) by hydrolysis of A) and condensation polymerization by neutralization. The purpose is to prevent the formation of a liquid phase separate from this aqueous solvent phase and to perform some polymerization before forming a second liquid phase by mixing with a hydrophobic material and / or a non-aqueous solvent. This is to prevent different monomers from being disproportionated and distributed on the prepolymer as much as possible. That is, in order to prevent the formation of polymers having different compositions due to the distribution of monomers between the two or more liquid phases from the beginning. Therefore, in the case of using one or several compounds (B) selected from the group of compounds (B) produced by hydrolyzing the compound (A), (1) m = 2 or 3, and (2) having at least one R that is amphiphilic in at least one of the continuous phase or the dispersed phase, in particular, having at least one hydrophilic R, and more particularly, at least one R having a number average molecular weight of 100 The method of using at least one compound (B) having ˜50000 polypeptide or polyoxyethylene having a number average degree of polymerization of 1 to 2000 is a preferred method for allowing the prepolymer to exist stably. In addition, the method of preparing the prepolymer by hydrolyzing the compound (A) in a viscous solution such as an aqueous gelatin solution stably presents the prepolymer when the prepolymer is unstable and readily precipitates. Another preferred way to do this. Thereafter, it is preferable to prepare an emulsion by mixing the prepolymer in this aqueous solvent with a hydrophobic substance and / or a non-aqueous solvent. The purpose is to aim at causing condensation of the prepolymers by localizing the prepolymer prepared in advance at the interface when the second liquid phase is added.
[0022]
Further, the composition formula of the prepolymer and the organopolysiloxane constituting the wall film in the present invention is represented, for example, by the following general formula (III).
(R_ThreeSiO_1/2) H (R₂SiO) i (RSiO_3/2) J (SiO₂) K ......... (III)
[0023]
In the general formula (III), R is an organic group in which a carbon atom is directly bonded to the silicon atom in the general formula (III). When two or more R are bonded on one silicon atom, R is May be different from each other or the same. However, depending on the degree of hydrolysis of the compound (B) obtained by hydrolyzing the compound (A) and the degree of condensation reaction of the compound (B), all the silicon atoms are eliminated from their hydroxyl groups and alkoxy groups. In the above general formula (III), not all but a part of oxygen in the general formula (III) may be condensed (R′O_1/2) P (HO_1/2) QHr (O_1/2) (-R) (...) (IV) [In the formula (IV), R 'is an alkyl group, subscripts p, q and r are 0 or a positive integer and p + q + r = 2. Further, the values of p, q, and r may be different for each oxygen of the general formula (III). (−r) means r (O_1/2) Means to be subtracted from the composition formula] may be added. In addition, the composition formula components shown in parentheses (brackets) immediately before the subscripts h, i, and j may be all the same or different. That is, (R_ThreeSiO_1/2) Has three Rs, and all three Rs may be the same or different, and h (R_ThreeSiO_1/2) May all be the same or not necessarily the same. Also, (R₂There are two Rs in the SiO) part, but the two Rs may all be the same or different. i (R₂The SiO) may all be the same or not necessarily the same. Furthermore, j (RSiO_3/2) May all be the same or not necessarily the same. For example, even in the case of a polymer composed of one derived from methyltriethoxysilane and one derived from phenyltriethoxysilane, RSiO_3/2Means everything. Here, touching on the relationship between the prepolymer and the organopolysiloxane constituting the wall film, SiOH on the prepolymer is SiL on another prepolymer (L is a hydroxyl group, an alkoxy group, a halogen group, a carboxy group, an amino group). Etc.) and a condensation reaction such as SiOH + SiL → SiOSi, and grows into a larger polymer to form an organopolysiloxane that constitutes the wall film. As a composition formula of the organopolysiloxane that constitutes the wall film, The general formula (III) is the same as that of the prepolymer. Further, the ranges of h, i, j, and k are values sufficient to form microcapsules when the above general formula (III) represents the organopolysiloxane constituting the wall film. When the general formula (III) represents a prepolymer, the prepolymer is transitional and changes with time. However, the range of h, i, j, and k is within the range of the general formula (III). Is an integer of 0 or a positive integer shown below. Also, (R’O_1/2) P (HO_1/2) QHr (O_1/2The number of added moles of (-r) depends on the degree of hydrolysis of the compound (B) obtained by hydrolyzing the compound (A) and the degree of condensation reaction of the compound (B). Any range may be used as long as the organopolysiloxane constituting the wall film is sufficiently formed.
[0024]
In the production method of the present invention, the compound (A) is preferably used alone or in combination. Furthermore, the ratio is important when selecting the compound (A) and when using a plurality of types of compounds (A). The compound (A) reacts as the compound (B) in the condensation polymerization reaction.
[0025]
  When the compound (A) is used, the compound (A) having a hydrophilic group, the compound (A) having a hydrophobic group, and the compound (A) having a parent fluorocarbon groupBothA compound (A) selected from the group consisting of a compound (A) having an amphiphilic group and a compound (A) having a surface-active group, the prepolymer becomes amphiphilic in at least one of a continuous phase and a dispersed phase. Thus, it is preferable to use one or a combination of several. However, the term “amphiphilic” as used herein means having affinity for both of the two types of media that do not mix with each other. Furthermore, the amphiphilic group here is a group in which one group has both different amphiphilic groups such as a hydrophilic group and a hydrophobic group.
[0026]
That is, the compound (A) used in the condensation polymerization reaction may be a combination of the compound (A) such that the prepolymer becomes a substance that is lyophilic in at least one of the continuous phase and the dispersed phase. preferable.
[0027]
As the compound (A) having a hydrophilic group, R in the general structural formula (I) representing the compound (A) preferably has a hydrophilic group, and one or more R having a hydrophilic group is present on one silicon atom. It is preferable. In addition, a hydrophobic group or a hydrophilic fluorocarbon group which is another amphiphilic substituent may be bonded to R having a hydrophilic group. However, with respect to the combination of the compound (A) having a hydrophilic group and an aqueous solvent, the compound (B) produced after hydrolysis of the compound (A) with an acid or alkali, or other philicity when neutralized It is preferable to select the compound (A) having a hydrophilic group such that the prepolymer formed by condensation with the compound (B) derived from the compound (A) having R is stably dispersed.
[0028]
Examples of the hydrophilic group include polyethers such as polyoxyethylene, polyoxypropylene, and polyoxyethylene polyoxypropylene copolymer, saccharides or amino sugars ranging from monosaccharides to polysaccharides such as pullulan, sorbitol, chitin, and chitosan, Protein, antibody, hydrolyzed protein, polyamino acid, carboxylic acid or salt / derivative thereof, polycarboxylic acid or salt / derivative thereof, sulfuric acid or salt / derivative thereof, phosphoric acid or salt / derivative thereof, sulfonic acid or salt / derivative thereof, Examples thereof include phosphonic acid or a salt / derivative thereof, a quaternary ammonium group, an amine or a salt thereof, a polyamine or a salt thereof, and any one or a plurality of functional groups thereof are preferably bonded to R. However, the hydrophilic group is not limited to those exemplified above. Examples of R that binds to the hydrophilic groups exemplified above include -CH₂-,-(CH₂)₂-,-(CH₂)_Three-,-(CH₂)_ThreeOCH₂CH (OH) CH₂-,-(CH₂)_ThreeNHCO- and the like, and a silicon atom is bonded to the left side of the partial structural formula, and the hydrophilic group is bonded to the right side.
[0029]
As a specific example of the compound (A) having a hydrophilic group, a polymer manufactured by Shin-Etsu Chemical Co., Ltd. having a polyether such as polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene copolymer as the hydrophilic group is used. There are oxyethylene-modified silicones [for example, KF-354 (trade name)], polyethoxypropyltrimethoxysilane [for example, KBM-641 (trade name)], and γ-glycidoxypropyltriethoxysilane or γ -N- [2-hydroxy-3- (3'-trihydroxysilyl) propoxy] propyl hydrolyzed protein derived from glycidoxypropylmethyldiethoxysilane and a hydrophilic substance having a hydrophilic group as described above, N- [2-hydroxy-3- (3′-dihydroxymethylsilyl) ) Propoxy] propyl hydrolyzed protein (JP-A-8-67608) and the like, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ- [N- (β-aminoethyl) amino]. Propylmethyldimethoxysilane, γ- [N- (β-aminoethyl) amino] propyltrimethoxysilane, γ- [N- (β-aminoethyl) amino] propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ Silane coupling agents such as aminopropyltriethoxysilane, γ- (N-phenylamino) propyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane And a hydrophilic substance having a hydrophilic group as described above And the like compounds derived (A) from. However, the compound (A) having a hydrophilic group is not limited to those exemplified above.
[0030]
As the compound (A) having a hydrophilic group, one or more kinds of those exemplified above are used.
[0031]
For polyethers such as the above polyoxyethylene, polyoxypropylene, and polyoxyethylene polyoxypropylene copolymers, the total number average degree of polymerization of oxyethylene and oxypropylene is preferably 1 to 2000, and particularly preferably 4 to 800.
[0032]
Examples of the hydrolyzed protein include animal-derived proteins such as collagen, elastin, keratin, fibroin (silk), sericin (silk), casein, and conchiolin, wheat protein, soybean protein, sesame protein, and zein (corn protein). A hydrolyzate of a microbial protein such as a plant protein or yeast protein such as yeast protein is preferable, but is not limited thereto. Furthermore, the number average molecular weight of the hydrolyzed protein is preferably 100 to 50000, particularly preferably 200 to 5000.
[0033]
In the compound (A) having a hydrophobic group, R preferably has a hydrophobic group, and it is preferable that one or more R having a hydrophobic group is present on one silicon atom. Further, the parent fluorocarbon group may be bonded to R having a hydrophobic group.
[0034]
Examples of the hydrophobic group include linear hydrocarbons, branched hydrocarbons, unsaturated hydrocarbons, aromatics, esters, and the like, and any one or a plurality of functional groups are preferably bonded to R. . However, the hydrophobic group is not limited to those exemplified above.
[0035]
Specific examples of the compound (A) having a hydrophobic group include, for example, methyldiethoxysilane, methyldichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Dimethyldichlorosilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, diphenyldichlorosilane, hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, stearoxypropyltri Methoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris- (β-methoxyethoxy) silane, vinyltrichlorosilane γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltri From methoxysilane, octadecyldimethyl- (3-trimethoxysilylpropyl) ammonium chloride, dimethylhexadecyl- (3-trimethoxysilylpropyl) ammonium chloride, further from vinyltrimethoxysilane to vinyltriethoxysilane, vinyltris- (Β-methoxyethoxy) silane, vinyltrichlorosilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, γ- [N- (β-aminoethyl) amino] propylmethyldimethoxysilane, γ- [N- (β-aminoethyl) amino] propyltrimethoxysilane, γ- [N- (β-amino) Ethyl) amino] propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (N-phenylamino) propyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyl Trimethoxysilane, γ-isocyanate There is a compound (A) derived from a silane coupling agent such as tetrapropyltriethoxysilane and a hydrophobic substance having a hydrophobic group as described above. Further, specific examples in which X in the general structural formula (I) representing the compound (A) is a siloxy group include octamethylcyclotetrasiloxane, dihydrogenhexamethylcyclotetrasiloxane, trihydrogenpentamethylcyclotetrasiloxane, etc. There is. However, the compound (A) having a hydrophobic group is not limited to those exemplified above.
[0036]
As the compound (A) having a hydrophobic group, one or more kinds of those exemplified above are used.
[0037]
As the compound (A) having a parent fluorocarbon group, R in the general structural formula (I) representing the compound (A) preferably has a parent fluorocarbon group, and R having a parent fluorocarbon group is one silicon atom. Preferably there is one or more above.
[0038]
Examples of the compound (A) having a parent fluorocarbon group include C₈F₁₇CH₂CH₂Si (OCH_Three)_Three, CF_ThreeCH₂CH₂Si (OCH_Three)_Threeand so on. Further, from vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris- (β-methoxyethoxy) silane, vinyltrichlorosilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyl Methyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxy Silane, γ- [N- (β-aminoethyl) amino] propylmethyldimethoxysilane, γ- [N- (β-aminoethyl) amino] propyltrimethoxysilane, γ- [N- (β-aminoethyl) amino Propyltri Ethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (N-phenylamino) propyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ- There is a compound (A) derived from a silane coupling agent extending to isocyanate propyltriethoxysilane and a parent fluorocarbon substance. However, the compound (A) having a parent fluorocarbon group is not limited to those exemplified above.
[0039]
As the compound (A) having a parent fluorocarbon group, one or more kinds of those exemplified above are used.
[0040]
Specific examples of the compound (A) having both a hydrophilic group and a hydrophobic group have already been exemplified above as the compound (A) having a hydrophilic group. For example, N- [2-hydroxy- 3- (3′-dihydroxymethylsilyl) propoxy] propyl hydrolyzed protein.
[0041]
In the case of encapsulated microcapsules dispersed in water or a hydrophilic continuous phase, the hydrophilic group of the compound (A) having a hydrophilic group is a polyether such as polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene copolymer In this case, the total number average degree of polymerization of oxyethylene and oxypropylene is preferably 10 to 1000, particularly preferably 20 to 400. In the case of hydrolyzed protein, the number average molecular weight is preferably 200 to 50000, particularly preferably 400 to 5000, The molar ratio in terms of monomer of the compound (A) having a hydrophilic group (including the case where a hydrophilic group and a hydrophobic group are present in one R) and the compound (A) having a hydrophobic group is 1 to 0 to 1 as a monomer. 1000, especially 1: 2 to 1: 200 is preferred.
[0042]
When a monomethyl compound (A) in which only one R is a methyl group is used as the compound (A) having a hydrophobic group, the compound is selected from the group consisting of methyltriethoxysilane, methyltrimethoxysilane, and methyltrichlorosilane. At least one, or for example, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethyldichlorosilane, octamethylcyclotetrasiloxane, phentriethoxysilane, hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane and stearoxy At least one selected from the group consisting of propyltrimethoxysilane is used in combination, but the molar ratio in terms of monomer between the monomethyl type compound (A) and the other having a hydrophobic group is from 100 to 0 to 0. 100, in particular 100: 3 to 100 pairs 80 are preferred.
However, the monomethyl type compound (A) and other compounds having a hydrophobic group are not limited to the above examples.
[0043]
In the case of encapsulated microcapsules dispersed in a hydrophobic continuous phase or a non-aqueous continuous phase, the hydrophilic group of the compound (A) having a hydrophilic group is polyoxyethylene, polyoxypropylene, polyoxyethylene polyoxypropylene copolymer or the like. In the case of such polyethers, the total degree of polymerization of oxyethylene and oxypropylene is preferably 3 to 20, particularly 5 to 10, and in the case of hydrolyzed proteins, the number average molecular weight is 100 to 2000, particularly 200 to 1000. Preferably, the molar ratio in terms of monomers of the compound (A) having a hydrophilic group and the compound (A) having a hydrophobic group is preferably from 1 to 5 to 1 to 1000, and more preferably from 1 to 10 to 1 to 200. When the monomethyl compound (A) having one methyl group on the silicon atom is used as the compound (A) having a hydrophobic group, the compound is selected from the group consisting of methyltriethoxysilane, methyltrimethoxysilane, and methyltrichlorosilane. At least one, or for example, dimethyldiethoxysilane, dimethyldimethoxysilane, dimethyldichlorosilane, octamethylcyclotetrasiloxane, phentriethoxysilane, hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane and stearoxy In combination with at least one selected from the group consisting of propyltrimexylsilane, the molar ratio in terms of monomer between the monomethyl type compound (A) and the other having a hydrophobic group is from 0 to 100 00: 100, in particular 10 to 100 from 80 to 100 are preferred. However, the monomethyl type compound (A) and other compounds having a hydrophobic group are not limited to the above examples.
[0044]
Next, hydrolysis of the compound (A) will be described.
[0045]
As a medium for hydrolysis of the compound (A), water is usually used. In addition, a small amount of organic solvent soluble in water, salts, protein denaturing agents such as urea, etc. may be added to the water. Good. The addition of these additives is effective when neutralization after hydrolysis of the compound (A) or emulsification by mixing with the second liquid phase is performed at a temperature of 0 ° C. or less. It is. Furthermore, in the process from hydrolysis of compound (A) to formation of prepolymer via compound (B), the reaction rate is controlled so that the condensation reaction does not become too fast, and precipitation accompanying insolubilization of the prepolymer is caused. In order to prevent and stabilize the solution, it is one preferable method to use a medium having a viscosity of 10 to 2000 mPa · s in the state before adding the silicon compound that constructs the wall film of the encapsulated microcapsule, One preferable method is to use an aqueous gelatin solution having a viscosity of 10 to 2000 mPa · s. The hydrolysis of the compound (A) is preferably performed at −5 ° C. to 90 ° C., particularly 5 ° C. to 75 ° C. with sufficient stirring. Hydrolysis of compound (A) may be on the acidic side or the basic side, but it depends on the nature of compound (A) depending on which side is used.
[0046]
Examples of thickening substances for preparing a medium having a viscosity of 10 to 2000 mPa · s include, for example, polyvinyl alcohol, polyacrylic acid amide, sodium carboxymethyl cellulose, carboxymethyl dextran, hydroxyethyl cellulose, carrageenan, chitin, chitosan, Examples include polypeptides, gelatin, and sericin.
[0047]
When the hydrolysis of the compound (A) is performed on the acidic side, it is preferably performed at pH 1 to 5, particularly pH 2 to 4. Although depending on the combination and concentration of the compound (A), if the acidity during hydrolysis is too strong, the core substance may not be sufficiently taken in later, or a glassy substance may be partially formed. As an acid to be used, for example, an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, or an organic acid such as acetic acid may be used. In particular, a hydrolyzate of compound (A) in which the hydrolyzate of animal-derived proteins such as collagen, elastin, keratin, fibroin (silk), sericin (silk), casein, conchiolin is a hydrophilic group will be obtained. In the case where the compound (A) is hydrolyzed on the acidic side, a preferable result can be obtained when an encapsulated microcapsule is finally obtained.
[0048]
When the hydrolysis of the compound (A) is performed on the basic side, it is preferably performed at pH 7.5 to 11.5, particularly pH 8 to 10. Depending on the combination and concentration of compound (A), hydrolysisTimeIf the basicity is too strong, the core material may not be sufficiently taken in later, or some glassy material may be formed. Examples of the alkali to be used include sodium hydroxide and potassium hydroxide. In particular, when trying to obtain a hydrolyzate of compound (A) in which the hydrolyzate of plant-derived protein such as wheat protein, soybean protein, and sesame protein has a hydrophilic group, hydrolysis of compound (A) It is preferable to perform the step on the basic side to obtain a preferable result in finally obtaining encapsulated microcapsules.
[0049]
Subsequent to hydrolysis of the compound (A), neutralization is performed.
[0050]
Neutralization is preferably performed at −30 ° C. to 80 ° C., particularly −5 ° C. to 55 ° C. with sufficient stirring. The acid or alkali used for neutralization is preferably the one exemplified in the above hydrolysis.
[0051]
Next, mixing and emulsification with the core substance and / or the second liquid phase will be described. The mixing / emulsification with the core substance and / or the second liquid phase is, for example, in the case of encapsulated microcapsules dispersed in water or a hydrophilic dispersion medium, by preparing a prepolymer in an aqueous dispersion medium, Add only liquid core material (second liquid phase) or core material and its solvent (second liquid phase). In the case of encapsulated microcapsules dispersed in a hydrophobic dispersion medium or a non-aqueous dispersion medium, when the core substance is soluble or hydrophilic in an aqueous solvent, for example, it can be added as it is to an aqueous solvent dispersion of a prepolymer or It means adding by dissolving in an aqueous solvent and separately emulsifying by mixing with a solvent that becomes a continuous phase in a second liquid phase that is not miscible with the aqueous solvent. In this case, a core substance may be added after inversion emulsification. In the present invention, since a neutral core material can be contained, a microcapsule that encapsulates a substance other than neutral can be produced. Mixing and emulsification with the core substance and / or the second liquid phase is preferably performed at -30 ° C to 95 ° C, particularly -5 ° C to 60 ° C. Examples of the core substance to be included are as follows.
[0052]
For example, “water”, “higher fatty acids”, “hydrocarbons”, “organic solvents”, “esters”, “phenols”, “silicones”, “silanes”, “metal alkoxides”, “higher” "Alcohols", "Animal and vegetable oils", "Extract components", "Electron-donating color-forming organic compounds", "Dyes", "UV absorbers", "Vitamins", "Medicinal components", "Aroma components" ”,“ Salts ”,“ amino acids, proteins, saccharides, etc. ”,“ enzymes ”,“ fluorocarbon substances ”, etc., and more specific examples are as follows.
[0053]
Examples of the “higher fatty acids” include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, undecylene acid, lanolin fatty acid, isostearic acid, linoleic acid, oleic acid, linolenic acid. Examples include acid, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid, and the like.
[0054]
Examples of “hydrocarbons” include liquid paraffin, isoparaffin, ozokerite, pristane, ceresin, petrolatum, microcrystalline wax, and the like.
[0055]
Examples of the “organic solvent” include hexane, heptane, octane, benzene, toluene, xylene, chlorobenzene, ethyl acetate, butyl acetate and the like.
[0056]
Examples of the “esters” include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate , Myristyl lactate, lanolin lactate, methyl isostearate, isocetyl stearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, monoisostearic acid-n-alkyl glycol, propylene glycol dicaprate , Neopentyl glycol dicaprate, glyceryl tricaprate, isostearyl neopentanoate, diisostearyl malate, mono Glyceryl thetearate, glyceryl distearate, glyceryl di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexanoate, trimethylolpropane triisostearate, neopentyl glycol di-2-ethylhexanoate, tetra-2- Pentaerythritol ethylhexanoate, glyceryl tri-2-ethylhexanoate, cetyl 2-ethylhexanoate, 2-ethylhexyl isononanoate, isononyl isononanoate, isodecyl isononanoate, isotridecyl isononanoate, 2-ethylhexyl palmitate, trimyristin Glyceryl acid, glyceryl trioctanoate, glyceryl triisopalmitate, castor oil fatty acid methyl, oleyl oleate, glyceryl acetate, 2-heptylun palmitate Sil, diisopropyl adipate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, adipic acid-2-heptylundecyl, ethyl laurate, di-2-ethylhexyl sebacate, myristate-2- Examples include hexyl decyl, 2-hexyl decyl palmitate, 2-hexyl decyl adipate, -2-hexyl decyl succinate, and diisopropyl sebacate.
[0057]
Examples of the “phenols” include t-butylphenol, nonylphenol, dodecylphenol, α-naphthol, β-naphthol, hydroquinone monomethyl ether, p-chlorophenol, p-promophenol, o-phenylphenol, p-phenylphenol, methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl p-hydroxybenzoate, 3-isopropylcatechol, pt-butylcatechol, 4,4'-methylenediphenol, bisphenol A, 1,2-dihydroxy Naphthalene, chlorocatechol, bromocatechol, 2,4-dihydroxybenzophenone, phenolphthalein, methyl gallate, ethyl gallate, propyl gallate, hexyl gallate, octyl gallate, gallic acid Examples include dodecyl acid, cetyl gallate, stearyl gallate, tannic acid, phenolic resin, zinc salicylate, and zinc t-butylsalicylate.
[0058]
Examples of the “silicones” include dimethylpolysiloxane, methylphenylpolysiloxane, dimethylsiloxane / methylstearoxysiloxane copolymer, dimethylsiloxane / methylmethoxysiloxane copolymer, dimethylsiloxane / methylethoxysiloxane copolymer, trimethyl Examples include siloxysilicic acid, methylcyclopolysiloxane, methylhydrogenpolysiloxane, highly polymerized methylpolysiloxane, and cross-linked methylpolysiloxane.
[0059]
Examples of the “silanes” include methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, tetramethoxysilane, tetraethoxy Silane etc. are mentioned.
[0060]
Examples of the “metal alkoxide” include trimethyl borate, triethyl borate, tetraethyl titanate, tetraisopropyl titanate and the like.
[0061]
Examples of the “higher alcohols” include capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, aralkyl alcohol, behenyl alcohol, oleyl alcohol, cetostearyl alcohol, monostearyl glyceryl ether, 2-decyltetradecanol, Examples include 2-hexyl decanol, 2-hexyl decanol, 2-octyl dodecanol, 2-heptyl undecanol, lanolin alcohol, cholesterol, phytosterol, and isostearyl alcohol.
[0062]
Examples of the “animal and vegetable oil” include apogado oil, camellia oil, macadamia nut oil, corn oil, olive oil, evening primrose oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, sasanqua oil, castor oil, hydrogenated castor oil , Flaxseed oil, safflower oil, cottonseed oil, hydrogenated cottonseed oil, soybean oil, hydrogenated soybean oil, peanut oil, teaseed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, cinnamon oil, jojoba oil, germ oil, almond Oil, cacao oil, coconut oil, hydrogenated coconut oil, horse fat, turtle oil, mink oil, squalane, squalene, orange luffy oil, beef tallow, hardened beef tallow, beef bone fat, beef leg fat, sheep fat, tallow fat, whale Fat, hardened whale fat, fish oil, hardened fish oil, lanolin, lanolin alcohol, hydrogenated lanolin, lanolin acetate, liquid lanolin, lanolin fatty acid isopropyl, lanolin fatty acid co Steryl, reduced lanolin, polyoxyethylene lanolin alcohol ether, polyoxyethylene lanolin alcohol acetate, lanolin fatty acid polyethylene glycol, polyoxyethylene hydrogenated lanolin alcohol ether, carnauba wax, candelilla wax, jojoba wax, hard lanolin, moclaw, sugarcane wax, cotton Examples thereof include wax, bayberry wax, ibota wax, montan wax, nukarou, shellac wax, jojoba wax, beeswax, whale wax, jojoba alcohol, abietic acid, and hydrogenated abietic acid.
[0063]
Examples of the “electron-donating color-forming organic compound” include diaryl phthalides, polyaryl carbinols, leucooramines, acyl auramines, aryl auramines, rhodamine-β-lactams, indolines. , Spiropyrans, fluorans and the like. Specific examples thereof include crystal violet lactone, malachite green lactone, Michler hydrol, crystal violet carbinol, malachite green carbinol, N- (2,3-dichlorophenyl). ) Leucooramine, N-benzoylolamine, N-acetylolamine, N-phenylolamine, rhodamine-β-lactam, 2- (phenyliminoethanedilidene) -3,3-dimethylindoline, N-3, 3-trimethylin Dorinobenzspirolane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-7-methoxyfluorane, 3-diethylamono-6-benzyloxyfluorane, 1,2-benz-6-diethylaminofluor Examples include oran.
[0064]
Examples of the “pigments” include colorless white pigments such as titanium dioxide and zinc oxide, inorganic red pigments such as iron oxide (Bengara) and iron titanate, inorganic brown pigments such as γ-iron oxide, and yellow iron oxide. , Inorganic yellow pigments such as ocher, inorganic black pigments such as black iron oxide, carbon black, low-order titanium oxide, inorganic purple pigments such as mango violet and cobalt violet, chromium oxide, chromium hydroxide, cobalt titanate, etc. Inorganic green pigments, inorganic blue pigments such as ultramarine blue and bitumen, red 201, red 202, red 204, red 205, red 218, red 220, red 225, red 226, red 228 No., red 405, orange 201, orange 203, orange 204, yellow 401, green 202, blue 404, organic dyes, red 3, red 04, Red 106, Red 227, Red 230, Red 401, Red 505, Orange 205, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Green 3, Purple 201 Zirconium such as Blue No. 11, organic pigments such as barium or aluminum lake, natural pigments such as chlorophyll and β-carotene, mica titanium, bengara-treated mica titanium, yellow iron oxide-treated mica titanium, black iron oxide-treated mica titanium, oxidized Iron / yellow iron oxide treated mica titanium, bitumen treated mica titanium, carmine treated mica titanium, chromium oxide treated mica titanium, carbon black treated mica titanium, etc. In addition, talc, kaolin, mica, kin mica, sericite, muscovite, synthetic mica, safmica, lithia mica, vermiculite, etc. Fluoroapatite, hydroxyapatite, ceramic powder, metal soap (such as zinc myristate, calcium palmitate, aluminum stearate), boron nitride, silica-alumina, silica-magnesia, bentonite, fuller's earth, sansei clay, activated clay, montmorillonite , Inorganic powder such as attapul guide, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, styrene / acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder And organic powders.
[0065]
Examples of the “ultraviolet absorber” include salicylic acid-based ultraviolet absorbers such as phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone. 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2- Benzophenone ultraviolet absorbers such as hydroxy-4-methoxy-5-sulfobenzophenone or derivatives thereof, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-t) -Butyl fluoride Nyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3', 5'-di -T-amylphenyl) benzotriazole, 2- [2'-hydroxy-3 '-(3 ", 4", 5 ", 6" -detrahydrophthalimidomethyl) -5'-methylphenyl] -benzotriazole, 2- (2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-undecyl-5′-methylphenyl) benzotri Sol, 2- (2′-hydroxy-3′-tridecyl-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-4 ′-(2 ″ -ethylhexyl) oxyphenyl] benzotriazole, 2- [ 2'-hydroxy-4 '-(2 "-ethyloctyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4'-(2" -propyloctyl) oxyphenyl] benzotriazole, 2- [2 ' -Hydroxy-4 '-(2 "-propylheptyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4'-(2" -propylhexyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy -4 ′-(1 ″ -ethylhexyl) oxyphenyl] benzotriazole, 2- [2′-hydroxy-4 ′ -(1 "-ethylheptyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4 '-(1" -ethyloctyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4'-( 1 "-propyloctyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4 '-(1" -propylheptyl) oxyphenyl] benzotriazole, 2- [2'-hydroxy-4'-(1 " -Propylhexyl) oxyphenyl] benzotriazole, methyl-3- [3-t-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol (molecular weight about 300) Induction of condensate, paramethoxycinnamic acid such as 2-methoxyhexyl paramethoxycinnamate Or derivatives thereof, derivatives of paraaminobenzoic acid such as paradimethylaminobenzoic acid-2-ethylhexyl or esters thereof, derivatives of cinnamic acid such as benzyl cinnamate or esters thereof, anthranilate, salicylate, derivatives of benzoxazole 2,4,6-tri- (p-anilino) -1- (carboxy-2'-ethylhexyl) -1,3,5-triazine, 4-t-butyl-4'-methoxydibenzoylmethane and 4- Examples thereof include derivatives of dibenzoylmethane such as isopropyldibenzoylmethane, furanone derivatives, ferulic acid or esters thereof, and γ-oryzanol.
[0066]
Examples of “vitamins” include vitamins such as vitamin A, vitamin B, vitamin C, vitamin D, vitamin E, thiamine hydrochloride, pyridoxine hydrochloride, calcium pantothenate, bisbenchamine, methylmethionine sulfonium chloride, and derivatives thereof, Examples thereof include phosphoric acid-L-ascorbyl magnesium, sulfuric acid-L-ascorbyl magnesium disodium, tocopherol acetate, and the like.
[0067]
Examples of the “medicinal ingredient” include sulfa drugs such as sulfamethomidine, calcium foveate, papaverine hydrochloride, diltiazem hydrochloride, circulatory drugs such as reserpine, trimethquinol hydrochloride, bromhexine hydrochloride, and tipepidine hibenzate. Respirators, antitussives, benzylpenicillin potassium, benzylpenicillin sodium, phenoxymethylpenicillin potassium, ampicillin antibiotics, 5-fluorouracil, N- (2-tetrahydrofuryl) -5-fluorouracil, bleomycin hydrochloride Antitumor agents such as thimepidium bromide, lidocaine hydrochloride, chlorpromazine hydrochloride, antihistamines such as diphenhydramine hydrochloride, chlorpheniramine maleate, aspirin, quini hydrochloride Antipyretic analgesic / anti-inflammatory agents such as sulpyrine, bactericides such as salicylic acid, hinokitiol, sulfur and parabens, preservatives, photosensitizers, cysteine or derivatives thereof, guaiazulene or derivatives thereof, glutathione or derivatives thereof, etc. It is done.
[0068]
Examples of the “extraction component” include oil-soluble arnica extract, aloe extract, oil-soluble licorice extract, chamomile extract, oil-soluble chamomile extract, oil-soluble licorice extract, gardenia extract, oil-soluble mulberry extract, oil-soluble burdock extract, and oil-soluble collagen. Extract, oil-soluble salvia extract, oil-soluble chicory extract, oil-soluble shinano extract, oil-soluble birch extract, oil-soluble horsetail extract, oil-soluble Achillea millefolium extract, oil-soluble sage extract, assembly extract, thyme extract, chimpi extract, oil-soluble teigurumi extract, Oil-soluble Toki extract, oil-soluble Toki-Senka extract, oil-soluble carrot extract, oil-soluble rosette extract, oil-soluble loquat leaf extract, oil-soluble placenta extract, oil-soluble hop extract, oil-soluble malonie extract, oil-soluble peach leaf extract, mugwort extract, oil Sex Yokuininekisu, lavender extract, lemon extract, orange extract, oil-soluble rosemary extract, such as oil-soluble royal jelly extract. Examples include herbal medicinal components such as green tea, tsunaka tea, rooibos tea, camellia flower, yellow rice, and a persimmon extract containing tannins, flavonoids, and various salts thereof.
[0069]
“Aroma components” include, for example, almond, anise, caraway, cassia, cedar leaf, cedarwood, cinnamon, citronella, clove, eucalyptus, geranium, grapefruit, lavender, lemon, lemon grass, rose oil, lime, orange flower (neroli) , Nutmeg, Onion, Garlic, Orange, Riganum, Oris, Peppermint, Pine, Pine needles, Rosemary, Sandlewood, Sassafras, Spearmint, Thyme, Coffee, Tea, Cherry, Apple, Pineapple, Banana, Peach, Vanilla The oil which has is mentioned.
[0070]
Examples of “salts” include calcium carbonate, magnesium carbonate, magnesium silicate, calcium silicate, aluminum silicate, barium silicate, barium sulfate, strontium silicate, metal tungstate, silica, zeolite, barium sulfate, calcined Calcium sulfate (baked gypsum), calcium phosphate, lithium chloride, sodium chloride, potassium chloride, ammonium chloride, lithium bromide, sodium bromide, potassium bromide, lithium iodide, sodium iodide, potassium iodide, iodine, sodium sulfate, Examples thereof include salts such as potassium sulfate, ammonium sulfate, ammonium nitrate, lime nitrogen, lime superphosphate, calcined phosphorus fertilizer, and sodium phosphate.
[0071]
Examples of “amino acid, protein, saccharide, etc.” include amino acids or peptides such as potassium aspartate, magnesium aspartate, sodium glutamate, lysine hydrochloride, glutathione, collagen, elastin, keratin, fibroin, sericin, casein, conchiolin. Examples include animal-derived proteins such as wheat protein, soybean protein, and plant-derived proteins such as sesame protein, microorganism-derived proteins such as yeast protein or hydrolysates of these proteins, placental extracts, mucopolysaccharides, urea, etc. It is done.
[0072]
Examples of the “enzyme” include enzymes such as lipase, protease, superoxide dismutase, lysozyme, alkaline phosphatase, amylase, pancreatin, glutathione peroxidase, and catalase.
[0073]
“Fluorocarbon substances” include fomblin HC / 04 (trade name) and fomblin HC / 25 (trade name) which are liquid perfluoroethers which are a kind of polyoxyperfluoroalkanes manufactured by Montefluos (Milan, Italy). ), Fomblin HC / R (trade name) and the like.
[0074]
One or more of the above can be combined to form the core material.
However, the core substance is not limited to those exemplified above.
[0075]
In the case of encapsulated microcapsules dispersed in a hydrophobic continuous phase or a non-aqueous continuous phase, higher fatty acids, hydrocarbons, organic solvents, esters, silicones, higher alcohols exemplified as the core material are used as the continuous phase. One or more of animal and vegetable oils may be used in combination, and may be liquid throughout the capsule preparation process. Of the organic solvents, those having a boiling point equal to or lower than that of water may be used as long as water can be driven out of the system azeotropically.
[0076]
In emulsion preparation, for example, a round bottom cylindrical glass reaction vessel with an internal diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer, with a central particle size of 1 to 20 μm, mainly in the range of a particle size of 0.3 to 100 μm. In the case of adjusting the particle diameter within the range, it is preferable to stir the reaction solution at 50 to 1000 rpm, particularly 300 to 1000 rpm.
[0077]
In emulsion preparation, for example, after stirring the reaction solution with a mechanical stirrer, the particle size is adjusted with a homomixer mainly in the range of particle size of 0.1 to 30 μm and the center particle size of 0.5 to 5 μm. When performing, it is preferable to process a reaction liquid at 1000-20000 rpm by a homomixer, especially 5000-10000 rpm.
[0078]
In emulsion preparation, for example, after stirring the reaction solution with a mechanical stirrer and treating with a homomixer, the particle size is mainly 0.1 to 1 μm with a microfluidizer and the center particle size is 0.2 to When adjusting the particle diameter in the range of 0.8 μm, 300 to 5000 kg / cm with a microfluidizer.²It is preferable to treat with.
[0079]
One of the purposes of processing with a homomixer or a microfluidizer is to reduce the particle size, but the other purpose was applied by this treatment as a result of adding a strengthening treatment of the wall film later. This is to produce an encapsulated microcapsule that does not break the wall membrane when a certain amount of shearing force is applied.
[0080]
The microcapsules in the present invention include both microcapsules and nanocapsules. Generally, microcapsules have a particle size of 1 μm or more and less than 1 mm, and nanocapsules have a particle size of less than 1 μm.
[0081]
Next, with the compound (A), which is an intermediate for the production of encapsulated microcapsulessurfaceThe processing will be described.
[0082]
Production of encapsulated microcapsules Encapsulated microcapsules can be produced without surface treatment with the intermediate compound (A). However, according to the production method of the present invention, it is considered that silanol groups not participating in condensation remain on the surface of the uncured capsule immediately after emulsification. This silanol group serves as a foothold for condensing with the newly added compound (A) or the hydrolyzate compound (B) to impart new properties to the capsule surface.
[0083]
When the compound (A) for surface treatment is a compound (A) that easily hydrolyzes in water, such as chlorosilane such as trimethylchlorosilane or hexamethyldisilazane, this neutral emulsion solution is added to the neutral emulsion solution. It is preferable to neutralize by adding this compound (A).
[0084]
When the surface treatment compound (A) is an alkoxysilane such as trimethylethoxysilane, the compound (B) obtained by adding the neutral solution to a slightly acidic or basic state following emulsificationThe alkoxysilaneNeeds to be hydrolyzed once. Even when the compound (A) having a silanol group is used for the surface treatment as it is from the beginning, it is necessary to add the compound (A) by making the neutral compound (A) solution slightly acidic or basic following emulsification. . Next, the compound (A) is fixed on the capsule surface by neutralization. However, when adjusting the pH, care must be taken not to break the capsule, and a pH of 3 to 6.5 is preferable in the treatment on the acidic side. In the treatment on the basic side, pH 7.5 to 10 is preferable. Although it illustrates later about the compound (A) used for this surface treatment, it is not restricted to them.
[0085]
In addition, for the purpose of surface treatment, it may prevent aggregation of the encapsulated microcapsules. In order to prevent aggregation of the encapsulated microcapsules, after the emulsion preparation, trimethylchlorosilane, trimethylethoxysilane, t-butyldimethylchlorosilane, It is preferable to add a compound (A) having three alkyl groups on a silicon atom, such as hexamethyldisiloxane and hexamethyldisilazane.
[0086]
Further, after preparation of the emulsion, as a compound (A) having a cationic group as an organic substituent, for example, octadecyldimethyl- (3-trimethoxysilylpropyl) ammonium chloride is added and hydrolyzed to neutralize, thereby encapsulating microcapsules The surface of can be made cationic.
[0087]
  After emulsion preparation, methyldiethoxysilane, methyldichlorosilane, methyltrimethoxysilane, MeTitritriethoxysilane, methyltrichlorosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldichlorosilane, octamethylcyclotetrasiloxane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltrichlorosilane, diphenyldimethoxysilane, diphenyldiethoxysilane , Diphenyldichlorosilane, hexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, stearoxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris- (β-methoxyethoxy) silanevinyltrichlorosilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-meta Lilooxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, octadecyldimethyl- (3-trimethoxysilyl) Propyl) ammonium chloride, hexadecyldimethyl- (3-trimethoxysilylpropyl) ammonium chloride, methoxy (ethoxy) n (propoxy) mpropylmethyl dialkoxysilane, methoxy (ethoxy) n (propoxy) mpropyltrialkoxysilane Compound (A), N- [2-hydroxy-3- (3′-trihydroxysilyl) propoxy] propyl hydrolyzed protein, N- [2-hydroxy-3- (3′-dihydroxy) (Methylsilyl) propoxy] propyl hydrolyzed protein such as γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and other substances (A), and β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, γ- [N- (β-aminoethyl) amino] propylmethyldimethoxysilane, γ- [N- (β-aminoethyl) amino] propyltrimethoxysilane, γ- [N- (β-aminoethyl) amino] propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ- (N-phenylamino) propyltrimethoxysilane, vinyltrimethoxysilane, Vinyltriethoxysilane, vinyltris- (β-methoxy Ethoxy) silane vinyltrichlorosilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-chloropropyltrimethoxy Encapsulated by adjusting pH and neutralizing compound (A) derived from silane coupling agent and other substances ranging from silane, γ-mercaptopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane Various properties of the surface of the microcapsule can be modified, and various functions can be imparted.
[0088]
A plurality of the above series of surface treatments may be combined.
[0089]
In the curing treatment, the polycondensation reaction proceeds further by removing alcohol generated by hydrolysis of alkoxysilane, which is a kind of compound (A), dehydration by elapse of time or heating, dehydration outside the reaction system, etc. By doing so, the strength of the wall membrane of the encapsulated microcapsule can be increased. The heating temperature is preferably 30 ° C. or higher at low temperature of the reaction solution, and the boiling point may be changed by pressure, but heating at a temperature at which the water in the reaction system boils is particularly preferable. The above-mentioned dehydration over time means that siloxane condensation naturally dehydrates and condenses at a neutral pH, and thus means dehydration over a mere time, and the above dehydration outside the reaction system is For example, it means distilling (removing the liquid formed by cooling the solvent vapor out of the reaction system without returning it to the reaction system).
[0090]
In the encapsulated microcapsule thus obtained, the weight of the core substance is preferably in the range of 0.01 to 99% by weight with respect to the encapsulated microcapsule. The ratio of the weight of the core substance to the weight of the encapsulated microcapsules is hereinafter referred to as “encapsulation rate”. As described above, according to the present invention, since the range of the inclusion rate is wide, the thickness of the wall film can be easily adjusted while correlating the inclusion rate and the particle size. In addition, the encapsulated microcapsules are sufficiently water resistant when used near a neutral pH.
[0091]
Furthermore, the strength of the capsule depends on the type of compound (A) used, the particle size, the curing conditions, and the encapsulation rate. For example, in the case of a microcapsule manufactured for cosmetics having a particle size of 1 to 2 μm and an encapsulation rate of 90% No disintegration was observed even when it was used in the skin after blended into cosmetics through a mechanical mixing process.
[0092]
The encapsulated microcapsules produced according to the present invention can be processed into a powder by freeze drying or spray drying.
[0093]
The uptake rate of the core substance into the encapsulated microcapsules produced according to the present invention is 5 to 99.99% by weight, and in many cases 60 to 99% by weight. This uptake rate indicates what percentage of the core material that has been introduced is taken into the capsule, and is different from the above-mentioned inclusion rate. According to the present invention, in many cases, the uptake rate is sufficiently high, and purification such as removal of the core material that has not been taken in is not always necessary, but the purification method is as follows.
[0094]
One of the purification methods is to add a liquid phase that does not mix with the liquid phase in which the capsules are dispersed and that does not disperse the capsules, mix the two liquid phases well, and then decantate when both liquid phases are separated. Alternatively, there is a method in which impurities are transferred to another liquid phase by separating both liquid phases by liquid separation. Centrifugation may be used when it is difficult to separate both liquid phases. When the two liquid phases are difficult to separate, a liquid phase miscible with the liquid phase in which the capsules are dispersed may be added to wash and separate the capsules.
[0095]
As another purification method, there is a method of fractionating encapsulated microcapsules that have settled or floated by centrifugation. In the case of this method, after the dispersion, impurities are removed together with the solvent, and the capsule is dispersed again in a solvent that can be dispersed. This is repeated.
[0096]
Still another purification method is an ultrafiltration method. In this purification method by ultrafiltration, impurities eluted by ultrafiltration are removed, and the concentrated encapsulated microcapsules are dispersed again in a solvent that can be dispersed. This is repeated.
[0097]
【The invention's effect】
In the encapsulated microcapsule of the present invention, the wall film has thermal, mechanical stability and light resistance, which are general basic properties of organopolysiloxane, and is bioinert. In the present invention, the encapsulated microcapsules can be produced directly from the compound (A) such as alkoxysilane, halogenated silane, hydrogensilane, or polysiloxane, which is advantageous in terms of cost. In addition, combining various compounds (A) provides great flexibility in designing encapsulated microcapsules according to the purpose.
[0098]
The encapsulated microcapsules of the present invention having such various properties are pharmaceuticals, liquid crystals, chemical products, recording materials, cosmetics, fragrances, enzymes, agriculture, adhesives, fibers, foods, catalysts, detergents, dyes, paints. Widely applicable for rust preventives and baths.
[0099]
  In addition, the encapsulated microcapsule of the present invention has a number of bonds involved in condensation on a silicon atom in the production.3Since the compound (B) which is 1 to 1 is polycondensed, the weight ratio of the wall membrane to the contents can be selected within a wide range, and the thickness and particle diameter of the wall membrane are adjusted in association with this, thereby forming a dense network It is possible to prepare various types of wall membranes having a certain thickness, wall membranes having an appropriate substance permeability, high-strength wall membranes, or moderately soft wall membranes.
[0100]
【Example】
Other objects, features and advantages of the present invention will become apparent from the following descriptive description with reference to various embodiments of the present invention, which are presented for illustrative purposes only, It is not intended to limit the scope of the invention. Moreover, unless otherwise indicated,% is% by weight.
[0101]
Example 1
Encapsulated microcapsules of 2-methoxyhexyl paramethoxycinnamate having a wall film of organopolysiloxane composed of hydrolyzate copolymer of methoxy (ethoxy) npropyldihydroxymethylsilane, methyltriethoxysilane and phenyltriethoxysilane Manufacturing of
[0102]
1) Preparation of prepolymer
The top lid is equipped with a dropping funnel and a reflux condenser, and a round-bottom cylindrical glass reaction vessel with an inner diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer. KF-354A (trade name), a condensate of methoxy (ethoxy) npropyldihydroxymethylsilane sealed at both ends with a trimethylsilyl group] 10 g and 18% hydrochloric acid 0.2 g were added and stirred at 50 ° C. Then, a mixture of 4.4 g of methyltriethoxysilane and 1.2 g of phenyltriethoxysilane was dropped from the dropping funnel. The mixture was further stirred at 50 ° C. for 6 hours. Next, 1.6 g of a 4% aqueous sodium hydroxide solution was added dropwise while continuing the stirring to adjust the pH to 7.0, followed by stirring at 50 ° C for 1 hour.
[0103]
2) Addition and emulsification of core material
While stirring the reaction solution prepared in 1) at 600 rpm, 5.4 g of paramethoxycinnamic acid-2-ethylhexyl was added, and the mixture was further stirred at 600 rpm for 4 hours.
[0104]
3) Aggregation prevention and wall film hardening treatment
While stirring the reaction solution prepared in 2) in a reaction vessel at 50 ° C. and 600 rpm, 0.5 g of trimethylchlorosilane was added, and 1 g of a 20% aqueous sodium hydroxide solution was immediately added dropwise. The temperature of the reaction solution was gradually raised to reflux. The alcohol-containing vapor was distilled off, and the mixture was further heated to reflux for 6 hours with stirring at 150 rpm. The reaction solution was cooled at 150 rpm with stirring at room temperature to obtain encapsulated microcapsules.
[0105]
Analysis method 1
About 10 g of the dispersion liquid of the encapsulated microcapsules obtained was accurately weighed, and the moisture content of the dispersion liquid of the encapsulated microcapsules was measured with an infrared moisture meter LIBOR EB-280MOC (trade name) manufactured by Shimadzu Corporation. Measured, and based on the result, the weight of the non-aqueous part [encapsulated microcapsule + free core substance (core substance not incorporated into the capsule) + ash content (ash)] in the dispersion containing the produced microcapsules Ask. That is, as in Example 1, in the case of an oil-in-water capsule, the weight of the dispersion containing the capsule is the weight of “water + encapsulated microcapsules + free core substance + ash”. When moisture is measured by Analysis Method 1, the result shows the weight of the non-aqueous portion [encapsulated microcapsules + free core substance + ash (ash)] in the dispersion.
[0106]
Analysis method 2
The concentration of Na in the capsule dispersion is measured with an ICP emission spectroscopic analyzer SPS1700HVR (trade name) manufactured by Seiko Denshi Kogyo Co., Ltd., and the weight of NaCl in the dispersion containing the produced microcapsules is calculated. As described in the analysis method 1 above, the dispersion containing capsules also contains ash (ash), but it is considered that NaCl accounts for most of the ash other than silica. Therefore, the amount of NaCl is determined by this analysis method 2, and the result is used as the amount of ash when determining the inclusion rate described later.
[0107]
Analysis method 3
About 1 g of the dispersion liquid of the obtained encapsulated microcapsules is accurately weighed and transferred to a 500 ml separatory funnel while washing with about 100 ml of water. Add 100 ml of n-hexane, shake well, and let stand. After the liquid phase is separated, 100 ml of n-hexane extract is transferred to another container. This liquid separation operation is repeated three times, and the obtained n-hexane extracts are combined and concentrated to make exactly 100 ml. Take 1 μl of this n-hexane extract with a microsyringe, apply it to a liquid chromatograph, and take it into a microcapsule present in about 1 g of a dispersion of encapsulated microcapsules obtained from a standard concentration calibration curve prepared separately. The weight of the free core substance (in the case of Example 1, paramethoxycinnamic acid-2-ethylhexyl) was determined, and then the weight of the free core substance in the dispersion containing the microcapsules generated by calculation was determined.
[0108]
Analysis method 4
About 0.1 g of the obtained dispersion liquid of the encapsulated microcapsules is accurately weighed, 5 ml of 5N sodium hydroxide aqueous solution is added thereto, and the mixture is stirred at 50 ° C. for 1 hour and cooled to room temperature. This is washed with about 100 ml of water and transferred to a 500 ml separatory funnel. Add 100 ml of n-hexane, shake well, and let stand. After the liquid phase is separated, 100 ml of n-hexane extract is transferred to another container. This liquid separation operation is repeated three times, and the obtained n-hexane extracts are combined and concentrated to make exactly 100 ml. Take 1 μl of this n-hexane solution with a microsyringe, apply it to a liquid chromatograph, and take it into a microcapsule present in about 0.1 g of a dispersion of encapsulated microcapsules obtained from a standard concentration calibration curve prepared separately. Of the free core material (paramethoxycinnamate-2-ethylhexyl in the case of Example 1) and the core material (paramethoxycinnamate-2-ethylhexyl in the case of Example 1) incorporated into the microcapsules. Determine the total weight.
[0109]
[(Value of analysis method 4) − (value of analysis method 3)] / [(value of analysis method 1) − (value of analysis method 2) − (value of analysis method 3)] × 100 The core substance taken into the capsule (paramethoxycinnamic acid-2-ethylhexyl in the case of Example 1) is shown by weight% with respect to the weight of the microcapsule. That is, the value of Analysis Method 4 is “core substance taken into capsule (paramethoxycinnamic acid-2-ethylhexyl in the case of Example 1) and free core substance (core substance not taken into capsule)” Since the value of Analysis Method 3 is the weight of the “free core substance”, [(Analysis Method 4 Value) − (Analysis Method 3 Value)] of the molecule in the above formula is [ (Incorporated core substance + free core substance) − (free core substance)], and indicates the weight of “core substance incorporated into capsule”.
[0110]
On the other hand, the value of Analysis Method 1 is the weight of “encapsulated microcapsules + free core substance + ash”, the value of Analysis Method 2 is substantially the amount of “ash”, and the value of Analysis Method 3 is “free [(Analysis method 1 value)-(Analysis method 2 value)-(Analysis method 3 value)]] of the denominator in the above formula is [(encapsulated microcapsule + Free core substance + ash content)-(ash content)-(free core material)], and the weight of “encapsulated microcapsules”. Thus, since the numerator is the weight of the “core substance incorporated in the capsule” and the denominator is the weight of the “encapsulated microcapsule”, the above formula [(value of analysis method 4) − (analysis method 3 Value)] / [(value of analysis method 1) − (value of analysis method 2) − (value of analysis method 3)] × 100 indicates the inclusion rate.
[0111]
Analysis method 5
About 0.1 g of the obtained encapsulated microcapsule dispersion is taken, and about 5 ml of water is added thereto. One drop of this is taken as a preparation and covered with a cover glass, and then observed with an optical microscope at a magnification of 1000 times, and the particle size distribution is determined visually.
[0112]
Analysis method 6
The particle size distribution of the obtained encapsulated microcapsules is measured with SALD-2000 (trade name) manufactured by Shimadzu Corporation.
[0113]
Test method 1
Place 1 drop (about 50 μl) of a dispersion of encapsulated microcapsules diluted 20-fold between 2 glass plates of 1 cm square and 2 mm thickness, place it on a horizontal solid table, and place 1.5 kg from above / Cm²Apply pressure. After applying pressure, observe whether the capsule bursts with a microscope. However, it may protrude when it is pinched or when pressure is applied, and it is wiped off during microscopic observation.
[0114]
The dispersion of the encapsulated microcapsules obtained in Example 1 was analyzed by the analysis methods 1 to 5 as described below.
[0115]
130 g of capsules with a diameter of 0.3-5 μm, mainly 1-2 μm, in water
Ingredient excluding water: 14.8%
Free 2-methoxyhexyl paramethoxycinnamate in dispersion 0.4%
26% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
[0116]
Further, when the encapsulated microcapsules obtained in Example 1 were examined for whether or not the capsules were ruptured by Test Method 1, the capsules did not rupture.
[0117]
Comparative Example 1
In the manufacture of 2-methoxyhexyl paramethoxycinnamate having a wall film of organopolysiloxane composed of hydrolyzate copolycondensate of methoxy (ethoxy) npropyldihydroxymethylsilane, methyltriethoxysilane and phenyltriethoxysilane When performing polymerization at the interface between the continuous phase and the core material
[0118]
1) Preparation of capsule wall membrane
The top lid is equipped with a dropping funnel and a reflux condenser, and a circular cylindrical glass reaction vessel with an inner diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer is prepared in advance with 90 g of water and polyoxyethylene-modified silicone [manufactured by Shin-Etsu Chemical Co., Ltd. KF-354A (trade name)] 10 g and 18% hydrochloric acid 0.2 g were added, and a mixture of 4.4 g of methyltriethoxysilane and 1.2 g of phenyltriethoxysilane was added dropwise from a dropping funnel while stirring at 50 ° C. did. Further, after stirring at 50 ° C. for 6 hours, 5.4 g of 2-methoxyhexyl paramethoxycinnamate was added while stirring the reaction solution at 600 rpm. Furthermore, after stirring at 600 rpm for 4 hours, 1.9 g of 4% aqueous sodium hydroxide solution was added dropwise with stirring to adjust the pH to 7.0, followed by stirring at 50 ° C. for 1 hour.
[0119]
2) Prevention of aggregation and hardening of wall film
3 g of trimethylchlorosilane was added while stirring the reaction solution prepared in 1) at 50 ° C. and 600 rpm in a reaction vessel, and 5.6 g of 5N sodium hydroxide aqueous solution was immediately added dropwise. The temperature of the reaction solution was gradually raised to reflux. The alcohol-containing vapor was distilled off, and the mixture was further heated to reflux for 6 hours while stirring at 150 rpm. The reaction solution was cooled at 150 rpm with stirring at room temperature to obtain a product. The sticky substance adhered to the reaction vessel wall, and only an amount of oil similar to the added paramethoxycinnamic acid-2-ethylhexyl was separated.
[0120]
Example 1A
Encapsulated microcapsules of 2-methoxyhexyl paramethoxycinnamate having a wall film of organopolysiloxane composed of hydrolyzate copolycondensate of methoxy (ethoxy) npropyltrimethoxysilane, methyltriethoxysilane and phenyltriethoxysilane Manufacturing of
[0121]
1) Preparation of prepolymer
The top lid is equipped with a dropping funnel and a reflux condenser, and a 12-cm round bottom cylindrical glass reaction vessel equipped with a mechanical stirrer is charged with 97 g of water and polyethoxypropyltrimethoxysilane in advance [Shin-Etsu Chemical Co., Ltd. KBM-641 (trade name)] 3 g and 0.2% 18% hydrochloric acid were added, and a mixture of 4.2 g of methyltriethoxysilane and 1.2 g of phenyltriethoxysilane was added from a dropping funnel while stirring at 50 ° C. It was dripped. Furthermore, it stirred at 50 degreeC for 6 hours. Next, 1.7 g of 4% aqueous sodium hydroxide solution was added dropwise while continuing the stirring to adjust the pH to 7.0, followed by stirring at 20 ° C. for 1 hour.
[0122]
2) Addition and emulsification of core material
While stirring the reaction solution prepared in 1) at 600 rpm, 4.0 g of paramethoxycinnamic acid-2-ethylhexyl was added, and stirring was further continued at 600 rpm for 4 hours.
[0123]
3) Aggregation prevention and wall film hardening treatment
While stirring the reaction solution prepared in 2) in a reaction vessel at 50 ° C. and 600 rpm, 1.0 g of trimethylchlorosilane was added, and 1.8 g of 20% aqueous sodium hydroxide solution was immediately added dropwise. The temperature of the reaction solution was gradually raised to reflux. The alcohol-containing vapor was distilled off, and the mixture was further heated to reflux for 6 hours while stirring at 150 rpm. The reaction solution was cooled at 150 rpm with stirring at room temperature to obtain encapsulated microcapsules.
[0124]
The dispersion of the encapsulated microcapsules obtained in Example 1A was analyzed according to the analytical methods 1 to 5 as follows.
[0125]
107 g dispersion of capsules with a diameter of 0.3 to 10 μm, mainly 1 to 2 μm
Ingredients excluding water 14.0%
Free paramethoxycinnamate-2-ethylhexyl 0.5% in dispersion
28% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
[0126]
In Example 1, a polyether-modified silicone such as KF-354A (trade name) is used as the hydrophilic group-containing compound (A), and this is hydrolyzed to prepare a prepolymer, and a core substance is added to the emulsion. In this way, the encapsulated microcapsules could be produced, but when the polymer was generated at the interface between the core substance and the continuous phase as in Comparative Example 1, the encapsulated microcapsules were not formed, The polymer and core material were separated. Further, in Example 1A, trialkoxysilane having a polyether group such as KBK-641 (trade name) was used as the compound (A) having a hydrophilic group. Could be manufactured.
[0127]
Further, when the encapsulated microcapsules obtained in Example 1A were examined for whether or not the capsules ruptured according to Test Method 1, the capsules did not rupture.
[0128]
Example 2
N- [2-hydroxy-3- (3′-trihydroxysilyl) propoxy] propyl hydrolyzed collagen, organopolysiloxane composed of hydrolyzate copolycondensate of methyltriethoxysilane and phenyltriethoxysilane was used as a wall film. Of encapsulated microcapsules of 2-methoxyhexyl paramethoxycinnamate
[0129]
1) Preparation of prepolymer
The top lid was equipped with a dropping funnel and a reflux condenser, and a round bottom cylindrical glass reaction vessel having an inner diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer was previously filled with 135 g of water and N- [2-hydroxy-3- (3′- Trihydroxysilyl) propoxy] propyl hydrolyzed collagen (molecular weight of hydrolyzed collagen is about 2000 in terms of number average molecular weight) 15 g and 3.6% of 18% hydrochloric acid are added, and 45.9 g of methyltriethoxysilane with stirring at 50 ° C. And 12.4 g of phenyltriethoxysilane were added dropwise from the dropping funnel.
[0130]
Furthermore, it stirred at 50 degreeC for 6 hours. Next, 2.9 g of 25% aqueous sodium hydroxide solution was added dropwise while continuing the stirring to adjust the pH to 7.0, followed by stirring at 50 ° C. for 1 hour.
[0131]
2) Addition and emulsification of core material
While stirring the reaction solution prepared in 1) at 600 rpm, 389 g of paramethoxycinnamic acid-2-ethylhexyl was added. Further, stirring was continued at 600 rpm for 4 hours.
[0132]
3) Atomization
The reaction solution prepared in 2) was transferred to a homomixer container and atomized by applying the homomixer at 50 ° C. and 6000 rpm for 90 minutes.
[0133]
4) Aggregation prevention and wall film hardening treatment
While adding 3.0 g of trimethylchlorosilane while stirring the reaction solution prepared in 3) at 50 ° C. and 600 rpm in the original reaction vessel, 4.4 g of 25% aqueous sodium hydroxide solution was immediately added dropwise. The temperature of the reaction solution was gradually raised to reflux. The alcohol-containing vapor was distilled off, and the mixture was further heated to reflux for 2 hours while stirring at 150 rpm.
The reaction solution was cooled at 150 rpm with stirring at room temperature to obtain encapsulated microcapsules.
[0134]
The dispersion of the encapsulated microcapsules obtained in Example 2 was analyzed according to the analytical methods 1 to 5 as follows.
[0135]
850 g of a microcapsule dispersion in water having a diameter of 0.3 to 5 μm, mainly 1 to 2 μm
50% ingredient excluding water
Free paramethoxycinnamate-2-ethylhexyl 4% in dispersion
84% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
[0136]
Thereafter, free 2-methoxyhexyl paramethoxycinnamate in the dispersion is removed by washing with hexane, and hydroxysilane having hydrolyzed collagen (molecular weight is about 2000 in terms of number average molecular weight) as a hydrophilic group is used. Encapsulated microcapsules of 2-methoxyhexyl paramethoxycinnamate were obtained in a purified state. In addition, in the agglomeration prevention and wall film curing treatment of 4) above, if a series of treatments of addition of methyltrichlorosilane and subsequent neutralization were omitted, there was no difference with the present example with the naked eye, According to the results, the microcapsule particles adhered to each other and a part of the aggregation was observed. However, such aggregation was not recognized in this example.
Further, when the encapsulated microcapsules obtained in Example 2 were examined for whether or not the capsules were ruptured according to Test Method 1, the capsules did not rupture.
[0137]
Example 2A
N- [2-hydroxy-3- (3′-trihydroxysilyl) propoxy] propyl hydrolyzed collagen, organopolysiloxane composed of hydrolyzate copolycondensate of methyltriethoxysilane and phenyltriethoxysilane was used as a wall film. Of encapsulated microcapsules of a mixture of 2-methoxyhexyl paramethoxycinnamate and 4-t-butyl-4'-methoxydibenzoylmethane
[0138]
1) Preparation of prepolymer
The top lid was equipped with a dropping funnel and a reflux condenser, and a round bottom cylindrical glass reaction vessel having an inner diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer was previously filled with 135 g of water and N- [2-hydroxy-3- (3′- Trihydroxysilyl) propoxy] propyl hydrolyzed collagen (molecular weight of hydrolyzed collagen is about 2000 in terms of number average molecular weight) 15 g and 3.6% of 18% hydrochloric acid are added, and 45.9 g of methyltriethoxysilane with stirring at 50 ° C. And 12.4 g of phenyltriethoxysilane were added dropwise from the dropping funnel.
[0139]
Furthermore, after stirring at 50 ° C. for 6 hours, the mixture was once cooled to 20 ° C., and 2.9 g of 25% aqueous sodium hydroxide solution was added dropwise while continuing stirring to adjust the pH to 7.0. Stir for hours.
[0140]
2) Addition and emulsification of core material
19.5 g of 4-t-butyl-4'-methoxydibenzoylmethane was previously dissolved in 78.2 g of 2-methoxyhexyl paramethoxycinnamate while stirring the reaction solution prepared in 1) at 600 rpm. And stirring was continued for 4 hours at 600 rpm.
[0141]
3) Atomization
The reaction solution prepared in 2) was transferred to a homomixer container and atomized by applying the homomixer at 50 ° C. and 6000 rpm for 90 minutes.
[0142]
4) Aggregation prevention and wall film hardening treatment
While adding 3.0 g of trimethylchlorosilane while stirring the reaction solution prepared in 3) at 50 ° C. and 600 rpm in the original reaction vessel, 4.4 g of 25% aqueous sodium hydroxide solution was immediately added dropwise. The temperature of the reaction solution was gradually raised to reflux. The alcohol-containing vapor was distilled off, and the mixture was further heated to reflux for 2 hours while stirring at 150 rpm. The reaction solution was cooled at 150 rpm with stirring at room temperature to obtain encapsulated microcapsules.
[0143]
The dispersion of the encapsulated microcapsules obtained in Example 2A was analyzed according to the analytical methods 1 to 5 as follows.
[0144]
315 g of a dispersion in water of a capsule having a diameter of 0.3 to 5 μm, mainly 1 to 2 μm
Ingredients excluding water 42.3%
Free 2-methoxyhexyl paramethoxycinnamate in dispersion 0.2%
Free 4-t-butyl-4'-methoxydibenzoylmethane 0.2% in dispersion
56% 2-methoxyhexyl paramethoxycinnamate in capsule weight
14% 4-t-butyl-4'-methoxydibenzoylmethane in capsule weight
[0145]
As described above, in Example 2A, in addition to paramethoxycinnamic acid-2-ethylhexyl, 4-t-butyl-4′-methoxydibenzoylmethane is simultaneously encapsulated in a microcapsule as the second core substance. I was able to.
[0146]
Further, when the encapsulated microcapsules obtained in Example 2A were examined for whether or not the capsules were ruptured according to Test Method 1, the capsules did not rupture.
[0147]
Example 2B
N- [2-hydroxy-3- (3′-trihydroxysilyl) propoxy] propyl hydrolyzed wheat protein, methyltriethoxysilane and phenyltriethoxysilane hydrolyzate copolymer Of encapsulated microcapsules of 2-methoxyhexyl paramethoxycinnamate
[0148]
1) Preparation of prepolymer
In a reaction vessel made of a round bottom cylindrical glass equipped with a dropping funnel and a reflux condenser on the top lid and equipped with a mechanical stirrer and having an inner diameter of 12 cm and a capacity of 2 liters, 283 g of water and N- [2-hydroxy-3- (3′- Trihydroxysilyl) propoxy] propyl hydrolyzed wheat protein (molecular weight of hydrolyzed wheat protein is about 400 in number average) 16.8 g and 20% aqueous sodium hydroxide solution 4.5 g are added and stirred at 50 ° C. A mixture of 24 g of triethoxysilane and 8.2 g of phenyltriethoxysilane was dropped from a dropping funnel.
[0149]
Furthermore, it stirred at 50 degreeC for 6 hours. Next, 4.1 g of 18% hydrochloric acid was added dropwise while continuing stirring, and the pH was adjusted to 7.0, followed by stirring at 50 ° C. for 1 hour.
[0150]
2) Addition and emulsification of core material
While stirring the reaction solution prepared in 1) at 600 rpm, 12.3 g of paramethoxycinnamic acid-2-ethylhexyl was added. Further, stirring was continued at 600 rpm for 4 hours.
[0151]
3) Atomization
The reaction solution prepared in 2) was transferred to a homomixer container and atomized by applying the homomixer at 50 ° C. and 6000 rpm for 90 minutes.
[0152]
4) Aggregation prevention and wall film hardening treatment
While stirring the reaction solution prepared in 3) in the original reaction vessel at 50 ° C. and 600 rpm, 1.2 g of trimethylchlorosilane was added and immediately 1.4 g of 20% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 5.5. did. The temperature of the reaction solution was gradually raised to reflux. The alcohol-containing vapor was distilled off, and the mixture was further heated to reflux for 2 hours while stirring at 150 rpm. The reaction solution was cooled at 150 rpm with stirring at room temperature to obtain encapsulated microcapsules.
[0153]
The dispersion of the encapsulated microcapsules obtained in Example 2B was analyzed according to the analytical methods 1 to 5 as follows.
[0154]
595 g of capsule dispersion in water with a diameter of 0.3-5 μm, mainly 1-2 μm
11% excluding water
0.03% free paramethoxycinnamic acid-2-ethylhexyl in dispersion
23.8% para-methoxycinnamic acid-2-ethylhexyl in capsule weight
[0155]
As described above, in Example 2B, encapsulated microcapsules could be produced using the compound (A) having hydrolyzed wheat protein as a hydrophilic group. The hydrolysis of the compound (A) was performed basic.
[0156]
Further, when the encapsulated microcapsules obtained in Example 2B were examined for whether or not the capsules ruptured according to Test Method 1, the capsules did not rupture.
[0157]
Comparative Example 2
When hydrolysis was carried out on the acidic side instead of hydrolysis on the basic side of silane in Example 2B, a large amount of adhesive substance adhered to the inner wall of the reaction vessel, and the production of the microcapsules could not be continued.
[0158]
Example 2C
N- [2-hydroxy-3- (3′-trihydroxysilyl) propoxy] propyl hydrolyzed soy protein, methylpolyethoxysilane and phenyltriethoxysilane hydrolyzate copolymer Of encapsulated microcapsules of 2-methoxyhexyl paramethoxycinnamate
[0159]
1) Preparation of prepolymer
The top lid was equipped with a dropping funnel and a reflux condenser, and in a round bottom cylindrical glass reaction vessel having an internal diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer, 177 ml of water and N- [2-hydroxy-3- (3′- 9.3 g of trihydroxysilyl) propoxy] propyl hydrolyzed soy protein (molecular weight of hydrolyzed soy protein is about 350 in terms of number average molecular weight) and 3.5 g of 20% aqueous sodium hydroxide solution were added and stirred at 50 ° C., MethyltriEtA mixture of 10 g of xysilane and 2.7 g of phenyltriethoxysilane was dropped from a dropping funnel. Furthermore, after stirring at 50 ° C. for 6 hours, 3.2 g of 18% hydrochloric acid was added dropwise with stirring to adjust the pH to 7.0, followed by stirring at 50 ° C. for 1 hour.
[0160]
2) Addition and emulsification of core material
While stirring the reaction solution prepared in 1) at 600 rpm, 6.5 g of paramethoxycinnamic acid-2-ethylhexyl was added, and stirring was further continued at 600 rpm for 4 hours.
[0161]
3) Atomization
The reaction solution prepared in 2) was transferred to a homomixer container and atomized by applying the homomixer at 50 ° C. and 6000 rpm for 90 minutes.
[0162]
4) Aggregation prevention and wall film hardening treatment
While stirring the reaction solution prepared in 3) in an original reaction vessel at 50 ° C. and 600 rpm, 2.4 g of trimethylchlorosilane was added, and 1.2 g of 20% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 5.5. . The temperature of the reaction solution was gradually raised to reflux. The alcohol-containing vapor was distilled off, and the mixture was further heated to reflux for 6 hours while stirring at 150 rpm. The reaction solution was cooled at 150 rpm with stirring at room temperature to obtain encapsulated microcapsules.
[0163]
The dispersion of the encapsulated microcapsules obtained in Example 2C was analyzed according to the analytical methods 1 to 5 as follows.
[0164]
360 g dispersion of capsules with a diameter of 0.3-5 μm, mainly 1-2 μm in water
Ingredient excluding water 7.6%
Free paramethoxycinnamate-2-ethylhexyl 0.5% in dispersion
27.0% para-methoxycinnamic acid-2-ethylhexyl in capsule weight
[0165]
As described above, in Example 2C, encapsulated microcapsules could be produced using the compound (A) having hydrolyzed soy protein (molecular weight is about 350 in terms of number average molecular weight) as a hydrophilic group. In Example 2C, the hydrolysis of the compound (A) was performed basic.
[0166]
Further, when the encapsulated microcapsules obtained in Example 2C were examined for whether or not the capsules burst according to Test Method 1, the capsules did not burst.
[0167]
Example 2D
In place of phenyltriethoxysilane in Example 2, 8.7 g of hexyltrimethoxysilane [KBM-3063 (trade name) of Shin-Etsu Chemical Co., Ltd.] was used, 38.3 g of methyltriethoxysilane was used, Encapsulated microcapsules were produced in the same manner as in Example 2 except that 87.4 g of acid-2-ethylhexyl was used and no treatment with methyltrichlorosilane was performed.
[0168]
The dispersion of the encapsulated microcapsules obtained in Example 2D was analyzed according to the analytical methods 1 to 5, and the results were as follows.
[0169]
507 g of capsule dispersion in water with a diameter of 0.3-5 μm, mainly 1-2 μm
Ingredient excluding water 23.6%
Free 2-methoxyhexyl paramethoxycinnamate in dispersion 0.2%
70% 2-methoxyhexyl paramethoxycinnamate in capsule weight
[0170]
Further, when the encapsulated microcapsules obtained in Example 2D were examined for whether or not the capsules ruptured according to Test Method 1, the capsules did not rupture.
[0171]
Example 2E
Instead of phenyltriethoxysilane in Example 2, 6.7 g of decyltrimethoxysilane [KBM-3103C (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.] was used, 30.0 g of methyltriethoxysilane was used, and paramethoxy was used. Encapsulated microcapsules were produced in the same manner as in Example 2, except that 6.7 g of 2-ethylhexyl cinnamate was used and the treatment with methyltrichlorosilane was not performed.
[0172]
The dispersion of the encapsulated microcapsules obtained in Example 2E was analyzed according to the analytical methods 1 to 5 as follows.
[0173]
300 g of a capsule having a diameter of 0.3 to 5 μm, mainly 1 to 2 μm, in water
Ingredient excluding water 11.9%
Free paramethoxycinnamate-2-ethylhexyl 0.1% in dispersion
18% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
[0174]
In Example 2E and Example 2D above, hydroxysilane having a hydrophobic group different from that in Example 2 was used, but encapsulated microcapsules could be produced in the same manner as Example 2.
[0175]
Further, when the encapsulated microcapsules obtained in Example 2E were examined for whether or not the capsules ruptured according to Test Method 1, the capsules did not rupture.
[0176]
Example 2F
Instead of N- [2-hydroxy-3- (3′-trihydroxysilyl) propoxy] propyl hydrolyzed collagen in Example 2, N- [2-hydroxy-3- having a peptide moiety number average molecular weight of about 2000 Encapsulated microcapsules were produced in the same manner as in Example 2 except that 15 g of (3′-dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen was used.
[0177]
The dispersion of the encapsulated microcapsules obtained in Example 2F was analyzed according to the analytical methods 1 to 5, and the results were as follows.
[0178]
687 g of capsule dispersion in water with a diameter of 0.3-5 μm, mainly 1-2 μm
Ingredients excluding water: 54.3%
Free paramethoxycinnamate-2-ethylhexyl 5% in dispersion
82% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
[0179]
In this Example 2F, instead of N- [2-hydroxy-3- (3′-trihydroxysilyl) propoxy] propyl hydrolyzed collagen in Example 2, N- [2-hydroxy-3- (3′- Although dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen was used, encapsulated microcapsules could be produced in the same manner as in Example 2.
[0180]
Further, when the encapsulated microcapsules obtained in Example 2F were examined for rupture of the capsules according to Test Method 1, the capsules did not rupture.
[0181]
Example 2G
N- [2-hydroxy-3- (3′-dihydroxymethylsilyl) propoxy] propyl instead of N- [2-hydroxy-3- (3′-trihydroxysilyl) propoxy] propyl hydrolyzed collagen in Example 2 Using 15 g of hydrolyzed collagen, 22.8 g of stearoxypropyltrimethoxysilane [KBM-6000 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.] instead of phenyltriethoxysilane, and paramethoxycinnamic acid-2- An encapsulated microcapsule was produced in the same manner as in Example 2 except that 60 g of ethylhexyl was used.
[0182]
The dispersion of the encapsulated microcapsules obtained in Example 2G was analyzed according to the analytical methods 1 to 5 as follows.
[0183]
400 g of a dispersion of capsules having a diameter of 0.3 to 5 μm, mainly 1 to 2 μm, in water
25% ingredient excluding water
6% free paramethoxycinnamic acid-2-ethylhexyl in dispersion
40% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
[0184]
In Example 2G, hydroxysilane having a hydrophobic group different from that of Example 2F was used, but encapsulated microcapsules could be produced in the same manner as Example 2F.
[0185]
Further, when the encapsulated microcapsules obtained in Example 2G were examined for rupture of the capsules according to Test Method 1, the capsules did not rupture.
[0186]
Example 2H
In place of 45.9 g of methyltriethoxysilane in Example 2, 19.1 g of dimethyldiethoxysilane and 23.0 g of methyltriethoxysilane were used, and 97.7 g of 2-methoxyhexyl paramethoxycinnamate was used. In the same manner as in Example 2, encapsulated microcapsules were produced.
[0187]
The dispersion of the encapsulated microcapsules obtained in Example 2H was analyzed according to the analytical methods 1 to 5, and the results were as follows.
[0188]
460 g of capsule dispersion in water with a diameter of 0.3-5 μm, mainly 1-2 μm
Ingredients excluding water 27.1%
Free 2-methoxyhexyl paramethoxycinnamate in dispersion 1.0%
70% 2-methoxyhexyl paramethoxycinnamate in capsule weight
[0189]
In Example 2H, a part of trihydroxysilane in Example 2 was replaced with dihydroxysilane, but encapsulated microcapsules could be produced in the same manner as Example 2.
[0190]
Further, when the encapsulated microcapsules obtained in Example 2H were examined for whether or not the capsules ruptured according to Test Method 1, the capsules did not rupture.
[0191]
Example 2I
An encapsulated microcapsule was produced in the same manner as in Example 2H, except that 9.6 g of octamethylcyclotetrasiloxane was used instead of dimethyldiethoxysilane in Example 2H.
[0192]
The dispersion of the encapsulated microcapsules obtained in Example 2I was analyzed according to the analytical methods 1 to 5 as follows.
[0193]
425 g of capsule dispersion in water with a diameter of 0.3-5 μm, mainly 1-2 μm
Ingredient excluding water 25.1%
Free 2-methoxyhexyl paramethoxycinnamate in dispersion 1.0%
70% 2-methoxyhexyl paramethoxycinnamate in capsule weight
[0194]
In Example 2I, the compound (A) in Example 2H was replaced with alkoxysilane from cyclic siloxane, but encapsulated microcapsules could be produced in the same manner as Example 2H.
[0195]
Further, when the encapsulated microcapsules obtained in Example 2I were examined for whether or not the capsules ruptured according to Test Method 1, the capsules did not rupture.
[0196]
Example 2J
Encapsulated in the same manner as in Example 2F, except that 16.2 g of isopropyl isostearate and 4.1 g of abietic acid were used instead of paramethoxycinnamic acid-2-ethylhexyl in Example 2F and no homomixer treatment was performed. Microcapsules were produced.
[0197]
The dispersion of the encapsulated microcapsules obtained in Example 2J was analyzed according to the analytical methods 1 to 5 as follows.
[0198]
226 g of a dispersion in water of capsules having a diameter of 1 to 100 μm, mainly 10 to 50 μm
30% ingredient excluding water
Free abietic acid in dispersion 1.0%
Abietic acid 5.7% in capsule weight
[0199]
In Example 2J, abietic acid, which is a solid resin at room temperature, could be dissolved in isopropyl isostearate and encapsulated in a capsule.
[0200]
Further, when the encapsulated microcapsules obtained in Example 2J were examined according to Test Method 1 to determine whether or not the capsules burst, capsules having a particle size of about 8 μm or more burst. In particular, when the capsule having a particle size of 8 to 15 μm was ruptured, it was observed that the core material exuded from the capsule, and the wall membrane and the core material were each rounded and formed into a figure 8 shape. .
[0201]
Example 2K
Instead of N- [2-hydroxy-3- (3′-dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen in Example 2F, N- [2-hydroxy-3- having a peptide moiety number average molecular weight of about 1000 Encapsulated microcapsules were produced in the same manner as in Example 2F, except that 15 g of (3′-dihydroxymethylsilyl) propoxy] propyl hydrolyzed silk protein (fibroin) was used.
[0202]
The dispersion of the encapsulated microcapsules obtained in Example 2K was analyzed according to the analytical methods 1 to 5 as follows.
[0203]
375 g of capsule dispersion in water with diameter of 1-100 μm, mainly 10-50 μm
20% ingredient excluding water
Free abietic acid in dispersion 1.0%
Abietic acid 5.5% in capsule weight
[0204]
In Example 2K, unlike Example 2J, a compound (A) having hydrolyzed silk protein (fibroin) as a hydrophilic group was used. However, encapsulated microcapsules can be produced in the same manner as Example 2J. It was.
[0205]
Further, when the encapsulated microcapsules obtained in Example 2K were examined for rupture according to Test Method 1, capsules having a particle size of about 8 μm or more were ruptured. In particular, when the capsule having a particle size of 8 to 15 μm was ruptured, it was observed that the core material exuded from the capsule, and the wall membrane and the core material were each rounded and formed into a figure 8 shape. .
[0206]
Example 2L
Manufacture of castor oil-encapsulated microcapsules
[0207]
Example 2F except that 10.5 g of castor oil was used instead of paramethoxycinnamic acid-2-ethylhexyl in Example 2F, 38.2 g of methyltriethoxysilane was used, and 10.3 g of phenyltriethoxysilane was used. Similarly, encapsulated microcapsules were produced.
[0208]
The dispersion of the encapsulated microcapsules obtained in Example 2L was analyzed according to the above analytical methods 1 to 5, and was as follows.
[0209]
300 g of a capsule having a diameter of 0.3 to 5 μm, mainly 1 to 2 μm, in water
15% ingredient excluding water
Free castor oil in dispersion 1.5%
20% castor oil in capsule weight
[0210]
In Example 2L, it was possible to produce castor-encapsulated microcapsules that were viscous oil at room temperature.
[0211]
Further, when the encapsulated microcapsules obtained in Example 2L were examined for whether or not the capsules ruptured according to Test Method 1, the capsules did not rupture.
[0212]
Example 2M
In Example 2, 17.0 g of methyltriethoxysilane and 4.6 g of phenyltriethoxysilane were added, and at the same time, 0.5 g of octadecyldimethyl- (3-trimethoxysilylpropyl) ammonium chloride was added. Instead of [2-hydroxy-3- (3′-trihydroxysilyl) propoxy] propyl hydrolyzed collagen, N- [2-hydroxy-3- (3′-dihydroxymethylsilyl) having a peptide moiety number average molecular weight of about 2000 ) Propoxy] Encapsulated microcapsules were produced in the same manner as in Example 2 except that 16.7 g of propyl hydrolyzed collagen was used.
[0213]
The dispersion of the encapsulated microcapsules obtained in Example 2M was analyzed according to the analytical methods 1 to 5 as follows.
[0214]
370 g of a dispersion in water of a capsule having a diameter of 0.3 to 5 μm, mainly 1 to 2 μm
Ingredient excluding water 11.9%
Free paramethoxycinnamate-2-ethylhexyl 0.14% in dispersion
21.4% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
[0215]
In Example 2M, encapsulated microcapsules could be produced using the compound (A) having a cationic group as one of the monomer components of the organopolysiloxane that constructs the wall membrane.
[0216]
Further, when the encapsulated microcapsules obtained in Example 2M were examined according to Test Method 1 to see if the capsules ruptured, the capsules did not rupture.
[0217]
Example 2N
Production of encapsulated microcapsules of retinol palmitate
[0218]
An encapsulated microcapsule was produced in the same manner as in Example 2, except that 4.6 g of retinol palmitate and 4.6 g of isopropyl isostearate were used instead of 2-methoxyhexyl paramethoxycinnamate in Example 2.
[0219]
The dispersion of the encapsulated microcapsules obtained in Example 2N was analyzed according to the analytical methods 1 to 5 as follows.
[0220]
310 g of a dispersion of capsules having a diameter of 0.3 to 5 μm, mainly 1 to 2 μm, in water
Ingredient excluding water: 14.8%
Free retinol palmitate 0.1% in dispersion
9.9% retinol palmitate in capsule weight
[0221]
In Example 2N, it was possible to produce encapsulated microcapsules by dissolving viscous retinol palmitate in isopropyl isostearate.
[0222]
Further, when the encapsulated microcapsules obtained in Example 2N were examined for whether or not the capsules ruptured according to Test Method 1, the capsules did not rupture.
[0223]
Example 2O
Production of encapsulated microcapsules of tocophenol acetate
[0224]
An encapsulated microcapsule was produced in the same manner as in Example 2 except that 4.6 g of tocophenol acetate and 4.6 g of isopropyl isostearate were used instead of 2-methoxyhexyl paramethoxycinnamate in Example 2.
[0225]
The dispersion of the encapsulated microcapsules obtained in Example 2O was analyzed according to the analytical methods 1 to 5, and the results were as follows.
[0226]
324 g of capsule dispersion in water with a diameter of 0.3 to 10 μm, mainly 2 to 7 μm
Ingredients excluding water 14.3%
Free tocopherol acetate 0.1% in dispersion
9.8% tocopherol acetate in capsule weight
[0227]
In Example 2O, microcapsules encapsulated with tocopherol acetate, which is a derivative of vitamin E, could be produced.
[0228]
Further, when the encapsulated microcapsules obtained in Example 2O were examined for rupture according to Test Method 1, capsules having a particle size of about 8 μm or more were ruptured. Especially when capsules with a particle size of 8-10 μm are ruptured, the core substance
It was observed that the capsules exuded, and the wall membrane and the core material were rounded and formed in a figure 8 shape.
[0229]
Example 3
Before the treatment of trimethylchlorosilane in Example 2, 3.0 g of 18% hydrochloric acid was put in the reaction solution, 10.6 g of octadecyldimethyl- (3-trimethoxysilylpropyl) ammonium chloride was added, and 25% aqueous sodium hydroxide solution was added. An encapsulated microcapsule was produced in the same manner as in Example 2 except that 2.4 g was added for neutralization.
[0230]
The dispersion of the encapsulated microcapsules obtained in Example 3 was analyzed according to the analytical methods 1 to 5 as follows.
[0231]
820 g of a dispersion of capsules with a diameter of 0.3-5 μm, mainly 1-2 μm, in water
Ingredient excluding water 61.1%
1% free 2-methoxyhexyl paramethoxycinnamate in dispersion
76% 2-methoxyhexyl paramethoxycinnamate in capsule weight
[0232]
In the manufacturing process of the encapsulated microcapsules of Example 3, a series of treatment of addition of octadecyldimethyl- (3-trimethoxysilylpropyl) ammonium chloride and subsequent neutralization and addition of methyltrichlorosilane and subsequent neutralization When a series of treatments were omitted, observation with the naked eye was not different from that of this example, but microscopic observation revealed that microcapsule particles were stuck together and partly aggregated. However, such aggregation was not recognized in this example.
[0233]
Further, when the encapsulated microcapsules obtained in Example 3 were examined for whether or not the capsules were ruptured according to Test Method 1, the capsules did not rupture.
[0234]
Example 4
N- [2-hydroxy-3- (3′-dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen, organopolysiloxane composed of hydrolyzate copolycondensate of methyltriethoxysilane and phenyltriethoxysilane was used as a wall film. Of encapsulated microcapsules of 2-methoxyhexyl paramethoxycinnamate
[0235]
1) Preparation of prepolymer
In a reaction vessel made of a round bottom cylindrical glass equipped with a dropping funnel and a reflux condenser on the top lid and equipped with a mechanical stirrer and having an inner diameter of 12 cm and a capacity of 2 liters, 405 g of water and N- [2-hydroxy-3- (3′- Dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen (molecular weight of hydrolyzed collagen is about 2000 in terms of number average molecular weight) 45 g and 10.8 g of 18% hydrochloric acid are added and 137.7 g of methyltriethoxysilane is stirred at 50 ° C. And 37.1 g of phenyltriethoxysilane were added dropwise from the dropping funnel.
[0236]
Furthermore, after stirring at 50 ° C. for 6 hours, 8.7 g of a 25% aqueous sodium hydroxide solution was added dropwise while continuing the stirring to adjust the pH to 7.0, followed by stirring at 50 ° C. for 1 hour.
[0237]
2) Addition and emulsification of core material
While stirring the reaction solution prepared in 1) at 600 rpm, 126.9 g of paramethoxycinnamic acid-2-ethylhexyl was added, and stirring was further continued at 600 rpm for 4 hours.
[0238]
3) Atomization
About half of the reaction solution prepared in 2) was transferred to a homomixer container and applied to the homomixer at 50 ° C. and 6000 rpm for 90 minutes. Further, this processing solution is treated at 50 ° C. and 1500 kg / cm.²Then, the mixture was subjected to a microfluidizer [M110-E / H (trade name) manufactured by Microfluidics International Corporation] five times for atomization.
[0239]
4) Aggregation prevention and wall film hardening treatment
While adding 1.0 g of trimethylchlorosilane while stirring the reaction solution prepared in 3) in an original reaction vessel at 50 ° C. and 600 rpm, 1.48 g of 25% aqueous sodium hydroxide solution was immediately added dropwise. The temperature of the reaction solution was gradually raised to reflux. The alcohol-containing vapor was distilled off, and the mixture was further heated to reflux for 6 hours while stirring at 150 rpm. The reaction solution was cooled at 150 rpm with stirring at room temperature to obtain encapsulated microcapsules.
[0240]
The dispersion of the encapsulated microcapsules obtained in Example 4 was analyzed according to the analytical methods 1 to 4 and analytical method 6 as follows. In Example 4, since the atomization was performed using the microfluidizer as described above, the obtained encapsulated microcapsules were in the nanocapsule region. Therefore, regarding the encapsulated microcapsules obtained in Example 4, the particle size distribution cannot be obtained by visual observation using an optical microscope according to Analysis Method 5, and SALD-2000 (trade name of Analysis Method 6). ) To measure the particle size distribution.
[0241]
250 g dispersion of capsules with a diameter of 0.3-1 μm, mainly 0.4-0.7 μm in water
20% ingredient excluding water
Free paramethoxycinnamate-2-ethylhexyl 0.1% in dispersion
50% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
[0242]
Further, when the encapsulated microcapsules obtained in Example 4 were examined for rupture of the capsules according to Test Method 1, the capsules did not rupture.
[0243]
Example 4A
The remaining half of the reaction solution prepared in 2) “Addition and emulsification of core material” in Example 4 was finished without performing atomization treatment with a microfluidizer in “Atomization” in 3). In the same manner as in Example 4, encapsulated microcapsules were produced.
[0244]
The dispersion of the encapsulated microcapsules obtained in Example 4A was analyzed according to the analysis methods 1 to 4 and analysis method 6, and the results were as follows.
[0245]
250 g of capsule with a diameter of 0.3-5 μm, mainly 1-2 μm, in water
20% ingredient excluding water
Free paramethoxycinnamate-2-ethylhexyl 0.1% in dispersion
50% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
[0246]
When the encapsulated microcapsules obtained in Example 4A were examined for whether or not the capsules ruptured according to Test Method 1, the capsules did not rupture.
[0247]
When microfluidizer treatment was adopted as in Example 4, an encapsulated microcapsule with a particle size belonging to nanocapsules was obtained, but the intermediate product of the same batch was not microfluidized. In Example 4A, nanocapsules as in Example 4 were not obtained, and only encapsulated microcapsules having a particle size belonging to microcapsules could be obtained.
[0248]
Example 5
Spray dry treatment of encapsulated microcapsules
[0249]
1) Preparation of prepolymer
The top lid was equipped with a dropping funnel and a reflux condenser, and in a round bottom cylindrical glass reaction vessel having an inner diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer, 210 g of water and N- [2-hydroxy-3- (3′- Dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen (molecular weight of hydrolyzed collagen is about 2000 in terms of number average molecular weight) 90 g and 18% hydrochloric acid 21.8 g were added and methyl triethoxysilane 45.9 g with stirring at 50 ° C. And 10.5 g of hexyltrimethoxysilane was added dropwise from the dropping funnel. Furthermore, after stirring at 50 ° C. for 6 hours, 22 g of 25% aqueous sodium hydroxide solution was added dropwise while continuing stirring to adjust the pH to 7.0, and then stirred at 50 ° C. for 1 hour.
[0250]
2) Addition and emulsification of core material
While stirring the reaction solution prepared in 1) at 600 rpm, 389 g of paramethoxycinnamic acid-2-ethylhexyl was added, and stirring was further continued at 600 rpm for 4 hours.
[0251]
3) Atomization
The reaction solution prepared in 2) was transferred to a homomixer container and atomized by applying the homomixer at 50 ° C. and 6000 rpm for 90 minutes.
[0252]
4) Curing treatment
The reaction solution prepared in 3) was heated to reflux for 2 hours while stirring at 150 rpm in the original reaction vessel. The reaction solution was cooled at 150 rpm with stirring at room temperature to obtain encapsulated microcapsules.
[0253]
When the dispersion of the encapsulated microcapsules obtained in Example 5 was analyzed according to the analysis method 5, it was a dispersion in water of capsules having a diameter of 0.3 to 5 μm, mainly 1 to 2 μm.
[0254]
5) Spray drying
When a part of the product obtained in 4) was spray-dried, it became a powder. When 0.1 g of this powder was placed in 10 ml of water and well stirred and dispersed and observed according to analytical method 5, the results were the same as before spray drying.
[0255]
Example 5A
Freeze-drying treatment of encapsulated microcapsules
[0256]
When a part of the product obtained in 4) of Example 5 was lyophilized without being spray dried, it became a powder. When 0.1 g of this powder was again added to 10 ml of water and stirred well to disperse and observed according to analytical method 5, the results were the same as before spray drying.
[0257]
Example 6
Purification of encapsulated microcapsules using a centrifuge
[0258]
8.7 g of hexyltrimethoxysilane was used instead of phenyltriethoxysilane in Example 2, and N- [2-hydroxy-3- (3′-trihydroxysilyl) propoxy] propyl hydrolyzed collagen was used instead of N- [ 15 g of 2-hydroxy-3- (3′-dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen (the molecular weight of hydrolyzed collagen is about 2000 in terms of number average molecular weight) was used, 38.3 g of methyltriethoxysilane was used, and paramethoxy was used. Encapsulated microcapsules were produced in the same manner as in Example 2 except that 35.3 g of 2-ethylhexyl cinnamate was used and no treatment with methyltrichlorosilane was performed.
[0259]
The obtained encapsulated microcapsule was centrifuged (4000 rpm, 10 minutes), the supernatant was removed, 2 to 5 volumes of water was added to the precipitate and suspended again, and then centrifuged again (4000 rpm, 10 minutes). Min). This operation was repeated three times to obtain encapsulated microcapsules with adjusted concentrations.
[0260]
The dispersion of the encapsulated microcapsules obtained in Example 6 was analyzed according to the above analytical methods 1 to 5, and was as follows.
[0261]
150 g of capsules with a diameter of 0.3-5 μm, mainly 1-2 μm, in water
Ingredients excluding water 44%
Free paramethoxycinnamate-2-ethylhexyl 0.1% in dispersion
50% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
NaCl 0.34% in dispersion prior to centrifuge treatment
0.02% NaCl in dispersion after centrifuge treatment
[0262]
Thus, it was confirmed that NaCl decreased by the centrifuge treatment.
[0263]
Example 6A
Purification by ultrafiltration of the encapsulated microcapsules obtained in Example 2F
[0264]
A part of the encapsulated microcapsules obtained in Example 2F was subjected to ultrafiltration, and then 2 to 5 volumes of water was added to the residue and dispersed again, followed by ultrafiltration again. This operation was repeated three times to obtain encapsulated microcapsules with adjusted concentrations.
[0265]
The dispersion of the encapsulated microcapsules obtained in Example 6A was analyzed according to the above analytical methods 1 to 5, and was as follows.
[0266]
200 g of capsule in water with a diameter of 1-10 μm, mainly 3-7 μm
20% ingredient excluding water
Free paramethoxycinnamate-2-ethylhexyl 0.1% in dispersion
50% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
NaCl in dispersion prior to ultrafiltration 0.38%
NaCl 0.03% in dispersion after ultrafiltration treatment
[0267]
Thus, it was confirmed that NaCl was reduced by the ultrafiltration treatment.
[0268]
Example 7
N- [2-hydroxy-3- (3′-dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen, organopolysiloxane composed of a hydrolyzate copolycondensate of dimethyldiethoxysilane and hexyltrimethoxysilane was used as a wall film. Of W / O type encapsulated microcapsules
[0269]
1) Preparation of prepolymer
The top lid was equipped with a dropping funnel and a reflux condenser, and was charged in advance with 131 g of water and N- [2-hydroxy-3- (3′- TheHydroxymethylCyril) propoxy] propyl hydrolyzed collagen (molecular weight of hydrolyzed collagen is approximately 400 in terms of number average molecular weight) 9 g and 18% hydrochloric acid 8 g were added, and 20.6 g of dimethyldiethoxysilane and hexyltrimethoxy were stirred at 50 ° C. A mixture of 57.3 g of silane was dropped from the dropping funnel.
[0270]
Furthermore, after stirring at 50 ° C. for 6 hours, 6.3 g of a 25% aqueous sodium hydroxide solution was added dropwise while continuing the stirring to adjust the pH to 7.0, followed by stirring at 50 ° C. for 1 hour.
[0271]
2) Addition of oil phase and inversion emulsification
While stirring the reaction solution prepared in 1) at 600 rpm, 150 g of toluene was added, and the stirring was continued at 600 rpm for 4 hours.
[0272]
3) Atomization
The reaction solution prepared in 2) was transferred to a homomixer container and atomized by applying the homomixer at 50 ° C. and 6000 rpm for 90 minutes.
[0273]
4) Aggregation prevention and wall film hardening treatment
3 g of trimethylchlorosilane was added to the reaction solution prepared in 3) while stirring at 50 ° C. and 600 rpm in the original reaction vessel, and immediately 4.4 g of 25% aqueous sodium hydroxide solution was added dropwise and gradually stirred at 600 rpm. While raising the temperature of the reaction solution to reflux, 85% of water was distilled off. Furthermore, it was made to heat and reflux for 6 hours, stirring at 150 rpm. The reaction solution was cooled at 150 rpm with stirring at room temperature to obtain encapsulated microcapsules.
[0274]
The dispersion of the encapsulated microcapsules obtained in Example 7 was analyzed according to the analytical method 5 and was as follows.
[0275]
241 g of a dispersion of 0.3 to 5 μm diameter, mainly 1 to 2 μm capsules in toluene
[0276]
Water droplets were observed on the glass surface when the dispersion was applied onto a glass plate and the film formed by evaporation of toluene was scratched. The dispersion was mixed with water and allowed to stand to separate into two layers, and the capsules were dispersed in the toluene layer. From this, it was found that a microcapsule having a hydrophobic surface and enclosing water could be produced.
[0277]
Example 7A
The amount of hexyltrimethoxysilane used in Example 7 was changed from 573.3 g to 86.0 g, and the use of dimethyldiethoxysilane was stopped, and the toluene used in the addition of the oil phase and inversion emulsification in 2) Instead of 160 g of isopropyl isostearate, the prepolymer solution prepared in 1) was added to this isopropyl isostearate, and 4) an equimolar amount of hydroxylation was substituted for sodium hydroxide during the aggregation prevention and wall film curing treatment. An encapsulated microcapsule was produced in the same manner as in Example 7, except that 30.8 g of 35% aqueous potassium chloride solution was added simultaneously with mixing with isopropyl isostearate using potassium.
[0278]
The dispersion of the encapsulated microcapsules obtained in Example 7A was analyzed according to the analytical method 5 and was as follows.
[0279]
280 g as a dispersion in isopropyl isostearate of capsules with a diameter of 0.3-5 μm, mainly 1-2 μm
[0280]
When the dispersion of Example 7A was mixed with water and allowed to stand, it was separated into two layers, and the encapsulated microcapsules were dispersed in the isopropyl isostearate layer. Thus, in Example 7A, unlike Example 7, W / O-type encapsulated microcapsules could be produced without using dialkoxysilane.
[0281]
Further, when the encapsulated microcapsules obtained in Example 7A were examined for whether or not the capsules ruptured according to Test Method 1, the capsules did not rupture.
[0282]
Example 7B
In place of dimethyldiethoxysilane and hexyltrimethoxysilane in Example 7, 71.6 g of hexyltrimethoxysilane and 16.7 g of phenyltriethoxysilane were used, and 36% L-ascorbic acid aqueous solution was simultaneously added to 34. 4 g was added and encapsulated microcapsules were produced in the same manner as in Example 7 except that 50% of water was distilled off before processing with a homomixer.
[0283]
The dispersion of the encapsulated microcapsules obtained in Example 7B was analyzed according to the analytical method 5 and was as follows.
[0284]
216 g as a dispersion in toluene of 0.3 to 5 μm diameter, mainly 1 to 2 μm capsules
[0285]
Water droplets were observed on the glass surface when the dispersion formed in Example 7B was applied onto a glass plate and the film formed by evaporation of toluene was scratched. When this dispersion was mixed with water and allowed to stand, it was separated into two layers, and the encapsulated microcapsules were dispersed in the toluene layer.
[0286]
Further, when the encapsulated microcapsules obtained in Example 7B were examined for whether or not the capsules burst according to Test Method 1, the capsules did not burst.
[0287]
Example 7C
235 g of diisobutyl adipate was used in place of toluene in Example 7, and 106 g of a 10% aqueous solution of 2-phosphate-L-ascorbylmagnesium was added at the same time as this diisobutyl adipate was added, and purified by centrifugation according to Example 6. After the treatment with a homomixer, most of the water was distilled off at 40 ° C. under reduced pressure, and then the remaining water was distilled off by heating at normal pressure to produce encapsulated microcapsules in the same manner as in Example 7. .
[0288]
The dispersion of the encapsulated microcapsules obtained in Example 7C was analyzed according to the analytical method 5 and was as follows.
[0289]
324 g as a dispersion in diisobutyl adipate of capsules with a diameter of 0.3-5 μm, mainly 1-2 μm
[0290]
In addition, 200 ml of n-hexane was added to 20 g of the dispersion obtained in Example 7C, extracted with 100 ml of water, and measured with an ultraviolet / visible spectrophotometer UV-1600 (trade name) manufactured by Shimadzu Corporation. It was found that 10% of 2-phosphate-L-ascorbyl magnesium added was free. Further, 50 ml of chloroform was added to 2 g of the dispersion obtained in Example 7C, and the mixture was stirred at 50 ° C. for 1 hour. The capsule was broken, extracted with 100 ml of water and measured with an ultraviolet spectrophotometer. It was found that 95% of 2-phosphate-L-ascorbyl magnesium was recovered. As a result, it was found that the uptake rate was 85%. Furthermore, it was revealed that free 2-phosphate-L-ascorbyl magnesium can be removed by extraction with water and washing.
[0291]
When the dispersion of Example 7C was mixed with water and allowed to stand, it was separated into two layers, and the encapsulated microcapsules were dispersed in the diisobutyl adipate layer.
[0292]
Further, when the encapsulated microcapsules obtained in Example 7C were examined for rupture of the capsules according to Test Method 1, the capsules were not ruptured.
[0293]
Example 8
N- [2-hydroxy-3- (3′-dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen, tetraethoxysilane and C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH _Three ) _Three Production of liquid perfluoroether-encapsulated microcapsules with organopolysiloxane made of hydrolyzate copolycondensate of [KBM-7803 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.]
[0294]
1) Preparation of prepolymer
The top lid was equipped with a dropping funnel and a reflux condenser, and in a round bottom cylindrical glass reaction vessel having an inner diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer, 90 g of water and N- [2-hydroxy-3- (3′- 10 g of dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen (the molecular weight of hydrolyzed collagen is about 2000 in terms of number average molecular weight) and 2.4 g of 18% hydrochloric acid are added, and 19.0 g of tetraethoxysilane is stirred at 50 ° C. And the above-mentioned KBM-7803 [trade name, C made by Shin-Etsu Chemical Co., Ltd.₈F₁₇CH₂CH₂Si (OCH_Three)_Three] Of 3.2 g was added dropwise from the dropping funnel.
[0295]
Furthermore, after stirring at 50 ° C. for 12 hours, 100 g of a 0.6% aqueous sodium hydroxide solution was added dropwise while continuing stirring to adjust the pH to 7.0, followed by stirring at 50 ° C. for 1 hour.
[0296]
2) Addition and emulsification of liquid perfluoroether
Fomblin HC / R (trade name) which is a liquid perfluoroether while stirring the reaction solution prepared in 1) at 500 rpm [manufactured by Montefluos (Milan, Italy), average molecular weight: 6250, CF_Three[(OCF (CF_ThreeCF₂) N (OCF₂) M] OCF_Three, N / m = 20 to 40] 6.8 g and the above-mentioned KBM-7803 [trade name, Shin-Etsu Chemical Co., Ltd. C₈F₁₇CH₂CH₂Si (OCH_Three)_Three] And 3.2 g of the mixture were added, and stirring was further continued at 500 rpm for 4 hours.
[0297]
3) Atomization
The reaction solution prepared in 2) was transferred to a homomixer container and atomized by applying the homomixer at 50 ° C. and 6000 rpm for 90 minutes.
[0298]
4) Aggregation prevention and wall film hardening treatment
While adding 1.23 g of trimethylchlorosilane while stirring the reaction solution prepared in 3) at 50 ° C. and 500 rpm in the original reaction vessel, immediately drop 1.2 g of 25% aqueous sodium hydroxide solution and stirring at 500 rpm. The temperature of the reaction solution was gradually raised and refluxed, and further heated and refluxed for 6 hours while stirring at 150 rpm. The reaction solution was cooled at 150 rpm with stirring at room temperature to obtain encapsulated microcapsules as a milky white dispersion.
[0299]
The dispersion of the encapsulated microcapsules obtained in Example 8 was analyzed in accordance with Analysis Method 1 and Analysis Method 5 as follows.
[0300]
110 g as a dispersion in water of capsules having a diameter of 5 to 10 μm
% Of ingredients excluding water 17.1%
[0301]
This dispersion could be lyophilized.
[0302]
Further, when the encapsulated microcapsules obtained in Example 8 were examined for whether or not the capsules ruptured according to Test Method 1, capsules having a particle size of about 8 μm or more were ruptured. In particular, when the capsule having a particle size of 8 to 10 μm was ruptured, it was observed that the core material exuded from the capsule, and the wall film and the core material were each rounded and formed into a figure 8 shape. .
[0303]
Comparative Example 8
1) Preparation of capsule wall membrane
The top lid was equipped with a dropping funnel and a reflux condenser, and in a round bottom cylindrical glass reaction vessel having an inner diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer, 90 g of water and N- [2-hydroxy-3- (3′- 10 g of dihydroxymethylsilyl) propoxy] propyl hydrolyzed collagen (the molecular weight of hydrolyzed collagen is about 2000 in terms of number average molecular weight) and 2.4 g of 18% hydrochloric acid are added, and 19.0 g of tetraethoxysilane is stirred at 50 ° C. And the above-mentioned KBM-7803 [trade name, C made by Shin-Etsu Chemical Co., Ltd.₈F₁₇CH₂CH₂Si (OCH_Three)_Three9.5 g of the mixture was dropped from the dropping funnel.
[0304]
Furthermore, after stirring at 50 ° C. for 12 hours, 100 g of a 0.6% aqueous sodium hydroxide solution was added dropwise while continuing stirring to adjust the pH to 7.0, followed by stirring at 50 ° C. for 1 hour.
[0305]
2) Addition and emulsification of liquid perfluoroether
Fomblin HC / R (trade name) which is a liquid perfluoroether while stirring the reaction solution prepared in 1) at 500 rpm [manufactured by Montefluos (Milan, Italy), average molecular weight: 6250, CF_Three[(OCF (CF_ThreeCF₂) N (OCF₂) M] OCF_Three, N / m = 20-40] was added, and stirring was further continued at 500 rpm for 4 hours.
[0306]
3) Atomization
The reaction solution prepared in 2) was transferred to a homomixer container and atomized by applying the homomixer at 50 ° C. and 6000 rpm for 90 minutes.
[0307]
4) Aggregation prevention and wall film hardening treatment
While adding 1.23 g of trimethylchlorosilane while stirring the reaction solution prepared in 3) at 50 ° C. and 500 rpm in the original reaction vessel, immediately drop 1.2 g of 25% aqueous sodium hydroxide solution and stirring at 500 rpm. The temperature of the reaction solution was gradually raised and refluxed, and further heated and refluxed for 6 hours while stirring at 150 rpm. The reaction was cooled at room temperature with stirring at 150 rpm. The appearance separated into three layers was observed.
[0308]
The dispersion of the encapsulated microcapsules obtained in Comparative Example 8 was analyzed according to the analytical method 5 and was as follows.
[0309]
No particles were observed by microscopic observation.
260g as a separation liquid in 3 layers
[0310]
In Comparative Example 8, the encapsulated microcapsules could not be produced. In Example 8, C, which is the compound (A) having a perfluoroalkane group used in Comparative Example 8, was used.₈F₁₇CH₂CH₂Si (OCH_Three)_ThreeBy adding a part of [KBM-7803 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd.] together with the core substance, it was possible to produce microcapsules encapsulating liquid perfluoroether.
[0311]
Example 9
Preparation of microcapsules encapsulating 2-methoxyhexyl paramethoxycinnamate using organopolysiloxane as a wall membrane from hydrolyzate copolycondensate of methyltriethoxysilane in gelatin aqueous solution
[0312]
1) Preparation of prepolymer
The top lid is equipped with a dropping funnel and reflux condenser, and 120 g of water is placed in a round bottom cylindrical glass reaction vessel with an inner diameter of 12 cm and a capacity of 2 liters equipped with a mechanical stirrer, and 6 g of gelatin as a thickener is added and heated. And dissolved. This liquid was cooled to 20 ° C., and the viscosity was adjusted to 50 mPa · s. The solution was acidified by adding 5.5 g of 10% hydrochloric acid, 12.8 g of phenyltriethoxysilane was added, and the mixture was stirred at 20 ° C. for 30 minutes. Next, 48 g of methyltriethoxysilane was added and dissolved by stirring for 10 minutes.
[0313]
2) Addition and emulsification of core material
To the liquid prepared in 1), 2.5 g of a 25% aqueous sodium hydroxide solution was added to adjust the pH to 7.0, and 100 g of paramethoxycinnamic acid-2-ethylhexyl was immediately added while stirring at 600 rpm. did.
[0314]
3) Atomization
The liquid prepared in 2) was further stirred at 20 ° C. for 10 minutes, diluted with 60 g of water, and then atomized with a homomixer at 40 ° C. and 6000 rpm for 60 minutes.
[0315]
4) Aggregation prevention and wall film hardening treatment
The emulsion atomized in 3) was kept at 40 ° C., 1.0 g of hexamethyldisilazane was added dropwise with stirring, and 1.0 g of 25% aqueous sodium hydroxide solution was added to adjust the pH to 7.0. Was gradually raised to distill off the alcohol-containing vapor, followed by heating to reflux for 6 hours. After cooling, a dispersion of encapsulated microcapsules was obtained.
[0316]
5) Removal of gelatin and free 2-methoxyhexyl paramethoxycinnamate
The dispersion obtained in 4) was separated with a centrifuge, the supernatant was discarded, and the residue was washed with 100 ml of water. The same operation was performed 5 times to remove gelatin and free 2-methoxyhexyl paramethoxycinnamate. Finally, 100 ml of water was added to the residue to obtain a dispersion of encapsulated microcapsules.
[0317]
The dispersion of the encapsulated microcapsules obtained in Example 9 was analyzed according to the above analytical methods 1 to 5, and was as follows.
[0318]
200 g of capsule suspension in water with a diameter of 1-30 μm, mainly 10-20 μm
50% ingredient excluding water
Free paramethoxycinnamate-2-ethylhexyl 4% in dispersion
75% paramethoxycinnamic acid-2-ethylhexyl in capsule weight
[0319]
In Example 9, a microcapsule encapsulated in 2-methoxyhexyl paramethoxycinnamate having an organopolysiloxane consisting of a hydrolyzate copolycondensate of methyltriethoxysilane in a gelatin aqueous solution as a wall film is stably produced. We were able to.
[0320]
Further, when the encapsulated microcapsules obtained in Example 9 were examined as to whether or not the capsules were ruptured according to Test Method 1, capsules having a particle size of about 8 μm or more were ruptured. In particular, when the capsule having a particle size of 8 to 15 μm was ruptured, it was observed that the core material exuded from the capsule, and the wall membrane and the core material were each rounded and formed into a figure 8 shape. .

Claims (5)

An encapsulated microcapsule encapsulating a hydrophobic core substance inside a space formed by a wall film,
The wall film has the following general structural formula (I)
RnSiX (4-n) (I)
[Wherein, n is an integer of 1 to 3, R is an organic group in which a carbon atom is directly bonded to a silicon atom, and n Rs may be the same or different. (4-n) X is at least one group selected from the group consisting of a hydroxyl group, hydrogen, an alkoxy group, a halogen group, a carboxy group, an amino group, and a siloxy group.
A hydrolyzate of two or more compounds (A) selected from the group of compounds (A) represented by the following general structural formula (II):
RnSi (OH) mY (4-mn) (II)
[Wherein, m is an integer of 1 to 3, n is an integer of 1 to 3, m + n ≦ 4, R is an organic group in which a carbon atom is directly bonded to a silicon atom, and n Rs may be the same, May be different. (4-mn) Y is at least one group selected from the group consisting of an alkoxy group, hydrogen and a siloxy group.
2 or more compounds (B) selected from the group of compounds (B) represented by the formula (1) are synthesized by direct condensation polymerization in a continuous phase-dispersed phase system in which the continuous phase is water and the dispersed phase is hydrophobic. Made of organopolysiloxane,
The two or more compounds (B) include a hydrolyzate of a silane compound in which R is an organic group containing a hydrophilic hydrolyzed protein, and a hydrolyzate of a silane compound in which R is an organic group having a hydrophobic group; And at least one of them is m is 3,
An encapsulated microcapsule , wherein a hydrophobic core substance is encapsulated in a space formed by a wall film made of the organopolysiloxane . The encapsulated microcapsule obtained by further treating the surface of the wall membrane of the encapsulated microcapsule according to claim 1 with a compound (A). A method for producing an encapsulated microcapsule that encapsulates a hydrophobic core substance inside a space formed by a wall film,
The wall film is represented by the following general structural formula (I)
RnSiX (4-n) (I)
[Wherein, n is an integer of 1 to 3, R is an organic group in which a carbon atom is directly bonded to a silicon atom, and n Rs may be the same or different. (4-n) X is at least one group selected from the group consisting of a hydroxyl group, hydrogen, an alkoxy group, a halogen group, a carboxy group, an amino group, and a siloxy group.
A hydrolyzate of two or more compounds (A) selected from the group of compounds (A) represented by the following general structural formula (II):
RnSi (OH) mY (4-mn) (II)
[Wherein, m is an integer of 1 to 3, n is an integer of 1 to 3, m + n ≦ 4, R is an organic group in which a carbon atom is directly bonded to a silicon atom, and n Rs may be the same, May be different. (4-mn) Y is at least one group selected from the group consisting of an alkoxy group, hydrogen and a siloxy group.
In the case where two or more compounds (B) selected from the group of compounds (B) represented by the formula (1) are used, a hydrolyzate of a silane compound in which R is an organic group containing a hydrophilic hydrolyzed protein, and R is A hydrolyzate of a silane compound which is an organic group having a hydrophobic group, and at least one of them is a compound (B) having at least one m of 3, a continuous phase is water, and a dispersed phase is It is composed of an organopolysiloxane synthesized by direct condensation polymerization in a continuous phase-dispersed phase system that is hydrophobic, and the hydrophobic core substance is placed inside the space formed by the wall film composed of the organopolysiloxane. A method for producing an encapsulated microcapsule comprising encapsulating. After a step of preparing a prepolymer by polycondensation of the compound in an aqueous solvent (B), characterized in that through the process of preparing an emulsion by mixing the prepolymer and the hydrophobic core substance in the aqueous solvent The method for producing encapsulated microcapsules according to claim 3 , wherein the polycondensation reaction further proceeds by dehydration by elapse of time or heating, dehydration to the outside of the reaction system, and the like. The manufacturing method of the encapsulated microcapsule which further processes the surface of the encapsulated microcapsule of Claim 3 or 4 with a compound (A).