CN1120745C - Microcapsule containing core material and its producing method - Google Patents

Microcapsule containing core material and its producing method Download PDF

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CN1120745C
CN1120745C CN 99109444 CN99109444A CN1120745C CN 1120745 C CN1120745 C CN 1120745C CN 99109444 CN99109444 CN 99109444 CN 99109444 A CN99109444 A CN 99109444A CN 1120745 C CN1120745 C CN 1120745C
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core material
microcapsules
compound
group
contain
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CN1253032A (en
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吉冈正人
濑川昭博
濑川江见
野坂浩司
吉原照美
安达敬
新谷博
植田有香
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NARIWAKASEI CO Ltd
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Abstract

A microcapsule containing core material and a capsule wall, in which the capsule wall of the microcapsule comprises:organopolysiloxane synthesized by polycondensing one or more compounds represented by the general formula (II):wherein, m represents an integer from 1 to 4; n represents an integer from 0 to 3; m+n<=4; R represents an organic group in which a carbon atom is directly connected to a silicone atom, and when n is greater than 1, each of the R groups may be the same or different; and Y represents at least one group selected from the group consisting of an alkoxy group, hydrogen and siloxy group, and when (4-m-n) is greater than 1, each of the groups Y may be the same or different.

Description

The microcapsules and the production method thereof that contain core material
The present invention relates to a kind of microcapsules and production method thereof that contains core material.Specifically, the present invention relates to a kind of microcapsules, it has a kind of microcapsule wall of being made up of organopolysiloxane, this organopolysiloxane is to carry out polycondensation by a kind of specific silicol to obtain, and have heat and mechanical stability, and light resistance, and right and wrong are bioactive.
Microcapsules of the present invention can be used for, for example, medicine, liquid crystal, chemicals, the record material, cosmetics, spices, enzyme, agricultural, adhesive, fiber, food, catalyst, washing agent, dyestuff, paint vehicle, anticorrisive agent, solvent, etc.Their object lesson comprises and contains aspirin, the microcapsules of vitamin or liquid crystal, and pressure-sensitive carbon paper contains ultra-violet absorber, dyestuff, pigment, spices, menthol, pesticide, adhesive, capsule, contain the capsule of the anticorrisive agent that is useful on rivet etc., and be not limited to above-mentioned these purposes.
Because organopolysiloxane has good performance, for example, heat and mechanical stability, key propertys such as light resistance and abiotic activity, it has purposes widely in a lot of fields.And in the microcapsules field, for example sense stricto microcapsules and nanocapsule field, the capsule wall of being attempted utilizing organopolysiloxane or its analog to form by the people is produced microcapsules.
For example, United States Patent (USP) 3257330 discloses a kind of production and has contained the method for organopolysiloxane as coloured micelle of matrix.But, when a kind of alkoxy silane with hydrophobic organic group, MTES etc. for example, when being used as the raw material of matrix, after being hydrolyzed and being neutralized then, this polymer composition forms a kind of precipitation in the aqueous solution.As a result, be difficult to produce microcapsules by a kind of hydrophobicity core material is carried out polymerization with a kind of hydrolysate of alkoxy silane in the aqueous solution.
On the other hand, United States Patent (USP) 3551346 discloses a kind of method, and wherein, polysiloxanes is synthetic from a kind of trialkoxy silane in the production of microcapsules.But this polysiloxanes does not have the enough intensity (admitting in this United States Patent (USP)) as capsule wall.Thereby, this U.S. Patent Publication a kind of production have the method for the microcapsules of double-decker capsule wall, this method is that the condensing method by routine forms a capsule wall more simultaneously and carries out.In addition, it is believed that, owing to during the polysiloxanes capsule wall that newly formed of three alcoxyl silane is confined in one mutually, can not be used to produce capsule wall more than a certain amount of three alcoxyl silane.Thereby this method can not be considered to the universal method of the microcapsules that a kind of production only is made up of the polysiloxanes capsule wall.
And, JP-B-60-25185, JP-B-3-10309, JP-B-5-70496, JP-B-7-62109 etc. disclose some examples, and wherein, microcapsule wall is by a kind of polysiloxanes with group of the function that can participate in crosslinked and polymerization is carried out crosslinked production.But, be difficult to have a kind of special polysiloxanes that participates in the functional group of crosslinked and polymerization and operate to this.
As mentioned above, be difficult to produce a kind of microcapsules according to conventional method with capsule wall of forming by organopolysiloxane.
Directly using the organopolysiloxane capsule wall of these performances to make microcapsules from the silicol precursor manufacturing with different performance also is favourable on expense.And, be applicable to that the microcapsules of a purpose can easily design by various silicol alkane precursors are made up.For example, can produce various capsule walls, for example, have the capsule wall of fine and close network, have the capsule wall of suitable permeance property, perhaps have high-intensity capsule wall or suitable soft capsule wall.But current the use when having low-molecular-weight hydroxyl silane precursor is difficult to produce microcapsules at control example such as aggregate rate under the condition of solubility etc.
The purpose of this invention is to provide a kind of microcapsules that contain a kind of core material, wherein, these microcapsules contain a kind of capsule wall of being made up of the organosiloxane with superperformance.Another object of the present invention provides a kind of being used for from common available silicon compound easily and the high productivity method of producing this microcapsules.
The inventor has in depth studied the method for directly producing the microcapsules with capsule wall of being made up of organopolysiloxane from the hydroxyl silane precursor in order to address the above problem.As a result, the inventor finds that above-mentioned purpose can reach by following condition: with one or more compound (A) hydrolysis of selecting the compound of free style (I) expression, produce the compound (B) that one or more select the compound of free style (II) expression:
R nSiX (4-n)(I) wherein, n represents one from 0 to 3 integer; R represents that a kind of wherein carbon atom directly is connected the organic group on the silicon atom, and when n greater than 1 the time, each R group can be identical or different; X represents to be selected from hydroxyl, hydrogen, alkoxyl, halogen group, at least one in the carboxyl, amino and siloxy, and when (4-n) greater than 1 the time, each X group can be identical or different; With
R nSi (OH) mY (4-m-n)(II) wherein, m represents one from 1 to 4 integer; N represents one from 0 to 3 integer; M+n≤4; R represents that a kind of wherein carbon atom directly is connected the organic group on the silicon atom, and when n greater than 1 the time, each R group can be identical or different; Y represents to be selected from alkoxyl, at least one in hydrogen and the siloxy, and when (4-m-n) greater than 1 the time, each Y group can be identical or different; As long as compound (B) contain at least a wherein m=2 or 3 and at least one R group to a kind of compound in continuous phase and the decentralized photo at least with formula (II) expression of compatibility; And compound (B) is by bunching, with the synthetic organopolysiloxane that constitutes capsule wall.Thereby finished the present invention.
Term " continuous phase " disperses mutually with a kind of with the medium that " decentralized photo " is illustrated respectively in before a kind of dispersion of microcapsule wall formation usually.In this manual, after forming, microcapsule wall also used outside phase with mutually inner, and expression " continuous phase " and " decentralized photo " respectively.
According to the present invention, but the organopolysiloxane immediate subordinate of formation microcapsule wall is come synthetic in the compound (B) of so-called hydroxyl silane.And above-mentioned organopolysiloxane can constitute production and contain the necessary capsule wall of microcapsules of core material, thereby does not need to form capsule wall by the condensing method of routine.
The invention provides a kind of microcapsules and a kind of capsule wall that contains core material, wherein, the capsule wall of these microcapsules contains: by with a kind of compound (B), monomer whose or monomer mixture, carry out bunching and synthetic organopolysiloxane, wherein compound (B) contains one or more compounds by formula (II) expression:
R nSi (OH) mY (4-m-n)(II) wherein, m represents one from 1 to 4 integer; N represents one from 0 to 3 integer; M+n≤4; R represents that a kind of wherein carbon atom directly is connected the organic group on the silicon atom, and when n greater than 1 the time, each R group can be identical or different; Y represents to be selected from alkoxyl, at least one in hydrogen and the siloxy, and when (4-m-n) greater than 1 the time, each Y group can be identical or different; As long as compound (B) contain at least a wherein m=2 or 3 and at least one R group to a kind of compound in continuous phase and the decentralized photo at least with formula (II) expression of compatibility.
The present invention also provides a kind of a kind of method that contains the microcapsules of core material that is used to produce, and this method comprises a kind of process, and wherein, compound (B) is by bunching, to synthesize organopolysiloxane and to form capsule wall.
Compound of the present invention (B) is used to produce has the microcapsules that are closed core material wherein.It normally the monomer by hydrolysis compound (A) or monomer mixture obtain, wherein, compound (A) contains one or more compounds by formula (I) expression:
R nSiX (4-n)(I) wherein, n represents one from 0 to 3 integer; R represents that a kind of wherein carbon atom directly is connected the organic group on the silicon atom, and when n greater than 1 the time, each R group can be identical or different; X represents to be selected from hydroxyl, hydrogen, alkoxyl, halogen group, at least one in the carboxyl, amino and siloxy, and when (4-n) greater than 1 the time, each X group can be identical or different; As long as compound (A) contains at least a wherein at least one R group to a kind of compound with formula (I) expression of compatibility in continuous phase and the decentralized photo at least.
In the present invention, " microcapsules " are meant a kind of for example microcapsules, the capsule of nanocapsule etc., and thereby compare with typically sense stricto " microcapsules ", it has comparatively wide significance.For example, generally speaking, sense stricto " microcapsules " are meant the capsule with 1 μ m to 1mm granular size, and " nanocapsule " is meant the capsule that has less than 1 μ m granular size.Like this, unless specialize herein, " microcapsules " are meant sensu lato microcapsules in this manual, comprise microcapsules and nanocapsule.Phrase " microcapsules that contain core material " is meant the microcapsules that contain core material in the space that capsule wall forms.
Compound (B) is the one group of compound that is selected from a kind of of formula (II) expression or contains two or more compounds.At least a compound that constitutes compound (B) is the compound of wherein m=2 or 3 formula (II) expression.At least a compound that constitutes compound (B) is a kind of like this compound, and this compound has at least one at least a R group with compatibility in continuous phase and the decentralized photo.
The capsule wall that contains the microcapsules of core material of the present invention forms by the synthetic organopolysiloxane of bunching compound (B).
The condensation of compound (B) is in a kind of its Chinese style (II)-SiOH group and the another kind of molecule that constitutes compound (B) in or another kind of prepolymer-SiL-(wherein L represents leaving group, for example, hydroxyl etc.) formation-SiOSi-connects the reaction of key.By this condensation reaction, formed the organopolysiloxane that constitutes capsule wall.
As mentioned above, in the production of the microcapsules that contain core material of the present invention, the condensation of compound (B) is carried out to a certain degree, and to prepare the prepolymer of compound (B) before forming at organopolysiloxane, it constitutes capsule wall.Thereby this prepolymer also constitutes by the organopolysiloxane that is formed by condensation reaction.
The organopolysiloxane of the formation capsule wall of the present invention of above-mentioned formation or the general formula of prepolymer are as follows: (R 3SiO 1/2) h(R 2SiO) i(RsiO 3/2) j(SiO 2) k(R ' O 1/2) p(III) wherein, R represents that a kind of wherein carbon atom directly is connected the organic group on the silicon atom, perhaps represent hydrogen, and when two or more R groups existed, they can be identical or different; H, i, j, k represent 0 or positive integer; R ' expression alkyl or hydrogen; P represents 0 or positive integer; And, 0≤h+p≤j+2k+2.
As mentioned above, if the two or more R groups in the formula (III) are connected on the carbon atom, these R groups can be identical or different.Inferior horn h, the formula in the i, j bracket in front can be all identical or different.For example, at (R 3SiO 1/2) hIn R can be all identical or different.
The organopolysiloxane that constitutes prepolymer becomes the big polymer that great achievement constitutes capsule wall gradually, at this moment undertaken by the SiL on the SiOH on the prepolymer and another prepolymer (wherein, L represents the leaving group of a kind of for example hydroxyl etc.) that condensation reaction carries out.Thereby, though constitute the organopolysiloxane of capsule wall and constitute prepolymer organopolysiloxane the two all by above-mentioned formula (III) expression, the h in general formula (III), i, j, the value of k and p is different in prepolymer and capsule wall.That is to say that when above-mentioned formula (III) expression constituted the organopolysiloxane of capsule wall, at least one among I and the j was a kind of like this positive integer, thereby obtain to be enough to form the polymer of microcapsule wall.When above-mentioned formula (III) expression constituted the organopolysiloxane of prepolymer, h, i, j and k represented 0 or a kind of h when constituting the organic poly-silica of capsule wall less than formula (III) expression, i, the positive integer of the value of j and k.The value of P depends on the degree of the hydrolysis of the compound (B) that the hydrolysis by compound (A) obtains, and the degree that contracts and react of compound (B).Its residing scope is that the organopolysiloxane that constitutes prepolymer and capsule wall is enough to form.
In the synthetic organopolysiloxane of the bunching of compound (B), can partly keep alkoxyl on the silicon atom, hydroxyls etc. perhaps do not keep.
The hydrolysis that is used to produce the compound (B) that wherein contains a kind of microcapsules of core material of the present invention and is by compound (A) obtains.Compound (A) is a kind of compound or two or more combination of compounds that is selected from formula (I) expression.
Be used to produce the method that contains the microcapsules of core material of the present invention and comprise the steps: that successively (1) prepares compound (B) by the hydrolysis of compound (A), (2) carry out bunching by the neutralization of compound (B), (3) mix also emulsification and (4) curing processing mutually with a kind of core material and/or a kind of second solution.
Except that above-mentioned steps, if desired, before above-mentioned curing schedule, also can carry out a kind of " coating is handled " or a kind of " surface treatment of compound (A) " (hereinafter being called " surface treatment ") as mentioned below.
The example that is used for preparation method's of the present invention compound (A) comprises a kind of compound or the one group of compound that carries a kind of hydrophilic radical, carry a kind of compound or one group of compound of a kind of hydrophobic grouping, carry a kind of compound or one group of compound that a kind of and a kind of fluorocarbon or tetraalkoxysilane have the group of compatibility.Carry a kind of compound or one group of compound of a kind of parents' group, carry a kind of compound or one group of compound of a kind of surface active groups, or the like.Term used herein " amphiphilic " is meant that two kinds of media that can not mix are mutually all had compatibility, and parents' group is a kind of group group of hydrophilic radical and hydrophobic group for example with two different compatibilities that carries.
The compound (A) that is used for preparation method of the present invention can be made up of a kind of or one group of compound, perhaps is made up of several or several groups of compounds.For example, compound (A) can be made up of compound that carries a kind of hydrophilic radical and the compound that carries a kind of hydrophobic grouping.
The kind of compound (A), and when compound (A) is made up of several compounds or several groups of compounds, the condensation of the compound (B) that the selection of the ratio of several compounds and/or several groups of compounds is preferably obtained by the hydrolysis of compound (A) and the prepolymer that forms have compatibility at least a in continuous phase and the decentralized photo, and resulting prepolymer is stabilized dispersion.
In the compound that carries hydrophilic radical of forming compound (A), the R group in the formula (I) preferably carries a kind of hydrophilic radical, and the R group that carries hydrophilic radical links to each other in silicon atom.The two or more R groups that carry hydrophilic radical can be connected on the silicon atom.When a plurality of hydrophilic radicals linked to each other with a R group, these a plurality of hydrophilic radicals can comprise two or more hydrophilic radicals.Except that hydrophilic radical, the group that a kind of hydrophobic grouping or a kind of and carbon fluorine have compatibility can be connected on this R group that carries hydrophilic radical.
The example that produces the compound of hydrophilic radical in compound (A) comprises polyethers, for example, and polyoxyethylene, polyoxypropylene, and polyoxyethylene-polyoxypropylene copolymer; The carbohydrate that comprises polysaccharide and monose, for example, amylopectin, sorbierite, chitin, chitan or amino sugar, protein, antibody, aminosal, polyaminoacid, carboxylic acid, or their salt or derivative, polycarboxylic acid or its salt or derivative, sulfuric acid or its salt or derivative, phosphoric acid or its salt or derivative, sulfonic acid or its salt or derivative, phosphonic acids or its salt or derivative, quaternary ammonium group, amine or their salt, polyamines or its salt, or the like.The compound of generation hydrophilic radical is not limited to above-mentioned these in compound (A).The example of the group that forms hydrophilic radical R as being connected with above-mentioned hydrophilic radical comprises-CH 2-,-(CH 2) 2-,-(CH 2) 3-,-(CH 2) 3OCH 2CH (OH) CH 2-,-(CH 2) 3NHCO-,-(CH 2) 3CH (CH 2COOH) CO-,-(CH 2) 3CH (COOH) CH 2CO-, etc., silicon atom is connected the left end of this partial structural formula, and above-mentioned hydrophilic radical is connected the right-hand member of this structural formula.
The polysiloxanes that the example that carries hydrophilic radical and constitute the compound of compound (A) comprises polyoxyethylene-modification [for example, KF-354 (trade name)] it carries the polyethers as hydrophilic radical, for example, polyoxyethylene, polyoxypropylene and polyoxyethylene-polyoxypropylene copolymer, poly-ethoxy propyl trimethoxy silicane [for example, KBM-641 (trade name), by Shin-Etsu Chemical Co., Ltd produces], be derived from N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group of γ-glycidoxypropyl triethoxysilane and protein hydrolysate] propyl group protein hydrolysate, be derived from N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group of γ-glycidoxypropyl methyldiethoxysilane and protein hydrolysate (JP-A-8-67608)] propyl group protein hydrolysate, with aforesaid compound and the silicon silane coupler that is derived from the hydrophilic substance that carries hydrophilic radical, for example, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-[N-(beta-aminoethyl) amino] propyl group methyl dimethoxysilane, γ-[N-(beta-aminoethyl) amino] propyl trimethoxy silicane, γ-[N-(beta-aminoethyl) amino] propyl-triethoxysilicane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-(N-phenyl amino) propyl trimethoxy silicane, γ-r-chloropropyl trimethoxyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-isocyanates propyl-triethoxysilicane, 3-triethoxysilylpropyltetrasulfide amber pool acid anhydrides etc.The compound that carries hydrophilic radical and constitute compound (A) is not limited to above-mentioned these examples.
About above-mentioned polyethers, for example, polyoxyethylene, polyoxypropylene and polyoxyethylene-polyoxypropylene copolymer, the number-average degree of polymerization of preferred oxygen ethene and oxypropylene are 1 to 2000, particularly 4 to 800.
Above-mentioned N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] propyl group protein hydrolysate and N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] example of protein hydrolysate comprises in the propyl group protein hydrolysate, but be not limited to, the hydrolysate of the protein of animal origin, for example, collagen, elastin laminin, keratin, the silk fibroin, sericin, casein and conchiolin; The albumen of plant origin, for example, wheat gluten, soybean protein, sesame protein, zeins (zein); And microbe-derived albumen, for example, Yeast protein.The protelytic number-average molecular weight of preferred water is about 100 to 50000, particularly about 200 to 5000.
In a kind of compound of the formation compound (A) that carries hydrophobic grouping, the R group in the preferred formula (I) carries a kind of hydrophobic grouping, and the R group that carries hydrophobic grouping is connected on the silicon atom.The two or more R groups that carry hydrophobic grouping can be connected on the silicon atom, and a plurality of hydrophobic grouping is connected on the R group.These a plurality of hydrophobic groupings can comprise two or more hydrophobic groupings.Except hydrophobic grouping, the group that a kind of and carbon fluorine has compatibility can be connected on the R group that carries hydrophobic grouping.
The example of hydrophobic grouping comprises straight-chain hydrocarbons, branched-chain hydrocarbons, unsaturated hydrocarbons, aromatic compound, ester etc.Preferred the one or more of these functional groups are connected on the R, though hydrophobic grouping is not limited to above compound of giving an example.
The concrete example that carries hydrophobic grouping and constitute the compound of compound (A) comprises methyldiethoxysilane, dimethyl dichlorosilane (DMCS), MTMS, MTES, methyl trichlorosilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyldichlorosilane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl trichlorosilane, dimethoxydiphenylsilane, the diphenyl diethoxy silane, diphenyl dichlorosilane, the hexyl trimethoxy silane, octyltri-ethoxysilane, the decyl trimethoxy silane, stearic acyloxy propyl trimethoxy silicane, vinyltrimethoxy silane, VTES, vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl trichlorosilane, γ-second butylene acyloxy propyl group methyl dimethoxysilane, γ-second butylene acyloxy propyl trimethoxy silicane, γ-second butylene acyloxy propyl group methyldiethoxysilane, γ-second butylene acyloxy propyl-triethoxysilicane, γ-r-chloropropyl trimethoxyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, octadecyl dimethyl-(3-trimethoxy-silylpropyl) ammonium chloride, dimethyl cetyl-(3-trimethoxy-silylpropyl) ammonium chloride etc., concrete example also comprises the aforesaid compound that is derived from the hydrophobic substance that carries hydrophobic grouping, and silane coupler, for example, vinyltrimethoxy silane, VTES, vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl trichlorosilane, γ-second butylene acyloxy propyl group methyl dimethoxysilane, γ-second butylene acyloxy propyl trimethoxy silicane, γ-second butylene acyloxy propyl group methyldiethoxysilane, γ-second butylene acyloxy propyl-triethoxysilicane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-[N-(beta-aminoethyl) amino] propyl group methyl dimethoxysilane, γ-[N-(beta-aminoethyl) amino] propyl trimethoxy silicane, γ-[N-(beta-aminoethyl) amino] propyl-triethoxysilicane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-[N-phenyl amino] propyl trimethoxy silicane, γ-r-chloropropyl trimethoxyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-isocyanates propyl-triethoxysilicane and 3-triethoxysilylpropyltetrasulfide succinyl oxide.And the concrete example as the compound of formula (I) expression comprises that wherein X is a siloxy, prestox ring tetrasilane, dihydro pregnancy basic ring tetrasilane and three hydrogen pentamethyl ring tetrasilanes.The compound that carries hydrophobic group and constitute compound (A) is not limited to above-claimed cpd.
Have in the compound of compatibility carrying a kind of and carbon fluorine, this R group of preferred formula (I) expression carries a kind of group that has compatibility with the carbon fluorine, and this carries the R group that has a group of compatibility with the carbon fluorine and is connected on the silicon atom.Carry two or more R groups that a kind of and carbon fluorine have compatibility and can be connected on the silicon atom, and the group that a plurality of and carbon fluorine has a compatibility can be connected on this R group.The group that this a plurality of and carbon fluorine have compatibility can comprise the group that two or more and carbon fluorine have compatibility.
Carry the example that has the group of compatibility with the carbon fluorine and constitute the compound of compound (A) and comprise C 8F 17CH 2CH 2Si (OCH 3) 3, CF 3CH 2CH 2Si (OCH 3) 3And the material derived compounds and the silane coupler that have compatibility with the carbon fluorine, for example, vinyltrimethoxy silane, VTES, vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl trichlorosilane, γ-second butylene acyloxy propyl group methyl dimethoxysilane, γ-second butylene acyloxy propyl trimethoxy silicane, γ-second butylene acyloxy propyl group methyldiethoxysilane, γ-second butylene acyloxy propyl-triethoxysilicane, γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl methyldiethoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-[N-(beta-aminoethyl) amino] propyl group methyl dimethoxysilane, γ-[N-(beta-aminoethyl) amino] propyl trimethoxy silicane, γ-[N-(beta-aminoethyl) amino] propyl-triethoxysilicane, gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-[N-phenyl amino] propyl trimethoxy silicane, γ-r-chloropropyl trimethoxyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-isocyanates propyl-triethoxysilicane and 3-triethoxysilylpropyltetrasulfide succinyl oxide.Carry the compound that has the group of compatibility with the carbon fluorine and constitute compound (A) and be not limited to the above-mentioned compound of enumerating.
The concrete example that has hydrophilic radical and hydrophobic grouping and constitute the compound of compound (A) comprise by the hydrolysis substituting group for example alkoxyl etc. produce N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] compound of propyl group protein hydrolysate.
When the microcapsules of being made by compound (A) that contain core material are scattered in the water or in the hydrophilic continuous phase time, (A) is as follows for compound.
Hydrophilic radical in compound (A) is a for example polyoxyethylene of a kind of polyethers, and when polyoxypropylene, and polyoxyethylene-polyoxypropylene copolymer, the total number-average degree of polymerization of preferred oxygen ethene and oxypropylene is 10 to 1000, particularly about 20 to 400.When compound (A) when being protein hydrolysate, preferably its number-average molecular weight is 200 to 50000, particularly about 400 to 5000.
Preferably carrying the compound (A) and the molar ratio that carries the compound (A) of hydrophobic grouping of hydrophilic radical (comprising that the R group carries the situation of hydrophilic radical and hydrophobic grouping simultaneously), in monomer, is about 1: 0 to 1: 1000, particularly about 1: 2 to 1: 200.
When a kind of monomethyl type compound, in its Chinese style (I) only a R group be methyl, when being used as the compound (A) that carries hydrophobic grouping, the preferred a kind of compound that is selected from down group that uses at least: MTES, MTMS and methyl trichlorosilane, perhaps this compound and at least a compound that is selected from down group are used in combination: dimethyldiethoxysilane, dimethyldimethoxysil,ne, dimethyldichlorosilane, octamethylcy-clotetrasiloxane, phenyl triethoxysilane, hexyl trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy silane and stearic acyloxy propyl trimethoxy silicane.Monomethyl type compound can be 100: 0 to 0: 100 with the molar ratio that carries other compound of hydrophobic grouping in monomer, but preferably this molar ratio is about 100: 3 to 100: 80.This monomethyl type compound and other the compound that carries hydrophobic grouping are not limited to the above compound of enumerating.
When the microcapsules of being made by compound (A) that contain core material were scattered in on-waterborne or the hydrophobic continuous phase, (A) was as follows for compound.
Hydrophilic radical in compound (A) is a for example polyoxyethylene of a kind of polyethers, and when polyoxypropylene, and polyoxyethylene-polyoxypropylene copolymer, the total number-average degree of polymerization of preferred oxygen ethene and oxypropylene is 3 to 20, particularly 5 to 10.When compound (A) when being protein hydrolysate, preferably its number-average molecular weight is 100 to 2000, particularly about 200 to 1000.
When a kind of monomethyl type compound, in its Chinese style (I) only a R group be methyl, when being used as the compound (A) that carries hydrophobic grouping, the preferred a kind of compound that is selected from down group that uses at least: MTES, MTMS and methyl trichlorosilane, perhaps this compound and at least a compound that is selected from down group are used in combination: dimethyldiethoxysilane, dimethyldimethoxysil,ne, dimethyldichlorosilane, octamethylcy-clotetrasiloxane, phenyl triethoxysilane, hexyl trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy silane and stearic acyloxy propyl trimethoxy silicane.Monomethyl type compound can be 100: 0 to 0: 100 with the molar ratio that carries other compound of hydrophobic grouping in monomer, but preferably this molar ratio is about 10: 100 to 80: 100.This monomethyl type compound and other the compound that carries hydrophobic grouping are not limited to the above compound of enumerating.
The hydrolysis of compound (A) is described below.
Compound (B) normally hydrolysis by compound (A) obtains.Make the medium of water as this hydrolysis.In addition, water-soluble a spot of organic solvent, salt, protein modifier for example urea etc. also can add in the entry.Neutralize after compound (A) hydrolysis, perhaps emulsified by mixing mutually with second solution is when carrying out below 0 ℃, and the adding of these additives is effectively, and is a kind of method for optimizing.And, in the hydrolysis and process of compound (A) by compound (B) preparation prepolymer, preferably using viscosity before the adding of compound (A) is the medium of 10 to 2000 milli pascal seconds, thereby the control reaction speed makes the unlikely rising of speed of condensation reaction too fast, prevent formation, and make solution-stabilized at the insoluble effect postprecipitation of prepolymer.Have the thickener that viscosity is 10 to 2000 milli pascal second media, polyvinyl alcohol, polyacrylamide, sodium carboxymethylcellulose as preparation, Sensor Chip CM 5, hydroxyethylcellulose, carageenan, chitin, chitan, polypeptide, gelatin, sericins etc. can be used as example.Particularly, the aqueous gelatin solution with 10 to 2000 milli pascal second viscosity can be used as example.
The hydrolysis of preferred compound (A) is at-5 ℃ to 90 ℃, particularly carries out under 5 ℃ to 75 ℃ temperature, and thoroughly stirs (promptly under stirring condition).
The hydrolysis of compound can be carried out under acidity or alkaline pH.The selection of these character depends on the character of compound (A).
When the hydrolysis of compound (A) is when carrying out under acid pH, preferably at pH1-5, particularly preferably in carrying out under the pH2-4.When acidity was strong excessively in the hydrolysis, core material may be not enough to combination subsequently wherein, but partly form a kind of transparency material, though it depends on the formation and the concentration of compound (A).The example of operable acid comprises organic acid, for example acetate etc., and inorganic acid, hydrochloric acid for example, sulfuric acid, phosphoric acid etc.Particularly, (A) carries a kind of hydrophilic radical when compound, this hydrophilic radical be animal origin protein for example, collagen, elastin laminin, keratin, the silk fibroin, sericin, the hydrolysate of casein and conchiolin, if the hydrolysis of compound (A) is when carrying out under acid pH, the microcapsules that contain core material that obtain have best result.
When hydrolysis is when alkaline pH carries out,, particularly carry out at pH8 to 10 preferably at pH7.5 to 11.5.When the hydrolysis neutral and alkali is crossed when strong, core material may be not enough to subsequently in conjunction with wherein, but partly form a kind of transparency material, though it depends on the formation and the concentration of compound (A).The example of operable alkali comprises for example NaOH, potassium hydroxide, etc.Particularly work as compound (A) and carry a kind of hydrophilic radical, this hydrophilic radical is the protein wheat gluten for example that derives from plant, the hydrolysate of soybean protein and sesame protein, if the hydrolysis of compound (A) is when carrying out under alkaline pH, the microcapsules that contain core material that obtain have best result.
The bunching of the compound (B) that the hydrolysis by compound (A) obtains is normally undertaken by neutralization.
This neutralization reaction is particularly carried out under-5 ℃ to 55 ℃ preferably at-30 ℃ to 80 ℃, and fully stirs.As the bronsted lowry acids and bases bronsted lowry that is used for neutralization reaction, can be used as example with the identical compound of describing in the said hydrolyzed reaction.As the medium of neutralization reaction, water can be used as example.
In production method of the present invention, the production of compound (B) and bunching by neutralization reaction be reflected at the core material and/or second liquid mix mutually with emulsification before be carried out to a certain degree, with the prepolymer of prepared beforehand compound (B).When using a kind of compound (B) at least, this compound carries at least one hydrophily R, particularly, carry at least one and have about 100 to 50000 the polypeptide of number-average molecular weight as R, the polyoxyethylene that perhaps has a number-average degree of polymerization 1 to 2000 is during as R, because prepolymer can be stabilized in the method, this method is particularly preferred.
Compound (B) with the core material and/or second liquid mix mutually with emulsification before the bunching degree of being undertaken by neutralization reaction can change according to other condition, as long as formed prepolymerization is stable.That is to say, must become at formed prepolymer and carry out before stable with mixing and the emulsification mutually of core material and/or second liquid.
Unstable and easily during precipitation when prepolymer, preferably in viscosity solution, for example carry out preparing the method for prepolymer in the aqueous gelatin solution etc. by the hydrolysis of compound (A), this is because prepolymer can be stabilized in this method.
Preferably after the preparation of prepolymer, the prepolymer in aqueous solvent mixes with a kind of hydrophobic substance and/or non-aqueous solvent, with the preparation emulsion.
In said method, after the mixing of hydrophobic substance and/or non-aqueous solvent, prepolymer causes mutual condensation to become bigger polymer, finally becomes the organopolysiloxane that constitutes capsule wall.
Then, as described below carrying out and core material and/or mixing and the emulsification mutually of second liquid.
Following method is one and mixes example with the method for emulsification mutually with the core material and/or second liquid.
Be scattered in the water or under the situation in the hydrophilic decentralized medium at the microcapsules that contain core material, prepolymer prepares in hydrophilic decentralized medium in this method, then, add the only core material in liquid form (the second liquid phase), perhaps core material and its solvent (second liquid mutually).
Be scattered at the microcapsules that contain core material under the situation of hydrophobic decentralized medium or nonaqueous dispersion medium, when core material is water-soluble or hydrophilic, in this method, in the aqueous solvent dispersion of prepolymer, with core material to be dissolved in the aqueous solvent or to add afterwards, and with the liquid that obtains with the immiscible solvent of aqueous solvent (second liquid mutually in continuous phase), make and put upside down mutually and emulsification.Core material can put upside down mutually with emulsification after add.
In the method for the invention, because core material can add, can produce a kind of containing under neutrallty condition at the microcapsules that are different from unsettled material under the neutral condition.With core material and/or second mutually mixing and emulsification normally at-30 ℃ to 90 ℃, particularly under-5 ℃ to 60 ℃, carry out.The example of employed core material is as follows.
The example of employed core material comprises water, and aliphatic acid is higher fatty acids particularly, hydro carbons, organic solvent, the ester class, phenols, siloxanes, silane, metal alkoxide, alcohols is higher alcohols particularly, and animal and plant oil extracts component, power supply colour developing organic compound, substance that show color, ultra-violet absorber, vitamin, effective ingredient, aroma constituent, anticorrisive agent, bactericide, salt; Amino acid and derivative thereof, protein, aminosal and derivative thereof, carbohydrate, polysaccharide, enzyme, class carbon fluorine material, or the like.Core material is not limited to above-mentioned substance.
The example of higher fatty acids comprises, capric acid, laurate, miristic acid, palmitic acid, stearic acid, behenic acid, 12-hydroxy stearic acid, undecenoic acid, wool aliphatic acid, isostearic acid, linoleic acid, oleic acid, linoleic acid, arachidonic acid, eicosapentaenoic acid, DHA etc.
The example of hydrocarbon comprises alkane, isoparaffin, ceresine, pristane, pure white ceresine, vaseline, Witcodur 272 etc.
Representative examples of organic comprises hexane, heptane, octane, benzene, toluene, dimethylbenzene, chlorobenzene, ethyl acetate, butyl acetate etc.
The example of ester comprises isopropyl miristate; the cetyl caprylate; octyl group dodecyl miristate; isopropyl cetylate; the butyl stearate; the hexyl laurate; miristylmiristate; Ceraphyl 140; hexyl decyl dimethyl-octa acid esters; the dodecyl lactate; the miristyl lactate; the lanolin lactate; the methyl isostearate; Permethyl 99A base stearate; cholesteryl 12-hydroxy stearic acid ester; ethylene glycol bisthioglycolate-2-Octyl Nitrite; the dipentaerythritol fatty ester; positive alkyl diol list isostearate; propylene glycol dicaprate, dimethyltrimethylene glycol dicaprate, glyceryl three decylates; isostearoyl base pivalate; two isostearoyl base malates, glycerol monostearate, glyceryl distearate; glyceryl two-2-heptyl hendecane acid esters; trimethylolpropane tris-2 ethyl hexanoic acid ester, trimethylolpropane tris isostearate, dimethyltrimethylene glycol two-2 ethyl hexanoic acid ester; pentaerythrite four-2 ethyl hexanoic acid ester; glyceryl three-2 ethyl hexanoic acid ester, cetyl 2 ethyl hexanoic acid ester, the different pelargonate of 2-ethylhexyl; the different pelargonate of different nonyl; the different pelargonate of isodecyl, the different pelargonate of different three decyls, 2-ethylhexyl palmitate; glyceryl trimiristate; glyceryl three caprylates, glyceryl three different palmitates, castor bean fatty acid oil methyl ester; the oleyl oleate; the glyceryl acetic acid esters, 2-heptyl undecyl palmitate, diisopropyl adipate ester; the diisobutyl adipate ester; N-lauroyl-L-glutamic acid-2-octyl group dodecyl ester, 2-heptyl undecyl adipate ester, ethyl laurate; two-2-ethylhexyl sebacate; 2-hexyl decyl miristate, 2-hexyl decyl palmitate, 2-hexyl decyl adipate ester; 2-hexyl decyl succinate, diisopropyl sebacate etc.
The example of phenol comprises tert-butyl phenol, nonyl phenol, dodecylphenol, alpha-Naphthol; betanaphthol, Hydroquinone monomethylether, parachlorophenol; p bromophenol, o-phenyl phenol, p-phenyl phenol; the methyl p-hydroxybenzoate, ethyl p-hydroxybenzoate, propyl para-hydroxybenzoate; 3-isopropyl catechol, p-tert-butyl catechol, 4; 4 '-methene biphenol, bisphenol-A, 1; the 2-dihydroxy naphthlene, chlorine catechol, bromine catechol; 2,4-dihydroxy benaophenonel, phenolphthalein; the methyl gallic acid ester, ethyl gallic acid ester, propyl group gallic acid ester; the hexyl gallic acid ester, octyl group gallic acid ester, dodecyl gallic acid ester; the palmityl gallic acid ester, stearyl gallic acid ester, tannic acid; phenol resin, zinc salicylate, tert-butyl group zinc salicylate etc.
The ion of siloxanes comprises dimethyl polysiloxane, methyl phenyl silicone, dimethyl siloxane-methyl stearic acid oxygen silicone copolymers, dimethyl siloxane-methyl methoxy radical siloxane copolymer, dimethyl siloxane-methyl ethoxy silicone copolymers, trimethylsiloxy group silicic acid, the methyl cyclopolysiloxane, methylhydrogenpolysi,oxane, high polymer methyl polysiloxane, cross-linking type methyl polysiloxane etc.
The example of silane comprises MTMS, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane, hexyl trimethoxy silane, octyl group trimethoxy silane, the decyl trimethoxy silane, tetramethoxy-silicane, tetraethoxysilane etc.
The example of metal alkoxide comprises, trimethyl borine acid esters, boron triethyl acid esters, tetraethyl titanate esters, tetra isopropyl titanate etc.
The example of higher aliphatic comprises, octanol, laruyl alcohol, miristyl alcohol, hexadecanol, octadecanol, arachidic alcohol, tadenan, oleyl alcohol, ketone octadecanol, single octadecane glyceryl ether, 2-decyl four decyl alcohol, 2-hexyl decyl alcohol, 2-hexyl dodecanol, the 2-octyldodecanol, 2-heptyl tip-nip, lanolin alcohol, cholesterol, phytosterol, isooctadecane alcohol etc.
The example of animal and plant oil comprises, avocado oil, tsubaki oil, macadamia nut oil, corn oil, olive oil, Efamast, rapeseed oil, egg oil, sesame oil, persic oil, wheat germ oil, camellia oil, castor oil, slaking castor oil, linseed oil, safflower oil, cottonseed oil, slaking cottonseed oil, soybean oil, the slaking soybean oil, peanut oil, tee nip oil, Japanese mace oil, rice chaff oil, chinese wood oil, Japanese tung oil, cinnamon oil, jojoba oil, embryo oil, apricot kernel oil, cupu oil, palm oil, slaking palm oil, horse fat oil, tortoise oil, ermine oil, spiny dogfish oil, spiny dogfish is rare, orangeroughy oil, butter, the slaking butter, neatsfoot stock, neat's foot oil, sheep oil, lard, train oil, slaking train oil, fish oil, slaking fish oil, lanolin oil, lanolin alcohol, hydrogenated lanolin, lanolin acetate, liquid lanolin, lanolin fatty acid isopropyl esters, cholesteryl lanonate, ring lanolin, polyoxyethylene lanolin alcohol ether, the polyoxyethylene lanolin alcohol acetic acid esters, polyethylene glycol lanolin fatty acid, polyethylene glycol hydrogenated lanolin alcohol ether, Brazil wax, Kan Taili wax, jojobawax, hard lanolin, Japan tallow, India's grain wax, cotton wax, myrtle wax, insect wax, montanwax, rice beans wax, lacca wax, jojoba wax, beeswax, train wax, jojoba alcohol, rosin acid, hydroabietic acid etc.
The example of the sub painted organic compound of powering comprises, diaryl 2-benzofuranone, and polyaryl methyl alcohol, colourless auramine, the acyl group auramine, the aryl auramine, if bright beta-lactam of dawn, indoline, spiral pyrans, fluorane etc.Its concrete example comprises, crystal violet lactone, malachite green lactone; bis(dimethylamino)benzhydrol; crystal violet methyl alcohol, malachite green methyl alcohol, N-(2; the 3-dichlorophenyl) colourless auramine; the N-benzoyl auramine, N-acetyl-auramine, N-phenyl auramine; if the dawn is bright-beta-lactam; 2-(phenylimino ethane dilidene)-3,3-dimethyl indoline, N-3; 3-trimethyl indolinyl benzo spirolane; 3-diethylamine-6-methyl-7-chlorine fluorane, 3-diethylamide-7-methoxyl group fluorane, 3-diethylamide-6-phenoxy group fluorane; 1,2-benzene-6-diethylamide fluorane etc.
The example of coloring material comprises, colourless white pigments, for example, titanium dioxide, zinc oxide etc., inorganic red pigment are iron oxide (red iron oxide) for example, iron titanates etc., inorganic brown are gamma-iron oxide etc. for example, and inorganic yellow pigment is yellow iron oxide for example, loess etc., inorganic black pigment, for example black iron oxide, carbon black, low titanium oxide etc., inorganic violet pigment is the mango purple for example, cobalt violet etc., inorganic green pigment is chromium oxide for example, chromium hydroxide, cobalt titanate etc., inorganic blue pigment, for example, the blue pigment that ultramarine is made, barba hispanica etc., organic dyestuff is for example, red 201, red 202, red 204, red 205, red 218, red 220, red 225, red 226, red 228, red 405, orange 201, orange 203, orange 204, yellow 401, green 202, blue 404 etc., zirconium, the organic pigment in barium or aluminium color lake etc., for example, red 3, red 104, red 106, red 227, red 230, red 401, red 505, orange 205, yellow 4, yellow 5, yellow 202, yellow 203, green 3, purple 201, blue 11 etc., natural pigment, for example, chlorophyll, beta carotene etc., mica titanium, the mica titanium of red ferric oxide-processing, the mica titanium of yellow ferric oxide-processing, the mica titanium that Black Rouge is handled, the mica titanium that iron oxide-yellow ferric oxide is handled, the mica titanium that ultramarine is handled, the mica titanium that fuchsin is handled, the mica titanium that chromium oxide is handled, the mica titanium that carbon black is handled etc.And their example comprises, talcum, kaolin, mica, phlogopite, sericite, white mica, synthetic mica, epidolite, lithia mica, vermiculite, organic powder for example, fluoridated apatite, hydroxyapatite, the pottery pulvis, metallic soap (zinc miristate, calcium palmitate, aluminum stearate etc.), Boron Nitride, tripoli-alumina, tripoli-magnesia, bentonite, bleaching earth, the japanic acid clay, atlapulgite, imvite, attapulgite etc.; And organic pulvis for example, polyamide pulvis (nylon pulvis), polyethylene pulvis, polymethyl methacrylate pulvis, the polystyrene pulvis, styrene-propene acid copolymer resin pulvis, 2,4-diaminourea-6-phenyl s-triazine resin pulvis, polytetrafluoroethylene (PTFE) pulvis, cellulose pulvis etc.
The example of ultra-violet absorber comprises; based on salicylic ultra-violet absorber; for example; phenyl salicylic acid esters; to the tert-butyl-phenyl salicylate; OPS p octylphenyl salicylate etc.; based on the ultra-violet absorber of benzophenone or their derivative; for example; 2; the 4-dihydroxy benaophenonel; 2-hydroxyl-4-methoxy benzophenone; 2-hydroxyl-4-octyloxy benzophenone; 2-hydroxyl-4-dodecyloxy benzophenone; 2; 2 '-dihydroxy-4; 4 '-dimethoxy-benzophenone; 2; 2 '-dihydroxy-4-methoxy benzophenone; 2-hydroxyl-4-methoxyl group-5-phenyl disulfide ketone etc.; 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) BTA; 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) BTA; 2-(2 '-hydroxyl-3 '; 5 '-two-tert-butyl-phenyl) BTA; 2-(2 '-hydroxyl-the 3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole; 2-(2 '-hydroxyl-3 '; 5 '-two-2-methyl-2-phenylpropane base)-the 5-chlorobenzotriazole; 2-(2 '-hydroxyl-3 '; 5 '-di-tert-pentyl-phenyl) BTA; 2-[2 '-hydroxyl-3 '-(3 "; 4 "; 5 "; 6 "-tetrahydrochysene phthalimidomethyl)-5 '-aminomethyl phenyl]-BTA; 2-(2 '-hydroxyl-3 '-dodecyl-5 '-aminomethyl phenyl) BTA, 2-(2 '-hydroxyl-3 '-undecyl-5 '-aminomethyl phenyl) BTA, 2-(2 '-hydroxyl-3 '-three decyl-5 '-aminomethyl phenyl) BTA; 2-[2 '-hydroxyl-4 '-(2 "-ethylhexyl) the oxygen phenyl] BTA; 2-[2 '-hydroxyl-4 '-(2 "-the ethyl octyl group) the oxygen phenyl] BTA, 2-[2 '-hydroxyl-4 '-(2 "-the propyl group octyl group) the oxygen phenyl] BTA, 2-[2 '-hydroxyl-4 '-(2 "-propylheptyl) the oxygen phenyl] BTA; 2-[2 '-hydroxyl-4 '-(2 "-the propyl group hexyl) the oxygen phenyl] BTA; 2-[2 '-hydroxyl-4 '-(1 "-ethylhexyl) the oxygen phenyl] BTA, 2-[2 '-hydroxyl-4 '-(1 "-the ethyl heptyl) the oxygen phenyl] BTA, 2-[2 '-hydroxyl-4 '-(1 "-the ethyl octyl group) the oxygen phenyl] BTA; 2-[2 '-hydroxyl-4 '-(1 "-propyl group octyl group) oxygen phenyl] BTA; 2-[2 '-hydroxyl-4 '-(1 "-propylheptyl) oxygen phenyl] BTA, 2-[2 '-hydroxyl-4 '-(1 "-propyl group hexyl) oxygen phenyl] BTA, the methyl-3-[3-tert-butyl group-5-(2H-BTA-2-yl)-4-hydroxy phenyl] propionic ester and polyethylene glycol condensation product (molecular weight: about 300); to the derivative or the ester of methoxy styrene acid; for example, 2-ethylhexyl be to the methoxy styrene ester, the derivative of ESCAROL 507 or ester; for example; 2-ethylhexyl ESCAROL 507 ester, the derivative of styrene acid or ester, for example; benzyl styrene acid esters; Anthranilate, the derivative of salicylate and benzoxazoles, 2; 4; 6-three-(to anilino-)-1-(carboxyl-2 '-ethylhexyl)-1,3,5-triazines; the derivative of dibenzoyl methane; for example, the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane and 4-isopropyl diphenyl formoxyl methane, franone derivative; forulic acid or its ester, gamma oryzanol etc.
The example of vitamin comprises vitamin and derivative thereof, for example, vitamin A, Cobastab, vitamin C, vitamin C, vitamin D, vitamin E, thiamine hydrochloride, vitamin B6 hydrochloride, calcium pantothenate, bisbentiamine, methylmethionine sulfonium chloride, etc.Specifically, L-ascorbyl-2-magnesium phosphate, L-ascorbyl-2-sodium phosphate, tocopherol acetate, etc.
The example of active drug component comprises, the sulphur medicine, for example, sulfamethomidine, circulatory system drug, for example, calcium hobatate, papaverine hydrochloride, diltiazem hydrochloride and reserpine, breathe and promote medicine such as trimethoxy alcohol hydrochloric acid, bromoacetylene hydrochloric acid, and tipepidinehibenzate, the cough-relieving apophlegmatic medicine, antibiotic, for example, benzyl penicillin sodium, benzyl penicillin potassium, phenoxy methylpenicillin potassium and ammonia Bian XiLin, carcinostatic, for example, 5 FU 5 fluorouracil, N-(2-tetrahydrofuran base)-5 FU 5 fluorouracil and hydrochloric acid bleomycin, therapeutic agent, for example, timepidiumbromide, lidocaine and chlorpromazine hydrochloride, antihistaminic, for example, diphenhydramine hydrochloride and diphenhydramine malate, antiphlogistic, for example, aspirin, quinine hydrochloride and sulpirin, bactericide, for example, salicylic acid, Japanese cypress, sulphur, the methyl of P-hydroxybenzoic acid, propyl group, butyl, ethyl ester etc., anticorrisive agent, in addition, light-sensitive material, the cyctein or derivatives thereof, azilex or derivatives thereof, glutathione or derivatives thereof etc.
The example that extracts component comprises, oil-soluble arnica extract, aloe extract, the dead nettle extract of dissolubility is arranged, the german chamomile extract, the oil-soluble Flos Chrysanthemi extract, the oil-soluble licorice, cape jasmine extract, the oil-soluble mulberry extract, oil-soluble burdock extract, oil-soluble collagen extract, oil-soluble salvia extract, oil-soluble lithospermum root extract, oil-soluble bodhi tree extract, oil-soluble birch white matter extract, oil-soluble wild horse tail (field horsetail) extract, the careless extract of oil-soluble the West work, the oil-soluble Sage extract, Japanese green gentian extract, common thyme extract, the orange peel extract, oil-soluble juglanus regia L. extract, oil-soluble ligusticum acutilobum root extract, the common marigold extract of oil-soluble, the oil-soluble carrot extract, oil-soluble wild rose extract, oil-soluble loquat-leaf extract, oil-soluble intacellin, oil-soluble hop extract, oil-soluble marronnier extract, oil-soluble peach leaves extract, mugwort extract, oil-soluble Coix plant extracts, the Lavandula plant extracts, lemon extract, citrus extract, the oil-soluble Rosmarinus officinalis extract, oil-soluble royal jelly extract, green tea contains the bark of eucommia tea or the ruibosu tea of tannic acid or flavonoids; Derive from former medicine of plant or animal or their various salt, for example, Japanese Chinese scholartree, scutellariae,radix and souhakuhi extract.
The example of flavor component comprises the oil with smell, for example, and almond, fennel a kind of reed mentioned in ancient books, caraway, Chinese cassia tree, cedar leaf, cedar wood, Chinese cassia tree, lemongrass, cloves, eucalyptus, fish pelargonium, grape, lavender, lemon, lemon grass (Cymbopogon citratus), attar of rose, sour shaddock, citrus flower (nerori oil) nutmeg, onion, garlic, citrus, lignum vitae, orris, peppermint oil, pine tree, pine needle, rosemary,, santal, sassafrases, spearmint, time, coffee, black tea, cherry, apple, pineapple, banana, pears, vanilla etc.
The example of salt comprises, calcium carbonate, magnesium carbonate, magnesium silicate, calcium silicates, alumina silicate, barium silicate, barium sulfate, strontium silicate, metal tungstates, silica, zeolite, barium sulfate, the calcium sulfate of roasting, calcium phosphate, lithium chloride, sodium chloride, potassium chloride, ammonium chloride, lithium bromide, sodium bromide, KBr, lithium iodide, sodium iodide, KI, iodine, sodium sulphate, potassium sulfate, ammonium sulfate, ammonium nitrate, calcium nitrate, perphosphoric acid calcium, the phosphate fertilizer of roasting, sodium phosphate etc.
Amino acid, protein, the example of carbohydrate etc. comprise amino acid or peptide class, for example, potassium aspartate, magnesium aminosuccinate, sodium glutamate, FE-5 and glutathione derive from the protein of animal, for example, collagen, elastin laminin, keratin, fibroin, sericin, casein, conchiolin derives from the protein of plant, for example, wheat gluten, soybean protein and sesame protein, derive from the protein of microorganism, for example, the hydrolysate of Yeast protein or this protein, intacellin, the mucous membrane polysaccharide, urea etc.
The example of enzyme comprises, lipase, protease, superoxides, dismutase, lysozyme, alkaline phosphatase, amylase, trypsase, glutathione peroxidase, catalase etc.
The example of class carbon fluorine material comprises, Fomblin HC/04 (trade name), and Fomblin HC/25 (trade name) and Fomblin HC/R (trade name), they are a kind of perfluor ether, and are a kind of by Monteflous (Milan, Italy) a kind of polyoxy perfluor alkane of Sheng Chaning.
One or more above-mentioned compounds can be used as core material.But, the material that core material is not limited to above enumerate.
As the material of continuous phase, in the preparation process of capsule, use a kind of material as liquid.Be scattered at the microcapsules that contain core material under the situation of a kind of hydrophobicity continuous phase or non-water continuous phase, the example of continuous state material comprises, higher fatty acids, hydrocarbon, organic solvent, ester, siloxanes, higher alcohol, the animal and plant wet goods, these are the example of core material.Wherein one or more materials are used as continuous state material.In organic solvent, the material with the boiling point that is lower than water also can use, as long as it can repel moisture in azeotropic point ground.
In emulsion preparation, to have granular size be 0.3 to 100 μ m when a kind of, and median particle size is that 1 to 20 μ m warp in is 12cm and is equipped with the 2-of mechanical agitator to rise when preparing in the round bottom column type glass reaction vessel, being stirred under 50 to 1000rpm of preferred reaction liquid carried out, and carries out under 300 to 1000rpm.
In the preparation of emulsion, when reactant liquor stirred by mechanical agitator by a kind of homogeneous mixer and the size of prepared particle substantially in 0.1 to 30 μ m and median particle size during at 0.5 to 5 μ m, preferred reaction solution, particularly carries out under 5000 to 10000rpm 1000 to 20000rpm by this homogeneous mixer.
In the preparation of emulsion, when reaction solution is stirred by a kind of mechanical agitator, handle by a kind of homogeneous mixer, prepare granular size substantially in about 0.1 to 1 μ m and median particle size during by little fluidizator (microfluidizer) then at 0.2 to 0.8 μ m, preferred reaction solution with this little fluidizator about 300 to 5000kg/cm 2Velocity process.
A purpose of handling with homogeneous mixer and little fluidizator is to reduce granular size.Another purpose is to produce the microcapsules that contain core material, and wherein, when carrying out this processing shearing force taking place, capsule wall is not cleaved.
The processing of homogeneous mixer or little fluidizator can repeat twice or repeatedly, to reduce granular size more.When ultra-violet absorber was used as core material, the reprocessing of homogeneous mixer or little fluidizator had another effect that reduces the free amount of ultra-violet absorber in dispersion usually.
For reducing granular size more, can carry out at ethanol, particularly at polyalcohol ethylene glycol for example, propane diols, the existence of glycerine etc. is the preparation emulsion down.When ultra-violet absorber was used as core material, this method had the effect that another one reduces the free amount of ultra-violet absorber in dispersion usually.
For reducing the size of particle more, also can in ultrasonic wave, carry out the preparation of emulsion.
The microcapsules that hereinafter description contained core material are used the surface treatment of compound (A) in preparation process.
Even in preparation process, do not use the surface treatment of compound (A) at the microcapsules that contain core material, can prepare the microcapsules that contain core material yet.But,, infer that a silanol groups that does not participate in condensation still is retained in the short time after emulsification on the capsule that does not have to solidify according to preparation method of the present invention.Thereby, preferably use the surface treatment of compound (A), with the cohesion of the microcapsules that prevent to contain core material.
When being used for surface-treated compound (A) is a kind of compound at water capacity facile hydrolysis, for example, when chlorosilane comprises trim,ethylchlorosilane and hexamethyl siloxanes, preferably add this compound (A) after the emulsification in emulsion, then, solution is neutralized.
When being used for surface-treated compound (A) is a kind of alkoxy silane for example during trimethylethoxysilane, need after emulsification this neutral solution be become acidity or alkalescence, and with this alkoxy silane hydrolysis once.When the compound that carries a silanol groups (A) when beginning to be used to surface treatment, need after emulsification, this neutral solution be become acid or alkaline a little.Then, compound (A) is fixed on the surface of capsule by neutralization reaction.Should carefully control the pH value, not make the capsule cracking.Under the situation that acid pH is handled, the pH value is preferably about 3 to 6.5.Under the situation that alkaline pH is handled, the pH value is preferably about 7.5 to 10.The example that is used for the compound (A) of superficiality processing is described below, but the compound that is not limited to exemplify.
Purpose of surface-treated is the cohesion that prevents to contain the microcapsules of core material.After emulsion preparation, preferably add a kind of compound (A) that on silicon atom, carries 3 alkyl, for example, trim,ethylchlorosilane, ethoxytrimethylsilane, tert-butyl chloro-silicane, HMDO, HMDS etc., thus prevent to contain the cohesion of the microcapsules of core material.
And, after emulsion preparation, can add and carry the compound (A) of cation group as organic substituent, for example, octadecyl dimethyl-(3-trimethoxy-silylpropyl) ammonium chloride, hydrolysis and neutralization make the surface of the microcapsules that contain core material be cationic.
And, after emulsion preparation, can make the character on the surface of the microcapsules that contain core material carry out various variations, and by control pH in and compound (A) obtain various modifications, this compound (A) for example comprises, methyldiethoxysilane, dimethyl dichlorosilane (DMCS), tetramethoxy-silicane, tetraethoxysilane, tetrachloro silicane, MTMS, MTES, methyl trichlorosilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyldichlorosilane, octamethylcy-clotetrasiloxane, phenyltrimethoxysila,e, phenyl triethoxysilane, phenyl trichlorosilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, diphenyl dichlorosilane, the hexyl trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy silane, stearic acyloxy propyl trimethoxy silicane, vinyltrimethoxy silane, VTES, vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl trichlorosilane, γ-second butylene acyloxy propyl group methyl dimethoxysilane, γ-second butylene acyloxy propyl trimethoxy silicane, γ-second butylene acyloxy propyl group methyldiethoxysilane, γ-second butylene acyloxy propyl-triethoxysilicane, γ-r-chloropropyl trimethoxyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-isocyanates propyl-triethoxysilicane, 3-triethoxysilylpropyltetrasulfide succinyl oxide, octadecyl dimethyl-(3-trimethoxy-silylpropyl) ammonium chloride, dimethyl cetyl-(3-trimethoxy-silylpropyl) ammonium chloride, methoxyl group (ethyoxyl) n(propoxyl group) mPropyl group methyl dialkoxy silicane, methoxyl group (ethyoxyl) n(propoxyl group) mThe propyl group methyl trialkoxysilane, be derived from the compound (A) of following material: γ-glycidoxypropyl triethoxysilane, γ-glycidoxypropyl methyldiethoxysilane and other material, for example, N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] propyl group protein hydrolysate and N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] propyl group protein hydrolysate, be derived from the compound (A) of silane coupler, for example, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-[N-(beta-aminoethyl) amino] propyl group methyl dimethoxysilane, γ-[N-(beta-aminoethyl) amino] propyl trimethoxy silicane, γ-[N-(beta-aminoethyl) amino] propyl-triethoxysilicane, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, γ-[N-phenyl amino] propyl trimethoxy silicane, vinyltrimethoxy silane, VTES, vinyl three ('beta '-methoxy ethyoxyl) silane, vinyl trichlorosilane, γ-second butylene acyloxy propyl group methyl dimethoxysilane, γ-second butylene acyloxy propyl trimethoxy silicane, γ-second butylene acyloxy propyl group methyldiethoxysilane, γ-second butylene acyloxy propyl-triethoxysilicane, γ-r-chloropropyl trimethoxyl silane, γ-Qiu Jibingjisanjiayangjiguiwan, γ-isocyanates propyl-triethoxysilicane and 3-triethoxysilylpropyltetrasulfide succinyl oxide and other material.
Above-mentioned surface treatment series may be incorporated in together.
During curing of the present invention is handled, the intensity that contains the microcapsule wall of core material can be improved by further carrying out the bunching reaction, this reaction is to be undertaken by the alcohol that produces in the hydrolysis of removing alkoxy silane, this alkoxy silane is a kind of compound (A), perhaps by because the dehydration that the passage of time takes place or by heating with remove moisture and wait and carry out from reaction system.Preferably 30 ℃ or higher of the temperature of reaction solution.The temperature that particularly preferably is reaction system is heated to boiling point, and is controlled though boiling temperature can be passed through controlled pressure.Because silicone condensation is carried out under neutral pH naturally, thereby because above-mentioned dehydration takes place in the passage of time.Dewatered method for example has evaporation (remove the condensed water that the cooling by solvent vapo(u)r produces from reaction system, it is got back in the reaction system) etc. from system.
In the microcapsules that contain core material that obtain like this, the weight of preferred core material based on the weight that contains core material in about 0.01 to 99% (weight).The weight of core material is called as " core weight ratio " hereinafter to this ratio of the weight that contains core material.According to the present invention, can obtain the core weight ratio of wide range, the thickness of capsule wall can be easily by corresponding and controlled with granular size with the core weight ratio.This microcapsules that contain core material have enough water proofing properties around neutral pH.
The intensity of capsule depends on the kind of employed compound (A), granular size, condition of cure, and core weight ratio.For example, produce again under the situation of microcapsules of the cosmetics be used to have granular size 1 to 2 μ m and core weight ratio 90%,, do not see that cracking is arranged even it is to be combined in the cosmetics and to be applied on the skin by the mechanical mixture method.
The microcapsules that contain core material according to method preparation of the present invention can be prepared into powder by freeze drying and the dry processing of spraying.
Core material is being about 50 to 99.9%, preferred 80 to 98% according to the uptake rate in the microcapsules that contain core material of method preparation of the present invention based on weight.This uptake rate has shown that the core material what have add is combined in the capsule.
Though the microcapsules that prepare in said method of the present invention have good effect, core material might not advance in the capsule in complete combination.Part core material may still be present in the continuous phase, and also continues as time goes by to infiltrate in the continuous phase.
When a part of core material remains in the continuous phase, and when continuing to infiltrate in the continuous phase as time goes by, variety of issue may take place from capsule.
For example, when core material remained in the continuous phase or infiltrate in the continuous phase, that emphasizes in the cosmetic field avoided contacting this target and just can not reaching of core material and skin.And, though someone proposes to advance microcapsules for combination of materials unstable and decolouring with a kind of as time goes by when being exposed to external environment, be used for insulating with external environment, and prevent to decolour as time goes by, if the combination of core material in capsule is incomplete, purpose of the present invention just can not reach fully.
Except above-mentioned purpose, another object of the present invention provides a kind of microcapsules with a kind of capsule wall, this capsule wall is to be made by specific organopolysiloxane, and a kind of method for preparing it, in this method, the amount that is not combined into the core material of capsule is reduced to minimum, and the amount that core material oozes out from capsule in use subsequently is reduced to minimum.
That is to say, the invention provides a kind of microcapsules that contain core material, wherein, capsule wall is that the wherein at least a compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes is added in this core material by synthetic organopolysiloxane is made by the condensation of compound (B).
The present invention also provides a kind of microcapsules that contain core material, wherein, capsule wall is by synthetic organosiloxane is made by the bunching of compound (B), and formed capsule wall is handled once at least with a kind of hydrolysate, and this hydrolysate is at least a compound that is selected from hydrolyzable silane and the hydrolyzable polysiloxanes.
The present invention also provides a kind of method that is used to prepare the microcapsules that contain core material, comprise that the wherein at least a compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes adds the step of core material and wherein compound (B) bunching formed the step that organopolysiloxane forms capsule wall.
The present invention also provides a kind of method that is used to prepare the microcapsules that contain core material, comprise the step that wherein the synthetic organopolysiloxane of compound (B) bunching is formed capsule wall, wherein once step is handled at least by a kind of hydrolysate in the surface of formed capsule wall, and this hydrolysate is at least a compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes.
In the microcapsules that contain core material of the present invention, at least a compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes is added in the core material, perhaps, handle once at least with a kind of hydrolysate on the surface of formed capsule wall, this hydrolysate is at least a compound that is selected from hydrolyzable silane and the hydrolyzable polysiloxanes, it is minimum that thereby the amount that makes the core material that is not combined into capsule is reduced to, and perhaps the core material that oozes out from capsule in use is afterwards reduced to minimum.
Herein, " hydrolyzable silane " and " hydrolyzable polysiloxanes " represents to produce by hydrolysis the silane and the polysiloxanes of silanol groups respectively.As being added into core material or being used to the surface-treated hydrolyzable silane of formed capsule wall and the example of hydrolyzable polysiloxanes comprises, dimethyl dichlorosilane (DMCS), methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane, MTMS, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, diphenyl diethoxy silane, the hexyl trimethoxy silane, octyltri-ethoxysilane, decyl trimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, and Me 3SiO (Me 2SiO) f[MeZSiO] gSiMe 3(f represents one from 5 to 50 integer, and g represents one from 2 to 100 integer, and z represents hydrogen or alkoxyl).Its more preferred example comprises, tetramethoxy-silicane, tetraethoxysilane, methyl trichlorosilane, Me 3SiO (Me 2SiO) f[MeZSiO] gSiMe 3(f represents one from 5 to 50 integer, and g represents one from 2 to 100 integer, f/g=0.1 to 20, and weight average molecular weight=200 are to 10000, z represents hydrogen, methoxy or ethoxy) etc.
At least a compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes is added in the core material usually in advance, and adds in the continuous phase with core material.
With at least a hydrolysate that is selected from hydrolyzable silane and the hydrolyzable polysiloxanes processing (hereinafter being called coat handles) of formed capsule surface is carried out once at least.It mix and emulsification after carry out, and usually before surface treatment, carry out before promptly preventing to condense the curing processing with capsule wall with compound (A) etc.This coat processing is undertaken by at least a compound that is selected from hydrolyzable silane and the hydrolyzable polysiloxanes of adding in continuous phase usually.This coat is handled to be preferably under the stirring condition and is carried out under the temperature approximately identical with emulsification with mixing.The addition of at least a compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes is 0.1 to 30 mole based on per 100 total mole numbers that are used for the Si that capsule wall forms, and is preferably 0.5 to 10 mole.
If uptake rate is enough high, need for example remove the purifying of the core material that is not combined into etc. usually.The example of the method for purifying is as follows.
Purification process is wherein to add a kind of powder capsule and liquid phase of not mixing mutually with other the liquid of dispersion capsule of being regardless of, said two kinds of liquid are mixed mutually fully, then two kinds of liquid are separated by decant(-ation) or fluid separation applications, two be separated after, impurity is transferred to other liquid phase.When two liquid are difficult for separately mutually, can adopt centrifugation.And, compatible when easily separated when two liquid, can further add the liquid that can mix mutually with the liquid that disperses capsule, capsule is washed and separate.
Another purification process is wherein will precipitate or the microcapsules that contain core material that float carry out fraction collection by centrifugation, and in this case, after above-mentioned steps, impurity and solvent are removed together.The microcapsules of collecting are dispersed in the solvent that can disperse capsule again.Repeat this process.
Another kind of purification process is the method by hyperfiltration.In this method by hyperfiltration, the impurity that goes out by the hyperfiltration wash-out is removed, and the microcapsules that concentrate is dispersed in again in the solvent of the microcapsules that can disperse to contain core material.Repeat this process.
The microcapsules right and wrong that contain core material of the present invention are bioactive, and its capsule wall has heat and mechanical stability and light resistance, and these are fundamental propertys of organopolysiloxane.Because containing the microcapsules of core material can be directly from for example alkoxy silane, halogenated silanes, hydrogen silane, the compound of polysiloxanes etc. (A) prepares, thereby the present invention also has the cheap characteristics of expense.In addition, many microcapsules that contain core material can design by the different compound (A) of combination according to various objectives.
Have this microcapsules that contain core material of the present invention of different nature and can be widely used in pharmacy, liquid crystal, chemical products, record material, cosmetics, spices, enzyme, agricultural, adhesive, fiber, food, catalyst, washing agent, dyestuff, paint vehicle, anticorrisive agent, solvent etc.
For example, when the microcapsules that contain core material of the present invention that use ultraviolet absorption material as core material were used to cosmetics, comparing with the situation that ultra-violet absorber itself wherein is combined into cosmetics had following advantage.
1. owing to see through the ultraviolet ray reduction of ultra-violet absorber to skin, the security of cosmetics is carried
High.
2. be difficult under normal conditions to obtain to stablize ingredients the ingredients system in, might obtain steady
Fixed ingredients.
3. when ultra-violet absorber itself is combined in the cosmetics, may need to add stabilizing agent,
To prevent the ultra-violet absorber flavescence.But, do not need this stabilizing agent in the present invention.
4. itself organized when the ultra-violet absorber of a kind of for example ethylhexyl methoxy cinnamic acid etc.
Fashionable, viscosity etc. can take place, and methoxyl group butyl benzene formoxyl methane etc. for example
When ultra-violet absorber is combined itself, can be settled out a kind of crystal and becomes coarse.
But in the present invention, these problems are solved, have improved the usability of cosmetics
Feel.And the adhesiveness of cosmetics improves.
5. itself to be combined into having of a kind of for example bath foam high moisture when a kind of ultra-violet absorber
In the time of in the ingredients of amount, need to add certain amount of surfactant.But, according to this
Bright, do not need to add surfactant or only need to add a spot of surfactant,
Thereby ultra-violet absorber can easily be combined into.And, the methoxyl group butyl benzene
Formoxyl methane etc. is difficult to be combined into, and this is because it demonstrates bad dissolubility,
And its solubility is owing to the influence that other combinations ancestral divides reduces.In the present invention,
Its combination is easy.That is to say,, (change with other combination partner according to the present invention
Make up the raw material of product, oil, solvent etc.) the compatibility raising.
6. ultraviolet radiation absorption effect (spf value) is promptly protected human body to avoid ultraviolet effect of shining and is carried
High.
When containing the microcapsules of ultra-violet absorber and be used to cosmetics as core material, the granular size of microcapsules is preferably 0.05 μ m to 50 μ m, 0.3 to 30 μ m more preferably, the combined amount of this ultra-violet absorber (weight) is preferably 0.1% to 50% based on the amount of microcapsules, and more preferably 0.5 to 30%.
When the microcapsules that contain core material of the present invention are used to pharmacy, cosmetics, during dyestuff etc., following component is used for microcapsules jointly: aliphatic acid is higher fatty acids particularly, hydrocarbon, organic solvent, ester, phenol, siloxanes, silane, metal alkoxide, alcohols is higher alcohols particularly, animal and plant oil extracts component, the sub painted organic compound of powering, dyestuff, ultra-violet absorber, vitamin, medicine effective ingredient, aroma constituent, anticorrisive agent, bactericide, salt; Amino acid and derivative thereof, protein, aminosal and derivative thereof, carbohydrate, polysaccharide, enzyme, class carbon fluorine material, or the like, they are listed in core material hereinbefore; And, surfactant, they are divided into cation, anion, nonionic and amphoteric surfactant etc., they comprise betaine type surfactant soap, aliphatic acid aminosal condensation product, sulfated surfactant, phosphate-type surfactant, polyester and derivative thereof.
Embodiment
Hereinafter purpose of the present invention is described with reference to various embodiment of the present invention, characteristics, and advantage, still, these are described just for illustrative purposes, do not limit scope of the present invention.In the following embodiments, all % and umber are all based on weight, unless stated otherwise.Analytical method 1
Correct weighing 10 grams contain the dispersion of the microcapsules of core material, and the moisture that will contain the dispersion of core material microcapsules is measured with infrared moisture meter LIBROR EB-280MOC (trade name is made by Shimadzu Corp).Calculate the weight [microcapsules+free core material (not being combined into the core material of the capsule)+ash content that contains core material] of the non-water section of the dispersion that contains microcapsules from this result.Under the situation of the medium-sized capsule of water, the weight that contains the dispersion of capsule is the weight of [water+contain the microcapsules+free core material+ash content of core material] at oil.When the content of water is when measuring according to this analytical method 1, calculate the weight [microcapsules+free core material+ash content that contains core material] of non-water section dispersion from this measurement result.Analytical method 2
The concentration of Na is measured by ICP emission spectrographic analysis device SPS1700HVR (trade name is made by Seiko Denshi Kogyo Ltd) in the capsules disperse body, and calculates the weight of NaCl in the dispersion that contains microcapsules.Described in above-mentioned analytical method 1, contain in the dispersion of microcapsules and be considered to also contain ash content, and in the ash content except that silica almost all compositions are NaCl.Thereby the amount of NaCl is measured by this analytical method 2, and this result is used as the amount of ash in calculating the core weight rate, and is as mentioned below.Analytical method 3
The microcapsules that contain core material of about 1 gram are correctly weighed, be transferred to then in the 500ml separatory funnel, use the water washing of 100ml simultaneously.Add the n-hexane of 100ml, mixture is fully shaken up, leave standstill then.After liquid is separated, the solution of the n-hexane of 100ml washing is transferred in the another one vessel.With this lock out operation triplicate, the solution of the n-hexane extracting that obtains is merged, and be concentrated into 100ml.The solution of this n-hexane extracting of 1 μ l is sucked in the micro-syringe, and carry out liquid-phase chromatographic analysis.The free core material that is not incorporated into microcapsules that exists in the microcapsules that contain core material of about 1 gram is measured based on the normal concentration calibration curve of other making, and calculates the weight of core material free in the dispersion that contains microcapsules.Analytical method 4
About 0.1 microcapsules that contain core material of being produced of gram are correctly weighed, and to the 5N sodium hydrate aqueous solution that wherein adds 5ml, and this mixture was stirred 1 hour at 50 ℃, be cooled to room temperature then.It is transferred in the 500ml separatory funnel then, uses the water washing of 100ml simultaneously.Add the n-hexane of 100ml, mixture is fully shaken up, leave standstill then.After liquid is separated, the solution of the n-hexane of 100ml washing is transferred in the another one vessel.With this lock out operation triplicate, the solution of the n-hexane extracting that obtains is merged, and be concentrated into 100ml.The solution of this n-hexane extracting of 1 μ l is sucked in the micro-syringe, and carry out liquid-phase chromatographic analysis.Free core material that is not incorporated into microcapsules that exists in the microcapsules that contain core material of about 0.1 gram and the gross weight that has been incorporated into the core material of microcapsules are measured based on the normal concentration calibration curve of other making.
The core weight ratio, amount with the core material that is incorporated into microcapsules is represented based on the weight percent of the weight of microcapsules, obtains by following formula: [(value that analytical method 4 obtains)-(value that analytical method 3 obtains)]/[(value that analytical method 1 obtains)-(value that analytical method 2 obtains)-(value that analytical method 3 obtains)] 100.Analytical method 5
The dispersion of about 0.1 microcapsules that contain core material that obtain that restrain is weighed, to the water that wherein adds about 5ml.This drips of solution on glass plate, and is covered with cover plate glass, then, is to observe under 1000 the light microscope in multiplication factor, observes the distribution situation of measuring granular size.Analytical method 6
The particle size distribution situation of the microcapsules that contain core material that obtain is measured by the SALD-2000 that ShimadzuCorp makes.Method of testing 1
The microcapsules that contain core material of 20 times of one (about 50 μ l) dilutions are clipped between the glass plate of two square 2mm thickness of 1cm, and place it on the horizontal hard substrate, and apply 1.5kg/cm from the top 2Pressure.After exerting pressure, observe microcapsules and whether break.
Embodiment 1 contains the 2-ethylhexyl to Methoxycinnamate and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is the hydrolysate by methoxyl group (ethyoxyl) n-pro-pyl dihydroxy methyl-monosilane, the copolymer of MTES and phenyl triethoxysilane form 1) preparation of the prepolymer of capsule wall
One is had interior through 12cm, be equipped with mechanical agitator, have 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 90 gram water of packing in advance, (KF-354A (trade name) is by Shin-EtsuSilicone Co. for the siloxanes that 10 gram polyoxyethylene are modified, Ltd makes, and prepares with the trimethyl silyl group replacement by the two ends with methoxyl group (ethyoxyl) n-pro-pyl dihydroxy methyl-monosilane) and 0.2 gram, 18% hydrochloric acid.The mixture of 4.4 gram MTESs and 1.2 gram phenyl triethoxysilanes is dropwise added wherein and stirs at 50 ℃ from addition funnel.This mixture is continued to stir 6 hours at 50 ℃, and then, adding dropwise adds 1.6 gram 4% sodium hydrate aqueous solutions and stirs, and control pH value is 7.0.Afterwards, this mixture was stirred 1 hour at 50 ℃.2) adding of core material and emulsification
With 5.4 gram 2-ethylhexyls to Methoxycinnamate adding method 1 under 600rpm stirs) in the reaction solution of preparation, and this mixture continued stirring 4 hours at 600rpm.3) curing of Ning Ju prevention and capsule wall is handled
With 0.5 gram trim,ethylchlorosilane under 600rpm stirs 50 ℃ of adding methods 2) in the solution of preparation, then, immediately with the adding of 1 gram, 20% aqueous sodium hydroxide.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is evaporated, and remaining mixture further is heated under 150rpm stirs refluxed 6 hours.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.Comparative example 1 is being contained the 2-ethylhexyl to Methoxycinnamate and having by methoxyl group (ethyoxyl) n-pro-pyl dihydroxy methyl-monosilane, the copolymerization of MTES and phenyl triethoxysilane is contracted in the preparation of microcapsules of the capsule wall that thing forms, and polymerization is carrying out at the interface between a kind of continuous phase and core material.1) preparation of capsule wall
Be equipped with mechanical agitator through 12cm with one in having, have 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 90 gram water of packing in advance, siloxanes that 10 gram polyoxyethylene are modified (KF-354A (trade name) is by Shin-EtsuSilicone Co., and Ltd makes) and 0.2 gram, 18% hydrochloric acid.The mixture of 4.4 gram MTESs and 1.2 gram phenyl triethoxysilanes is dropwise added wherein and stirs at 50 ℃ from addition funnel.This mixture is continued to stir 6 hours at 50 ℃, then, add 5.4 gram 2-ethylhexyls and stir at 600rpm to Methoxycinnamate and with reaction solution.This mixture is continued to stir 4 hours at 600rpm, then, dropwise add 1.9 gram 4% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.Afterwards, this mixture was stirred 1 hour at 50 ℃.2) curing of Ning Ju prevention and capsule wall is handled
With 3 gram trim,ethylchlorosilanes under 600rpm stirs 50 ℃ of adding methods 1) in the solution of preparation, then, immediately with 5.6 gram 5N aqueous sodium hydroxide addings.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is evaporated, and remaining mixture further is heated under 150rpm stirs refluxed 6 hours.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of product.A kind of adhesion material that sticks on the reaction utensil wall, and only will approximately separate with the oil of the 2-ethylhexyl that adds to the identical amount of Methoxycinnamate.
Embodiment 1A contains the 2-ethylhexyl to Methoxycinnamate and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is the hydrolysate by methoxyl group (ethyoxyl) n-pro-pyl dihydroxy methyl-monosilane, and the copolymer of MTES and phenyl triethoxysilane is formed
The microcapsules that contain core material with the method preparation identical with embodiment 1, just the siloxanes of modifying with the polyoxyethylene of 10 grams is replaced the poly-ethoxy propyl trimethoxy silicane of 3 grams (by Shin-EtsuSilicone Co., the KBM-641 that Ltd makes), 4% sodium hydrate aqueous solution, the 2-ethylhexyl is to Methoxycinnamate, the amount of trim,ethylchlorosilane and 20% sodium hydrate aqueous solution becomes 97 grams respectively, 4.2 gram, 1.7 gram, 4.0 gram, 1.0 and 1.8 grams, and the temperature that the pH value is controlled under the 7.0 back stirring conditions becomes 20 ℃.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 10 μ m, aqueous dispersion 107 gram that is mainly the capsule of 1 to 2 μ m is removed component 14.0 grams behind the moisture
In embodiment 1, the microcapsules that contain core material are that KF-354A (trade name) prepares as the compound that carries hydrophilic radical (A) by the siloxanes that uses polytrimethylene ether to modify, this material hydrolysis is obtained a kind of prepolymer, add core material and carry out emulsification.But, when a kind of polymer is preparation at the interface between core material and continuous phase, as described in comparative example 1, do not have to form the microcapsules that contain core material, and polymer is separated from core material.In embodiment 1A, though a kind of trialkoxy silane that carries the polytrimethylene ether group, KBK-641 (trade name) is used as the compound (A) that carries hydrophilic radical, has prepared the microcapsules that contain core material as embodiment 1.
The microcapsules that contain core material that obtain among the embodiment 1A are tested, whether broken in above-mentioned method of testing 1 to observe its capsule.Do not find that capsule has fragmentation.
Embodiment 2 contains the 2-ethylhexyl to Methoxycinnamate and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen of propyl group hydrolysis, the copolymer of MTES and phenyl triethoxysilane form 1) preparation of the prepolymer of capsule wall
One is had interior through 12cm, be equipped with mechanical agitator, having 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 135 gram water of packing in advance, 15 gram N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen (number-average molecular weight of collagen is 2000) and 3.6 of propyl group hydrolysis restrains 18% hydrochloric acid.The mixture of 45.9 gram MTESs and 12.4 gram phenyl triethoxysilanes is dropwise added wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 6 hours at 50 ℃, then, dropwise add 2.9 gram 25% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of core material and emulsification
With 389 gram 2-ethylhexyls to Methoxycinnamate adding method 1 under 600rpm stirs) in the reaction solution of preparation, and this mixture continued stirring 4 hours at 600rpm.3) micronize
With method 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.4) curing of Ning Ju prevention and capsule wall is handled
With 3.0 gram trim,ethylchlorosilanes under 600rpm stirs 50 ℃ of adding methods 2) in the reaction utensil of original use of solution of preparation, then, immediately with the adding of 4.4 grams, 25% aqueous sodium hydroxide.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is evaporated, and remaining mixture further is heated under 150rpm stirs refluxed 2 hours.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1-5, obtained following result.Have diameter 0.3 to 5 μ m, it is 4% to the amount of Methoxycinnamate that aqueous dispersion 850 gram that is mainly the capsule of 1 to 2 μ m is removed 2-ethylhexyl free in the component 50 gram dispersions behind the moisture.The 2-ethylhexyl that contains in the capsule is 84% to the amount of Methoxycinnamate.
Then, by oneself removes Methoxycinnamate with 2-ethyl free in the dispersion with hexane wash, under pure condition, obtain the microcapsules of a kind of 2-of containing ethylhexyl to cinnamate.When method 4) cohesion prevent handle with the curing of capsule wall in the adding of methyl trichlorosilane and a series of neutralisation treatment subsequently when being left out, detecting by an unaided eye does not have different with present embodiment, but, find the inter-adhesive of microcapsules and part cohesion with microscopic examination.In the present embodiment, do not see this cohesion.
The microcapsules that contain core material that obtain among the embodiment 2 are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.
Embodiment 2A contains the 2-ethylhexyl to the mixture of Methoxycinnamate and the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane; this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen of propyl group hydrolysis, the copolymer of MTES and phenyl triethoxysilane is formed
Contain the microcapsules of core material with the method preparation identical with embodiment 2, just with the 2-ethylhexyls of 389 grams to Methoxycinnamate with in advance the 19.5 gram 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethanes being dissolved in 78.2 gram 2-ethylhexyls to Methoxycinnamate and dropwise add 2.9 gram 25% sodium hydrate aqueous solutions and replace at 20 ℃ of mixtures that stir and obtain subsequently.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 315 gram that is mainly the capsule of 1 to 2 μ m is removed the component 42.3% behind the moisture
As mentioned above, in present embodiment 2A, except the 2-ethylhexyl to Methoxycinnamate, can be combined in the microcapsules simultaneously as the 4-tert-butyl group-the 4 '-methoxy dibenzoyl methylmethane of second kind of core material.
The microcapsules that contain core material that obtain among the embodiment 2A are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.
Embodiment 2B contains the 2-ethylhexyl to Methoxycinnamate and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] wheat gluten of propyl group hydrolysis, the copolymer of MTES and phenyl triethoxysilane form 2) preparation of the prepolymer of capsule wall
One is had interior through 12cm, be equipped with mechanical agitator, having 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 283 gram water of packing in advance, 16.8 gram N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] wheat gluten (number-average molecular weight of the wheat gluten of this hydrolysis is 400) and 4.5 of propyl group hydrolysis restrains 20% sodium hydrate aqueous solution.The mixture of 24 gram MTESs and 3.2 gram phenyl triethoxysilanes is dropwise added and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 6 hours at 50 ℃, then, dropwise add 4.1 gram 18% hydrochloric acid and stirring, control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of core material and emulsification
With 12.3 gram 2-ethylhexyls to Methoxycinnamate adding method 1 under 600rpm stirs) in the reaction solution of preparation, and this mixture continued stirring 4 hours at 600rpm.3) micronize
With method 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.4) curing of Ning Ju prevention and capsule wall is handled
With 1.2 gram trim,ethylchlorosilanes under 600rpm stirs 50 ℃ of adding methods 3) in the reaction utensil of original use of solution of preparation, then, with the adding of 1.4 grams, 20% aqueous sodium hydroxide, the pH value is controlled at 5.5 immediately.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is evaporated, and remaining mixture further is heated under 150rpm stirs refluxed 2 hours.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 595 gram that is mainly the capsule of 1 to 2 μ m is removed the component 11% behind the moisture
As mentioned above, in present embodiment 2B, be to use the compound of forming by the wheat gluten of hydrolysis that carries hydrophilic radical (A) to prepare the microcapsules that contain core material.The hydrolysis of compound (A) is carried out under alkali condition.The comparative example 2
Use step and the component identical with embodiment 2B, just the hydrolysis of silane is carried out at acid ph value, rather than carries out in the alkaline pH value as embodiment 2B.A large amount of cohesive materials that sticks to the reaction utensil inwall occurred, the preparation of microcapsules can't be carried out.
Embodiment 2C contains the 2-ethylhexyl to Methoxycinnamate and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] soybean protein of propyl group hydrolysis, the copolymer of MTES and phenyl triethoxysilane form 1) preparation of the prepolymer of capsule wall
Be equipped with mechanical agitator through 12cm with one in having, has a upper top cover that is equipped with an addition funnel and a reflux condenser, 2 liters of round bottom column glass reactors, the 177 gram water of packing in advance, 9.3 gram N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] soybean protein (number-average molecular weight of the soybean protein of this hydrolysis is about 350) and 3.5 of propyl group hydrolysis restrains 20% sodium hydrate aqueous solution.The mixture of 10 gram MTESs and 2.7 gram phenyl triethoxysilanes is dropwise added wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 6 hours at 50 ℃, then, dropwise add 3.2 gram 18% hydrochloric acid and stirring, control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of core material and emulsification
With 6.5 gram 2-ethylhexyls to Methoxycinnamate adding method 1 under 600rpm stirs) in the reaction solution of preparation, and this mixture continued stirring 4 hours at 600rpm.3) micronize
With method 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.4) curing of Ning Ju prevention and capsule wall is handled
With 2.4 gram trim,ethylchlorosilanes under 600rpm stirs 50 ℃ of adding methods 3) in the reaction utensil of original use of solution of preparation, then, with the adding of 1.2 grams, 20% aqueous sodium hydroxide, make the pH value be controlled in 5.5 immediately.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is evaporated, and remaining mixture further is heated under 150rpm stirs refluxed 6 hours.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 360 gram that is mainly the capsule of 1 to 2 μ m is removed the component 7.6% behind the moisture
As mentioned above, be to use the compound of forming by the soybean protein of hydrolysis that carries hydrophilic radical (A) to prepare the microcapsules that contain core material at present embodiment 2C.The hydrolysis of compound (A) is carried out under alkali condition.
The microcapsules that contain core material that obtain among the embodiment 2C are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.
Embodiment 2D
The microcapsules that contain core material with the method preparation identical with embodiment 2, the hexyl trimethoxy silane that only has been to use 8.7 grams is (by Shin-Etsu Silicone Co., Ltd. the KBM of Sheng Chaning), rather than phenyl triethoxysilane, MTES and 2-ethylhexyl are become 38.3 grams and 87.4 grams by this respectively to the amount of Methoxycinnamate, and, do not carry out with the processing of methyl trichlorosilane.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 507 gram that is mainly the capsule of 1 to 2 μ m is removed the component 23.6% behind the moisture
The microcapsules that contain core material that obtain among the embodiment 2D are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.
Embodiment 2E
The microcapsules that contain core material with the method preparation identical with embodiment 2, the decyl trimethoxy silane that only has been to use 6.7 grams is (by Shin-Etsu Silicone Co., Ltd. the KBM-3103C of Sheng Chaning), rather than phenyl triethoxysilane, MTES and 2-ethylhexyl are changed into 30.0 grams and 6.7 respectively to the amount of Methoxycinnamate and restrain, and do not use the processing of methyl trichlorosilane.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 300 gram that is mainly the capsule of 1 to 2 μ m is removed the component 11.9% behind the moisture
In embodiment 2D and 2E, be different among the embodiment 2 employedly even have the silicol of hydrophobic grouping, also prepared the microcapsules that contain core material.
The microcapsules that contain core material that obtain among the embodiment 2E are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.Embodiment 2F
The microcapsules that contain core material with the method preparation identical with embodiment 2, only be to use N-[2-hydroxyl-3-(3 '-dihydroxymethyl silicyl) propoxyl group of 15 grams] collagen of propyl group hydrolysis, the number-average molecular weight of its peptide moiety is about 2000, rather than N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen of propyl group hydrolysis.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 687 gram that is mainly the capsule of 1 to 2 μ m is removed the component 54.3% behind the moisture
As mentioned above, in embodiment 2F, even used N-[2-hydroxyl-3-(3 '-dihydroxy silicyl) propoxyl group] collagen of propyl group hydrolysis, rather than N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen of propyl group hydrolysis, also prepared the microcapsules that contain core material.
The microcapsules that contain core material that obtain among the embodiment 2F are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.
Embodiment 2G
The microcapsules that contain core material with the method preparation identical with embodiment 2, only be to use N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group of 15 grams] collagen of propyl group hydrolysis, rather than N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen of propyl group hydrolysis, the stearoyl-oxy propyl trimethoxy silicane that has used 22.8 grams is (by Shin-Etsu Silicone Co., Ltd. the KBM-6000 of Sheng Chaning), rather than phenyl triethoxysilane, and with the 2-ethylhexyl to the amount of Methoxycinnamate change into 60 the gram.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, it is 6% to the amount of Methoxycinnamate that aqueous dispersion 400 gram that is mainly the capsule of 1 to 2 μ m is removed 2-ethylhexyl free in component 25% dispersion behind the moisture.The 2-ethylhexyl that contains in the capsule is 40% to the amount of Methoxycinnamate.
As mentioned above, in embodiment 2G, be different from employed hydroxyl silane among the embodiment 2F, also prepared the microcapsules that contain core material with hydrophobic grouping even used.
The microcapsules that contain core material that obtain among the embodiment 2G are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.
Embodiment 2H
The microcapsules that contain core material with the method preparation identical with embodiment 2, just the MTESs of 45.9 grams are replaced by the MTESs of the dimethyldiethoxysilanes of 19.1 grams and 23.0 grams, and the 2-ethylhexyl is changed into 97.7 grams to the amount of Methoxycinnamate.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 460 gram that is mainly the capsule of 1 to 2 μ m is removed the component 27.1% behind the moisture
As mentioned above, in embodiment 2H,, the microcapsules that contain core material have also been prepared even the part of ortho-siliformic acid is replaced by dihydroxy silane.
The microcapsules that contain core material that obtain among the embodiment 2H are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.
Embodiment 2I
Prepare the microcapsules that contain core material with the method identical, only be to use the octyl group methyl cyclotetrasiloxanes of 9.6 grams with embodiment 2H, rather than dimethyldiethoxysilane.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 425 gram that is mainly the capsule of 1 to 2 μ m is removed the component 25.1% behind the moisture
As mentioned above, in embodiment 2I,, the microcapsules that contain core material have also been prepared even the alkoxy silane that uses among the embodiment 2H is replaced by cyclosiloxane.
The microcapsules that contain core material that obtain among the embodiment 2I are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.
Embodiment 2J
Contain the microcapsules of core material with the method identical preparation, only be to use the Emerest 2310s of 16.2 grams and the rosin acids of 4.1 grams, rather than the 2-ethylhexyl is to Methoxycinnamate, and do not carry out the processing of homogeneous mixer with embodiment 2F.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 1 to 100 μ m, aqueous dispersion 226 gram that is mainly the capsule of 10 to 50 μ m is removed the component 30% behind the moisture
As mentioned above, in embodiment 2J, by rosin acid being dissolved in the microcapsules that obtained containing rosin acid in the Emerest 2310, rosin acid at room temperature is a kind of hard resin.
The microcapsules that contain core material that obtain among the embodiment 2J are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule, find to have about 8 μ m of granular size or bigger capsule fragmentation.Specifically, have under the condition of 8 to 15 μ m granular sizes brokenly at capsule, observe oozing out of core material, and observe capsule wall and core material respectively ringwise, form a figure of eight.But, observe seldom fragmentation for having less than the capsule of 8 μ m granular sizes.Embodiment 2K
The microcapsules that contain core material with the method preparation identical with embodiment 2F, the peptide moiety number-average molecular weights that only have been to use 15 grams are N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group of about 1000] the silk fibroin of propyl group hydrolysis, rather than N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] collagen of propyl group hydrolysis.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 1 to 100 μ m, aqueous dispersion 375 gram that is mainly the capsule of 10 to 50 μ m is removed the component 20% behind the moisture
As mentioned above, in embodiment 2K,, the microcapsules of core material have still been obtained containing even used silk fibroin as hydrophilic radical with hydrolysis.
The microcapsules that contain core material that obtain among the embodiment 2K are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule, find to have about 8 μ m of granular size or bigger capsule fragmentation.Specifically, have under the condition of 8 to 15 μ m granular sizes brokenly at capsule, observe oozing out of core material, and observe capsule wall and core material respectively ringwise, form a figure of eight.But, observe seldom fragmentation for having less than the capsule of 8 μ m granular sizes.
Embodiment 2L
The microcapsules that contain core material with the method preparation identical with embodiment 2F, only be to use the castor bean oil of 10.5 grams, rather than the 2-ethylhexyl is to Methoxycinnamate, and the amount of MTES and phenyl triethoxysilane is changed into 38.2 grams and 10.3 respectively restrains.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 300 gram that is mainly the capsule of 1 to 2 μ m is removed the component 15% behind the moisture
As mentioned above, in embodiment 2L, obtained a kind of microcapsules that contain castor bean oil, castor bean oil at room temperature is a kind of viscous liquid.
The microcapsules that contain core material that obtain among the embodiment 2L are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not observe the capsule fragmentation.
Embodiment 2M
The microcapsules that contain core material with the method preparation identical with embodiment 2, just respectively the amount of MTES and phenyl triethoxysilane is changed into 17.0 grams and 4.6 grams, and with 0.5 gram octadecyl dimethyl-(3-trimethoxy-silylpropyl) ammonium chloride adding when adding them, and the peptide moieties that use 16.7 grams have N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group of about 2000 number-average molecular weight] collagen of propyl group hydrolysis, rather than N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen of propyl group hydrolysis.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 370 gram that is mainly the capsule of 1 to 2 μ m is removed the component 11.9% behind the moisture
As mentioned above, in embodiment 2M,, the microcapsules that contain core material have also been prepared even used compound with cation group monomer component as the organopolysiloxane that forms capsule wall.
The microcapsules that contain core material that obtain among the embodiment 2M are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.
Embodiment 2N
Contain the microcapsules of core material with the method preparation identical, only be to use the abienol palmitates of 4.6 grams and the Witconol 2310s of 4.6 grams, rather than the 2-ethylhexyl is to Methoxycinnamate with embodiment 2.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1-5, obtained following result.Have diameter 0.3 to 5 μ m, the amount that aqueous dispersion 310 gram that is mainly the capsule of 1 to 2 μ m is removed abienol palmitate free in component 14.8% dispersion behind the moisture is 0.1%.The amount of the abienol palmitate that contains in the capsule is 9.9%.
As mentioned above, in embodiment 2N, by the abienol palmitate is dissolved in the microcapsules that Witconol 2310 has obtained containing the abienol palmitate, it at room temperature is a viscosity.
The microcapsules that contain core material that obtain among the embodiment 2M are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.
Embodiment 20
Contain the microcapsules of core material with the method preparation identical, only be to use the tocopherol acetates of 4.6 grams and the Emerest 2310s of 4.6 grams, rather than the 2-ethylhexyl is to Methoxycinnamate with embodiment 2.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 10 μ m, aqueous dispersion 324 gram that is mainly the capsule of 2 to 7 μ m is removed the component 14.3% behind the moisture
As mentioned above, in embodiment 20, by tocopherol acetate being dissolved in the microcapsules that obtained containing tocopherol acetate in the Emerest 2310, tocopherol is a kind of derivative of vitamin E.
The microcapsules that contain core material that obtain among the embodiment 20 are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule, find to have about 8 μ m of granular size or bigger capsule fragmentation.Specifically, have under the condition of 8 to 10 μ m granular sizes brokenly at capsule, observe oozing out of core material, and observe capsule wall and core material respectively ringwise, form a figure of eight.But, observe seldom fragmentation for having less than the capsule of 8 μ m granular sizes.
Embodiment 3
The microcapsules that contain core material with the method preparation identical with embodiment 2, just before the processing of the trim,ethylchlorosilane in embodiment 2,18% hydrochloric acid with 3.0 grams add in the reaction solutions in advance, and add 10.6 gram octadecyl dimethyl-(3-trimethoxy-silylpropyl) ammonium chlorides and 2.4 grams, 25% sodium hydrate aqueous solution is used for neutralization.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 820 gram that is mainly the capsule of 1 to 2 μ m is removed the component 61.1% behind the moisture
In the preparation method of the microcapsules that contain core material of embodiment 3, when octadecyl dimethyl-adding of (3-trimethoxy-silylpropyl) ammonium chloride and the adding of a series of neutralisation treatment subsequently and methyl trichlorosilane and a series of neutralisation treatment subsequently are deleted, detecting by an unaided eye does not have different with present embodiment, but, find the inter-adhesive of microcapsules and part cohesion with microscopic examination.In present embodiment 3, do not see this cohesion.
The microcapsules that contain core material that obtain among the embodiment 3 are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.
Embodiment 4 contains the 2-ethylhexyl to Methoxycinnamate and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] collagen of propyl group hydrolysis, the copolymerization of MTES and phenyl triethoxysilane contract that thing forms 1) preparation of the prepolymer of capsule wall
Be equipped with mechanical agitator through 12cm with one in having, has a upper top cover that is equipped with an addition funnel and a reflux condenser, 2 liters of round bottom column glass reactors, the 405 gram water of packing in advance, 45 gram N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] collagen (number-average molecular weight of collagen is about 2000) and 10.8 of propyl group hydrolysis restrains 18% hydrochloric acid.The mixture of 137.7 gram MTESs and 37.1 gram phenyl triethoxysilanes is dropwise added wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 6 hours at 50 ℃, then, dropwise add 8.7 gram 25% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of core material and emulsification
126.9 gram 2-ethylhexyls are added in the reaction solution for preparing in the step 1) under 600rpm stirs Methoxycinnamate, and this mixture is continued to stir 4 hours at 600rpm.3) micronize
With step 2) in half reaction solution of pact of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.And, with the solution after handling with a microstream machine (microfluidizer) [M110-E/H (trade name) is by the Microfulidex.International.Corporation manufacturing] at 50 ℃ and 1500kg/cm 2Condition under handle 5 times so that component particlesization.4) curing of Ning Ju prevention and capsule wall is handled
With 1.0 gram trim,ethylchlorosilanes under 600rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 3), then, immediately 1.48 grams, 25% aqueous sodium hydroxide is added.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is evaporated, and remaining mixture further is heated under 150rpm stirs refluxed 6 hours.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 6, obtained following result.In embodiment 4, because micronize uses the microstream machine to carry out as mentioned above, the resulting microcapsules that contain core material are in the scope of nanocapsule.Thereby, about the microcapsules that contain core material among the embodiment 4, the distribution of its granular size can not be measured with the use observation by light microscope of analytical method 5, thereby the measurement of particle size distribution is to be undertaken by the SALD-2000 in the operational analysis method 6 (trade name).Have diameter 0.3 to 1 μ m, aqueous dispersion 250 gram that is mainly the capsule of 0.4 to 0.7 μ m is removed component 20 grams behind the moisture
The microcapsules that contain core material that obtain among the embodiment 4 are tested, whether broken with observation its capsule in above-mentioned method of testing 1.Do not find the capsule fragmentation.
Embodiment 4A
Contain the microcapsules of core material with the method preparation identical, just in step " 3) micronize ", use embodiment 4 steps 2 with embodiment 4) in preparation reaction solution remaining half, and do not carry out the micronize of microstream machine.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 6, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 250 gram that is mainly the capsule of 1 to 2 μ m is removed the component 20% behind the moisture
The microcapsules that contain core material that obtain among the embodiment 4A are tested, whether broken with observation its capsule in above-mentioned method of testing 1.Do not find the capsule fragmentation.
Embodiment 51) preparation of the prepolymer of capsule wall
Be equipped with mechanical agitator through 12cm with one in having, has a upper top cover that is equipped with an addition funnel and a reflux condenser, 2 liters of round bottom column glass reactors, the 210 gram water of packing in advance, 90 gram N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] collagen (number-average molecular weight of the collagen of this hydrolysis is about 2000) and 21.8 of propyl group hydrolysis restrains 18% hydrochloric acid.The restrain oneself mixture of ethyl triethoxy silicane alkane of 45.9 gram MTESs and 10.5 is dropwise added wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 6 hours at 50 ℃, then, dropwise add 22 gram 25% sodium hydrate aqueous solutions and stir control pH value to 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of core material and emulsification
389 gram 2-ethylhexyls are added in the reaction solution for preparing in the step 1) under 600rpm stirs Methoxycinnamate, and this mixture is continued to stir 4 hours at 600rpm.3) micronize
With step 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.4) curing of capsule wall is handled
With the solution for preparing in the step 3) in the original reaction utensil that uses, further be heated to backflow, stirred 2 hours at 150rpm simultaneously.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5, obtained following result.Have diameter 0.3 to 5 μ m, be mainly the aqueous dispersion 5 of the capsule of 1 to 2 μ m) spray-drying
The part of the product that obtains in the step 4) is carried out spray-drying obtain a kind of powder.This powder of 0.1 gram is added in the 10m1 water, and this mixture is disperseed by stirring fully, observe according to analytical method 5, with observe with spray-drying before identical observed result.
Embodiment 5A contains the freeze drying processing of the microcapsules of core material
With embodiment 4) part of the product that obtains in the step 4) is carried out freeze drying, rather than spray drying treatment, obtains a kind of powder.This powder of 0.1 gram is added in the 10ml water, fully stirs to make to mix and disperse, observe according to analytical method 5, with observe with spray-drying before viewed identical result.Embodiment 6 uses the whizzer purifying to contain the microcapsules of core material
The microcapsules that contain core material with the method preparation identical with embodiment 2, the hexyl trimethoxy silane of 8.7 grams rather than the phenyl triethoxysilane among the embodiment 2 only have been to use, used N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group of 15 grams] collagen (number-average molecular weight of the collagen of hydrolysis is about 2000) of propyl group hydrolysis, rather than N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen of propyl group hydrolysis, used the MTES of 38.3 grams, 35.3 the 2-ethylhexyl of gram is to Methoxycinnamate, and do not use the processing of methyl trichlorosilane.
The microcapsules that contain core material that obtain are carried out centrifugal (4000rpm, 10 minutes), remove supernatant, then, in precipitation, add the water of 2 to 5 times of volumes and suspension again.Then, carry out centrifugal (4000rpm, 10 minutes) again.With this operation triplicate, obtain having the microcapsules that contain core material of the concentration of control.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, aqueous dispersion 150 gram that is mainly the capsule of 1 to 2 μ m remove component 44% behind the moisture before centrifugation is handled in the dispersion NaCl content be 0.34%.NaCl content is 0.02% in the dispersion after centrifugation is handled.
As mentioned above, observe by centrifugation and handle, the content of NaCl reduces.
The microcapsules that contain core material of embodiment 6A by obtaining among the hyperfiltration purifying embodiment 2F
The part of the microcapsules that contain core material that obtain among the embodiment 2F is carried out hyperfiltration, then, in remaining material, add the water of 2 to 5 times of volumes and suspend again.Then, carry out hyperfiltration again.With this operation triplicate, obtain having the microcapsules that contain core material of the concentration of control.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 1 to 10 μ m, aqueous dispersion 200 gram that is mainly the capsule of 3 to 7 μ m remove component 20% behind the moisture before hyperfiltration is handled in the dispersion NaCl content be 0.38%.NaCl content is 0.03% in the dispersion after hyperfiltration is handled.
As mentioned above, observe by hyperfiltration and handle, the content of NaCl reduces.
The preparation of the microcapsules with a kind of capsule wall of making by organopolysiloxane of embodiment 7W/O type, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] hydrolysate of the collagen of propyl group hydrolysis, the copolymerization of dimethyldiethoxysilane and hexyl trimethoxy silane contract that thing forms 1) preparation of the prepolymer of capsule wall
Be equipped with mechanical agitator through 12cm with one in having, has a upper top cover that is equipped with an addition funnel and a reflux condenser, 2 liters of round bottom column glass reactors, the 131 gram water of packing in advance, 9 gram N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] collagen (number-average molecular weight of collagen is about 400) and 8 of propyl group hydrolysis restrains 18% hydrochloric acid.The restrain oneself mixture of ethyl triethoxy silicane alkane of 20.6 gram dimethyldiethoxysilanes and 57.3 is dropwise added wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 6 hours at 50 ℃, then, dropwise add 6.3 gram 25% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of oil phase with put upside down mutually and emulsification
150 gram toluene are added in the reaction solution for preparing in the step 1) under 600rpm stirs, and this mixture is continued to stir 4 hours at 600rpm.3) micronize
With step 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.4) curing of Ning Ju prevention and capsule wall is handled
With 3.0 gram trim,ethylchlorosilanes under 600rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 3), then, immediately 4.4 grams, 25% aqueous sodium hydroxide is added.The temperature of reaction solution is increased to backflow gradually, and 85% moisture is evaporated.Remaining mixture under stirring, 150rpm further is heated to backflow 6 hours.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5, obtained following result.Have diameter 0.3 to 5 μ m, be mainly toluene dispersion 241 grams of the capsule of 1 to 2 μ m
This dispersion is placed on the glass plate, will wipes off, the formation of sight glass plate surface water droplet by the film that toluene evaporates forms.This dispersion is being mixed with water, then, it is being left standstill the separation of observing two aspects.Capsules disperse is in toluene layer.Find from this observed result, can prepare a kind of microcapsules that contain water with hydrophobic surface.
Embodiment 7A
Contain the microcapsules of core material with the method preparation identical with embodiment 7, just the amount with the hexyl trimethoxy silane among the embodiment 7 changes over 86.0 grams from 573.3 grams; Do not use dimethyldiethoxysilane; In step 2) oil phase add and put upside down mutually with emulsification in, used 160 Witconol 2310s that restrain, rather than toluene; Prevent to condense in step 4) and handle, used equimolar potassium hydroxide with the curing of capsule wall, rather than NaOH; And when being sneaked into Witconol 2310 again, 35% potassium chloride solution of 30.8 grams adds.
The dispersion of the microcapsules that contain core material that obtain among the embodiment 7A is analyzed according to analytical method 5, obtained following result.In Witconol 2310, have diameter 0.3 to 5 μ m, be mainly dispersion 280 grams of the capsule of 1 to 2 μ m
After the dispersion among the embodiment 7A being mixed with water and leave standstill, mixture is separated into two-layer.The microcapsules that contain core material are scattered in the Witconol 2310 layer.Like this, use dialkoxy silicane useless and prepared the microcapsules that contain core material of w/o type in embodiment 7A.
The microcapsules that contain core material that obtain among the embodiment 7A are tested, whether broken with observation its capsule in above-mentioned method of testing 1.Do not find the capsule fragmentation.
Embodiment 7B
The microcapsules that contain core material with the method preparation identical with embodiment 7, the hexyl trimethoxy silane of 71.6 grams and the phenyl triethoxysilane of 16.7 grams only have been to use, rather than dimethyldiethoxysilane among the embodiment 7 and hexyl trimethoxy silane, the 36%L-aqueous ascorbic acid of 34.4 grams is added when adding toluene, before handling, 50% moisture distillation is removed with the homogeneous mixer.
The dispersion of the microcapsules that contain core material that obtain among the embodiment 7B is analyzed according to analytical method 5, obtained following result.Have diameter 0.3 to 5 μ m, be mainly toluene dispersion 216 grams of the capsule of 1 to 2 μ m
The dispersion that obtains among the embodiment 7B is placed on the glass plate, will wipes off, the formation of sight glass plate surface water droplet by the film that toluene evaporates forms.This dispersion is being mixed with water, then, it is being left standstill the separation of observing two aspects.Capsules disperse is in toluene layer.
The microcapsules that contain core material that obtain among the embodiment 7B are tested, whether broken with observation its capsule in above-mentioned method of testing 1.Do not find the capsule fragmentation.
Embodiment 7C
The microcapsules that contain core material with the method preparation identical with embodiment 7, only be to use the diisobutyl adipate ester of 235 grams, rather than the toluene among the embodiment 7,10%2-phosphoric acid-L-ascorbic acid base magnesium the aqueous solution that when adding the diisobutyl adipate ester, adds 106 grams, with product by the centrifugation purifying, and handle according to embodiment 6 usefulness homogeneous mixers, then, nearly all water under reduced pressure is distilled at 40 ℃ and removes, then, remaining moisture is distilled by heating under normal pressure and removes.
The dispersion of the microcapsules that contain core material that obtain among the embodiment 7C is analyzed according to analytical method 5, obtained following result.Have diameter 0.3 to 5 μ m, be mainly toluene dispersion 324 grams of the capsule of 1 to 2 μ m
The 200ml n-hexane is added in the dispersion that obtains among the embodiment 7C, with the extracting of 100ml water, and with ultraviolet. visible spectrophotometer UV-1600 measures (being made by Shimadzu Corp.), finds that the 10%2-phosphoric acid-L-ascorbyl magnesium that adds is released.And, in the chloroform of 50ml being added the 2 gram dispersions that embodiment 7C obtains, and with mixture when stirring 1 hour for 50 ℃, capsules break.It is used the extracting of 100ml water, and measure, find that 2-phosphoric acid-L-ascorbyl magnesium of 95% is recovered with ultraviolet spectrophotometer.Hence one can see that for the result, and uptake rate is 85%.Moreover, can find out obviously that free 2-phosphoric acid-L-ascorbyl magnesium can be removed by water extracting and washing.
After the dispersion among the embodiment 7C being mixed with water and leave standstill, mixture is separated into two-layer.The microcapsules that contain core material are scattered in the diisobutyl adipate ester layer.
The microcapsules that contain core material that obtain among the embodiment 7B are tested, whether broken with observation its capsule in above-mentioned method of testing 1.Do not find the capsule fragmentation.
Embodiment 8 has a kind of preparation of microcapsules of liquid perfluor ether of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] hydrolysate of the collagen of propyl group hydrolysis, tetraethoxysilane and C 8F 17CH 2CH 2Si (OCH 3) 3The copolymerization of (by Shin-Etsu Silicone Co., the KBM-7803 that Ltd. produces) contract that thing forms 1) preparation of the prepolymer of capsule wall
Be equipped with mechanical agitator through 12cm with one in having, has a upper top cover that is equipped with an addition funnel and a reflux condenser, 2 liters of round bottom column glass reactors, the 90 gram water of packing in advance, 10 gram N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] collagen (number-average molecular weight of the collagen of hydrolysis is about 2000) and 2.4 of propyl group hydrolysis restrains 18% hydrochloric acid.With 19.0 gram tetraethoxysilanes and 3.2 gram C 8F 17CH 2CH 2Si (OCH 3) 3The mixture of (by Shin-Etsu Silicone Co., the KBM-7803 that Ltd. produces) dropwise adds wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 12 hours at 50 ℃, then, dropwise add 100 gram 0.6% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of liquid perfluor ether and emulsification
With the perfluor ether of 6.8 grams, (by Moteflous Co., Ltd makes mean molecule quantity 6250, CF to Fomblin HC/R 3[(OCF (CF 3) CF 2) n (OCF 2) m] OCF 3, n/m=20-40) with 3.2 gram C 8F 17CH 2CH 2Si (OCH 3) 3The mixture of (by Shin-Etsu Silicone Co., the KBM-7803 that Ltd. produces) adds in the reaction solution for preparing in the step 1) under 500rpm stirs, and this mixture is continued to stir 4 hours at 500rpm.3) micronize
With step 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.4) curing of Ning Ju prevention and capsule wall is handled
With 1.23 gram trim,ethylchlorosilanes under 500rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 3), then, immediately 1.2 grams, 25% aqueous sodium hydroxide is added.The temperature of reaction solution under stirring, 500rpm is increased to backflow gradually at 50 ℃.And reaction solution continued to be heated under 150rpm stirs refluxed 6 hours.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Aqueous dispersion 110 gram with capsule of diameter 5 to the 10 μ m component 17.1% outside the branch that dewaters
This dispersion can be frozen drying.
The microcapsules that contain core material that obtain among the embodiment 8 are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule, find to have about 8 μ m of granular size or bigger capsule fragmentation.Specifically, have under the condition of 8 to 10 μ m granular sizes brokenly at capsule, observe oozing out of core material, and observe capsule wall and core material respectively ringwise, form a figure of eight.But, observe seldom fragmentation for having less than the capsule of 8 μ m granular sizes.The comparative example 31) preparation of the prepolymer of capsule wall
One is had interior through 12cm, be equipped with mechanical agitator, having 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 90 gram water of packing in advance, 10 gram N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] collagen (number-average molecular weight of the collagen of hydrolysis is about 2000) and 2.4 of propyl group hydrolysis restrains 18% hydrochloric acid.With 19.0 gram tetraethoxysilanes and 9.5 gram C 8F 17CH 2CH 2Si (OCH 3) 3The mixture of (by Shin-Etsu Silicone Co., the KBM-7803 that Ltd. produces) dropwise adds wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 12 hours at 50 ℃, then, dropwise add 100 gram 0.6% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of liquid perfluor ether and emulsification
With the perfluor ether of 6.8 grams, (by Moteflous Co., Ltd makes mean molecule quantity 6250, CF to Fomblin HC/R 3[(OCF (CF 3) CF 2) n (OCF 2) m] OCF 3, n/m=20-40) under 500rpm stirs, add in the reaction solution for preparing in the step 1), and this mixture continued to stir 4 hours at 500rpm.3) micronize
With step 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.4) curing of Ning Ju prevention and capsule wall is handled
With 1.23 gram trim,ethylchlorosilanes under 500rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 3), then, immediately 1.2 grams, 25% aqueous sodium hydroxide is added.The temperature of reaction solution under stirring, 500rpm is increased to backflow gradually.And reaction solution continued to be heated under 150rpm stirs refluxed 6 hours.Reaction solution is cooled to room temperature under 150rpm stirs, reaction solution is divided into three phases.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5, obtained following result.Under light microscope, do not see microcapsules.Obtained 260 and restrained the liquid that is divided into three phases.
In this comparative example, do not obtain containing the microcapsules of core material.But, in embodiment 8, wherein, when adding core material, added a part and had perfluoroalkyl group, C 8F 17CH 2CH 2Si (OCH 3) 3The compound of (by Shin-Etsu Silicone Co., the KBM-7803 that Ltd. produces) has obtained containing the microcapsules of liquid perfluor ether.
Embodiment 9 contains the core material of 2-ethylhexyl to Methoxycinnamate, preparation with microcapsules of a kind of capsule wall of making by organopolysiloxane, this organopolysiloxane by the copolymerization of MTES in the aqueous gelatin solution and phenyl triethoxysilane hydrolysate contract that thing forms 2) preparation of the prepolymer of capsule wall
One is had interior through 12cm, be equipped with mechanical agitator, have 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 120 gram water of packing in advance, wherein add 6 gram gelatin as thickener, and mixture is heated to the gelatin dissolving.Solution is cooled to 20 ℃, and viscosity is controlled at 50 milli pascal seconds, add 5.5 grams, 10% hydrochloric acid and make solution be acid, then, add 12.8 gram phenyl triethoxysilanes, and mixture was stirred 30 minutes at 20 ℃.Then, adding 48 restrains MTESs and mixture was stirred 10 minutes, with the dissolving inclusion.2) adding of core material and emulsification
The reaction solution for preparing in the step 1) is controlled at pH7.0 with 25% sodium hydrate aqueous solution, then, the 100 2-ethylhexyls that restrain is added in this reaction solution under 600rpm stirs Methoxycinnamate, obtain a kind of emulsion.3) micronize
With step 2) in the reaction solution of preparation stirred 10 minutes at 20 ℃, and dilute with 60 gram water.Then, handled 60 minutes under 40 ℃ and 6000rpm with a homogeneous mixer, so that component particlesization.4) curing of Ning Ju prevention and capsule wall is handled
1.0 gram hexaethyl disilazines are under agitation added in the emulsion for preparing in the step 3), and the temperature of this emulsion is controlled at 40 ℃, then, 1.0 grams, 25% sodium hydrate aqueous solution is added, the pH value is controlled at 7.0.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is distilled, and reaction solution is under agitation continued to be heated to backflow 6 hours.Reaction solution is cooled to room temperature, obtains a kind of microcapsules that contain core material.5) gelatin and 2-ethylhexyl removing to Methoxycinnamate
With whizzer the dispersion that obtains in the step 4) is separated, abandoning supernatant is washed rest solution by adding 100ml water.This operation is repeated 5 times, and gelatin and free 2-ethylhexyl are removed Methoxycinnamate.At last, in surplus materials, add 100ml water, obtain containing the dispersion of the microcapsules of core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 1 and 5, obtained following result.Has diameter 1 to 30 μ m, aqueous dispersion 200 gram that is mainly the capsule of 10 to the 20 μ m component 50% outside the branch that dewaters
In embodiment 9, contain the core material of 2-ethylhexyl to Methoxycinnamate, microcapsules with a kind of capsule wall of making by organopolysiloxane, this organopolysiloxane is contracted by the hydrolysate copolymerization of MTES, and thing forms, and can prepare with stable manner in gelatin solution.
The microcapsules that contain core material that obtain among the embodiment 9 are tested, whether broken to observe in the above-mentioned method of testing 1 its capsule, find to have about 8 μ m of granular size or bigger capsule fragmentation.Specifically, have under the condition of 8 to 10 μ m granular sizes brokenly at capsule, observe oozing out of core material, and observe capsule wall and core material respectively ringwise, form a figure of eight.But, observe seldom fragmentation for having less than the capsule of 8 μ m granular sizes.Embodiment 10 contains the 2-ethylhexyl to Methoxycinnamate, preparation with microcapsules of a kind of capsule wall of making by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolysate of the collagen of propyl group hydrolysis, the copolymerization of MTES and phenyl triethoxysilane contract that thing forms 1) preparation of the prepolymer of capsule wall
One is had interior through 12cm, be equipped with mechanical agitator, having 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 135 gram water of packing in advance, 15 gram N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen (number-average molecular weight of the collagen of hydrolysis is about 2000) and 3.6 of propyl group hydrolysis restrains 18% hydrochloric acid.Restrain MTESs (by Shin-Etsu Silicone Co. with 45.9, Ltd. the KBE-13 of Sheng Chaning) and the mixtures of 12.4 gram phenyl triethoxysilanes (by Shin-Etsu Silicone Co., the KBM-103 that Ltd. produces) dropwise add wherein and stir at 50 ℃ from addition funnel.
This mixture is continued to stir 6 hours at 50 ℃, then, dropwise add 2.9 gram 25% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.2) adding of core material and emulsification
The 2-ethylhexyl of 389 grams is restrained AZ-6101 (Me to Methoxycinnamate (by the MCX of Nippon Roche K.K. production) and 3.9 3SiO (Me 2SiO) α[MeSi (EtO) O] βSiMe 3, by Nippon Unicar Co., Ltd. produces) mixture under 600rpm stirs, add in the reaction solution for preparing in the step 1), and this mixture is continued to stir 4 hours at 600rpm.3) micronize
With step 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.4) curing of Ning Ju prevention and capsule wall is handled
Restrain trim,ethylchlorosilanes (by Shin-Etsu Silicone Co. with 3.0, Ltd. the KA-31 of Sheng Chaning) under 250rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 3), then, immediately 4.4 grams, 25% aqueous sodium hydroxide is added.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is distilled, and remaining mixture is continued to be heated to backflow 2 hours under 150rpm stirs.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
In dispersion, free 2-ethylhexyl is 1.58% to the amount of Methoxycinnamate.
Embodiment 11
The microcapsules that contain core material with the method preparation identical with embodiment 10, only be to use the 2-ethylhexyl of 389 grams that Methoxycinnamate (by the MCX of Nippon Roche K.K. production) and 3.9 is restrained methylhydrogenpolysi,oxane (by Shin-Etsu Silicone Co., Ltd. the mixture KF-99P of Sheng Chaning), rather than the 2-ethylhexyls of 389 grams are to the AZ-6101 (Me of Methoxycinnamate and 3.9 grams 3SiO (Me 2SiO) α[MeSi (EtO) O] βSiMe 3, by Nippon Unicar Co., Ltd. produces) mixture.
In dispersion, free 2-ethylhexyl is 1.55% to the amount of Methoxycinnamate.
Embodiment 12
The microcapsules that contain core material with the method preparation identical with embodiment 10, only be to use the 2-ethylhexyl of 389 grams that Methoxycinnamate (by the MCX of Nippon Roche K.K. production) and 3.9 is restrained tetraethoxysilanes (by Shin-Etsu Silicone Co., Ltd. the mixture KBE-04 of Sheng Chaning), rather than the 2-ethylhexyls of 389 grams are to the AZ-6101 (Me of Methoxycinnamate and 3.9 grams 3SiO (Me 2SiO) α[MeSi (EtO) O] βSiMe 3, by Nippon Unicar Co., Ltd. produces) mixture.
In dispersion, free 2-ethylhexyl is 1.05% to the amount of Methoxycinnamate.
Embodiment 13 contains the 2-ethylhexyl to Methoxycinnamate and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolysate of the collagen of propyl group hydrolysis, MTES, the copolymerization of phenyl triethoxysilane and tetraethoxysilane contract that thing forms 1) preparation of the prepolymer of capsule wall
One is had interior through 12cm, be equipped with mechanical agitator, having 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 135 gram water of packing in advance, 15 gram N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen (number-average molecular weight of the collagen of hydrolysis is about 2000) and 3.6 of propyl group hydrolysis restrains 18% hydrochloric acid.Restrain MTESs (by Shin-Etsu Silicone Co. with 45.9, Ltd. the KBE-13 of Sheng Chaning), 12.4 the gram phenyl triethoxysilane is (by Shin-Etsu Silicone Co., Ltd. the KBM-103 of Sheng Chaning) and the mixture of the tetraethoxysilanes of 3.6 grams (by Shin-Etsu Silicone Co., the KBE-04 that Ltd. produces) dropwise add wherein and stir at 50 ℃ from addition funnel.
This mixture is continued to stir 6 hours at 50 ℃, then, dropwise add 2.9 gram 25% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.2) adding of core material and emulsification
The 2-ethylhexyl of 389 grams is restrained tetraethoxysilanes (by Shin-Etsu Silicone Co. to Methoxycinnamate (by the MCX of Nippon Roche K.K. production) and 3.9, Ltd. the mixture KBE-04 of Sheng Chaning) adds in the reaction solution for preparing in the step 1) under 600rpm stirs, and this mixture is continued to stir 4 hours at 600rpm.3) micronize
With step 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.4) skin of capsule wall is handled
Restrain methyl trichlorosilanes (by Shin-Etsu Silicone Co. with 1.28, Ltd. the KA-31 of Sheng Chaning) and the MTESs of 6.0 grams (by Shin-Etsu Silicone Co., Ltd. the KBE-13 of Sheng Chaning) under 250rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 3), then, this mixture is continued to stir 1 hour at 250rpm.Then, the adding of 4.05 grams, 25% sodium hydrate aqueous solution is neutralized.In and after 30 minutes, repeat same operation.5) curing of Ning Ju prevention and capsule wall is handled
Restrain trim,ethylchlorosilanes (by Shin-Etsu Silicone Co. with 3.0, Ltd. the KA-31 of Sheng Chaning) under 250rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 4), then, immediately 4.4 grams, 25% aqueous sodium hydroxide is added.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is distilled, and remaining mixture is continued to be heated to backflow 2 hours under 150rpm stirs.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
In dispersion, free 2-ethylhexyl is 0.20% to the amount of Methoxycinnamate.
Embodiment 13A
Contain the microcapsules of core material with the method preparation identical, just do not use tetraethoxysilane with embodiment 13.
In dispersion, free 2-ethylhexyl is 2.36% to the amount of Methoxycinnamate.
Embodiment 14 contains the 2-ethylhexyl to Methoxycinnamate and tetraethyl silane and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolysate of the sericin of propyl group hydrolysis, MTES, the copolymerization of phenyl triethoxysilane and tetraethoxysilane contract that thing forms 1) preparation of the prepolymer of capsule wall
One is had interior through 12cm, be equipped with mechanical agitator, having 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 115.2 gram water of packing in advance, 12.8 gram N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] sericin (number-average molecular weight of the sericin of hydrolysis is about 2000) and 5.0 of propyl group hydrolysis restrains 18% hydrochloric acid.Restrain MTESs (by Shin-Etsu Silicone Co. with 27.0, Ltd. the KBE-13 of Sheng Chaning), 7.3 the mixture of the tetraethoxysilane of gram phenyl triethoxysilane (by Shin-Etsu Siljcone Co., the KBM-103 that Ltd. produces) and 2.1 grams dropwise adds wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 5 hours at 50 ℃, then, dropwise add 4.4 gram 25% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.2) adding of core material and emulsification
The 2-ethylhexyl of 244 grams is restrained tetraethoxysilanes (by Shin-Etsu Silicone Co. to Methoxycinnamate (by the MCX of Nippon Roche K.K. production) and 2.44, Ltd. the mixture KBE-04 of Sheng Chaning) adds being cooled in 20 ℃ the reaction solution of preparing in the step 1) under 700rpm stirs, and this mixture is continued to stir 4 hours at 700rpm.3) micronize
With step 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 60 minutes under 50 ℃ and 5000rpm of this homogeneous mixer, so that component particlesization.4) skin of capsule wall is handled
Restrain methyl trichlorosilane (by Shin-Etsu Silicone Co. with 0.76, Ltd. the KA-31 of Sheng Chaning) and the MTESs of 3.6 grams (by Shin-Etsu Silicone Co., the KBE-13 that Ltd. produces) under 350rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 3).Then, 5.0 grams, 25% sodium hydrate aqueous solution is added.5) curing of Ning Ju prevention and capsule wall is handled
Restrain trim,ethylchlorosilanes (by Shin-Etsu Silicone Co. with 1.1, Ltd. the KA-31 of Sheng Chaning) under 400rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 4), then, after stirring 1 hour, 2.3 grams, 25% aqueous sodium hydroxide is added.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is distilled, and remaining mixture is continued to be heated to backflow 2 hours under 250rpm stirs.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
In dispersion, free 2-ethylhexyl is 0.16% to the amount of Methoxycinnamate.
After this dispersion was placed 1 day, the 2-ethylhexyl that dissociates in the mensuration dispersion was 0.63% to the amount of Methoxycinnamate.
Embodiment 15
Contain the microcapsules of core material with the method preparation identical, just do not use 2.44 gram tetraethoxysilanes (by Shin-Etsu Silicone Co., the KBE-04 of Ltd. production) with embodiment 14.
In dispersion, free 2-ethylhexyl is 1.35% to the amount of Methoxycinnamate.
After this dispersion was placed 1 day, the 2-ethylhexyl that dissociates in the mensuration dispersion was 1.61% to the amount of Methoxycinnamate.
Embodiment 16 contains the 2-ethylhexyl to Methoxycinnamate and tetraethyl silane and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolysate of the sericin of propyl group hydrolysis, MTES, the copolymerization of hexyl triethoxysilane and tetraethoxysilane contract, and thing forms
Contain the microcapsules of core material with the method preparation identical with embodiment 14, just the 2-ethylhexyl that adds as core material is changed into 266 grams and 2.66 respectively to the amount of Methoxycinnamate and tetraethyl silane and restrains; 7.3 the gram phenyl triethoxysilane is replaced by the hexyl trimethoxy silane of 6.3 grams (by Shin-Etsu Silicone Co., the KBM-3063C that Ltd. produces); And the amount of 25% sodium hydrate aqueous solution is respectively from 4.4 grams, and 5.0 grams and 2.3 grams are made into 5.4 grams, and 4.8 grams and 3.6 restrain.
In dispersion, free 2-ethylhexyl is 0.38% to the amount of Methoxycinnamate.
Embodiment 17
Contain the microcapsules of core material with the method preparation identical, just in core material, do not add the tetraethoxysilanes (by Shin-Etsu Silicone Co., the KBE-04 that Ltd. produces) of 2.44 grams with embodiment 16.
In dispersion, free 2-ethylhexyl is 1.34% to the amount of Methoxycinnamate.
Embodiment 18 contains the 2-ethylhexyl to Methoxycinnamate and tetraethyl silane and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolysate of the collagen of propyl group hydrolysis, MTES, the copolymerization of phenyl triethoxysilane and tetraethyl silane contract that thing forms 1) preparation of the prepolymer of capsule wall
One is had interior through 12cm, be equipped with mechanical agitator, having 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 180 gram water of packing in advance, 20 gram N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen (number-average molecular weight of the collagen of hydrolysis is about 2000) and 4.8 of propyl group hydrolysis restrains 18% hydrochloric acid.Restrain MTESs (by Shin-Etsu Silicone Co. with 61.2, Ltd. the KBE-13 of Sheng Chaning), 16.5 the mixture of the tetraethoxysilane of gram phenyl triethoxysilane (by Shin-Etsu Silicone Co., the KBM-103 that Ltd. produces) and 4.8 grams dropwise adds wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 4 hours at 50 ℃, then, dropwise add 3.8 gram 25% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.2) adding of core material and emulsification
The 2-ethylhexyl of 69.7 grams is restrained tetraethoxysilane (by Shin-Etsu Silicone Co. to Methoxycinnamate (by the MCX of Nippon Roche K.K. production) and 0.697, Ltd. the mixture KBE-04 of Sheng Chaning) adds in the reaction solution for preparing in the step 1) under 600rpm stirs, and this mixture is continued to stir 4 hours at 600rpm.3) micronize
With step 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.4) the outer processing
Restrain methyl trichlorosilanes (by Shin-Etsu Silicone Co. with 1.7, Ltd. the KA-13 of Sheng Chaning) and the MTESs of 8.15 grams (by Shin-Etsu Silicone Co., the KBE-13 that Ltd. produces) under 250rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 3).After stirring 1 hour, 5.46 grams, 25% aqueous sodium hydroxide is added.
After continuing to stir 30 minutes, restrain methyl trichlorosilanes (by Shin-Etsu SiliconeCo. with 1.7, Ltd. the KA-13 of Sheng Chaning) and the MTESs of 8.15 grams (by Shin-EtsuSilicone Co., the KBE-13 that Ltd. produces) add in the solution that is produced once more.Afterwards, the solution that is produced was stirred 1 hour again, then, 5.46 grams, 25% aqueous sodium hydroxide is added.5) curing of Ning Ju prevention and capsule wall is handled
Restrain trim,ethylchlorosilanes (by Shin-Etsu Silicone Co. with 5.0, Ltd. the KA-31 of Sheng Chaning) under 600rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 4), then, after stirring 1 hour, 7.36 grams, 25% aqueous sodium hydroxide is added.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is distilled, and remaining mixture is continued to be heated to backflow 2 hours under 250rpm stirs.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
In dispersion, free 2-ethylhexyl is 0.06% to the amount of Methoxycinnamate.
After this dispersion was placed 1 day, the 2-ethylhexyl that dissociates in the mensuration dispersion was 0.39% to the amount of Methoxycinnamate.
Embodiment 19
Contain the microcapsules of core material with the method preparation identical, just do not use the tetraethoxysilane (by Shin-Etsu Silicone Co., the KBE-04 of Ltd. production) of 0.697 gram with embodiment 18.
In dispersion, free 2-ethylhexyl is 0.13% to the amount of Methoxycinnamate.
After this dispersion was placed 1 day, the 2-ethylhexyl that dissociates in the mensuration dispersion was 0.77% to the amount of Methoxycinnamate.
Embodiment 20 contains the 2-ethylhexyl to Methoxycinnamate and tetraethyl silane and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolysate of the collagen of propyl group hydrolysis, MTES, the copolymerization of hexyl triethoxysilane and tetraethoxysilane contract, and thing forms
Contain the microcapsules of core material with the method preparation identical with embodiment 18, just the 2-ethylhexyl that adds as core material is changed into 70.3 grams and 0.703 respectively to the amount of Methoxycinnamate and tetraethyl silane and restrains; 16.5 the gram phenyl triethoxysilane is replaced by the hexyl trimethoxy silane of 14.15 grams.
In dispersion, free 2-ethylhexyl is 0.13% to the amount of Methoxycinnamate.
After this dispersion was placed 1 day, the 2-ethylhexyl that dissociates in the mensuration dispersion was 0.63% to the amount of Methoxycinnamate.
Embodiment 21
Contain the microcapsules of core material with the method preparation identical, just do not add the tetraethoxysilane of 0.703 gram in the core material with embodiment 20.
In dispersion, free 2-ethylhexyl is 0.15% to the amount of Methoxycinnamate.
After this dispersion was placed 1 day, the 2-ethylhexyl that dissociates in the mensuration dispersion was 1.00% to the amount of Methoxycinnamate.Analytical method 7
With about 0.1 the gram the microcapsules that contain core material that obtain weigh, adds one have diameter 27mm and the height 55mm the screw socket vial in, and the adding about 5mL water.Also this pipe is added a cover to the n-hexane that wherein adds 10ml, middle body is fixed on the horizontal direction immediately, and the motor that uses a 150rpm makes it center on one to keep vertical rotation axes of symmetry to be rotated, to extract free 2-ethylhexyl to Methoxycinnamate.After rotating 2 minutes, the hexane layer of 100 μ l is transferred in the 10ml measuring cup with micro sample adding appliance, and adds n-hexane to the check weighing line.It is known as sample A.This vial is continued rotation 2 minutes, and carry out same processing.It is known as sample B.The 2-ethylhexyl is to the concentration of Methoxycinnamate among use liquid chromatogram measurement sample A and the sample B.If the measurement result of sample A is called as a, the measurement result of sample B is called as b, and then the difference (b-a) between analysis result b and the analysis result a can be taken as the discharge in 2 minutes.Measurement result a also comprises the discharge in 2 minutes, i.e. (b-a), and the amount of free fraction, thereby a-(b-a) can be taken as the amount of free 2-ethylhexyl to Methoxycinnamate.
Embodiment 22 contains the 2-ethylhexyl to Methoxycinnamate and tetraethyl silane and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolysate of the sericin of propyl group hydrolysis, MTES, the copolymerization of phenyl triethoxysilane and tetraethoxysilane contract that thing forms 1) preparation of the prepolymer of capsule wall
One is had interior through 12cm, be equipped with mechanical agitator, having 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 90 gram water of packing in advance, 10 gram N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] sericin (number-average molecular weight of the sericin of hydrolysis is about 2000) and 3.6 of propyl group hydrolysis restrains 18% hydrochloric acid.Restrain MTESs (by Shin-Etsu Silicone Co. with 24, Ltd. the KBE-13 of Sheng Chaning), 6.45 the mixture of the tetraethoxysilane of gram phenyl triethoxysilane (by Shin-Etsu Silicone Co., the KBM-103 that Ltd. produces) and 1.86 grams dropwise adds wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 4 hours at 50 ℃, be cooled to 20 ℃ then.Then, dropwise add 2.45 gram 25% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.2) adding of core material and emulsification
The reaction solution that obtains in step 1) stirred after 30 minutes, the 2-ethylhexyl of 257.4 grams is restrained tetraethoxysilanes (by Shin-Etsu Silicone Co. to Methoxycinnamate (by the MCX of Nippon Roche K.K. production) and 2.6, Ltd. the mixture KBE-04 of Sheng Chaning) 20 ℃ of addings wherein, and continues this mixture to stir 4 hours at 600rpm under 600rpm stirs.3) micronize
With step 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer.Then, the solution that produces is transferred in the original reaction vessels, and under 50 ℃ and 6000rpm, stirred 14 hours.Afterwards, the mixture that is produced is transferred in the vessel of homogeneous mixer, and under 50 ℃ and 6000rpm, handled 60 minutes, so that component particlesization with this homogeneous mixer.4) skin of capsule wall is handled
Restrain methyl trichlorosilane (by Shin-Etsu Silicone Co. with 0.67, Ltd. the KA-13 of Sheng Chaning) and the MTESs of 3.2 grams (by Shin-Etsu Silicone Co., Ltd. the KBE-13 of Sheng Chaning) under 250rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 3), and the mixture that is produced stirred 1 hour at 250rpm again.Then, the adding of 2.2 grams, 25% sodium hydrate aqueous solution is neutralized.5) curing of Ning Ju prevention and capsule wall is handled 2.0 gram trim,ethylchlorosilanes (by Shin-Etsu Silicone Co., Ltd. the KA-31 of Sheng Chaning) under stirring, 250rpm adds in the solution for preparing in the step 4) at 50 ℃, after stirring 1 hour, 2.8 grams, 25% aqueous sodium hydroxide is added then.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is distilled, and remaining mixture is continued to be heated to backflow 2 hours under 150rpm stirs.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Have diameter 0.3 to 5 μ m, the aqueous dispersion of capsule that is mainly 1 to 3 μ m is in dispersion, and free 2-ethylhexyl is 1.686% to the amount of Methoxycinnamate.The 2-ethylhexyl that leaked out in 2 minutes is 0.1138% to the amount of Methoxycinnamate.
Embodiment 22A
Contain the microcapsules of core material with the method preparation identical with embodiment 22, just tetraethoxysilane is not used in the preparation of prepolymer.The aqueous dispersion of capsule with diameter 1 to 5 μ m is in dispersion, and free 2-ethylhexyl is 0.210% to the amount of Methoxycinnamate.The 2-ethylhexyl to the seepage speed of Methoxycinnamate be 0.0348%/minute.
Embodiment 231) carry out step " preparation of the prepolymer of capsule wall " and " adding of core material and emulsification " among the embodiment 22 in an identical manner.2) micronize
The reaction solution for preparing in the step 1) is transferred in the vessel of a homogeneous mixer, and under 50 ℃ and 6000rpm, handled 90 minutes, so that component particlesization with this homogeneous mixer.3) step of carrying out in an identical manner among the embodiment 22 " adds the skin processing of cyst wall " and " prevention of cohesion and the curing of capsule wall are handled ", obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Have diameter 0.3 to 5 μ m, the aqueous dispersion of capsule that is mainly 1 to 3 μ m is in dispersion, and free 2-ethylhexyl is 0.7767% to the amount of Methoxycinnamate.The 2-ethylhexyl that leaked out in 2 minutes is 0.3801% to the amount of Methoxycinnamate.
Embodiment 241) preparation of the prepolymer of capsule wall
Carry out the step " preparation of the prepolymer of capsule wall " of embodiment 22 in an identical manner, be MTES, phenyl triethoxysilane, the amount of tetraethyl silane and 25% sodium hydrate aqueous solution is changed into 21.6 grams respectively, 5.73 gram, 1.67 grams and 2.2 grams.Because the amount of 25% sodium hydrate aqueous solution is 2.2 grams, the pH of resulting solution is controlled in 7.0.2) adding of core material and emulsification
Carry out " adding of core material and emulsification " among the embodiment 22 in an identical manner, just the amount of Methoxycinnamate and tetraethyl silane is changed respectively is that 228.2 grams and 2.3 restrain to the 2-ethylhexyl.3) micronize
In the mode identical with embodiment 22 to step 2) in the reaction solution that obtains carry out micronize.4) skin of capsule wall is handled
The sodium hydrate aqueous solution of 0.25 gram 25% under stirring, 250rpm is dropwise added in the solution for preparing in the step 3) at 50 ℃, add 0.585 gram methyl trichlorosilane then (by Shin-EtsuSilicone Co., Ltd. the KA-13 of Sheng Chaning) and the MTESs of 2.78 grams (by Shin-Etsu Silicone Co., Ltd. the mixture KBE-13 of Sheng Chaning), and the mixture that is produced stirred 1 hour again.Then, the adding of 1.9 grams, 25% sodium hydrate aqueous solution is neutralized.5) curing of Ning Ju prevention and capsule wall is handled
With with embodiment 22 in identical mode carry out step " prevention of cohesion and the curing of capsule wall ", just the amount of trim,ethylchlorosilane and 25% sodium hydrate aqueous solution is changed into 1.2 grams and 1.7 respectively and is restrained, and obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.The aqueous dispersion of capsule with diameter 1 to 5 μ m is in dispersion, and free 2-ethylhexyl is 0.818% to the amount of Methoxycinnamate.The 2-ethylhexyl to Methoxycinnamate ooze out speed be 0.0551%/minute.
Embodiment 251) preparation of the prepolymer of capsule wall
Carry out the step of embodiment 22 in an identical manner " preparation of the prepolymer of capsule wall ", just do not add tetraethyl silane, and after pH is controlled in 7.0, add the propane diols of 4.0 grams.2) adding of core material and emulsification
Carry out " adding of core material and emulsification " among the embodiment 22 in an identical manner, just the amount of Methoxycinnamate and tetraethyl silane is changed respectively is that 250 grams and 2.5 restrain to the 2-ethylhexyl.3) micronize
In the mode identical with embodiment 22 to step 2) in the reaction solution that obtains carry out micronize, just the rotary speed with the homogeneous mixer changes over 8000rpm.4)
With with embodiment 22 in identical mode the reaction solution that obtains in the step 3) is carried out step " skin of capsule wall handles " and " prevention of condensing and the curing of capsule wall ", obtain a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Have diameter 0.3 to 3 μ m, the aqueous dispersion of capsule that mainly is 1 to 3 μ m is in dispersion, and free 2-ethylhexyl is 0.7994% to the amount of Methoxycinnamate.The 2-ethylhexyl that oozed out in 2 minutes is 0.2722% to the amount of Methoxycinnamate.
Embodiment 26
With with embodiment 25 in identical mode prepare the microcapsules that contain core material, just with the propane diols of 4.0 grams with glycerine replacements with 4.0 grams.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Have diameter 0.3 to 3 μ m, the aqueous dispersion of capsule that mainly is 1 to 3 μ m is in dispersion, and free 2-ethylhexyl is 0.7028% to the amount of Methoxycinnamate.The 2-ethylhexyl that oozed out in 2 minutes is 0.0219% to the amount of Methoxycinnamate.
Embodiment 27 contains the 2-ethylhexyl to Methoxycinnamate and tetraethyl silane and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolysate of the sericin of propyl group hydrolysis, MTES, the copolymerization of octyltri-ethoxysilane contract, and thing forms
With with embodiment 25 in identical mode prepare the microcapsules that contain core material, just with octyltri-ethoxysilane (by Nippon UniCarCo., the A-137 that the Ltd. produces) replacement of the phenyl triethoxysilanes of 6.45 grams with 7.5 grams.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Have diameter 0.3 to 3 μ m, the aqueous dispersion of capsule that mainly is 1 to 3 μ m is in dispersion, and free 2-ethylhexyl is 0.4925% to the amount of Methoxycinnamate.The 2-ethylhexyl that oozed out in 2 minutes is 0.0695% to the amount of Methoxycinnamate.
Embodiment 28 contains the 2-ethylhexyl to Methoxycinnamate and the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane; this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolysate of the sericin of propyl group hydrolysis; MTES, the copolymerization of phenyl triethoxysilane contract that thing forms 1) preparation of the prepolymer of capsule wall
One is had interior through 12cm, be equipped with mechanical agitator, having 2 liters of round bottom column glass reactors that are equipped with the upper top cover of an addition funnel and a reflux condenser 90 gram water of packing in advance, 10 gram N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] sericin (number-average molecular weight of the sericin of hydrolysis is about 2000) and 4.0 of propyl group hydrolysis restrains 18% hydrochloric acid.Restrain MTESs (by Shin-Etsu Silicone Co. with 24.3, Ltd. the KBE-13 of Sheng Chaning), 6.6 the mixture of gram phenyl triethoxysilane (by Shin-Etsu Silicone Co., the KBM-103 that Ltd. produces) dropwise adds wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 4 hours at 50 ℃.Then, dropwise add 4.0 gram 20% sodium hydrate aqueous solutions and 1.0 grams and be scattered in 40 EDTA-2Na and the stirrings that restrain in the water, add 20 gram ethanol then, control pH value is 7.0.2) adding of core material, emulsification and micronize
The reaction solution for preparing in the step 1) is transferred in the vessel of a homogeneous mixer; and under 50 ℃ and 9000rpm, handled 90 minutes with this homogeneous mixer; and dropwise add the 203 2-ethylhexyls that restrain to Methoxycinnamate (by the MCX of Nippon Roche K.K. production); 50.8 the tetraethoxysilane of the gram 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane (being produced by Nippon Roche K.K.) and 2.5 grams is (by Shin-Etsu Silicone Co.; Ltd. the mixture KBE-04 of Sheng Chaning) is so that component particlesization.
Then, the solution that produces is transferred in the original reaction vessels, and under 50 ℃ and 600rpm, stirs.Afterwards, the mixture that is produced is transferred in the vessel of homogeneous mixer, and under 50 ℃ and 6000rpm, handled 60 minutes, so that component particlesization with this homogeneous mixer.3) skin of capsule wall is handled
Restrain methyl trichlorosilane (by Shin-Etsu Silicone Co. with 0.68, Ltd. the KA-13 of Sheng Chaning) and the MTESs of 3.24 grams (by Shin-Etsu Silicone Co., Ltd. the KBE-13 of Sheng Chaning) under 400rpm stirs, add steps 2 at 50 ℃) in the reaction utensil of original use of the solution for preparing, and the mixture that is produced stirred 1 hour again.Then, 2.7 grams, 20% aqueous sodium hydroxide is added.5) curing of Ning Ju prevention and capsule wall is handled
Restrain trim,ethylchlorosilanes (by Shin-Etsu Silicone Co. with 2.0, Ltd. the KA-31 of Sheng Chaning) under stirring, 400rpm adds in the solution for preparing in the step 4) at 50 ℃, after stirring 1 hour, 3.7 grams, 20% aqueous sodium hydroxide is added then.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is distilled, and remaining mixture is continued to be heated to backflow 2 hours under 400rpm stirs.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Has diameter 1 to 20 μ m, component 60.72% outside aqueous dispersion 436.0 gram that is mainly the capsule of 1 to 3 μ m dewaters is in dispersion, and free 2-ethylhexyl is 0.5658% to the amount of Methoxycinnamate.The 2-ethylhexyl to Methoxycinnamate ooze out speed be 0.0254%/minute.
Embodiment 29
With with embodiment 28 in identical mode prepare the microcapsules that contain core material, just with the glycerine replacements of the methyl alcohol of 20 grams with 4.5 grams.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Has diameter 1 to 10 μ m, component 60.13% outside aqueous dispersion 460 gram that is mainly the capsule of 1 to 3 μ m dewaters is in dispersion, and free 2-ethylhexyl is 0.5151% to the amount of Methoxycinnamate.The 2-ethylhexyl to Methoxycinnamate ooze out speed be 0.0254%/minute.
Embodiment 30
With with embodiment 28 in identical mode prepare the microcapsules that contain core material, only be to use the 1.0 gram EDTA-2Na and 4.5 that are dispersed in the 40 gram water to restrain the mixture of propane diols, rather than be dispersed in the 40 1.0 gram EDTA-2Na that restrain in the water, add the ethanol of 20 grams then.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Has diameter 1 to 15 μ m, component 59.8% outside aqueous dispersion 466.2 gram that is mainly the capsule of 1 to 3 μ m dewaters is in dispersion, and free 2-ethylhexyl is 0.1848% to the amount of Methoxycinnamate.The 2-ethylhexyl to Methoxycinnamate ooze out speed be 0.0192%/minute.
Embodiment 31
With with embodiment 28 in identical mode prepare the microcapsules that contain core material, the 1.0 gram EDTA-2Na and 4.5 grams 1 that are dispersed in the 40 gram water only have been to use, the mixture of 3-butanediol, rather than be dispersed in the 40 1.0 gram EDTA-2Na that restrain in the water, add the ethanol of 20 grams then.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Has diameter 1 to 20 μ m, component 60.7% outside aqueous dispersion 460.4 gram that is mainly the capsule of 1 to 3 μ m dewaters is in dispersion, and free 2-ethylhexyl is 0.5317% to the amount of Methoxycinnamate.The 2-ethylhexyl to Methoxycinnamate ooze out speed be 0.0391%/minute.
Embodiment 32
With with embodiment 28 in identical mode prepare the microcapsules that contain core material, just the amount of MTES and phenyl triethoxysilane is changed over 16.2 grams and 4.4 respectively and is restrained.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Has diameter 1 to 10 μ m, component 58.4% outside aqueous dispersion 394.0 gram that is mainly the capsule of 1 to 3 μ m dewaters is in dispersion, and free 2-ethylhexyl is 0.5477% to the amount of Methoxycinnamate.The 2-ethylhexyl to Methoxycinnamate ooze out speed be 0.0088%/minute.
Embodiment 33 contains the 2-ethylhexyl to Methoxycinnamate and the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane; this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolysate of the sericin of propyl group hydrolysis; MTES, the copolymerization of octyltri-ethoxysilane contract, and thing forms
With with embodiment 30 in identical mode prepare the microcapsules that contain core material, just with the phenyl triethoxysilanes of 6.6 grams with 7.5 gram octyltri-ethoxysilane (by Nippon UniCarCo., the A-137 that Ltd. produces) replacement.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Component 60.27% outside aqueous dispersion 463.9 gram with capsule of diameter 1 to 15 μ m dewaters is in dispersion, and free 2-ethylhexyl is 1.5579% to the amount of Methoxycinnamate.The 2-ethylhexyl to Methoxycinnamate ooze out speed be 0.3406%/minute.
Embodiment 341) carry out the step preparation of the prepolymer of capsule wall " 1) " and the adding and the emulsification of core material " 2) " among the embodiment 30 in an identical manner.2) adding of core material, emulsification and micronize
The reaction solution for preparing in the step 1) is transferred in the vessel of a homogeneous mixer; and under 50 ℃ and 9000rpm, handled 90 minutes with this homogeneous mixer; and under reduced pressure (500mmHg) dropwise adds the 2-ethylhexyl of 203 grams to Methoxycinnamate (by the MCX of Nippon Roche K.K. production); 50.8 the tetraethoxysilane of the gram 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane (being produced by Nippon Roche K.K.) and 2.5 grams is (by Shin-Etsu Silicone Co.; Ltd. the mixture KBE-04 of Sheng Chaning) is so that component particlesization.
Then, the solution that produces is transferred in the original reaction vessels, and under 50 ℃ and 600rpm, stirs.Afterwards, the mixture that is produced is transferred in the vessel of homogeneous mixer, and under 50 ℃ and 6000rpm, handled 60 minutes, so that component particlesization with this homogeneous mixer.3) step of carrying out in an identical manner among the embodiment 30 " adds the skin processing of cyst wall " and " prevention of cohesion and the curing of capsule wall are handled ", obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Has diameter 1 to 20 μ m, component 59.55% outside aqueous dispersion 466.1 gram that is mainly the capsule of 1 to 3 μ m dewaters is in dispersion, and free 2-ethylhexyl is 0.5812% to the amount of Methoxycinnamate.The 2-ethylhexyl to Methoxycinnamate ooze out speed be 0.1262%/minute.
Embodiment 351) prepare prepolymer in the mode identical with embodiment 30.2) adding of core material, emulsification and micronize
The reaction solution for preparing in the step 1) is transferred in the vessel of a homogeneous mixer; and with this homogeneous mixer at 50 ℃; handle in 90 minutes in ultrasonic wave and under the 9000rpm; the 2-ethylhexyl that dropwise adds 203 grams is to Methoxycinnamate (by the MCX of Nippon Roche K.K. production); 50.8 the mixture of the gram 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane (being produced by Nippon Roche K.K.) and 2.5 gram tetraethoxysilanes (by the KBE-04 of Shin-Etsu Silicone Co.Ltd production) is so that component particlesization.Then, the solution that produces in original reaction vessels, is stirred under 50 ℃ and 600rpm.Afterwards, the mixture that is produced is transferred in the vessel of homogeneous mixer, and under 50 ℃ and 6000rpm, handled 60 minutes, so that component particlesization with this homogeneous mixer.3) carry out the step skin of the capsule wall " handle " and " prevention of cohesion and the curing of capsule wall processing " among the embodiment 30 in an identical manner, obtain a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Has diameter 1 to 20 μ m, component 60.48% outside aqueous dispersion 445.9 gram that is mainly the capsule of 1 to 3 μ m dewaters is in dispersion, and free 2-ethylhexyl is 0.7385% to the amount of Methoxycinnamate.The 2-ethylhexyl to Methoxycinnamate ooze out speed be 0.0147%/minute.
Embodiment 361) carry out the step preparation of the prepolymer of capsule wall " 1) " among the embodiment 28 in an identical manner, just be controlled in and added 2.4 tetraethoxysilanes that restrain after 7.0 (by Shin-Etsu Silicone Co. at pH, Ltd. the ethanol that the KBE-04 of Sheng Chaning), do not add 20 grams.2) adding of core material and emulsification
The reaction solution for preparing in the step 1) under handling, 600rpm is added the mixture of the 2-ethylhexyl of 202.64 grams to Methoxycinnamate (by the MCX of Nippon Roche K.K. production) and the 50.66 gram 4-tert-butyl groups-4 '-methoxy dibenzoyl methylmethane (producing) by Nippon Roche K.K.; then, resulting solution was stirred 2 hours at 600rpm.3) micronize
With step 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer.Then, the solution that produces is transferred in the original reaction vessels, and under 50 ℃ and 600rpm, stirred 15 hours.Afterwards, the mixture that is produced is transferred in the vessel of homogeneous mixer, and under 50 ℃ and 6000rpm, handled 60 minutes, so that component particlesization with this homogeneous mixer.4) step of carrying out in an identical manner among the embodiment 30 " adds the skin processing of cyst wall " and " prevention of cohesion and the curing of capsule wall are handled ", obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.Component 59.36% outside aqueous dispersion with capsule of diameter 2 to 20 μ m dewaters is in dispersion, and free 2-ethylhexyl is 0.9315% to the amount of Methoxycinnamate.The 2-ethylhexyl to Methoxycinnamate ooze out speed be 0.3521%/minute.Reference example 1
N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] preparation of propyl group poly (sodium aspartate)
(by Ajinomono Co., the Aquadew SPA-30 that Inc. produces) carries out electrodialysis with the poly-aspartate sodium solution, then, concentration is controlled at 20% and pH is controlled at about 11, prepares the solution that is used to react.
The solution of preparing is packed in the glass reaction vessel, be heated to 60 ℃ and stir.When reaction solution reaches 60 ℃, dropwise add γ-glycosyloxy propyl trimethoxy silicane (by Shin-Etsu Silicone Co. from addition funnel, Ltd. the KBE-403 of Sheng Chaning), and with mixture stir 5 hours (use amount of γ-glycosyloxy propyl trimethoxy silicane is about 3.1 grams of per 100 gram reaction solutions) at 60 ℃.
The active principle concentration of compound of reaction is controlled in 15%.
Embodiment 37 contains the 2-ethylhexyl to Methoxycinnamate and tetraethyl silane and have a kind of preparation of microcapsules of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolysate of propyl group poly (sodium aspartate), MTES, the copolymerization of phenyl triethoxysilane and tetraethoxysilane contract that thing forms 1) preparation of the prepolymer of capsule wall
In one had through 2 liters of round bottom column glass reactors of 12cm 90 gram water of packing in advance, 10 N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group of obtaining of gram reference examples 1] propyl group poly (sodium aspartate) (number-average molecular weight of poly (sodium aspartate) is about 1000) and 10 restrains 18% hydrochloric acid.Restrain MTESs (by Shin-Etsu Silicone Co. with 12.3, Ltd. the KBE-13 of Sheng Chaning), 3.3 the mixture of the tetraethoxysilane of gram phenyl triethoxysilane (by Shin-Etsu Silicone Co., the KBM-103 that Ltd. produces) and 1.9 grams dropwise adds wherein and stirs at 50 ℃ from addition funnel.
This mixture is continued to stir 4 hours at 55 ℃, be cooled to 25 ℃ then.Then, dropwise add 10 gram 20% sodium hydrate aqueous solutions and stirring, control pH value is 7.0.2) adding of core material and emulsification
The 2-ethylhexyl of 160.7 grams is restrained tetraethoxysilanes (by Shin-Etsu Silicone Co. to Methoxycinnamate (by the MCX of Nippon Roche K.K. production) and 1.6, Ltd. the mixture KBE-04 of Sheng Chaning) adds wherein under 600rpm stirs, and this mixture is continued to stir 2 hours at 600rpm.3) micronize
With step 2) in the reaction solution of preparation be transferred in the vessel of a homogeneous mixer, and with the processing 90 minutes under 50 ℃ and 6000rpm of this homogeneous mixer, so that component particlesization.4) skin of capsule wall is handled
Restrain methyl trichlorosilane (by Shin-Etsu Silicone Co. with 0.3, Ltd. the KA-13 of Sheng Chaning) and the MTESs of 6 grams (by Shin-Etsu Silicone Co., Ltd. the KBE-13 of Sheng Chaning) under 450rpm stirs in the reaction utensil of 50 ℃ of original uses that add the solution for preparing in the step 3), and the mixture that is produced stirred 1 hour at 450rpm again.Then, the adding of 0.4 gram, 20% sodium hydrate aqueous solution is neutralized.5) curing of Ning Ju prevention and capsule wall is handled
Restrain trim,ethylchlorosilane (by Shin-Etsu Silicone Co. with 0.5, Ltd. the KA-31 of Sheng Chaning) under stirring, 450rpm adds in the solution for preparing in the step 4) at 50 ℃, after 450rpm stirs 1 hour, 0.6 gram, 20% aqueous sodium hydroxide is added then.The temperature of reaction solution is increased to backflow gradually.The steam that contains alcohol is distilled, and remaining mixture is continued to be heated to backflow 3 hours under 150rpm stirs.Reaction solution is cooled to room temperature under 150rpm stirs, obtains a kind of microcapsules that contain core material.
The resulting dispersion that contains the microcapsules of core material is analyzed according to analytical method 5 and 7, obtained following result.The component 50.50% analytical method 8SPF value outside aqueous dispersion with diameter 5 μ m or littler capsule dewaters and the mensuration of ultraviolet transmittance
Working sample is applied on the surgery belt (TRANSPORETAPE that is produced by 3M company), with the ultraviolet ray irradiation, (UV-1000S is by LABSPHERE Corp to measure the amount of transmitted light with the APF analyzer., US produces).Numerical value among the embodiment is the average of 40 numerical value.When measuring spf value and ultraviolet transmittance, the amount of the sample that applies on the surgery belt is 2 μ l/cm 2With a certain amount.The calculating of spf value SPF = &Sigma; 290 nm 400 nm E ( &lambda; ) &epsiv; ( &lambda; ) / &lsqb; &Sigma; 290 nm 400 nm ( E ( &lambda; ) &epsiv; ( &lambda; ) ) / ( MFP ( &lambda; ) ) &rsqb; E (λ): the spatial distribution ε of daylight (λ): the behavior spectral line MPF (λ) of delaying type photochemistry erythema: in the mensuration of the mutual transmissivity analytical method 9 skin transmitances of each wavelength
To in 30 minutes, thaw under the room temperature at the Yucatan of-80 ℃ of freezing preservations Micropig skin (boar that grew 5 months, Japanese Charsliver), remove the unnecessary fat of adhesion on the skin, and then, this skin will be cut into the 2cm square be used for measuring.Sample is applied to sees through test on the skin that obtains like this.
Should see through measure that the Franz type diffusion cell that is to use improvement carries out (area that applies sample is 1.1cm 2, accept phase: 16ml).The sample of 0.1ml preparation is placed the donor phase, and kept 24 hours at 37 ℃.After 24 hours, with the pure water flush away of the sample on the skin surface.Then, epidermis is separated with hypodermis.They are used the homogenate of 5ml methyl alcohol, centrifugation (3000rpm, 30 minutes), separation of supernatant, and by a membrane filtration (CAM, 0.80 μ m, ADAVANTEC TOYO).Then, measure the concentration of ultra-violet absorber by HPLC.
The condition that HPLC measures:
HPLC:Shimadzu LC-6A system (making) by Shimmadzu Corp.
Chromatographic column: TSK-GEL ODS-120T 4.6mm 150mm (making) by Tosoh Corp.
Phase flows: methyl alcohol: water=9: 1
Flow rate: 1.0ml/min
Detector: ultraviolet spectrophotometer SPD-6A (making) by Shimadzu Corp.
Detect wavelength: 310nm embodiment 38
Measure embodiment 22A according to analytical method 8, sample that obtains in 24 and 28 and 2-ethylhexyl are to the ultraviolet transmittance of Methoxycinnamate at wavelength 310nm, and gained the results are shown in following table.
Embodiment 22A Embodiment 24 Embodiment 28 The 2-ethylhexyl is to the methyl cinnamic acid ester
Applied amount 1 * 1 54.1 61.1 64.5 72.2
Applied amount 2 * 2 48.7 54.5 58.1 72.2
Ultraviolet transmittance 1.7 1.0 1.75 2.2
* 1 applied amount 1: at 80cm 2Belt on amount (mg) * 2 applied amounts 2 of dry after-applied sample: at 80cm 2Belt on the amount (mg) of the ultra-violet absorber that contains though the embodiment 22A that applies, the amount of the sample that obtains in 24 and 28 is less than the 2-ethylhexyl that the applies amount to Methoxycinnamate, embodiment 22A, 24 and 28 ultraviolet transmittance is less than the ultraviolet transmittance of 2-ethylhexyl to Methoxycinnamate.
Embodiment 39
Measure the microcapsules that obtain among the embodiment 28 and the 2-ethylhexyl skin transmitance to 50% (weight) isopropyl miristate solution of Methoxycinnamate according to analytical method 9, gained the results are shown in following table.
Concentration in the epidermis (μ g/cm 3) Concentration in the hypodermis (μ g/cm 3)
The microcapsules that obtain among the embodiment 28 5 1700
The 2-ethylhexyl is to Methoxycinnamate/isopropyl miristate solution 52 12000
As can be seen, the microcapsules that obtain among the embodiment 28 have suppressed ultra-violet absorber the penetrating in skin contained in the capsule.Embodiment 40, and the comparative example 4: the liquid base
The weighing stearic acid, beeswax, hydrogenated lanolin, Witconol 2310, saualane, and Span-83, and in 80 ℃ of dissolvings (solution 1).Difference weighing triethanolamine, 1, the 3-butanediol, the microcapsules that contain core material that partially purified water and embodiment 13 obtain are heated to 85 ℃, and under agitation add gradually in the solution 1.After being cooled to 45 ℃, add a kind of perfume, ice-cooled to about 40 ℃ (solution 2).
Respectively with titanium oxide, zinc oxide, kaolin, talcum and iron oxide are weighed, and to wherein adding remaining pure water.With the dispersion fully in a homogeneous mixer of this mixture, then, add solution 2, and mixture is further stirred and dispersion fully, obtain being used for the sample of embodiment 40.
Obtain comparative example 4 sample in the same way, only be to use the 2-ethylhexyl, rather than contain the microcapsules of core material Methoxycinnamate.
The 2-ethylhexyl that contains in the microcapsules of Shi Yonging is to Methoxycinnamate in the present embodiment, ultra-violet absorber, amount and comparative example in the amount of the ultra-violet absorber that is combined into identical.This is equally applicable to following embodiment and comparative example.
The amount of any one component that is combined is all based on weight among embodiment and the comparative example, and when the amount that is combined was not the amount of solid constituent, the concentration of solid constituent was described in the bracket of component title back.This is equally applicable among following embodiment and the comparative example.
Combined amount (W/W%)
Embodiment 40 The comparative example 4
1 Titanium oxide 0.60 0.60
2 Zinc oxide 2.00 2.00
3 Kaolin 3.00 3.00
4 Talcum 4.00 4.00
5 Iron oxide 1.00 1.00
6 Stearic acid 2.00 2.00
7 Beeswax 1.20 1.20
8 Hydrogenated lanolin 1.00 1.00
9 Witconol 2310 2.00 2.00
10 Saualane 2.00 2.00
11 Span-83 0.40 0.40
12 Triethanolamine 0.50 0.50
13 1, the 3-butanediol 2.80 2.80
14 Lecithin 0.20 0.20
15 Anticorrisive agent 0.30 0.30
16 Perfume 0.50 0.50
17 Pure water Add to 100 Add to 100
A Microcapsules 62.60 -
B The 2-ethylhexyl is to Methoxycinnamate - 30.00
Measure the spf value of the liquid base that is produced by analytical method 8, the result is as follows.
Spf value
Embodiment 40 20.8
The comparative example 4 18.8
The preparation back short time, outward appearances interior and after 3 months were as follows.
Outward appearance (after the preparation immediately) Outward appearance (after 3 months)
Embodiment 40 Homogeneous Homogeneous
The comparative example 4 Homogeneous Condense, separate
The liquid base of embodiment 40 is better than the liquid base among the comparative example 4 on preventing ultraviolet performance.Though made up a large amount of 2-ethylhexyls to Methoxycinnamate, as time goes by precipitation does not take place and separate, that is to say to have good stability.And when the liquid base of embodiment 40 was used to skin, greasy feeling was very little, and viscosity is suppressed.Embodiment 41, and the comparative example 5
Use the microcapsules that contain core material that obtain among the embodiment 22A, obtained having the solid base of following prescription in the mode similar to embodiment 40 and comparative example 4.
Combined amount (W/W%)
Embodiment 41 The comparative example 5
1 Titanium oxide 20.00 20.00
2 Zinc oxide 3.00 3.00
3 Kaolin 6.00 6.00
4 Talcum 8.00 8.00
5 Iron oxide 4.00 4.00
6 Beeswax 8.40 8.40
7 The castor bean oil that polyoxyethylene solidifies 0.60 0.60
8 Brazil wax 1.20 1.20
9 Olive oil 13.50 13.50
10 The castor bean oil of purifying 6.00 6.00
11 The oleyl sodium phosphate 0.60 0.60
12 Anticorrisive agent 0.30 0.30
13 Perfume 0.30 0.30
14 Octyldodecanol Add to 100 Add to 100
A Microcapsules 16.50 -
B The 2-ethylhexyl is to Methoxycinnamate - 10.00
The spf value of resulting solid base sample of preparation with 4 times of octyldodecanol dilutions is measured with analytical method 8, and the result is as follows.
Spf value
Embodiment 41 16.7
The comparative example 5 14.0
The amount of product with 0.5 gram is applied on the back of the hand, " to the adhesiveness of skin " assessed in 10 people's group, the result is as follows.
The assessment that adheres to
Think the good number of product of embodiment 41 7
Think comparative example 5 the good number of product 3
The solid base that is better than comparative example 5 at the solid base of embodiment 41 aspect the adhesiveness of skin.Embodiment 42, and the comparative example 6
Use the microcapsules that contain core material that obtain among the embodiment 36, obtained having the Tropical Gold Sunscreen of following prescription in the mode similar to embodiment 40 and comparative example 4.
Combined amount (W/W%)
Embodiment 42 The comparative example 6
1 Alkyl acrylate-alkylmethacrylate-polyoxyethylene (20) stearoyl ether copolymer emulsion (30%) 0.60 0.60
2 Hydroxyethylcellulose 0.30 0.30
3 Pure water 20.00 20.00
4 NaOH (1% aqueous solution) 3.00 3.00
5 Pure water 20.00 20.00
6 Propane diols 8.00 8.00
7 EDTA-2Na 0.20 0.20
8 Anticorrisive agent 0.30 0.30
9 Pure water Add to 100 Add to 100
A Microcapsules 9.4 -
B The 2-ethylhexyl is to Methoxycinnamate - 4.00
C The 4-tert-butyl group-4 '-methoxy dibenzoyl base 1.00
When resulting Tropical Gold Sunscreen is difficult to obtain the coating of homogeneous when using on a small quantity, thereby, common consumption is doubled (4 μ l/cm 2) test.By the spf value that analytical method 8 obtains, UVA transmissivity and UVB transmissivity are as follows.
Spf value UVA transmissivity e (%) UVA transmissivity e (%)
Embodiment 42 10.7 33.1 7.6
The comparative example 6 7.7 43.6 10.6
Can find out obviously that from The above results the Tropical Gold Sunscreen among the embodiment 42 has good ultraviolet resistance.
The preparation back short time, outward appearances interior and after 3 months were as follows.
Outward appearance (after the preparation immediately) Outward appearance (after 3 months)
Embodiment 42 The homogeneous emulsion The homogeneous emulsion
The comparative example 6 Thick emulsion and translucent Separate
The result who observes as time goes by shows, can stablize combination even the product of embodiment 42 is not combined in the prescription system of activating agent therein as mentioned above.Embodiment 43, and the comparative example 7
Use the microcapsules that contain core material that obtain among the embodiment 36, obtained having the suncream of following prescription in the mode similar to embodiment 40 and comparative example 4.
Combined amount (W/W%)
Embodiment 43 The comparative example 7
1 Alkyl acrylate-alkylmethacrylate-polyoxyethylene (20) stearoyl ether copolymer emulsion (30%) * 1 1.00 1.00
2 Carboxyl vinyl polymer * 2 (1% aqueous solution) 50.00 50.00
3 Cetearyl alcohol acyl 2 ethyl hexanoic acid ester (2) 5.00 5.00
4 Concentrate glycerine 3.00 3.00
5 EDTA-2Na 0.20 0.20
6 Anticorrisive agent 0.20 0.20
7 Triethanolamine 1.30 1.30
8 Pure water 10.00 10.00
9 Pure water Add to 100.0 Add to 100.0
A Microcapsules 18.7 -
B The 2-ethylhexyl is to Methoxycinnamate - 8.00
C The 4-tert-butyl group-4 '-methoxy dibenzoyl base 2.00
* 1 Aculyn 22 (producing) * 2 Carbopole 940 (producing) by BF Goodrich Company by ROHM and HAAS
The spf value of resulting suncream, the result of UVA transmissivity and UVB transmissivity is as follows.In comparative example 7, product separates, heterogeneity, thereby, should after thermal agitation, take a sample, and resulting sample is tested.
Spf value UVA transmissivity (%) UVB transmissivity (%)
Embodiment 43 4.7 50.9 19.0
The comparative example 7 3.8 56.2 23.7
As follows in the short time after the preparation with the outward appearance after 3 months.
Outward appearance (after the preparation immediately) Outward appearance (after 3 months)
Embodiment 43 The homogeneous emulsion The homogeneous emulsion
The comparative example 7 Separate Separate
From The above results as can be known, microcapsules of the present invention can easily be combined in the ingredients, have good stable as time goes by.Thereby, also be possible even in cosmetics, be combined into ultra-violet absorber, and the combination of ultra-violet absorber is difficult under normal condition.Embodiment 44, and the comparative example 8
Use the microcapsules that contain core material that obtain among the embodiment 28, obtained having the milky lotion of following prescription in the mode similar to embodiment 40 and comparative example 4.
Combined amount (W/W%)
Embodiment 44 The comparative example 8
1 The castor bean oil of polyoxyethylene (10) slaking 5.00 5.00
2 Isopropyl myristate 6.00 6.00
3 Atoleine #70 5.00 5.00
4 Jojoba oil 5.00 5.00
5 Dolomol 0.80 0.80
6 Zinc oxide 3.00 3.00
7 Magnesium sulfate 0.30 0.30
8 Concentrate glycerine 5.00 5.00
9 EDTA-2Na 0.10 0.10
10 Tocopherol acetate 1.00 1.00
11 Anticorrisive agent 0.30 0.30
12 Pure water Add to 100 Add to 100
A Microcapsules 16.5 -
B The 2-ethylhexyl is to methoxyl group meat esters of silicon acis - 10.00
The milky lotion that obtains is measured spf value with analytical method 8, and the result is as follows.
Spf value
Embodiment 44 15.7
The comparative example 8 12.4
The amount of this product with 0.5 gram is applied on the back of the hand, " to the adhesiveness of skin " assessed in 10 people's group, the result is as follows.
The assessment that adheres to
Think the bad number of product of embodiment 44 3
Think comparative example 8 the bad number of product 7
The milky lotion that is better than comparative example 8 at the milky lotion of embodiment 44 aspect the adhesiveness of skin.Embodiment 45, and the comparative example 9
Use the microcapsules that contain core material that obtain among the embodiment 13, obtained having the suncream of following prescription in the mode similar to embodiment 40 and comparative example 4.
Combined amount (W/W%)
Example 45 The comparative example 9
1 Stearic acid 2.5 2.5
2 Hexadecanol 1.5 1.5
3 Vaseline 5.0 5.0
4 Atoleine #70 10.0 10.0
5 Polyoxyethylene (20) oleyl ether 2.0 2.0
6 Anticorrisive agent 0.3 0.3
7 Polyethylene glycol 14000 3.0 3.0
8 Triethanolamine 2.0 2.0
9 Pure water Add to 100 Add to 100
A Microcapsules 41.7 -
B The 2-ethylhexyl is to methoxyl group meat esters of silicon acis - 20.00
The spf value of resulting suncream is measured with analytical method 8, and the result is as follows.
Spf value
Embodiment 45 12.5
The comparative example 9 11.5
As follows in the short time after the preparation with the outward appearance after 3 months.
Outward appearance (after the preparation immediately) Outward appearance (after 3 months)
Embodiment 45 White homogeneous emulsion White homogeneous emulsion
The comparative example 9 White homogeneous emulsion Separate flavescence
From The above results as can be known, these microcapsules have good stable as time goes by and prevent the sunblock compositions flavescence.Embodiment 46, and the comparative example 10
Use the microcapsules that contain core material that obtain among the embodiment 22A, obtained having the agent for treatment of hair of following prescription in the mode similar to embodiment 40 and comparative example 4.
Combined amount (W/W%)
Embodiment 46 The comparative example 10
1 Polyacrylamide, polyoxyethylene-sorbierite olein, the mixture of atoleine and volatility isoparaffin 2.0 2.0
2 The copolymer of poly-(oxygen ethene, oxypropylene) and methyl polysiloxane 5.0 5.0
3 22-ethylhexyl isoparmitate 2.0 2.0
4 Chlorination N-[2-hydroxyl-3-(palm oil alkyl dimethyl ammonia) propyl group] collagen of hydrolysis 0.3 0.3
11 Anticorrisive agent 0.3 0.3
12 Pure water Add to 100 Add to 100
A Microcapsules 4.9 -
B The 2-ethylhexyl is to Methoxycinnamate - 3.0
The spf value of resulting agent for treatment of hair is measured with analytical method 8, and the result is as follows.
Spf value
Embodiment 46 6.2
The comparative example 10 5.6
The amount of this product with 0.2 gram is applied on the bundle of hair of soaking in advance of 1 gram, then with this bundle of hair drying.Carry out one group of 10 people's compatibility assessment, the result is as follows.
The assessment that adheres to
Think the good number of product of embodiment 46 9
Think comparative example 10 the good number of product 1
The agent for treatment of hair of embodiment 46 is better than comparative example 10 agent for treatment of hair aspect compatibility.Embodiment 47, and the comparative example 11
Use the microcapsules that contain core material that obtain among the embodiment 24, obtained having the lipstick of following prescription in the mode similar to embodiment 40 and comparative example 4.
Combined amount (W/W%)
Embodiment 47 The comparative example 11
1 Beeswax 7.0 7.0
2 Candelira wax 10.5 10.5
3 Methyl polysiloxane 11.2 11.2
4 Castor bean oil 15.0 15.0
5 Atoleine #70 18.0 18.0
6 Glycerine three isostearates 15.0 15.0
7 Mica 10.0 10.0
8 Iron oxide 3.6 3.6
9 Second red (Red No.2) 0.2 0.2
10 Pure water Add to 100 Add to 100
A Microcapsules 5.2 -
B The 2-ethylhexyl is to Methoxycinnamate - 3.0
With resulting lipstick with 2 times of atoleine dilutions, the spf value of the sample that obtains like this with analytical method 8 mensuration, the result is as follows.
Spf value
Embodiment 47 8.2
The comparative example 11 7.8
The result shows that the lipstick of embodiment 47 has good ultraviolet resistance.Embodiment 48, and the comparative example 12
Use the microcapsules that contain core material that obtain among the embodiment 28, obtain having the emulsion of following prescription in the mode similar to embodiment 40 and comparative example 4.
Combined amount (W/W%)
Embodiment 48 The comparative example 12
1 Carboxyl vinyl polymer 0.30 0.30
2 Potassium hydroxide 0.15 0.15
3 1, the 3-butanediol 5.00 5.00
4 Two glycerine 2.00 2.00
5 Hydroxyl ethane tetra-na diphosphate 0.09 0.09
6 To the oxybenzoic acid ester 0.25 0.25
7 Pure water Add to 100.0 Add to 100.0
A Microcapsules 10.0 -
B The 2-ethylhexyl is to Methoxycinnamate - 4.5
Resulting emulsion is measured spf value with analytical method 8, and the result is as follows.
Spf value
Embodiment 48 5.4
The comparative example 12 5.0
The emulsion of embodiment 48 has good ultraviolet resistance.
Prepared sample is carried out the skin permeability with analytical method 9 measure, the result is as follows.
Concentration in the epidermis (μ g/cm 3) Concentration in the hypodermis (μ g/cm 3)
Embodiment 48 1,100 2.5
The comparative example 12 4,900 50
As can be seen, the emulsion of embodiment 48 has suppressed the ultra-violet absorber that is combined and has infiltrated skin.

Claims (27)

1. microcapsules that contain core material and capsule wall, wherein, the capsule wall of these microcapsules contains:
By compound (B), the mixture of monomer or monomer, at the synthetic organopolysiloxane of-30 ℃ of-80 ℃ of bunchings that carry out, wherein, compound (B) contains one or more compounds by general formula (II) expression:
R nSi(OH) mY (4-m-n) (II)
Wherein, m represents one from 1 to 4 integer; N represents one from 0 to 3 integer; M+n≤4; R represents that a kind of wherein carbon atom directly is connected the organic group on the silicon atom, and when n greater than 1 the time, each R group can be identical or different; Y represents to be selected from alkoxyl, at least one in hydrogen and the siloxy, and when (4-m-n) greater than 1 the time, each Y group can be identical or different; As long as compound (B) contain at least a wherein m=2 or 3 and at least one R group at least a in continuous phase and the decentralized photo had the compound of formula (II) expression of compatibility; And compound (B) is that the mixture of monomer or monomer obtains by hydrolysis compound (A) under the condition of-5 ℃-90 ℃ and pH 1-5 and pH 7.5-11.5, and wherein, compound (A) contains one or more compounds by following formula (I) expression:
R nSiX (4-n)(I) wherein, n and R are as defined above; X represents to be selected from hydroxyl, hydrogen, alkoxyl, halogen group, at least a in the carboxyl, amino and siloxy, and when (4-n) greater than 1 the time, each X group can be identical or different; As long as compound (A) contains at least a compound that at least a formula (I) with R group of compatibility in continuous phase and the decentralized photo is represented that has.
2. according to the described microcapsules that contain core material of claim 1, wherein, the compound that at least a formula (II) that is contained by compound (B) is represented has a kind of R group that carries hydrophilic radical.
3. according to the described microcapsules that contain core material of claim 2, wherein, this hydrophilic radical is the protein of a kind of polyethers or a kind of hydrolysis.
4. according to the described microcapsules that contain core material of claim 3, wherein, this hydrophilic radical is a polyoxyethylene, polyoxypropylene or polyoxyethylene-polyoxypropylene copolymer.
5. according to the described microcapsules that contain core material of claim 3, wherein, this hydrophilic radical is N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] albumen or N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group of propyl group hydrolysis] propyl group protein hydrolysate.
6. according to the described microcapsules that contain core material of claim 4, wherein, this described polyoxyethylene, polyoxypropylene or polyoxyethylene-polyoxypropylene copolymer has 1 to 2000 number-average degree of polymerization.
7. according to the described microcapsules that contain core material of claim 5, wherein, the protein of described each hydrolysis has 100 to 50000 number-average molecular weight.
8. according to the described microcapsules that contain core material of claim 1, wherein, at least a compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes is present in the core material of microcapsules.
9. according to the described microcapsules that contain core material of claim 1, wherein, handle once at least with at least a hydrolysate that is selected from the compound of hydrolyzable silane and hydrolyzable polysiloxanes on the capsule wall of these microcapsules surface.
10. according to the described microcapsules that contain core material of claim 1, wherein, the surface of capsule wall is with compound (A), and the mixture of monomer or monomer is handled, and wherein, compound (A) contains one or more compounds by following formula (I) expression:
R nSiX (4-n) (I)
Wherein, n represents one from 0 to 3 integer; R represents that a kind of wherein carbon atom directly is connected the organic group on the silicon atom, and when n greater than 1 the time, each R group can be identical or different; X represents to be selected from hydroxyl, hydrogen, alkoxyl, halogen group, at least a in the carboxyl, amino and siloxy, and when (4-n) greater than 1 the time, each X group can be identical or different;
As long as compound (A) contains at least a compound that at least a formula (I) with R group of compatibility in continuous phase and the decentralized photo is represented that has.
11. according to the described microcapsules that contain core material of claim 8, wherein, at least a compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes is a dimethyl dichlorosilane (DMCS), methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane, MTMS, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, the diphenyl diethoxy silane, hexyl trimethoxy silane, octyltri-ethoxysilane, the decyl trimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, or Me 3SiO (Me 2SiO) f[MeZSiO] gSiMe 3, wherein, f represents one from 5 to 50 integer, and g represents one from 2 to 100 integer, and z represents hydrogen or alkoxyl.
12. according to the described microcapsules that contain core material of claim 9, wherein, at least a compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes is a dimethyl dichlorosilane (DMCS), methyl trichlorosilane, dimethyldichlorosilane, trim,ethylchlorosilane, phenyl trichlorosilane, diphenyl dichlorosilane, MTMS, MTES, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, the diphenyl diethoxy silane, hexyl trimethoxy silane, octyltri-ethoxysilane, the decyl trimethoxy silane, tetramethoxy-silicane, tetraethoxysilane, or Me 3SiO (Me 2SiO) f[MeZSiO] gSiMe 3, wherein, f represents one from 5 to 50 integer, and g represents one from 2 to 100 integer, and z represents hydrogen or alkoxyl.
13. a production is according to the method for the microcapsules that contain core material and capsule wall of any one among the claim 1-12, it may further comprise the steps successively:
(1) by the monomer of hydrolysis compound (A) or the mixture of monomer under the condition of-5 ℃-90 ℃ and pH 1-5 and pH 7.5-11.5, prepare the monomer of compound (B) or the mixture of monomer, wherein, compound (B) contains one or more compounds by general formula (II) expression:
R nSi(OH) mY (4-m-n) (II)
Wherein, m represents one from 1 to 4 integer; N represents one from 0 to 3 integer; M+n≤4; R represents that a kind of wherein carbon atom directly is connected the organic group on the silicon atom, and when n greater than 1 the time, each R group can be identical or different; Y represents to be selected from alkoxyl, at least one in hydrogen and the siloxy, and when (4-m-n) greater than 1 the time, each Y group can be identical or different; As long as compound (B) contain at least a wherein m=2 or 3 and at least one R group at least a in continuous phase and the decentralized photo had the compound of formula (II) expression of compatibility,
Wherein, compound (A) contains one or more compounds by following formula (I) expression:
R nSiX (4-n) (I)
Wherein, n represents one from 0 to 3 integer; R represents that a kind of wherein carbon atom directly is connected the organic group on the silicon atom, and when n greater than 1 the time, each R group can be identical or different; X represents to be selected from hydroxyl, hydrogen, alkoxyl, halogen group, at least a in the carboxyl, amino and siloxy, and when (4-n) greater than 1 the time, each X group can be identical or different,
As long as compound (A) contains at least a compound that at least a formula (I) with R group of compatibility in continuous phase and the decentralized photo is represented that has;
(2) pass through in-30 ℃-80 ℃ and bunching compound (B), form prepolymer;
(3) this prepolymer and the core material and/or second liquid are mixed mutually also emulsification;
(4) by further the prepolymer bunching being solidified the capsule wall of said microcapsules.
14. contain the method for the microcapsules of core material according to the described preparation of claim 13, wherein, the compound of at least a formula (II) expression that is contained by compound (B) has a kind of R group that carries hydrophilic radical.
15. contain the method for the microcapsules of core material according to the described preparation of claim 14, wherein, this hydrophilic radical is the protein of a kind of polyethers or a kind of hydrolysis.
16. contain the method for the microcapsules of core material according to the described preparation of claim 15, wherein, this hydrophilic radical is a kind of polyoxyethylene with number-average degree of polymerization of 1 to 2000, polyoxypropylene or polyoxyethylene-polyoxypropylene copolymer.
17. contain the method for the microcapsules of core material according to the described preparation of claim 15, wherein, this hydrophilic radical is a kind of N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group with number-average molecular weight of 100 to 50000] albumen or N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group of propyl group hydrolysis] propyl group protein hydrolysate.
18. contain the method for the microcapsules of core material according to the described preparation of claim 13, wherein also comprise in core material, adding the step that is selected from least a compound in hydrolyzable silane and the hydrolyzable polysiloxanes.
19. contain the method for the microcapsules of core material according to the described preparation of claim 13, wherein also comprise the step of handling the capsule wall surface with the hydrolysate that is selected from least a compound in hydrolyzable silane and the hydrolyzable polysiloxanes.
20. contain the method for the microcapsules of core material according to the described preparation of claim 13, wherein also comprise the step of handling the capsule wall surface with a kind of compound (A).
21. contain the method for the microcapsules of core material according to the described preparation of claim 13, wherein, to form the step of prepolymer all be to have before in the medium of viscosity of 10 to 2000 milli pascal seconds and carry out adding compound (A) to the bunching for preparing compound (B) and compound (B) of the hydrolysis by compound (A).
22. contain the method for the microcapsules of core material according to the described preparation of claim 21, wherein, said medium is a kind of aqueous gelatin solution with viscosity 10 to 2000 milli pascal seconds.
23. according to the described microcapsules that contain core material of claim 1, wherein, this core material contains ultra-violet absorber.
24. according to the described microcapsules that contain core material of claim 23, wherein, ultra-violet absorber be the 2-ethylhexyl to Methoxycinnamate, or the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane.
25. one kind contains the described preparation that contains the microcapsules of core material of claim 23.
26. according to the described preparation of claim 25, it is a kind of cosmetics or a kind of pharmaceutical preparation.
27. according to the described preparation of claim 26, wherein said preparation is applied on skin or the hair.
CN 99109444 1998-10-29 1999-07-02 Microcapsule containing core material and its producing method Expired - Fee Related CN1120745C (en)

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CN100512945C (en) * 2007-06-15 2009-07-15 浙江大学 Method of preparing temperature sensitive nano microcapsule by using small molecule hydrocarbon as template
EP2335818A1 (en) * 2009-07-09 2011-06-22 Altachem Holdings NV Leach-proof microcapsules, the method for preparation and use of leach-proof microcapsules
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