CN1253032A - Microcapsule containing core material and its producing method - Google Patents

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 microcapsule and the production method thereof that contain core material

The present invention relates to a kind of microcapsule and production method thereof that contains core material.Specifically, the present invention relates to a kind of microcapsule, 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.

Microcapsule of the present invention can be used for, for example, medicine, liquid crystal, chemicals, the record material, cosmetics, spice, enzyme, agricultural, binding agent, fiber, food, catalyst, detergent, dyestuff, paint vehicle, antiseptic, solvent, etc.Their object lesson comprises and contains aspirin, the microcapsule of vitamin or liquid crystal, and pressure-sensitive carbon paper contains UV absorbent, dyestuff, pigment, spice, Mentholum, insecticide, binding agent, capsule, contain the capsule of the antiseptic 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 microcapsule field, for example sense stricto microcapsule and nanocapsule field, the capsule wall of being attempted utilizing organopolysiloxane or its analog to form by the people is produced microcapsule.

For example, United States Patent (USP) 3257330 discloses a kind of production and has contained the method for organopolysiloxane as coloured micelle of substrate.But, when a kind of alkoxy silane with hydrophobic organic group, MTES etc. for example, when being used as the raw material of substrate, after being hydrolyzed and being neutralized then, this polymer composition forms a kind of precipitation in aqueous solution.As a result, be difficult to produce microcapsule by a kind of hydrophobicity core material is carried out polymerization with a kind of hydrolysate of alkoxy silane in 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 microcapsule.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 microcapsule 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,, can not be used to produce capsule wall more than a certain amount of three alcoxyl silane because the polysiloxanes capsule wall that three alcoxyl silane are newly formed is confined in the inner phase.Thereby this method can not be considered to the universal method of the microcapsule 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 the group that can participate in crosslinked and polymeric function is carried out crosslinked production.But, be difficult to have a kind of special polysiloxanes that participates in crosslinked and polymeric functional group and operate to this.

As mentioned above, be difficult to produce a kind of microcapsule according to conventional method with capsule wall of forming by organopolysiloxane.

Directly using the organopolysiloxane capsule wall of these performances to make microcapsule from the silicol precursor manufacturing with different performance also is favourable on expense.And, be applicable to that the microcapsule 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 microcapsule at control example such as aggregate rate under the condition of solubility etc.

The purpose of this invention is to provide a kind of microcapsule that contains a kind of core material, wherein, this microcapsule contains 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 microcapsule.

The inventor has in depth studied the method for directly producing the microcapsule 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 chemical compound (A) hydrolysis of selecting the chemical compound of free style (I) expression, produce the chemical compound (B) that one or more select the chemical 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 chemical compound (B) contain at least a wherein m=2 or 3 and at least one R group to a kind of chemical compound in continuous phase and the decentralized photo at least with formula (II) expression of affinity; And chemical compound (B) is by bunching, with the synthetic organopolysiloxane that constitutes capsule wall.Thereby finished the present invention.

Term " continuous phase " and " decentralized photo " be illustrated respectively in usually microcapsule wall form before medium in a kind of the dispersion with a kind of mutually dispersive.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 chemical compound (B) of so-called hydroxyl silane.And above-mentioned organopolysiloxane can constitute production and contain the necessary capsule wall of microcapsule of core material, thereby does not need to form capsule wall by the condensing method of routine.

The invention provides a kind of microcapsule and a kind of capsule wall that contains core material, wherein, the capsule wall of this microcapsule contains: by with a kind of chemical compound (B), monomer whose or monomer mixture, carry out bunching and synthetic organopolysiloxane, wherein chemical compound (B) contains one or more chemical 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 chemical compound (B) contain at least a wherein m=2 or 3 and at least one R group to a kind of chemical compound in continuous phase and the decentralized photo at least with formula (II) expression of affinity.

The present invention also provides a kind of a kind of method that contains the microcapsule of core material that is used to produce, and this method comprises a kind of process, and wherein, chemical compound (B) is by bunching, to synthesize organopolysiloxane and to form capsule wall.

Chemical compound of the present invention (B) is used to produce has the microcapsule that is closed core material wherein.It normally the monomer by hydrolysis compound (A) or monomer mixture obtain, wherein, chemical compound (A) contains one or more chemical 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 chemical compound (A) contains at least a wherein at least one R group to a kind of chemical compound with formula (I) expression of affinity in continuous phase and the decentralized photo at least.

In the present invention, " microcapsule " is meant a kind of for example microcapsule, the capsule of nanocapsule etc., and thereby compare with typically sense stricto " microcapsule ", it has comparatively wide significance.For example, generally speaking, sense stricto " microcapsule " is 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, " microcapsule " is meant sensu lato microcapsule in this manual, comprises microcapsule and nanocapsule.Phrase " microcapsule that contains core material " is meant the microcapsule that contains core material in the space that capsule wall forms.

Chemical compound (B) is the one group of chemical compound that is selected from a kind of of formula (II) expression or contains two or more chemical compounds.At least a chemical compound that constitutes chemical compound (B) is the chemical compound of wherein m=2 or 3 formula (II) expression.At least a chemical compound that constitutes chemical compound (B) is a kind of like this chemical compound, and this chemical compound has at least one at least a R group with affinity in continuous phase and the decentralized photo.

The capsule wall that contains the microcapsule of core material of the present invention forms by the synthetic organopolysiloxane of bunching chemical compound (B).

The condensation of chemical compound (B) is in a kind of its Chinese style (II)-SiOH group and the another kind of molecule that constitutes chemical 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 microcapsule that contains core material of the present invention, the condensation of chemical compound (B) is carried out to a certain degree, and to prepare the prepolymer of chemical 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 chemical compound (B) that the hydrolysis by chemical compound (A) obtains, and the degree that contracts and react of chemical compound (B).Its residing scope is that the organopolysiloxane that constitutes prepolymer and capsule wall is enough to form.

In the synthetic organopolysiloxane of bunching by chemical compound (B), can partly keep alkoxyl on the silicon atom, hydroxyl etc. perhaps do not keep.

The hydrolysis that is used to produce the chemical compound (B) that wherein contains a kind of microcapsule of core material of the present invention and is by chemical compound (A) obtains.Chemical compound (A) is a kind of chemical compound or two or more combination of compounds that is selected from formula (I) expression.

Be used to produce the method that contains the microcapsule of core material of the present invention and comprise the steps: that successively (1) prepares chemical compound (B) by the hydrolysis of chemical compound (A), (2) carry out bunching by the neutralization of chemical compound (B), (3) mix mutually and emulsifying and (4) cured 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 chemical compound (A) " (hereinafter being called " surface treatment ") as mentioned below.

The example that is used for the chemical compound (A) of preparation method of the present invention comprises a kind of chemical compound or the one group of chemical compound that carries a kind of hydrophilic group, carry a kind of chemical compound or one group of chemical compound of a kind of hydrophobic group, carry a kind of chemical compound or one group of chemical compound that a kind of and a kind of fluorocarbon or tetraalkoxysilane have the group of affinity.Carry a kind of chemical compound or one group of chemical compound of a kind of parents' group, carry a kind of chemical compound or one group of chemical 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 affinity, and parents' group is a kind of group group of hydrophilic radical and hydrophobic group for example with two different affinitys that carries.

The chemical compound (A) that is used for preparation method of the present invention can be made up of a kind of or one group of chemical compound, perhaps is made up of several or several groups of chemical compounds.For example, chemical compound (A) can be made up of chemical compound that carries a kind of hydrophilic group and the chemical compound that carries a kind of hydrophobic group.

The kind of chemical compound (A), and when chemical compound (A) is made up of several chemical compounds or several groups of chemical compounds, the condensation of the chemical compound (B) that the selection of the ratio of several chemical compounds and/or several groups of chemical compounds is preferably obtained by the hydrolysis of chemical compound (A) and the prepolymer that forms have affinity at least a in continuous phase and the decentralized photo, and resulting prepolymer is stabilized dispersion.

In the chemical compound that carries hydrophilic group of forming chemical compound (A), the R group in the formula (I) preferably carries a kind of hydrophilic group, and the R group that carries hydrophilic group links to each other in silicon atom.The two or more R groups that carry hydrophilic group can be connected on the silicon atom.When a plurality of hydrophilic groups linked to each other with a R group, these a plurality of hydrophilic groups can comprise two or more hydrophilic groups.Except that hydrophilic group, the group that a kind of hydrophobic group or a kind of and carbon fluorine have affinity can be connected on this R group that carries hydrophilic group.

The example that produces the chemical compound of hydrophilic group in chemical compound (A) comprises polyethers, for example, and polyoxyethylene, polyoxypropylene, and polyoxyethylene-polyoxypropylene copolymer; The saccharide that comprises polysaccharide and monosaccharide, for example, amylopectin, sorbitol, chitin, chitan or amino sugar, protein, antibody, aminosal, polyamino acid, carboxylic acid, or their salt or derivant, polycarboxylic acid or its salt or derivant, sulphuric acid or its salt or derivant, phosphoric acid or its salt or derivant, sulfonic acid or its salt or derivant, phosphonic acids or its salt or derivant, quaternary ammonium group, amine or their salt, polyamines or its salt, or the like.The chemical compound of generation hydrophilic group is not limited to above-mentioned these in chemical compound (A).The example of the group that forms hydrophilic group R as being connected with above-mentioned hydrophilic group 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 group is connected the right-hand member of this structural formula.

The polysiloxanes that the example that carries hydrophilic group and constitute the chemical compound of chemical compound (A) comprises polyoxyethylene-modification [for example, KF-354 (trade name)] it carries the polyethers as hydrophilic group, 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 hydrolyzed protein] the propyl group hydrolyzed protein, be derived from N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group of γ-glycidoxypropyl methyldiethoxysilane and hydrolyzed protein (JP-A-8-67608)] the propyl group hydrolyzed protein, with aforesaid chemical compound and the silicon silane coupler that is derived from the hydrophilic substance that carries hydrophilic group, 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 anhydride etc.The chemical compound that carries hydrophilic group and constitute chemical 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 ethylene and oxypropylene are 1 to 2000, particularly 4 to 800.

Above-mentioned N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] propyl group hydrolyzed protein and N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] example of hydrolyzed protein comprises in the propyl group hydrolyzed protein, but be not limited to, the proteinic hydrolyzate of animal origin, for example, collagen protein, elastin laminin, keratin, the silkworm silk fibroin, sericin, casein and conchiolin; The albumen of plant origin, for example, wheat protein, soybean protein, sesame protein, zein (zein); And microbe-derived albumen, for example, yeast protein.The proteic number-average molecular weight of selective hydrolysis is about 100 to 50000, particularly about 200 to 5000.

In a kind of chemical compound of the formation chemical compound (A) that carries hydrophobic group, the R group in the preferred formula (I) carries a kind of hydrophobic group, and the R group that carries hydrophobic group is connected on the silicon atom.The two or more R groups that carry hydrophobic group can be connected on the silicon atom, and a plurality of hydrophobic group is connected on the R group.These a plurality of hydrophobic group can comprise two or more hydrophobic group.Except hydrophobic group, the group that a kind of and carbon fluorine has affinity can be connected on the R group that carries hydrophobic group.

The example of hydrophobic group 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 group is not limited to above chemical compound of giving an example.

The concrete example that carries hydrophobic group and constitute the chemical compound of chemical 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 chemical compound that is derived from the hydrophobic substance that carries hydrophobic group, 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 succinic anhydrides.And the concrete example as the chemical 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 chemical compound that carries hydrophobic group and constitute chemical compound (A) is not limited to above-claimed cpd.

Have in the chemical compound of affinity carrying a kind of and carbon fluorine, this R group of preferred formula (I) expression carries the group that a kind of and carbon fluorine have affinity, and this carries the R group that has a group of affinity 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 affinity and can be connected on the silicon atom, and the group that a plurality of and carbon fluorine has an affinity can be connected on this R group.The group that this a plurality of and carbon fluorine have affinity can comprise that two or more and carbon fluorine have the group of affinity.

Carry the example that has the group of affinity with the carbon fluorine and constitute the chemical compound of chemical compound (A) and comprise C ₈F ₁₇CH ₂CH ₂Si (OCH ₃) ₃, CF ₃CH ₂CH ₂Si (OCH ₃) ₃And have the material derived compounds and the silane coupler of affinity 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 succinic anhydrides.Carry the chemical compound that has the group of affinity with the carbon fluorine and constitute chemical compound (A) and be not limited to the above-mentioned chemical compound of enumerating.

The concrete example that has hydrophilic group and hydrophobic group and constitute the chemical compound of chemical compound (A) comprise by the hydrolysis substituent group for example alkoxyl etc. produce N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] chemical compound of propyl group hydrolyzed protein.

When the microcapsule of being made by chemical compound (A) that contains core material is scattered in the water or in the hydrophilic continuous phase time, (A) is as follows for chemical compound.

Hydrophilic group in chemical 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 ethylene and oxypropylene is 10 to 1000, particularly about 20 to 400.When chemical compound (A) when being hydrolyzed protein, preferably its number-average molecular weight is 200 to 50000, particularly about 400 to 5000.

Preferably carrying the chemical compound (A) and the molar ratio that carries the chemical compound (A) of hydrophobic group of hydrophilic group (comprising that the R group carries the situation of hydrophilic group and hydrophobic group simultaneously), in monomer, is about 1: 0 to 1: 1000, particularly about 1: 2 to 1: 200.

When a kind of monomethyl type chemical compound, in its Chinese style (I) only a R group be methyl, when being used as the chemical compound (A) that carries hydrophobic group, the preferred a kind of chemical compound that is selected from down group that uses at least: MTES, MTMS and methyl trichlorosilane, perhaps this chemical compound and at least a chemical 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 chemical compound can be 100: 0 to 0: 100 with the molar ratio that carries other chemical compound of hydrophobic group in monomer, but preferably this molar ratio is about 100: 3 to 100: 80.This monomethyl type chemical compound and other the chemical compound that carries hydrophobic group are not limited to the above chemical compound of enumerating.

When the microcapsule of being made by chemical compound (A) that contains core material was scattered in on-waterborne or the hydrophobic continuous phase, (A) was as follows for chemical compound.

Hydrophilic group in chemical 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 ethylene and oxypropylene is 3 to 20, particularly 5 to 10.When chemical compound (A) when being hydrolyzed protein, preferably its number-average molecular weight is 100 to 2000, particularly about 200 to 1000.

When a kind of monomethyl type chemical compound, in its Chinese style (I) only a R group be methyl, when being used as the chemical compound (A) that carries hydrophobic group, the preferred a kind of chemical compound that is selected from down group that uses at least: MTES, MTMS and methyl trichlorosilane, perhaps this chemical compound and at least a chemical 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 chemical compound can be 100: 0 to 0: 100 with the molar ratio that carries other chemical compound of hydrophobic group in monomer, but preferably this molar ratio is about 10: 100 to 80: 100.This monomethyl type chemical compound and other the chemical compound that carries hydrophobic group are not limited to the above chemical compound of enumerating.

The hydrolysis of chemical compound (A) is described below.

Chemical compound (B) normally hydrolysis by chemical 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 carbamide etc. also can add in the entry.When chemical compound (A) hydrolysis post neutralization, 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 chemical compound (A) by chemical compound (B) preparation prepolymer, preferably using viscosity before the adding of chemical compound (A) is 10 to 2000mPa.s medium, unlikely rising is too fast thereby controls reaction speed makes the speed of condensation reaction, prevent formation, and make solution-stabilized at the insoluble effect postprecipitation of prepolymer.Have the thickening agent that viscosity is 10 to 2000mPa.s media, polyvinyl alcohol, polyacrylamide, sodium carboxymethyl cellulose as preparation, Sensor Chip CM 5, hydroxyethyl-cellulose, carageenan, chitin, chitan, polypeptide, gelatin, sericins etc. can be used as example.Particularly, the aqueous gelatin solution with 10 to 2000mPa.s 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 chemical compound can be carried out under acidity or alkaline pH.The selection of these character depends on the character of chemical compound (A).

When the hydrolysis of chemical 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 chemical compound (A).The example of operable acid comprises organic acid, for example acetic acid etc., and mineral acid, hydrochloric acid for example, sulphuric acid, phosphoric acid etc.Particularly, (A) carries a kind of hydrophilic group when chemical compound, this hydrophilic group be animal origin protein for example, collagen protein, elastin laminin, keratin, the silkworm silk fibroin, sericin, the hydrolyzate of casein and conchiolin, if the hydrolysis of chemical compound (A) is when carrying out under acid pH, the microcapsule that contains core material that obtains has 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 chemical compound (A).The example of operable alkali comprises for example sodium hydroxide, potassium hydroxide, etc.Particularly work as chemical compound (A) and carry a kind of hydrophilic group, this hydrophilic group is the protein wheat protein for example that derives from plant, the hydrolyzate of soybean protein and sesame protein, if the hydrolysis of chemical compound (A) is when carrying out under alkaline pH, the microcapsule that contains core material that obtains has best result.

The bunching of the chemical compound (B) that the hydrolysis by chemical 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 chemical 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 chemical compound (B) and the bunching by neutralization reaction be reflected at mix with the core material and/or second liquid phase and emulsifying before be carried out to a certain degree, with the prepolymer of prepared beforehand chemical compound (B).When using a kind of chemical compound (B) at least, this chemical compound carries at least one hydrophilic 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.

Chemical compound (B) mix with the core material and/or second liquid phase and emulsifying 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, with the core material and/or second liquid phase mix and emulsifying must become at formed prepolymer and carries out before stable.

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 chemical 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 the mixing and emulsifying of the core material and/or second liquid phase.

Following method is an example that mixes with the core material and/or second liquid phase with emulsive method.

Be scattered in the water or under the situation in the hydrophilic disperse medium at the microcapsule that contains core material, prepolymer prepares in hydrophilic disperse medium in this method, then, add the only core material in liquid form (second liquid phase), perhaps core material and its solvent (second liquid phase).

Be scattered at the microcapsule that contains core material under the situation of hydrophobic disperse 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 (continuous phase in second liquid phase), make and put upside down mutually and emulsifying.Core material can put upside down mutually with emulsifying after add.

In the method for the invention, because core material can add, can produce a kind of containing under neutrallty condition at the microcapsule that is different from unsettled material under the neutral condition.With core material and/or second mutually mixing and emulsifying 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 fatty acid is higher fatty acids particularly, hydro carbons, organic solvent, esters, 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, UV absorbent, vitamin, effective ingredient, aroma constituent, antiseptic, antibacterial, salt; Aminoacid and derivant thereof, protein, aminosal and derivant thereof, saccharide, 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, lauric acid, miristic acid, Palmic acid, stearic acid, behenic acid, 12-hydroxy stearic acid, 9-undecylenic acid, Pilus Caprae seu Ovis fatty acid, isostearic acid, linoleic acid, oleic acid, linoleic acid, arachidonic acid, eicosapentaenoic acid, docosahexenoic acid 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 lanoline lactate; the methyl isostearate; Fancol ID 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 decanoins; isostearoyl base pivalate; two isostearoyl base malates, glycerol monostearate, glyceryl distearate; glyceryl two-2-heptyl hendecane acid esters; trimethylolpropane tris-2-ethylhexanoate, trimethylolpropane tris isostearate, dimethyltrimethylene glycol two-2-ethylhexanoate; tetramethylolmethane four-2-ethylhexanoate; glyceryl three-2-ethylhexanoate, cetyl 2-ethylhexanoate, 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 cetylate; glyceryl trimiristate; glyceryl three caprylates, glyceryl three different cetylates, castor bean fatty acid oil methyl ester; the oleyl oleate; the glyceryl acetas, 2-heptyl undecyl cetylate, 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 cetylate, 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, 4-hydroxydiphenyl; 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 high fatty alcohol comprises, capryl alcohol, lauryl alcohol, miristyl alcohol, hexadecanol, octadecanol, arachidic alcohol, tadenan, oleyl alcohol, ketone octadecanol, single octadecane glyceryl ether, 2-decyl four decanol, 2-hexyldecanol, 2-hexyl dodecanol, the 2-octyldodecanol, 2-heptyl tip-nip, lanolin alcohol, cholesterol, plant sterol, isooctadecane alcohol etc.

The example of animal and plant oil comprises, American Avocado Tree oil, tsubaki oil, macadamia nut oil, Semen Maydis oil, olive oil, Efamast, rapeseed oil, egg oil, Oleum sesami, persic oil, wheat germ oil, Camellia oil, Oleum Ricini, ripening Oleum Ricini, oleum lini, safflower oil, Oleum Gossypii semen, ripening Oleum Gossypii semen, soybean oil, the ripening soybean oil, Oleum Arachidis hypogaeae semen, tee nip oil, Japanese Semen Myristicae oil, rice chaff oil, Chinese wood oil, Japanese tung oil, Oleum Cinnamomi, jojoba oil, germ oil, almond oil, cupu oil, Petiolus Trachycarpi oil, ripening Petiolus Trachycarpi oil, horse fat oil, Oleum Testudinis, ermine oil, spiny dogfish oil, spiny dogfish is rare, orangeroughy oil, Adeps Bovis seu Bubali, the ripening Adeps Bovis seu Bubali, neatsfoot stock, neat's foot oil, Adeps Caprae seu ovis, Adeps Sus domestica, train oil, ripening train oil, fish oil, ripening fish oil, lanolin oil, lanolin alcohol, hydrogenated lanolin, lanolin acetate, liquid lanolin, lanolin fatty acid isopropyl esters, cholesteryl lanonate, ring lanoline, polyoxyethylene lanolin alcohol ether, the polyoxyethylene lanolin alcohol acetas, Polyethylene Glycol lanolin fatty acid, polyethylene glycol hydrogenated lanoline alcohol ether, Brazil wax, Kan Taili wax, jojobawax, hard lanoline, Japan wax, India's foxtail millet wax, Cotton Gossypii wax, myrtle wax, insect wax, montanwax, rice bean wax, lacca wax, jojoba wax, Cera Flava, train wax, jojoba alcohol, rosin acid, hydroabietic acid etc.

The example of sub painted organic compound of powering comprises, diaryl 2-benzofuranone, and polyaryl methanol, 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 oxalate lactone; bis(dimethylamino)benzhydrol; crystal violet methanol, malachite green oxalate methanol, N-(2; the 3-Dichlorobenzene base) 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 ferrum 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, lower titanium oxide etc., inorganic violet pigment is the Fructus Mangifera Indicae purple for example, cobalt violet etc., inorganic green pigment is chromium oxide for example, chromic oxide gel, 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 aluminum 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 ferrum 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, Muscovitum, phlogopite, sericite, white Muscovitum, synthetic mica, epidolite, lithium oxide Muscovitum, Vermiculitum, organic powder for example, fluoridated apatite, hydroxyapatite, the pottery powder, metallic soap (zinc miristate, calcium palmitate, aluminium stearate etc.), Boron Nitride, tripoli-Alumina, tripoli-magnesium oxide, bentonite, bleaching earth, the japanic acid clay, active in soil, montorillonite clay, attapulgite etc.; And organic powder for example, polyamide powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, the polystyrene powder, styrene-propene acid copolymer resin powder, 2,4-diaminourea-6-phenyl s-triazine resin powder, politef powder, cellulose powder etc.

The example of UV absorbent comprises; based on salicylic UV absorbent; for example; phenyl salicylic acid esters; to the tert-butyl-phenyl salicylate; OPS p octylphenyl salicylate etc.; based on the UV absorbent of benzophenone or their derivant; 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) benzotriazole; 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole; 2-(2 '-hydroxyl-3 '; 5 '-two-tert-butyl-phenyl) benzotriazole; 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) benzotriazole; 2-[2 '-hydroxyl-3 '-(3 "; 4 "; 5 "; 6 "-tetrahydrochysene phthalimidomethyl)-5 '-aminomethyl phenyl]-benzotriazole; 2-(2 '-hydroxyl-3 '-dodecyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-undecyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-3 '-three decyl-5 '-aminomethyl phenyl) benzotriazole; 2-[2 '-hydroxyl-4 '-(2 "-ethylhexyl) the oxygen phenyl] benzotriazole; 2-[2 '-hydroxyl-4 '-(2 "-the ethyl octyl group) the oxygen phenyl] benzotriazole, 2-[2 '-hydroxyl-4 '-(2 "-the propyl group octyl group) the oxygen phenyl] benzotriazole, 2-[2 '-hydroxyl-4 '-(2 "-propylheptyl) the oxygen phenyl] benzotriazole; 2-[2 '-hydroxyl-4 '-(2 "-the propyl group hexyl) the oxygen phenyl] benzotriazole; 2-[2 '-hydroxyl-4 '-(1 "-ethylhexyl) the oxygen phenyl] benzotriazole, 2-[2 '-hydroxyl-4 '-(1 "-the ethyl heptyl) the oxygen phenyl] benzotriazole, 2-[2 '-hydroxyl-4 '-(1 "-the ethyl octyl group) the oxygen phenyl] benzotriazole; 2-[2 '-hydroxyl-4 '-(1 "-propyl group octyl group) oxygen phenyl] benzotriazole; 2-[2 '-hydroxyl-4 '-(1 "-propylheptyl) oxygen phenyl] benzotriazole, 2-[2 '-hydroxyl-4 '-(1 "-propyl group hexyl) oxygen phenyl] benzotriazole, the methyl-3-[3-tert-butyl group-5-(2H-benzotriazole-2-yl)-4-hydroxy phenyl] propionic ester and Polyethylene Glycol condensation substance (molecular weight: about 300); to the derivant or the ester of methoxy styrene acid; for example, 2-ethylhexyl be to the methoxy styrene ester, the derivant of ESCAROL 507 or ester; for example; 2-ethylhexyl ESCAROL 507 ester, the derivant of styrene acid or ester, for example; benzyl styrene acid esters; o-aminobenzoa, the derivant of salicylate and benzoxazoles, 2; 4; 6-three-(to anilino-)-1-(carboxyl-2 '-ethylhexyl)-1,3,5-triazines; the derivant of dibenzoyl methane; for example, the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane and 4-isopropyl diphenyl formoxyl methane, franone derivant; ferulic acid or its ester, gamma oryzanol etc.

The example of vitamin comprises vitamin and derivant thereof, for example, vitamin A, vitamin B, 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 acetas, etc.

The example of active drug component comprises, the sulfur medicine, for example, sulfamethomidine, circulatory system drug, for example, calcium hobatate, papaverin hydrochloride, diltiazem hydrochloride and reserpine, breathe and promote medicine such as trimethoxy alcohol hydrochloric acid, bromoacetylene hydrochloric acid, and tipepidinehibenzate, the eliminating phlegm and stopping cough medicine, antibiotic, for example, benzyl penicillin sodium, benzyl penicillin potassium, phenoxy methylpenicillin potassium and ammonia Bian XiLin, carcinostatic, for example, 5-fluorouracil, N-(2-tetrahydrofuran base)-5-fluorouracil and hydrochloric acid bleomycin, therapeutic agent, for example, timepidiumbromide, lidocaine and chlorpromazine hydrochloride, hydryllin, for example, diphenhydramine hydrochloride and diphenhydramine malate, antiinflammatory, for example, aspirin, quinine hydrochloride and sulpirin, antibacterial, for example, salicylic acid, Japanese cypress, sulfur, the methyl of P-hydroxybenzoic acid, propyl group, butyl, ethyl ester etc., antiseptic, in addition, light-sensitive material, the cyctein or derivatives thereof, azilex or derivatives thereof, glutathion or derivatives thereof etc.

The example that extracts component comprises, oil-soluble Arnica montana extract, Aloe extract, the dead Herba Urticae Cannabinae extract of dissolubility is arranged, the Flos Matricariae chamomillae extract, the oil-soluble Flos Chrysanthemi extract, the oil-soluble Radix Glycyrrhizae extract, cape jasmine extract, the oil-soluble mulberry extract, oil-soluble Fructus Arctii 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 Gentiana lutea extract, common Thymi Serpylli Herba extract, the Pericarpium Citri tangerinae extract, oil-soluble juglanus regia L. extract, oil-soluble A.acutiloba (Sieb.et Zucc.) Kitag root extract, the common Calendula arvensis L. extract of oil-soluble, the oil-soluble Radix Dauci Sativae extract, oil-soluble wild rose extract, oil-soluble Folium Eriobotryae fermented product, oil-soluble intacellin, oil-soluble hop extract, oil-soluble marronnier extract, oil-soluble leaf of Fructus Persicae extract, mugwort extract, oil-soluble Coix plant extract, the Lavandula plant extract, citron extract, mandarin orange extract, the oil-soluble Herba Rosmarini Officinalis extract, oil-soluble royal jelly extract, green tea contains the Cortex Eucommiae tea or the ruibosu tea of tannic acid or flavonoid; Derive from former medicine of plant or animal or their various salt, for example, Japanese Sophora japonica L., scutellariae,radix and souhakuhi extract.

The example of flavor component comprises the oil with abnormal smells from the patient, for example, and Semen Armeniacae Amarum, fennel a kind of reed mentioned in ancient books, Herba Coriandri, Cortex Cinnamomi, cedar leaf, cedar wood, Cortex Cinnamomi, Herba Cymbopogonis Citrari, Flos Caryophylli, Eucalyptus, Flos Pelargonii, Fructus Vitis viniferae, Garden lavender, Fructus Citri Limoniae, lemon grass (Cymbopogon citratus), Oleum Rosae Rugosae, sour Fructus Citri grandis, mandarin orange flower (nerori oil) Semen Myristicae, Bulbus Allii Cepae, Bulbus Allii, mandarin orange, lignum vitae, orris, Oleum menthae, pinaster, Folium Pini, Herba Rosmarini Officinalis, Lignum Santali Albi, sassafrases, spearmint, time, coffee, postfermented tea, Fructus Pruni pseudocerasi, Fructus Mali pumilae, Fructus Ananadis comosi, Fructus Musae, pears, Rhizoma et radix valerianae etc.

The example of salt comprises, calcium carbonate, magnesium carbonate, magnesium silicate, calcium silicates, aluminium silicate, barium silicate, barium sulfate, strontium silicate, metal tungstates, Silicon stone, zeolite, barium sulfate, the calcium sulfate of roasting, calcium phosphate, lithium chloride, sodium chloride, potassium chloride, ammonium chloride, lithium bromide, sodium bromide, potassium bromide, lithium iodide, sodium iodide, potassium iodide, iodine, sodium sulfate, potassium sulfate, ammonium sulfate, ammonium nitrate, lime nitrate, perphosphoric acid calcium, the phosphate fertilizer of roasting, sodium phosphate etc.

Aminoacid, protein, the example of saccharide etc. comprise aminoacid or peptide class, for example, potassium aspartate, magnesium aspartate, sodium glutamate, lysine hydrochloride and glutathion derive from the protein of animal, for example, collagen protein, elastin laminin, keratin, fibroin, sericin, casein, conchiolin derives from the protein of plant, for example, wheat protein, soybean protein and sesame protein, derive from the protein of microorganism, for example, yeast protein or this proteinic hydrolyzate, intacellin, the mucosa polysaccharide, carbamide etc.

The example of enzyme comprises, lipase, protease, superoxides, dismutase, lysozyme, alkali phosphatase, amylase, trypsin, glutathion 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 chemical 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 capsular preparation process, use a kind of material as liquid.Be scattered at the microcapsule that contains 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 intimate mixing machine and prepared particulate size 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 intimate mixing machine.

In the preparation of emulsion, when reaction solution is stirred by a kind of mechanical agitator, handle by a kind of intimate mixing machine, 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 intimate mixing machine and little fluidizator is to reduce granular size.Another purpose is to produce the microcapsule that contains core material, and wherein, when carrying out this processing shearing force taking place, capsule wall is not cleaved.

The processing of intimate mixing machine or little fluidizator can repeat twice or repeatedly, to reduce granular size more.When UV absorbent was used as core material, the reprocessing of intimate mixing machine or little fluidizator had another effect that reduces the amount of free UV absorbent in dispersion usually.

For reducing granular size more, can carry out at ethanol, particularly at polyhydric alcohol ethylene glycol for example, propylene glycol, the existence of glycerol etc. is the preparation emulsion down.When UV absorbent was used as core material, this method had the effect that another one reduces the amount of free UV absorbent in dispersion usually.

For reducing particulate size more, also can in ultrasound wave, carry out the preparation of emulsion.

The microcapsule that hereinafter description is contained core material is used the surface treatment of chemical compound (A) in preparation process.

Even in preparation process, do not use the surface treatment of chemical compound (A) at the microcapsule that contains core material, can prepare the microcapsule that contains core material yet.But,, infer that a silanol groups that does not participate in condensation still is retained in the short time after emulsifying and does not have on the solidified capsule according to preparation method of the present invention.Thereby, preferably use the surface treatment of chemical compound (A), with the cohesion of the microcapsule that prevents to contain core material.

When being used for surface-treated chemical compound (A) is a kind of chemical compound at water capacity facile hydrolysis, for example, when chlorosilane comprises trim,ethylchlorosilane and hexamethyl siloxanes, preferably add this chemical compound (A) after the emulsifying in emulsion, then, solution is neutralized.

When being used for surface-treated chemical compound (A) is a kind of alkoxy silane for example during trimethylethoxysilane, need after emulsifying this neutral solution be become acidity or alkalescence, and with this alkoxy silane hydrolysis once.When the chemical compound that carries a silanol groups (A) when beginning to be used to surface treatment, need after emulsifying, this neutral solution be become acid or alkaline a little.Then, chemical compound (A) is fixed on the capsular surface by neutralization reaction.Should carefully control pH value, not make the capsule cracking.Under the situation that acid pH is handled, pH value is preferably about 3 to 6.5.Under the situation that alkaline pH is handled, pH value is preferably about 7.5 to 10.The example that is used for the chemical compound (A) of superficiality processing is described below, but the chemical compound that is not limited to exemplify.

Purpose of surface-treated is the cohesion that prevents to contain the microcapsule of core material.After emulsion preparation, preferably add a kind of chemical compound (A) that on silicon atom, carries 3 alkyl, for example, trim,ethylchlorosilane, ethoxytrimethylsilane, tert-butyl chloro-silicane, hexamethyl disiloxane, hexamethyldisiloxane etc., thus prevent to contain the cohesion of the microcapsule of core material.

And, after emulsion preparation, can add and carry the chemical 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 microcapsule that contains core material be cationic.

And, after emulsion preparation, can make the character on the surface of the microcapsule that contains core material carry out various variations, and by control pH in and chemical compound (A) obtain various modifications, this chemical 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 succinic anhydrides, 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 chemical 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 hydrolyzed protein and N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] the propyl group hydrolyzed protein, be derived from the chemical 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 succinic anhydrides and other material.

Above-mentioned surface treatment series may be incorporated in together.

In the cured of the present invention, 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 chemical 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 response system, it is got back in the response system) etc. from system.

In the microcapsule that contains core material that obtains 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 microcapsule that contains core material has enough water proofing properties around neutral pH.

Capsular intensity depends on the kind of employed chemical compound (A), granular size, condition of cure, and core weight ratio.For example, produce again under the situation of microcapsule 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 microcapsule that contains core material according to method preparation of the present invention can be prepared into powder by lyophilization and spraying dried.

Core material is being about 50 to 99.9%, preferred 80 to 98% according to the uptake rate in the microcapsule that contains 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 microcapsule for preparing in said method of the present invention has 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 microcapsule 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 microcapsule 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 capsular core material 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 microcapsule that contains core material, wherein, capsule wall is that the wherein at least a chemical 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 chemical compound (B).

The present invention also provides a kind of microcapsule that contains core material, wherein, capsule wall is by synthetic organosiloxane is made by the bunching of chemical compound (B), and formed capsule wall is handled once at least with a kind of hydrolyzate, and this hydrolyzate is at least a chemical 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 microcapsule that contains core material, comprise that the wherein at least a chemical compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes adds the step of core material and wherein chemical 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 microcapsule that contains core material, comprise the step that wherein the synthetic organopolysiloxane of chemical compound (B) bunching is formed capsule wall, wherein once step is handled at least by a kind of hydrolyzate in the surface of formed capsule wall, and this hydrolyzate is at least a chemical compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes.

In the microcapsule that contains core material of the present invention, at least a chemical 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 hydrolyzate on the surface of formed capsule wall, this hydrolyzate is at least a chemical compound that is selected from hydrolyzable silane and the hydrolyzable polysiloxanes, thereby it is minimum that the amount that is not combined into capsular core material 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 ₃Si0 (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 chemical 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 hydrolyzate 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 emulsifying after carry out, and usually before the surface treatment of usefulness chemical compound (A) etc., carry out before promptly preventing to condense the cured with capsule wall.This coat processing is undertaken by at least a chemical 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 emulsifying with mixing.The addition of at least a chemical 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 purification of the core material that is not combined into etc. usually.The example of the method for purification is as follows.

Purification process be wherein add a kind of be regardless of powder capsule with not with the mutually blended liquid phase of the capsular liquid phase of other dispersion, said two kinds of liquid phases are mixed 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 phases are difficult for separately, can adopt centrifugalize.And, when two liquid phases separate easily, can further add can with disperse the mutually blended liquid of capsular liquid phase, capsule is washed and separates.

Another purification process is wherein will precipitate or the microcapsule that contains core material that floats carries out fraction collection by centrifugalize, and in this case, after above-mentioned steps, impurity and solvent are removed together.The microcapsule of collecting is dispersed in again can disperses in the capsular solvent.Repeat this process.

Another kind of purification process is the method by ultra-filtration.In this method by ultra-filtration, the impurity that goes out by the ultra-filtration eluting is removed, and spissated microcapsule is dispersed in again in the solvent of the microcapsule that can disperse to contain core material.Repeat this process.

The microcapsule 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 microcapsule of core material can be directly from for example alkoxy silane, halogenated silanes, hydrogen silane, the chemical 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 chemical compound (A) of combination according to various objectives.

Have this microcapsule that contains core material of the present invention of different nature and can be widely used in pharmacy, liquid crystal, chemical products, record material, cosmetics, spice, enzyme, agricultural, binding agent, fiber, food, catalyst, detergent, dyestuff, paint vehicle, antiseptic, solvent etc.

For example, when the microcapsule that contains core material of the present invention that uses ultraviolet absorption material as core material was used to cosmetics, comparing with the situation that UV absorbent itself wherein is combined into cosmetics had following advantage.

1. owing to see through the ultraviolet reduction of UV absorbent to skin, the safety of cosmetics improves.

2. be difficult under normal conditions to obtain to stablize ingredients the ingredients system in, might obtain stable ingredients.

3. when UV absorbent itself is combined in the cosmetics, may need to add stabilizing agent, to prevent the UV absorbent flavescence.But, do not need this stabilizing agent in the present invention.

4. when the UV absorbent of a kind of for example ethylhexyl methoxy cinnamic acid etc. is combined itself; viscosity etc. can take place; and when the UV absorbent of for example methoxyl group butyl benzene formoxyl methane etc. 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 use feeling of cosmetics.And the adhesiveness of cosmetics improves.

5. when a kind of UV absorbent itself is combined in a kind of ingredients with high-moisture of for example bath foam, need to add certain amount of surfactant.But,, do not need to add surfactant or only need to add a spot of surfactant, thereby UV absorbent can easily be combined into according to the present invention.And methoxyl group butyl benzene formoxyl methane etc. is difficult to be combined into, and this is because it demonstrates bad dissolubility, and its dissolubility is owing to the influence that other combinations ancestral divides reduces.In the present invention, its combination is easy.That is to say, according to the present invention, with the compatibility raising of other combination partner (raw material of cosmetics, oil, solvent etc.).

6. ultra-violet absorption effect (spf value) promptly protects human body to avoid the effect raising of ultraviolet radiation.

When containing the microcapsule of UV absorbent and be used to cosmetics as core material, the granular size of microcapsule is preferably 0.05 μ m to 50 μ m, 0.3 to 30 μ m more preferably, the combined amount of this UV absorbent (weight) is preferably 0.1% to 50% based on the amount of microcapsule, and more preferably 0.5 to 30%.

When the microcapsule that contains core material of the present invention is used to pharmacy, cosmetics, during dyestuff etc., following component is used for microcapsule jointly: fatty 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, UV absorbent, vitamin, medicine active ingredient, aroma constituent, antiseptic, antibacterial, salt; Aminoacid and derivant thereof, protein, aminosal and derivant thereof, saccharide, 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, fatty acid aminosal condensation substance, sulfated surfactant, phosphate-type surfactant, polyester and derivant 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 microcapsule of core material, and the moisture that will contain the dispersion of core material microcapsule is measured with infrared moisture meter LIBROR EB-280MOC (trade name is made by Shimadzu Corp).Calculate the weight [microcapsule+free core material (not being combined into capsular the core material)+ash that contains core material] of the non-water section of the dispersion that contains microcapsule from this result.Under the medium-sized capsular situation of water, the weight that contains capsular dispersion is the weight of [water+contain the microcapsule+free core material+ash of core material] at oil.When the content of water is when measuring according to this analytical method 1, calculate the weight [microcapsule+free core material+ash 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 microcapsule.Described in above-mentioned analytical method 1, contain in the dispersion of microcapsule and be considered to also contain ash, and in the ash except that silicon oxide 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 microcapsule that contains core material of about 1 gram is correctly weighed, be transferred to then in the 500ml separatory funnel, use the water washing of 100ml simultaneously.Add the normal hexane of 100ml, mixture is fully shaken up, leave standstill then.After liquid phase separates, the solution of the normal hexane washing of 100ml is transferred in the another one vessel.With this lock out operation triplicate, the extractive solution of the normal hexane that obtains is merged, and be concentrated into 100ml.The extractive solution of this normal hexane 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 microcapsule that exists in the microcapsule that contains core material of about 1 gram is measured based on the normal concentration calibration curve of other making, and calculates the weight of free core material in the dispersion that contains microcapsule.Analytical method 4

About 0.1 microcapsule that contains core material of being produced of gram is 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 normal hexane of 100ml, mixture is fully shaken up, leave standstill then.After liquid phase separates, the solution of the normal hexane washing of 100ml is transferred in the another one vessel.With this lock out operation triplicate, the extractive solution of the normal hexane that obtains is merged, and be concentrated into 100ml.The extractive solution of this normal hexane of 1 μ l is sucked in the micro-syringe, and carry out liquid-phase chromatographic analysis.The gross weight of free core material that is not incorporated into microcapsule that exists in the microcapsule that contains core material of about 0.1 gram and the core material that has been incorporated into microcapsule is measured based on the normal concentration calibration curve of other making.

The core weight ratio, amount with the core material that is incorporated into microcapsule is represented based on the weight percent of the weight of microcapsule, 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 microcapsule that contains core material that obtains that restrains 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 optical microscope in amplification, observes the distribution situation of measuring granular size.Analytical method 6

The particle size distribution situation of the microcapsule that contains core material that obtains is measured by the SALD-2000 that ShimadzuCorp makes.Method of testing 1

The microcapsule that contains core material of 20 times of one (about 50 μ l) dilutions is clipped between the glass plate of two square 2mm thickness of 1cm, and places it on the horizontal hard substrate, and apply 1.5kg/cm from the top ²Pressure.After exerting pressure, observe microcapsule and whether break.Embodiment 1 contains 2-ethylhexyl p-methoxycinnamic acid ester and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is the hydrolyzate 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 ℃, then, add and dropwise add 1.6 gram 4% sodium hydrate aqueous solutions and stirring, the control pH value is 7.0.Afterwards, this mixture was stirred 1 hour at 50 ℃.2) adding of core material and emulsifying

With 5.4 gram 2-ethylhexyl p-methoxycinnamic acid esters adding method 1 under 600rpm stirs) in the reaction solution of preparation, and this mixture continued stirring 4 hours at 600rpm.3) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.Comparative example 1 is being contained 2-ethylhexyl p-methoxycinnamic acid ester and is being had by methoxyl group (ethyoxyl) n-pro-pyl dihydroxy methyl-monosilane, the copolymerization of MTES and phenyl triethoxysilane is contracted in the preparation of microcapsule 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, adding 5.4 restrains 2-ethylhexyl p-methoxycinnamic acid esters and reaction solution is stirred at 600rpm.This mixture is continued to stir 4 hours at 600rpm, then, dropwise add 1.9 gram 4% sodium hydrate aqueous solutions and stirring, the control pH value is 7.0.Afterwards, this mixture was stirred 1 hour at 50 ℃.2) cured of Ning Ju prevention and capsule wall

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 amount that only will be approximately identical with the 2-ethylhexyl p-methoxycinnamic acid ester that adds is separating of oil.Embodiment 1A contains 2-ethylhexyl p-methoxycinnamic acid ester and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is the hydrolyzate by methoxyl group (ethyoxyl) n-pro-pyl dihydroxy methyl-monosilane, and the copolymer of MTES and phenyl triethoxysilane is formed

The microcapsule that contains 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, 2-ethylhexyl p-methoxycinnamic acid ester, 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 pH value is controlled under the 7.0 back stirring conditions becomes 20 ℃.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 10 μ m, capsular aqueous dispersion 107 gram that is mainly 1 to 2 μ m is removed component 14.0 grams behind the moisture

In embodiment 1, the microcapsule that contains core material is that KF-354A (trade name) prepares as the chemical compound that carries hydrophilic group (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 emulsifying.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 microcapsule that contains 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 chemical compound (A) that carries hydrophilic group, has prepared the microcapsule that contains core material as embodiment 1.

The microcapsule that contains core material that obtains among the embodiment 1A is tested, whether broken in above-mentioned method of testing 1 to observe its capsule.Do not find that capsule has fragmentation.Embodiment 2 contains 2-ethylhexyl p-methoxycinnamic acid ester and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen protein 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 protein (number-average molecular weight of collagen protein 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, the control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of core material and emulsifying

With 389 gram 2-ethylhexyl p-methoxycinnamic acid esters 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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, so that component particlesization.4) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule 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 capsular aqueous dispersion 850 gram that is mainly 1 to 2 μ m is removed free 2-ethylhexyl p-methoxycinnamic acid ester in the component 50 gram dispersions behind the moisture is 4%.The amount of the 2-ethylhexyl p-methoxycinnamic acid ester that contains in the capsule is 84%.

Then, by the own p-methoxycinnamic acid ester of free 2-ethyl in the dispersion being removed, under pure condition, obtain the microcapsule of a kind of 2-of containing ethylhexyl to cinnamate with hexane wash.When method 4) the adding that prevents methyl trichlorosilane in the cured with capsule wall of cohesion 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 microcapsule and part cohesion with microscopic examination.In the present embodiment, do not see this cohesion.

The microcapsule that contains core material that obtains among the embodiment 2 is 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 mixture of 2-ethylhexyl p-methoxycinnamic acid ester and the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane; this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen protein of propyl group hydrolysis, the copolymer of MTES and phenyl triethoxysilane is formed

Contain the microcapsule of core material with the method preparation identical with embodiment 2, just with the 2-ethylhexyl p-methoxycinnamic acid esters of 389 grams with in advance the 19.5 gram 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethanes being dissolved in 78.2 gram 2-ethylhexyl p-methoxycinnamic acid esters and dropwise adding 2.9 gram 25% sodium hydrate aqueous solutions and replace at 20 ℃ of mixture that stir and obtain subsequently.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 315 gram that is mainly 1 to 2 μ m is removed the component 42.3% behind the moisture

As mentioned above, in present embodiment 2A,, can be combined in the microcapsule simultaneously as the 4-tert-butyl group-the 4 '-methoxy dibenzoyl methylmethane of second kind of core material except 2-ethylhexyl p-methoxycinnamic acid ester.

The microcapsule that contains core material that obtains among the embodiment 2A is tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.Embodiment 2B contains 2-ethylhexyl p-methoxycinnamic acid ester and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] wheat protein 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 protein (number-average molecular weight of the wheat protein 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, the control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of core material and emulsifying

With 12.3 gram 2-ethylhexyl p-methoxycinnamic acid esters 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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, so that component particlesization.4) cured of Ning Ju prevention and capsule wall

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, 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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 595 gram that is mainly 1 to 2 μ m is removed the component 11% behind the moisture

As mentioned above, in present embodiment 2B, be to use the chemical compound of forming by the wheat protein of hydrolysis that carries hydrophilic group (A) to prepare the microcapsule that contains core material.The hydrolysis of chemical 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 at alkaline pH value as embodiment 2B.A large amount of cohesive materials that sticks to the reaction utensil inwall occurred, the preparation of microcapsule can't be carried out.Embodiment 2C contains 2-ethylhexyl p-methoxycinnamic acid ester and has a kind of preparation of microcapsule 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, the control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of core material and emulsifying

With 6.5 gram 2-ethylhexyl p-methoxycinnamic acid esters 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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, so that component particlesization.4) cured of Ning Ju prevention and capsule wall

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 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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 360 gram that is mainly 1 to 2 μ m is removed the component 7.6% behind the moisture

As mentioned above, be to use the chemical compound of forming by the soybean protein of hydrolysis that carries hydrophilic group (A) to prepare the microcapsule that contains core material at present embodiment 2C.The hydrolysis of chemical compound (A) is carried out under alkali condition.

The microcapsule that contains core material that obtains among the embodiment 2C is tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.Embodiment 2D

The microcapsule that contains 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, the amount of MTES and 2-ethylhexyl p-methoxycinnamic acid ester is become 38.3 grams and 87.4 grams by this respectively, and, do not carry out with the processing of methyl trichlorosilane.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 507 gram that is mainly 1 to 2 μ m is removed the component 23.6% behind the moisture

The microcapsule that contains core material that obtains among the embodiment 2D is tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.Embodiment 2E

The microcapsule that contains 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, the amount of MTES and 2-ethylhexyl p-methoxycinnamic acid ester is changed into 30.0 grams and 6.7 grams respectively, and does not use the processing of methyl trichlorosilane.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 300 gram that is mainly 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 group, also prepared the microcapsule that contains core material.

The microcapsule that contains core material that obtains among the embodiment 2E is tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.Embodiment 2F

The microcapsule that contains 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 protein 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 protein of propyl group hydrolysis.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 687 gram that is mainly 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 protein of propyl group hydrolysis, rather than N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen protein of propyl group hydrolysis, also prepared the microcapsule that contains core material.

The microcapsule that contains core material that obtains among the embodiment 2F is tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.Embodiment 2G

The microcapsule that contains 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 protein of propyl group hydrolysis, rather than N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen protein 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 amount of 2-ethylhexyl p-methoxycinnamic acid ester change into 60 the gram.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, the amount that capsular aqueous dispersion 400 gram that is mainly 1 to 2 μ m is removed free 2-ethylhexyl p-methoxycinnamic acid ester in component 25% dispersion behind the moisture is 6%.The amount of the 2-ethylhexyl p-methoxycinnamic acid ester that contains in the capsule is 40%.

As mentioned above, in embodiment 2G, be different from employed hydroxyl silane among the embodiment 2F, also prepared the microcapsule that contains core material with hydrophobic group even used.

The microcapsule that contains core material that obtains among the embodiment 2G is tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.Embodiment 2H

The microcapsule that contains core material with the method preparation identical with embodiment 2, just the MTES of 45.9 grams is replaced by the MTES of the dimethyldiethoxysilane of 19.1 grams and 23.0 grams, and the amount of 2-ethylhexyl p-methoxycinnamic acid ester is changed into 97.7 grams.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 460 gram that is mainly 1 to 2 μ m is removed the component 27.1% behind the moisture

As mentioned above, in embodiment 2H,, also prepared the microcapsule that contains core material even the part of ortho-siliformic acid is replaced by dihydroxy silane.

The microcapsule that contains core material that obtains among the embodiment 2H is 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 microcapsule that contains 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 microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 425 gram that is mainly 1 to 2 μ m is removed the component 25.1% behind the moisture

As mentioned above, in embodiment 2I,, also prepared the microcapsule that contains core material even the alkoxy silane that uses among the embodiment 2H is replaced by cyclosiloxane.

The microcapsule that contains core material that obtains among the embodiment 2I is tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.Embodiment 2J

Prepare the microcapsule that contains core material with the method identical, only be to use the Emerest 2310s of 16.2 grams and the rosin acid of 4.1 grams with embodiment 2F, rather than 2-ethylhexyl p-methoxycinnamic acid ester, and do not carry out the processing of intimate mixing machine.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 1 to 100 μ m, capsular aqueous dispersion 226 gram that is mainly 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 microcapsule that has obtained containing rosin acid in the Emerest 2310, rosin acid at room temperature is a kind of hard resin.

The microcapsule that contains core material that obtains among the embodiment 2J is 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 microcapsule that contains 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 silkworm silk fibroin of propyl group hydrolysis, rather than N-[2-hydroxyl-3-(3 '-dihydroxy methyl silicane base) propoxyl group] collagen protein of propyl group hydrolysis.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 1 to 100 μ m, capsular aqueous dispersion 375 gram that is mainly 10 to 50 μ m is removed the component 20% behind the moisture

As mentioned above, in embodiment 2K,, still obtained containing the microcapsule of core material even used silkworm silk fibroin as hydrophilic group with hydrolysis.

The microcapsule that contains core material that obtains among the embodiment 2K is tested, whether broken to observe in the above-mentioned method of testing 1 its capsule, find to have granular size about g μ m 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 microcapsule that contains core material with the method preparation identical with embodiment 2F, only be to use the castor bean oil of 10.5 grams, rather than 2-ethylhexyl p-methoxycinnamic acid ester, and the amount of MTES and phenyl triethoxysilane is changed into 38.2 grams and 10.3 respectively restrain.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 300 gram that is mainly 1 to 2 μ m is removed the component 15% behind the moisture

As mentioned above, in embodiment 2L, obtained a kind of microcapsule that contains castor bean oil, castor bean oil at room temperature is a kind of viscous liquid.

The microcapsule that contains core material that obtains among the embodiment 2L is tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not observe the capsule fragmentation.Embodiment 2M

The microcapsule that contains 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 protein of propyl group hydrolysis, rather than N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen protein of propyl group hydrolysis.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 370 gram that is mainly 1 to 2 μ m is removed the component 11.9% behind the moisture

As mentioned above, in embodiment 2M,, also prepared the microcapsule that contains core material even used chemical compound with cation group monomer component as the organopolysiloxane that forms capsule wall.

The microcapsule that contains core material that obtains among the embodiment 2M is 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 microcapsule of core material with the method preparation identical, only be to use the abienol cetylates of 4.6 grams and the Witconol 2310s of 4.6 grams with embodiment 2, rather than 2-ethylhexyl p-methoxycinnamic acid ester.

The resulting dispersion that contains the microcapsule 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 capsular aqueous dispersion 310 gram that is mainly 1 to 2 μ m is removed free abienol cetylate in component 14.8% dispersion behind the moisture is 0.1%.The amount of the abienol cetylate that contains in the capsule is 9.9%.

As mentioned above, in embodiment 2N, by the abienol cetylate is dissolved in the microcapsule that Witconol 2310 has obtained containing the abienol cetylate, it at room temperature is a viscosity.

The microcapsule that contains core material that obtains among the embodiment 2M is 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 microcapsule of core material with the method preparation identical, only be to use the tocopherol acetass of 4.6 grams and the Emerest 2310s of 4.6 grams with embodiment 2, rather than 2-L base hexyl p-methoxycinnamic acid ester.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 10 μ m, capsular aqueous dispersion 324 gram that is mainly 2 to 7 μ m is removed the component 14.3% behind the moisture

As mentioned above, in embodiment 20, by tocopherol acetas being dissolved in the microcapsule that has obtained containing tocopherol acetas in the Emerest 2310, tocopherol is a kind of derivant of vitamin E.

The microcapsule that contains core material that obtains among the embodiment 20 is 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 microcapsule that contains 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 chloride and 2.4 grams, 25% sodium hydrate aqueous solution is used for neutralization.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 820 gram that is mainly 1 to 2 μ m is removed the component 61.1% behind the moisture

In the preparation method of the microcapsule that contains 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 microcapsule and part cohesion with microscopic examination.In present embodiment 3, do not see this cohesion.

The microcapsule that contains core material that obtains among the embodiment 3 is tested, whether broken to observe in the above-mentioned method of testing 1 its capsule.Do not find the capsule fragmentation.Embodiment 4 contains 2-ethylhexyl p-methoxycinnamic acid ester and has a kind of preparation of microcapsule 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 protein 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 protein (number-average molecular weight of collagen protein 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, the control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of core material and emulsifying

126.9 gram 2-ethylhexyl p-methoxycinnamic acid esters 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 half reaction solution of pact of preparation be transferred in the vessel of an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, 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) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule 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 microcapsule that contains core material is in the scope of nanocapsule.Thereby, about the microcapsule that contains 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, capsular aqueous dispersion 250 gram that is mainly 0.4 to 0.7 μ m is removed component 20 grams behind the moisture

The microcapsule that contains core material that obtains among the embodiment 4 is tested, whether broken with observation its capsule in above-mentioned method of testing 1.Do not find the capsule fragmentation.Embodiment 4A

Contain the microcapsule 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 microcapsule of core material is analyzed according to analytical method 1 and 6, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 250 gram that is mainly 1 to 2 μ m is removed the component 20% behind the moisture

The microcapsule that contains core material that obtains among the embodiment 4A is 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 protein (number-average molecular weight of the collagen protein 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 emulsifying

389 gram 2-ethylhexyl p-methoxycinnamic acid esters 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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, so that component particlesization.4) cured of capsule wall

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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 5, obtained following result.Have diameter 0.3 to 5 μ m, be mainly the capsular aqueous dispersion 5 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 10ml 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 lyophilization processing of the microcapsule of core material

With embodiment 4) part of the product that obtains in the step 4) is carried out lyophilization, 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 purification to contain the microcapsule of core material

The microcapsule that contains 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 protein (number-average molecular weight of the collagen protein of hydrolysis is about 2000) of propyl group hydrolysis, rather than N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] collagen protein of propyl group hydrolysis, used the MTES of 38.3 grams, 35.3 the 2-ethylhexyl p-methoxycinnamic acid ester of gram, and do not use the processing of methyl trichlorosilane.

The microcapsule that contains core material that obtains is 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 microcapsule that contains core material of the concentration of control.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 0.3 to 5 μ m, capsular aqueous dispersion 150 gram that is mainly 1 to 2 μ m remove component 44% behind the moisture before centrifugalize is handled in the dispersion NaCl content be 0.34%.NaCl content is 0.02% in the dispersion after centrifugalize is handled.

As mentioned above, observe by centrifugalize and handle, the content of NaCl reduces.The microcapsule that contain core material of embodiment 6A by obtaining among the ultra-filtration purification embodiment 2F

The part of the microcapsule that contains core material that obtains among the embodiment 2F is carried out ultra-filtration, then, in remaining material, add the water of 2 to 5 times of volumes and suspend again.Then, carry out ultra-filtration again.With this operation triplicate, obtain having the microcapsule that contains core material of the concentration of control.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Have diameter 1 to 10 μ m, capsular aqueous dispersion 200 gram that is mainly 3 to 7 μ m remove component 20% behind the moisture before ultra-filtration is handled in the dispersion NaCl content be 0.38%.NaCl content is 0.03% in the dispersion after ultra-filtration is handled.

As mentioned above, observe by ultra-filtration and handle, the content of NaCl reduces.The preparation of the microcapsule 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] hydrolyzate of the collagen protein 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 protein (number-average molecular weight of collagen protein 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, the 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 emulsifying

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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, so that component particlesization.4) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 5, obtained following result.Have diameter 0.3 to 5 μ m, be mainly capsular toluene dispersion 241 grams 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 microcapsule that contains water with hydrophobic surface.Embodiment 7A

Contain the microcapsule 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 emulsifying in, used 160 Witconol 2310s that restrain, rather than toluene; In step 4) prevents to condense cured with capsule wall, used equimolar potassium hydroxide, rather than sodium hydroxide; And when being sneaked into Witconol 2310 again, 35% potassium chloride solution of 30.8 grams adds.

The dispersion of the microcapsule that contains core material that obtains 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 capsular dispersion 280 grams 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 microcapsule that contains core material is scattered in the Witconol 2310 layer.Like this, use dialkoxy silicane useless and prepared the microcapsule that contains core material of w/o type in embodiment 7A.

The microcapsule that contains core material that obtains among the embodiment 7A is tested, whether broken with observation its capsule in above-mentioned method of testing 1.Do not find the capsule fragmentation.Embodiment 7B

The microcapsule that contains 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 intimate mixing machine.

The dispersion of the little glue Nang that contains core material that obtains among the embodiment 7B is analyzed according to analytical method 5, obtained following result.Have diameter 0.3 to 5 μ m, be mainly capsular toluene dispersion 216 grams 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 microcapsule that contains core material that obtains among the embodiment 7B is tested, whether broken with observation its capsule in above-mentioned method of testing 1.Do not find the capsule fragmentation.Embodiment 7C

The microcapsule that contains 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 centrifugalize purification, and handle according to embodiment 6 usefulness intimate mixing machines, 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 microcapsule that contains core material that obtains among the embodiment 7C is analyzed according to analytical method 5, obtained following result.Have diameter 0.3 to 5 μ m, be mainly capsular toluene dispersion 324 grams of 1 to 2 μ m

The 200ml normal hexane is added in the dispersion that obtains among the embodiment 7C,, and use ultraviolet with the extracting of 100ml water.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 microcapsule that contains core material is scattered in the diisobutyl adipate ester layer.

The microcapsule that contains core material that obtains among the embodiment 7B is tested, whether broken with observation its capsule in above-mentioned method of testing 1.Do not find glue Nang fragmentation.Embodiment 8 has a kind of preparation of microcapsule 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] hydrolyzate of the collagen protein 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 protein (number-average molecular weight of the collagen protein 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, the control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of liquid perfluor ether and emulsifying

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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, so that component particlesization.4) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Capsular aqueous dispersion 110 gram with diameter 5 to the 10 μ m component 17.1% outside the branch that dewaters

This dispersion can be frozen drying.

The microcapsule that contains core material that obtains among the embodiment 8 is 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 protein (number-average molecular weight of the collagen protein 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, the control pH value is 7.0.Afterwards, this mixture is continued to stir 1 hour at 50 ℃.2) adding of liquid perfluor ether and emulsifying

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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, so that component particlesization.4) cured of Ning Ju prevention and capsule wall

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 microcapsule of core material is analyzed according to analytical method 5, obtained following result.Under optical microscope, do not see microcapsule.Obtained 260 and restrained the liquid that is divided into three phases.

In this comparative example, do not obtain containing the microcapsule 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 chemical compound of (by Shin-Etsu Silicone Co., the KBM-7803 that Ltd. produces) has obtained containing the microcapsule of liquid perfluor ether.Embodiment 9 contains the core material of 2-ethylhexyl p-methoxycinnamic acid ester, preparation with microcapsule 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 hydrolyzate 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 thickening agent, and mixture heated to gelatin is dissolved.Solution is cooled to 20 ℃, and viscosity is controlled at 50mPa.s, 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 emulsifying

The reaction solution for preparing in the step 1) is controlled at pH7.0 with 25% sodium hydrate aqueous solution, then, the 100 2-ethylhexyl p-methoxycinnamic acid esters that restrain is added in this reaction solution under 600rpm stirs, 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 an intimate mixing machine, so that component particlesization.4) cured of Ning Ju prevention and capsule wall

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, 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 microcapsule that contains core material.5) gelatin and 2-ethylhexyl p-methoxycinnamic acid ester removes

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 p-methoxycinnamic acid ester are removed.At last, in surplus materials, add 100ml water, obtain containing the dispersion of the microcapsule of core material.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 1 and 5, obtained following result.Has diameter 1 to 30 μ m, capsular aqueous dispersion 200 gram that is mainly 10 to the 20 μ m component 50% outside the branch that dewaters

In embodiment 9, the core material that contains 2-ethylhexyl p-methoxycinnamic acid ester, microcapsule with a kind of capsule wall of making by organopolysiloxane, this organopolysiloxane is contracted by the hydrolyzate copolymerization of MTES, and thing forms, and can prepare with stable manner in gelatin solution.

The microcapsule that contains core material that obtains among the embodiment 9 is 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 2-ethylhexyl p-methoxycinnamic acid ester, preparation with microcapsule of a kind of capsule wall of making by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolyzate of the collagen protein 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 protein (number-average molecular weight of the collagen protein 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 mixture 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, the control pH value is 7.0.2) adding of core material and emulsifying

2-ethylhexyl p-methoxycinnamic acid ester (by the MCX of Nippon Roche K.K. production) and 3.9 gram AZ-6101 (Me with 389 grams 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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, so that component particlesization.4) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.

In dispersion, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 1.58%.Embodiment 11

The microcapsule that contains core material with the method preparation identical with embodiment 10, only be to use the 2-ethylhexyl p-methoxycinnamic acid ester (by the MCX of Nippon Roche K.K. production) and 3.9 of 389 grams to restrain methylhydrogenpolysi,oxane (by Shin-Etsu Silicone Co., Ltd. the mixture KF-99P of Sheng Chaning), rather than the AZ-6101 (Me of the 2-ethylhexyl p-methoxycinnamic acid esters of 389 grams and 3.9 grams ₃SiO (Me ₂SiO) _α[MeSi (EtO) O] _βSiMe ₃, by Nippon Unicar Co., Ltd. produces) mixture.

In dispersion, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 1.55%.Embodiment 12

The microcapsule that contains core material with the method preparation identical with embodiment 10, only be to use the 2-ethylhexyl p-methoxycinnamic acid ester (by the MCX of Nippon Roche K.K. production) and 3.9 of 389 grams to restrain tetraethoxysilanes (by Shin-Etsu Silicone Co., Ltd. the mixture KBE-04 of Sheng Chaning), rather than the AZ-6101 (Me of the 2-ethylhexyl p-methoxycinnamic acid esters of 389 grams and 3.9 grams ₃SiO (Me ₂SiO) _α[MeSi (EtO) O] _βSiMe ₃, by Nippon Unicar Co., Ltd. produces) mixture.

In dispersion, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 1.05%.Embodiment 13 contains 2-ethylhexyl p-methoxycinnamic acid ester and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolyzate of the collagen protein 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 protein (number-average molecular weight of the collagen protein 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, the control pH value is 7.0.2) adding of core material and emulsifying

The 2-ethylhexyl p-methoxycinnamic acid ester (by the MCX of Nippon Roche K.K. production) and 3.9 of 389 grams is restrained tetraethoxysilanes (by Shin-Etsu Silicone Co., 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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, 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) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.

In dispersion, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.20%.Embodiment 13A

Contain the microcapsule of core material with the method preparation identical, just do not use tetraethoxysilane with embodiment 13.

In dispersion, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 2.36%.Embodiment 14 contains 2-ethylhexyl p-methoxycinnamic acid ester and tetraethyl silane and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolyzate 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 Silicone 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, the control pH value is 7.0.2) adding of core material and emulsifying

The 2-ethylhexyl p-methoxycinnamic acid ester (by the MCX of Nippon Roche K.K. production) and 2.44 of 244 grams is restrained tetraethoxysilanes (by Shin-Etsu Silicone Co., 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 an intimate mixing machine, and with the processing 60 minutes under 50 ℃ and 5000rpm of this intimate mixing machine, 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) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.

In dispersion, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.16%.

After this dispersion was placed 1 day, the amount of measuring free 2-ethylhexyl p-methoxycinnamic acid ester in the dispersion was 0.63%.Embodiment 15

Contain the microcapsule 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, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 1.35%.

After this dispersion was placed 1 day, the amount of measuring free 2-ethylhexyl p-methoxycinnamic acid ester in the dispersion was 1.61%.Embodiment 16 contains 2-ethylhexyl p-methoxycinnamic acid ester and tetraethyl silane and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolyzate of the sericin of propyl group hydrolysis, MTES, the copolymerization of hexyl triethoxysilane and tetraethoxysilane contract, and thing forms

Contain the microcapsule of core material with the method preparation identical with embodiment 14, just the amount of 2-ethylhexyl p-methoxycinnamic acid ester that adds as core material and tetraethyl silane is changed into 266 grams and 2.66 respectively 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, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.38%.Embodiment 17

Contain the microcapsule 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, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 1.34%.Embodiment 18 contains 2-ethylhexyl p-methoxycinnamic acid ester and tetraethyl silane and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolyzate of the collagen protein 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 protein (number-average molecular weight of the collagen protein 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, the control pH value is 7.0.2) adding of core material and emulsifying

The 2-ethylhexyl p-methoxycinnamic acid ester (by the MCX of Nippon Roche K.K. production) and 0.697 of 69.7 grams is restrained tetraethoxysilane (by Shin-Etsu Silicone Co., 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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, 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, with the solution restir that produced 1 hour, then, 5.46 grams, 25% aqueous sodium hydroxide is added.5) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.

In dispersion, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.06%.

After this dispersion was placed 1 day, the amount of measuring free 2-ethylhexyl p-methoxycinnamic acid ester in the dispersion was 0.39%.Embodiment 19

Contain the microcapsule 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, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.13%.

After this dispersion was placed 1 day, the amount of measuring free 2-ethylhexyl p-methoxycinnamic acid ester in the dispersion was 0.77%.Embodiment 20 contains 2-ethylhexyl p-methoxycinnamic acid ester and tetraethyl silane and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolyzate of the collagen protein of propyl group hydrolysis, MTES, the copolymerization of hexyl triethoxysilane and tetraethoxysilane contract, and thing forms

Contain the microcapsule of core material with the method preparation identical with embodiment 18, just the amount of 2-ethylhexyl p-methoxycinnamic acid ester that adds as core material and tetraethyl silane is changed into 70.3 grams and 0.703 respectively and restrains; 16.5 the gram phenyl triethoxysilane is replaced by the hexyl trimethoxy silane of 14.15 grams.

In dispersion, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.13%.

After this dispersion was placed 1 day, the amount of measuring free 2-ethylhexyl p-methoxycinnamic acid ester in the dispersion was 0.63%.Embodiment 21

Contain the microcapsule 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, the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.15%.

After this dispersion was placed 1 day, the amount of measuring free 2-ethylhexyl p-methoxycinnamic acid ester in the dispersion was 1.00%.Analytical method 7

With about 0.1 the gram the microcapsule that contains core material that obtains 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 normal 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 p-methoxycinnamic acid ester.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 normal 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.Use the concentration of 2-ethylhexyl p-methoxycinnamic acid ester among liquid chromatograph measuring samples 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 p-methoxycinnamic acid ester.Embodiment 22 contains 2-ethylhexyl p-methoxycinnamic acid ester and tetraethyl silane and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolyzate 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, the control pH value is 7.0.2) adding of core material and emulsifying

The reaction solution that obtains in step 1) stirred after 30 minutes, the 2-ethylhexyl p-methoxycinnamic acid ester (by the MCX of Nippon Roche K.K. production) and 2.6 of 257.4 grams is restrained tetraethoxysilanes (by Shin-Etsu Silicone Co., 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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine.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 intimate mixing machine, and under 50 ℃ and 6000rpm, handled 60 minutes, so that component particlesization with this intimate mixing machine.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 with the mixture that produced 250rpm restir 1 hour.Then, the adding of 2.2 grams, 25% sodium hydrate aqueous solution is neutralized.5) cured of Ning Ju prevention and capsule wall restrains trim,ethylchlorosilanes (by Shin-Etsu Silicone Co. with 2.0, 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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 5 and 7, obtained following result.Have diameter 0.3 to 5 μ m, the capsular aqueous dispersion that is mainly 1 to 3 μ m is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 1.686%.The amount of the 2-ethylhexyl p-methoxycinnamic acid ester that leaked out in 2 minutes is 0.1138%.Embodiment 22A

Contain the microcapsule of core material with the method preparation identical with embodiment 22, just tetraethoxysilane is not used in the preparation of prepolymer.Capsular aqueous dispersion with diameter 1 to 5 μ m is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.210%.The seepage speed of 2-ethylhexyl p-methoxycinnamic acid ester is 0.0348%/minute.Embodiment 231) carry out step " preparation of the prepolymer of capsule wall " and " adding of core material and emulsifying " 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 an intimate mixing machine, and under 50 ℃ and 6000rpm, handled 90 minutes, so that component particlesization with this intimate mixing machine.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 cured of capsule wall ", obtains a kind of microcapsule that contains core material.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 5 and 7, obtained following result.Have diameter 0.3 to 5 μ m, the capsular aqueous dispersion that is mainly 1 to 3 μ m is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.7767%.The amount of the 2-ethylhexyl p-methoxycinnamic acid ester that leaked out in 2 minutes is 0.3801%.Embodiment 241) 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 ", 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 emulsifying

Carry out " adding of core material and emulsifying " among the embodiment 22 in an identical manner, just to be changed respectively be that 228.2 grams and 2.3 restrain to the amount of 2-ethylhexyl p-methoxycinnamic acid ester and tetraethyl silane.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 with the mixture restir that produced 1 hour.Then, the adding of 1.9 grams, 25% sodium hydrate aqueous solution is neutralized.5) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 5 and 7, obtained following result.Capsular aqueous dispersion with diameter 1 to 5 μ m is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.818%.2-ethylhexyl p-methoxycinnamic acid ester 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 propylene glycol of 4.0 grams.2) adding of core material and emulsifying

Carry out " adding of core material and emulsifying " among the embodiment 22 in an identical manner, just to be changed respectively be that 250 grams and 2.5 restrain to the amount of 2-ethylhexyl p-methoxycinnamic acid ester and tetraethyl silane.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 intimate mixing machine 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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 5 and 7, obtained following result.Have diameter 0.3 to 3 μ m, the capsular aqueous dispersion that mainly is 1 to 3 μ m is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.7994%.The amount of the 2-ethylhexyl p-methoxycinnamic acid ester that oozed out in 2 minutes is 0.2722%.Embodiment 26

With with embodiment 25 in identical mode prepare the microcapsule that contains core material, just with the propylene glycol of 4.0 grams with glycerol replacements with 4.0 grams.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 5 and 7, obtained following result.Have diameter 0.3 to 3 μ m, the capsular aqueous dispersion that mainly is 1 to 3 μ m is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.7028%.The amount of the 2-ethylhexyl p-methoxycinnamic acid ester that oozed out in 2 minutes is 0.0219%.Embodiment 27 contains 2-ethylhexyl p-methoxycinnamic acid ester and tetraethyl silane and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolyzate 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 microcapsule that contains 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 microcapsule of core material is analyzed according to analytical method 5 and 7, obtained following result.Have diameter 0.3 to 3 μ m, the capsular aqueous dispersion that mainly is 1 to 3 μ m is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.4925%.The amount of the 2-ethylhexyl p-methoxycinnamic acid ester that oozed out in 2 minutes is 0.0695%.Embodiment 28 contains 2-ethylhexyl p-methoxycinnamic acid ester and the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane and has the preparation of a kind of little glue Nang of the capsule wall of being made by organopolysiloxane; this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolyzate 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, the control pH value is 7.0.2) adding of core material, emulsifying and micronize

The reaction solution for preparing in the step 1) is transferred in the vessel of an intimate mixing machine; and under 50 ℃ and 9000rpm, handled 90 minutes with this intimate mixing machine; and dropwise add the 2-ethylhexyl p-methoxycinnamic acid esters (MCX that produces by Nippon Roche K.K.) of 203 grams; 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 intimate mixing machine, and under 50 ℃ and 6000rpm, handled 60 minutes, so that component particlesization with this intimate mixing machine.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 with the mixture restir that produced 1 hour.Then, 2.7 grams, 20% aqueous sodium hydroxide is added.5) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule 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 capsular aqueous dispersion 436.0 gram that is mainly 1 to 3 μ m dewaters is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.5658%.2-ethylhexyl p-methoxycinnamic acid ester ooze out speed be 0.0254%/minute.Embodiment 29

With with embodiment 28 in identical mode prepare the microcapsule that contains core material, just with the glycerol replacements of the methanol of 20 grams with 4.5 grams.

The resulting dispersion that contains the microcapsule 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 capsular aqueous dispersion 460 gram that is mainly 1 to 3 μ m dewaters is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.5151%.2-ethylhexyl p-methoxycinnamic acid ester ooze out speed be 0.0254%/minute.Embodiment 30

With with embodiment 28 in identical mode prepare the microcapsule that contains 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 propylene glycol, 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 microcapsule 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 capsular aqueous dispersion 466.2 gram that is mainly 1 to 3 μ m dewaters is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.1848%.2-ethylhexyl p-methoxycinnamic acid ester ooze out speed be 0.0192%/minute.Embodiment 31

With with embodiment 28 in identical mode prepare the microcapsule that contains 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 microcapsule 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 capsular aqueous dispersion 460.4 gram that is mainly 1 to 3 μ m dewaters is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.5317%.2-ethylhexyl p-methoxycinnamic acid ester ooze out speed be 0.0391%/minute.Embodiment 32

With with embodiment 28 in identical mode prepare the microcapsule that contains 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 microcapsule 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 capsular aqueous dispersion 394.0 gram that is mainly 1 to 3 μ m dewaters is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.5477%.2-ethylhexyl p-methoxycinnamic acid ester ooze out speed be 0.0088%/minute.Embodiment 33 contains 2-ethylhexyl p-methoxycinnamic acid ester and the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane; this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolyzate 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 microcapsule that contains 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 microcapsule of core material is analyzed according to analytical method 5 and 7, obtained following result.Component 60.27% outside capsular aqueous dispersion 463.9 gram with diameter 1 to 15 μ m dewaters is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 1.5579%.2-ethylhexyl p-methoxycinnamic acid ester 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 emulsifying of core material " 2) " among the embodiment 30 in an identical manner.2) adding of core material, emulsifying and micronize

The reaction solution for preparing in the step 1) is transferred in the vessel of an intimate mixing machine; and under 50 ℃ and 9000rpm, handled 90 minutes with this intimate mixing machine; and under reduced pressure (500mmHg) dropwise adds the 203 2-ethylhexyl p-methoxycinnamic acid esters that restrain (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 intimate mixing machine, and under 50 ℃ and 6000rpm, handled 60 minutes, so that component particlesization with this intimate mixing machine.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 cured of capsule wall ", obtains a kind of microcapsule that contains core material.

The resulting dispersion that contains the microcapsule 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 capsular aqueous dispersion 466.1 gram that is mainly 1 to 3 μ m dewaters is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.5812%.2-ethylhexyl p-methoxycinnamic acid ester ooze out speed be 0.1262%/minute.Embodiment 351) prepare prepolymer in the mode identical with embodiment 30.2) adding of core material, emulsifying and micronize

The reaction solution for preparing in the step 1) is transferred in the vessel of an intimate mixing machine; and with this intimate mixing machine at 50 ℃; handle in 90 minutes in ultrasound wave and under the 9000rpm; the 2-ethylhexyl p-methoxycinnamic acid ester (by the MCX of Nippon Roche K.K. production) that dropwise adds 203 grams; 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 intimate mixing machine, and under 50 ℃ and 6000rpm, handled 60 minutes, so that component particlesization with this intimate mixing machine.3) carry out the step skin of the capsule wall " handle " and " prevention of cohesion and the cured of capsule wall " among the embodiment 30 in an identical manner, obtain a kind of microcapsule that contains core material.

The resulting dispersion that contains the microcapsule 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 capsular aqueous dispersion 445.9 gram that is mainly 1 to 3 μ m dewaters is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.7385%.2-ethylhexyl p-methoxycinnamic acid ester 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 emulsifying

The reaction solution for preparing in the step 1) under handling, 600rpm is added the 2-ethylhexyl p-methoxycinnamic acid ester (by the MCX of Nippon Roche K.K. production) of 202.64 grams and the mixture of the 50.66 gram 4-tert-butyl groups-4 '-methoxy dibenzoyl methylmethane (being produced 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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine.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 intimate mixing machine, and under 50 ℃ and 6000rpm, handled 60 minutes, so that component particlesization with this intimate mixing machine.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 cured of capsule wall ", obtains a kind of microcapsule that contains core material.

The resulting dispersion that contains little glue Nang of core material is analyzed according to analytical method 5 and 7, obtained following result.Component 59.36% outside capsular aqueous dispersion with diameter 2 to 20 μ m dewaters is in dispersion, and the amount of free 2-ethylhexyl p-methoxycinnamic acid ester is 0.9315%.2-ethylhexyl p-methoxycinnamic acid ester 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 component concentration of compound of reaction is controlled in 15%.Embodiment 37 contains 2-ethylhexyl p-methoxycinnamic acid ester and tetraethyl silane and has a kind of preparation of microcapsule of the capsule wall of being made by organopolysiloxane, this organopolysiloxane is by N-[2-hydroxyl-3-(3 '-trihydroxy silicyl) propoxyl group] hydrolyzate 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, the control pH value is 7.0.2) adding of core material and emulsifying

The 2-ethylhexyl p-methoxycinnamic acid ester (by the MCX of Nippon Roche K.K. production) and 1.6 of 160.7 grams is restrained tetraethoxysilanes (by Shin-Etsu Silicone Co., 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 an intimate mixing machine, and with the processing 90 minutes under 50 ℃ and 6000rpm of this intimate mixing machine, 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 with the mixture that produced 450rpm restir 1 hour.Then, the adding of 0.4 gram, 20% sodium hydrate aqueous solution is neutralized.5) cured of Ning Ju prevention and capsule wall

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 microcapsule that contains core material.

The resulting dispersion that contains the microcapsule of core material is analyzed according to analytical method 5 and 7, obtained following result.Have diameter 5 μ m or littler capsular aqueous dispersion outside dewatering component 50.50% analytical method 8SPF value and the mensuration of ultraviolet transmittance

Working sample is applied to (by the TRANSPORETAPE of 3M company production) on the surgery belt, uses ultraviolet radiation, (UV-1000S is by LABSPHERE Corp for the amount of usefulness APF analyser measurement transillumination., 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 $\mathrm{SPF}=\underset{290\mathrm{nm}}{\overset{400\mathrm{nm}}{\mathrm{\&Sigma;}}}E\left(\mathrm{\&lambda;}\right)\mathrm{\&epsiv;}\left(\mathrm{\&lambda;}\right)/[\underset{290\mathrm{nm}}{\overset{400\mathrm{nm}}{\mathrm{\&Sigma;}}}\left(E\left(\mathrm{\&lambda;}\right)\mathrm{\&epsiv;}\left(\mathrm{\&lambda;}\right)\right)/\left(\mathrm{MEP}\left(\mathrm{\&lambda;}\right)\right)]$ E (λ): the spectral distribution ε of daylight (λ): the behavior spectral line MPF (λ) of delaying type photochemistry erythema: in the mensuration of the mutual absorbance analytical method 9 skin transmitances of each wavelength

To thaw at 30 minutes inner room relaxing the bowels with purgatives of warm nature 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 subcutaneous tissue.They are used the homogenate of 5ml methanol, centrifugalize (3000rpm, 30 minutes), separation of supernatant, and by a membrane filtration (cellulose acetate membrane, 0.80 μ m, ADAVANTEC TOYO).Then, measure the concentration of UV absorbent 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.

Mobile phase: methanol: 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 p-methoxycinnamic acid ester are at the ultraviolet transmittance of 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 UV absorbent that contains though the embodiment 22A that applies, the amount of the sample that obtains in 24 and 28 is less than the amount of the 2-ethylhexyl p-methoxycinnamic acid ester that applies, embodiment 22A, 24 and 28 ultraviolet transmittance is less than the ultraviolet transmittance of 2-ethylhexyl p-methoxycinnamic acid ester.Embodiment 39

Measure the skin transmitance of 50% (weight) isopropyl miristate solution of the microcapsule that obtains among the embodiment 28 and 2-ethylhexyl p-methoxycinnamic acid ester according to analytical method 9, gained the results are shown in following table.

	Concentration in the epidermis (μ g/cm 3)	Concentration in the subcutaneous tissue (μ g/cm 3)
			The microcapsule that obtains among the embodiment 28	????5	????1700
2-ethylhexyl p-methoxycinnamic acid ester/isopropyl miristate holds liquid	????52	????12000

As can be seen, the microcapsule that obtains among the embodiment 28 has suppressed UV absorbent the penetrating in skin contained in the capsule.Embodiment 40, and the comparative example 4: the liquid base

The weighing stearic acid, Cera Flava, hydrogenated lanolin, Witconol 2310, squalane, and Span-83, and in 80 ℃ of dissolvings (solution 1).Difference weighing triethanolamine, 1,3 butylene glycol, the microcapsule that contains core material that partially purified water and embodiment 13 obtain is heated to 85 ℃, and under agitation adds 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 ferrum oxide are weighed, and to wherein adding remaining pure water.With the dispersion fully in an intimate mixing machine 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 2-ethylhexyl p-methoxycinnamic acid ester, rather than contain the microcapsule of core material.

The 2-ethylhexyl p-methoxycinnamic acid ester that contains in the microcapsule of Shi Yonging in the present embodiment, UV absorbent, amount and comparative example in the amount of the UV absorbent 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	Ferrum oxide			????1.00	????1.00
????6	Stearic acid			????2.00	????2.00
		????7	Cera Flava			????1.20	????1.20
????8	Hydrogenated lanolin			????1.00	????1.00
		????9	Witconol 2310			????2.00	????2.00
????10	Squalane			????2.00	????2.00
		????11	Span-83			????0.40	????0.40
????12	Triethanolamine			????0.50	????0.50
		????13	1,3 butylene glycol			????2.80	????2.80
????14	Lecithin			????0.20	????0.20
		????15	Antiseptic			????0.30	????0.30
????16	Perfume			????0.50	????0.50
		????17	Pure water			Add to 100	Add to 100
????A	Microcapsule			????62.60	????-
		????B	2-ethylhexyl p-methoxycinnamic acid ester			????-	????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 the ultraviolet performance.Though made up a large amount of 2-ethylhexyl p-methoxycinnamic acid esters, 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 microcapsule that contains core material that obtains 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	Ferrum oxide			????4.00	????4.00
????6	Cera Flava			????8.40	????8.40
		????7	The solidified castor bean oil of polyoxyethylene			????0.60	????0.60
????8	Brazil wax			????1.20	????1.20
		????9	Olive oil			????13.50	????13.50
????10	The castor bean oil of purification			????6.00	????6.00
		????11	The oleyl sodium phosphate			????0.60	????0.60
????12	Antiseptic			????0.30	????0.30
		????13	Perfume			????0.30	????0.30
????14	Octyldodecanol			Add to 100	Add to 100
		????A	Microcapsule			????16.50	????-
????B	2-ethylhexyl p-methoxycinnamic acid ester			????-	????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 " to the adhesiveness of skin " in 10 people's group, assess, the result is as follows.

Adherent assessment
		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 microcapsule that contains core material that obtains 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	Hydroxyethyl-cellulose			????0.30	????0.30
		????3	Pure water			????20.00	????20.00
????4	Sodium hydroxide (1% aqueous solution)			????3.00	????3.00
		????5	Pure water			????20.00	????20.00
????6	Propylene glycol			????8.00	????8.00
		????7	????EDTA-2Na			????0.20	????0.20
????8	Antiseptic			????0.30	????0.30
		????9	Pure water			Add to 100	Add to 100
????A	Microcapsule			????9.4	????-
		????B	2-ethylhexyl p-methoxycinnamic acid ester			????-	????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 absorbance and UVB absorbance are as follows.

	Spf value	UVA absorbance e (%)	UVA absorbance 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 microcapsule that contains core material that obtains among the embodiment 36, obtained having the sunscreen cream 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	CVP Carbopol ETD2050 * 2 (1% aqueous solution)			????50.00	????50.00
		????3	Cetearyl alcohol acyl 2-ethylhexanoate (2)			????5.00	????5.00
????4	Concentrate glycerol			????3.00	????3.00
		????5	????EDTA-2Na			????0.20	????0.20
????6	Antiseptic			????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	Microcapsule			????18.7	????-
		????B	2-ethylhexyl p-methoxycinnamic acid ester			????-	????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 sunscreen cream, the result of UVA absorbance and UVB absorbance 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 absorbance (%)	UVB absorbance (%)
				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, microcapsule of the present invention can easily be combined in the ingredients, has good stable as time goes by.Thereby, also be possible even in cosmetics, be combined into UV absorbent, and the combination of UV absorbent is difficult under normal condition.Embodiment 44, and the comparative example 8

Use the microcapsule that contains core material that obtains 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) ripening			????5.00	????5.00
????2	????Isopropyl?myristate			????6.00	????6.00
		????3	Liquid paraffin #70			????5.00	????5.00
????4	????Jojoba?oil			????5.00	????5.00
		????5	Magnesium stearate			????0.80	????0.80
????6	Zinc oxide			????3.00	????3.00
		????7	Magnesium sulfate			????0.30	????0.30
????8	Concentrate glycerol			????5.00	????5.00
		????9	????EDTA-2Na			????0.10	????0.10
????10	Tocopherol acetas			????1.00	????1.00
		????11	Antiseptic			????0.30	????0.30
????12	Pure water			Add to 100	Add to 100
		????A	Microcapsule			????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 " to the adhesiveness of skin " in 10 people's group, assess, the result is as follows.

Adherent assessment
		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 microcapsule that contains core material that obtains among the embodiment 13, obtained having the sunscreen cream of following prescription in the mode similar to embodiment 40 and comparative example 4.

		Combined amount (W/W%)
				Embodiment 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	Liquid paraffin #70			????10.0	????10.0
		????5	Polyoxyethylene (20) oleyl ether			????2.0	????2.0
????6	Antiseptic			????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	Microcapsule			????41.7	????-
		????B	The 2-ethylhexyl is to methoxyl group meat esters of silicon acis			????-	????20.00

The spf value of resulting sunscreen cream 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, this microcapsule has good stable as time goes by and prevents the sunblock compositions flavescence.Embodiment 46, and the comparative example 10

Use the microcapsule that contains core material that obtains 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-sorbitol glycerol trioleate, the mixture of liquid paraffin and volatility isoparaffin			????2.0	????2.0
????2	The copolymer of poly-(oxygen ethylene, oxypropylene) and methyl polysiloxane			????5.0	????5.0
		????3	22-ethylhexyl isoparmitate			????2.0	????2.0
????4	Chlorination N-[2-hydroxyl-3-(Petiolus Trachycarpi oil alkyl dimethyl ammonia) propyl group] collagen protein of hydrolysis			????0.3	????0.3
		????11	Antiseptic			????0.3	????0.3
????12	Pure water			Add to 100	Add to 100
		????A	Microcapsule			????4.9	????-
????B	2-ethylhexyl p-methoxycinnamic acid ester			????-	????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 prior wetted bundle of hair 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.

Adherent assessment
		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 the compatibility.Embodiment 47, and the comparative example 11

Use the microcapsule that contains core material that obtains 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	Cera Flava			????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	Liquid paraffin #70			????18.0	????18.0
????6	Glycerol three isostearates			????15.0	????15.0
		????7	Muscovitum			????10.0	????10.0
????8	Ferrum 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	Microcapsule			????5.2	????-
????B	2-ethylhexyl p-methoxycinnamic acid ester			????-	????3.0

With resulting lipstick with 2 times of liquid paraffin 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 microcapsule that contains core material that obtains 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	CVP Carbopol ETD2050			????0.30	????0.30
????2	Potassium hydroxide			????0.15	????0.15
		????3	1,3 butylene glycol			????5.00	????5.00
????4	Two glycerol			????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	Microcapsule			????10.0	????-
		????B	2-ethylhexyl p-methoxycinnamic acid ester			?????-	????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 subcutaneous tissue (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 UV absorbent that is combined and has infiltrated skin.

Claims (28)

1. microcapsule that contains core material and capsule wall, wherein, the capsule wall of this microcapsule contains:

By chemical compound (B), monomer or monomeric mixture, the synthetic organopolysiloxane of bunching, wherein, chemical compound (B) contains one or more chemical 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 chemical 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 chemical compound of formula (II) expression of affinity.

2. according to the described microcapsule that contains core material of claim 1, wherein, chemical compound (B) is by hydrolysis compound (A), and monomer or monomeric mixture obtain, and wherein, chemical compound (A) contains one or more chemical 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 chemical compound (A) contains at least a chemical compound that at least a formula (I) with R group of affinity in continuous phase and the decentralized photo is represented that has.

3. according to the described microcapsule that contains core material of claim 1, wherein, the chemical compound that at least a formula (II) that is contained by chemical compound (B) is represented has a kind of R group that carries hydrophilic group.

4. according to the described microcapsule that contains core material of claim 3, wherein, this hydrophilic group is the protein of a kind of polyethers or a kind of hydrolysis.

5. according to the described microcapsule that contains core material of claim 4, wherein, this hydrophilic group is a polyoxyethylene, polyoxypropylene or polyoxyethylene-polyoxypropylene copolymer.

6. according to the described microcapsule that contains core material of claim 4, wherein, this hydrophilic group 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] the propyl group hydrolyzed protein.

7. according to the described microcapsule that contains core material of claim 5, wherein, this described polyoxyethylene, polyoxypropylene or polyoxyethylene-polyoxypropylene copolymer has 1 to 2000 number-average degree of polymerization.

8. according to the described microcapsule that contains core material of claim 6, wherein, the protein of described each hydrolysis has 100 to 50000 number-average molecular weight.

9. according to the described microcapsule that contains core material of claim 1, wherein, at least a chemical compound that is selected from hydrolyzable silane and hydrolyzable polysiloxanes is present in the core material of microcapsule.

10. according to the described microcapsule that contains core material of claim 1, wherein, handle once at least with at least a hydrolyzate that is selected from the chemical compound of hydrolyzable silane and hydrolyzable polysiloxanes on the capsule wall of this microcapsule surface.

11. according to the described microcapsule that contains core material of claim 1, wherein, the surface of capsule wall chemical compound (A), monomer or monomeric mixture are handled, and wherein, chemical compound (A) contains one or more chemical 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 chemical compound (A) contains at least a chemical compound that at least a formula (I) with R group of affinity in continuous phase and the decentralized photo is represented that has.

12. according to the described microcapsule that contains core material of claim 9, wherein, at least a chemical 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. according to the described microcapsule that contains core material of claim 10, wherein, at least a chemical 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.

14. a production contains the method for the microcapsule of core material and capsule wall, it may further comprise the steps successively:

(1) by the monomer or the monomeric mixture of hydrolysis compound (A), prepare the monomer or the monomeric mixture of chemical compound (B), wherein, chemical compound (B) contains one or more chemical 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 chemical 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 chemical compound of formula (II) expression of affinity,

Wherein, chemical compound (A) contains one or more chemical 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 chemical compound (A) contains at least a chemical compound that at least a formula (I) with R group of affinity in continuous phase and the decentralized photo is represented that has;

(2) pass through in and bunching chemical compound (B), form prepolymer;

(3) this prepolymer is mixed also emulsifying with the core material and/or second liquid phase;

(4) by further the prepolymer bunching being solidified the capsule wall of said microcapsule.

15. contain the method for the microcapsule of core material according to the described preparation of claim 14, wherein, the chemical compound of at least a formula (II) expression that is contained by chemical compound (B) has a kind of R group that carries hydrophilic group.

16. contain the method for the microcapsule of core material according to the described preparation of claim 15, wherein, this hydrophilic group is the protein of a kind of polyethers or a kind of hydrolysis.

17. contain the method for the microcapsule of core material according to the described preparation of claim 16, wherein, this hydrophilic group is a kind of polyoxyethylene with number-average degree of polymerization of 1 to 2000, polyoxypropylene or polyoxyethylene-polyoxypropylene copolymer.

18. contain the method for the microcapsule of core material according to the described preparation of claim 16, wherein, this hydrophilic group 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] the propyl group hydrolyzed protein.

19. contain the method for the microcapsule of core material according to the described preparation of claim 14, wherein also comprise in core material, adding the step that is selected from least a chemical compound in hydrolyzable silane and the hydrolyzable polysiloxanes.

20. contain the method for the microcapsule of core material according to the described preparation of claim 14, wherein also comprise the step of handling the capsule wall surface with the hydrolyzate that is selected from least a chemical compound in hydrolyzable silane and the hydrolyzable polysiloxanes.

21. contain the method for the microcapsule of core material according to the described preparation of claim 14, wherein also comprise the step of handling the capsule wall surface with a kind of chemical compound (A).

22. contain the method for the microcapsule of core material according to the described preparation of claim 14, wherein, to form the step of prepolymer all be to have before in the medium of 10 to 2000mPa.s viscosity and carry out adding chemical compound (A) to the bunching for preparing chemical compound (B) and chemical compound (B) of the hydrolysis by chemical compound (A).

23. contain the method for the microcapsule of core material according to the described preparation of claim 22, wherein, said medium is a kind of aqueous gelatin solution with viscosity 10 to 2000mPa.s.

24. according to the described microcapsule that contains core material of claim 1, wherein, this core material contains UV absorbent.

25. according to the described microcapsule that contains core material of claim 24, wherein, UV absorbent is a 2-ethylhexyl p-methoxycinnamic acid ester, or the 4-tert-butyl group-4 '-methoxy dibenzoyl methylmethane.

26. one kind contains the described preparation that contains the microcapsule of core material of claim 24.

27. according to the described preparation of claim 26, it is a kind of cosmetics or a kind of pharmaceutical preparation.

28. according to the described preparation of claim 27, wherein said preparation is applied on skin or the hair.