JPH01180244A - Microcapsule having multilayered external shell - Google Patents
Microcapsule having multilayered external shellInfo
- Publication number
- JPH01180244A JPH01180244A JP84088A JP84088A JPH01180244A JP H01180244 A JPH01180244 A JP H01180244A JP 84088 A JP84088 A JP 84088A JP 84088 A JP84088 A JP 84088A JP H01180244 A JPH01180244 A JP H01180244A
- Authority
- JP
- Japan
- Prior art keywords
- layered
- outer shell
- core material
- microcapsule
- layered wall
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003094 microcapsule Substances 0.000 title claims abstract description 74
- 239000011162 core material Substances 0.000 claims abstract description 54
- 230000008859 change Effects 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims description 12
- 238000010030 laminating Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 31
- 239000011347 resin Substances 0.000 abstract description 31
- 239000003086 colorant Substances 0.000 abstract description 12
- 238000012790 confirmation Methods 0.000 abstract 1
- 230000035882 stress Effects 0.000 description 43
- 239000000049 pigment Substances 0.000 description 23
- 239000000843 powder Substances 0.000 description 22
- 229920001577 copolymer Polymers 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 239000000126 substance Substances 0.000 description 12
- -1 polyethylene Polymers 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 230000004044 response Effects 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 8
- 229920002223 polystyrene Polymers 0.000 description 8
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 7
- 239000001055 blue pigment Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 230000008646 thermal stress Effects 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000001052 yellow pigment Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001054 red pigment Substances 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004040 coloring Methods 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000968 intestinal effect Effects 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000012463 white pigment Substances 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N alpha-Methyl-n-butyl acrylate Natural products CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 229940069428 antacid Drugs 0.000 description 2
- 239000003159 antacid agent Substances 0.000 description 2
- 230000001458 anti-acid effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000010582 Pisum sativum Nutrition 0.000 description 1
- 240000004713 Pisum sativum Species 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 239000000981 basic dye Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- YXTPWUNVHCYOSP-UHFFFAOYSA-N bis($l^{2}-silanylidene)molybdenum Chemical compound [Si]=[Mo]=[Si] YXTPWUNVHCYOSP-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- VVOLVFOSOPJKED-UHFFFAOYSA-N copper phthalocyanine Chemical compound [Cu].N=1C2=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC(C3=CC=CC=C33)=NC3=NC=1C1=CC=CC=C12 VVOLVFOSOPJKED-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021344 molybdenum silicide Inorganic materials 0.000 description 1
- 239000000983 mordant dye Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000000984 vat dye Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/20—After-treatment of capsule walls, e.g. hardening
- B01J13/22—Coating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing Of Micro-Capsules (AREA)
Abstract
Description
【発明の詳細な説明】
ｌ肌り汰■悠尖夏
本発明は、多層外殻マイクロカプセルに関し、さらに詳
しくは本発明は、エネルギー状態の変化に対応させて特
性を変化させることができる多層外殻マイクロカプセル
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a multilayer outer shell microcapsule, and more specifically, the present invention relates to a multilayer outer shell microcapsule whose properties can be changed in response to changes in energy state. Concerning shell microcapsules.
発明の技術的背景ならびにその問題点
マイクロカプセルの産業上の利用分野・応用分野は非常
に広範であり、既に多くの分野で実用化されている。こ
のようなマイクロカプセルは、基本的に芯材と、この芯
材の周囲に設けられた外殻（外壁）とからなる。Technical background of the invention and its problems The industrial fields of use and application of microcapsules are very wide, and they have already been put into practical use in many fields. Such microcapsules basically consist of a core material and an outer shell (outer wall) provided around the core material.
このようにマイクロカプセルの形態にすることの利点は
、主に取り扱いにくい物質あるいは不安定な物質を殻内
に封入することにより取り扱いが容易になる点にある。The advantage of forming microcapsules in this way is that substances that are difficult to handle or unstable are encapsulated within the shell, making them easier to handle.
すなわらマイクロカプセルの外殻は、芯材の保護のため
に設けられているのであって、使用しようとする物質は
一般には芯材中に含まれており、マイクロカプセルを使
用する際には、マイクロカプセルの外殻を破壊して、こ
の外殻により保護されていた芯材中に含まれる物質の特
性を表在化させて用いる。In other words, the outer shell of the microcapsule is provided to protect the core material, and the substance to be used is generally contained in the core material, so when using the microcapsule, , the outer shell of the microcapsule is destroyed, and the properties of the substance contained in the core material protected by the outer shell are exposed and used.
したがって、外殻は一般には芯材を保護するという作用
を有するのみであって、外殻の破壊状態を変化させるこ
とにより、外殻が有している特性を積極的に利用すると
いうようなマイクロカプセルの使用方法およびこのよう
な使用方法に用いられる特異な特性を有する外殻を持っ
たマイクロカプセルについてはまったく知られていない
。Therefore, the outer shell generally only has the function of protecting the core material, and by changing the state of destruction of the outer shell, the micro-structure actively utilizes the properties of the outer shell. There is nothing known about the use of capsules and the microcapsules with shells having unique properties for such use.
発明の目的
本発明は、新規な多層外殻マイクロカプセルを提供する
ことを目的とする。 。OBJECTS OF THE INVENTION The present invention aims to provide novel multilayer shell microcapsules. .
ざらに詳しくは、本発明は、エネルギー状態の変動に対
応させてマイクロカプセルの外殻の破壊状態あるいは特
性を変化させて、この破壊状態の相違に伴う変化を利用
することができる多層外殻マイクロカプセルを提供する
ことを目的とする。More specifically, the present invention provides a multilayer outer shell microcapsule that can change the fracture state or characteristics of the outer shell of the microcapsule in response to fluctuations in the energy state, and utilize changes accompanying the difference in the fracture state. The purpose is to provide capsules.
発明の概要
本発明に係る多層外殻マイクロカプセルは、芯材と、該
芯材外周に設けられた複数の層状壁が積層されてなる外
殻とを有するマイクロカプセルであって、該外殻が、こ
の外殻に加えられるエネルギーにより、外殻の最外層側
から芯材方向に層状壁が順次崩壊し若しくはその特性が
順次変化することにより、崩壊若しくは特性が変化した
該層状壁よりも芯材側に位置する他の層状壁の特性が該
外殼表面に表在化する２層以上の層状壁から構成されて
いることを特徴としている。Summary of the Invention The multilayer outer shell microcapsule according to the present invention is a microcapsule having a core material and an outer shell formed by laminating a plurality of layered walls provided on the outer periphery of the core material, the outer shell comprising: Due to the energy applied to this outer shell, the layered walls sequentially collapse from the outermost layer side of the outer shell toward the core material, or their properties change sequentially, so that the core material is lower than the layered wall whose properties have collapsed or changed. The other layered wall located on the side is characterized by being composed of two or more layered walls exposed on the surface of the outer shell.
本発明によれば、多層外殻マイクロカプセルが置かれた
環境のエネルギー状態の変動に伴って、外殻を構成する
２層以上の層状壁のうちの最外層側から層状壁が崩壊し
、若しくはその特性が変化して、その層状壁よりも芯材
側に位置する他の層状壁の特性が表在化するので、層状
壁の破壊状態を調べることにより、本発明の多層外殻マ
イクロカプセルの置かれた環境における機械的応力、化
学的応力、熱応力、電気的応力、磁気的応力および物理
化学的応力等の変動、すなわちエネルギー状態の変動を
認識、若しくは測定することができる。According to the present invention, as the energy state of the environment in which the multilayer outer shell microcapsule is placed changes, the layered wall collapses from the outermost layer side of the two or more layered walls constituting the outer shell, or The properties of the multilayered outer shell microcapsules of the present invention change, and the properties of other layered walls located closer to the core material than that layered wall become apparent. It is possible to recognize or measure variations in mechanical stress, chemical stress, thermal stress, electrical stress, magnetic stress, physicochemical stress, etc. in the environment, that is, variations in energy state.
また、上記のようなエネルギーの変動幅を予め設定する
ことにより、多層外殻を所望の段階まで破壊し、若しく
は変化させて所望の特性を表在化させることができる。Further, by setting the range of energy fluctuation in advance as described above, it is possible to destroy or change the multilayered shell to a desired stage to bring desired characteristics to the surface.
発明の詳細な説明
以下本発明に係る多層外殻マイクロカプセルについて具
体的に説明する。DETAILED DESCRIPTION OF THE INVENTION The multilayer shell microcapsules according to the present invention will be specifically described below.
第１図に本発明の多層外殻マイクロカプセルの一例の断
面図を模式的に示す。FIG. 1 schematically shows a cross-sectional view of an example of the multilayer shell microcapsule of the present invention.
本発明に係る多層外殻マイクロカプセルは、第１図に示
すように、芯材１と、この芯材１の外周に設けられた外
殻２とを有する。The multilayer outer shell microcapsule according to the present invention has a core material 1 and an outer shell 2 provided around the outer periphery of the core material 1, as shown in FIG.
芯材１を構成する素材は、本発明に係る多層外股マイク
ロカプセルの用途などを考慮して適宜選定することがで
きるが、本発明において、芯材１は、たとえば、熱可塑
性樹脂、熱硬化性樹脂等の樹脂成分、無機物、天然高分
子化合物、金属粉およびセラミックス等で構成すること
ができる。芯材１を構成する熱可塑性樹脂としては、ス
チレン樹脂、アクリル樹脂、たとえばポリエチレン、ポ
リプロピレン等のポリオレフィン樹脂、ナイロン樹脂、
シリコーン樹脂、フッ素樹脂、ポリエステル樹脂および
ポリアミド樹脂等が用いられ、熱硬化性樹脂としては、
エポキシ樹脂、ベンゾグアナミン樹脂およびフェノール
樹脂等が用いられる。The material constituting the core material 1 can be appropriately selected in consideration of the intended use of the multilayer outer microcapsule according to the present invention. It can be composed of resin components such as synthetic resins, inorganic substances, natural polymer compounds, metal powders, ceramics, and the like. The thermoplastic resin constituting the core material 1 includes styrene resin, acrylic resin, polyolefin resin such as polyethylene and polypropylene, nylon resin,
Silicone resins, fluororesins, polyester resins, polyamide resins, etc. are used, and thermosetting resins include:
Epoxy resin, benzoguanamine resin, phenol resin, etc. are used.
また、無機物としては、ガラスピーズ、アルミナおよび
シリカ等が用いられ、天然高分子としては、澱粉および
セルロース等が用いられる。ざらに、金属粉としてはフ
ェライト、鉄粉および亜鉛華等が用いられ、セラミック
スとしては、八ρ２ ｏ３、ＺｒＯおよびＴｉＯ２等が
用いられる。また、芯材に顔料などを含有させるなどの
方法により、芯材自体にエネルギー状態の変動によるす
べての層状壁が破壊されたことを表示させる機能を付与
することもできる。Further, as the inorganic substance, glass peas, alumina, silica, etc. are used, and as the natural polymer, starch, cellulose, etc. are used. In general, ferrite, iron powder, zinc white, etc. are used as metal powders, and 8ρ2 o3, ZrO, TiO2, etc. are used as ceramics. Furthermore, by adding a pigment or the like to the core material, it is possible to give the core material itself a function that indicates that all the layered walls have been destroyed due to changes in the energy state.
こ、れらの芯材１としては、球状、楕円体状等の種々の
形態のものを用いることができるが、特に本発明におい
ては、その表面に多少の凹凸を有するか、あるいは平滑
表面の球状の芯材を用いることが好ましい。These core materials 1 can be of various shapes, such as spherical or ellipsoidal, but in the present invention, the core material 1 may have some irregularities on its surface or may have a smooth surface. It is preferable to use a spherical core material.
また、これらの芯材１は、できるだけ粒子径が揃ってい
ることが望ましく、その平均粒子径は、通常は、０．０
５〜２００μｍであり、ざらに使用の態様を考慮すると
、０．５〜５０μｍのものが特に好ましい。In addition, it is desirable that these core materials 1 have particle diameters as uniform as possible, and the average particle diameter is usually 0.0
The thickness is 5 to 200 μm, and in consideration of the mode of use, 0.5 to 50 μm is particularly preferable.
上記のような芯材１の外周面には、外殻２が設けられて
いる。本発明において外殻２は、通常は、隣接する層状
壁とは特性の異なる２層以上の層状壁からなる。第１図
にｄ３いては、４層の層状壁３〜６を有する多層外殻マ
イクロカプセルが示されている。An outer shell 2 is provided on the outer peripheral surface of the core material 1 as described above. In the present invention, the outer shell 2 usually consists of two or more layered walls having different characteristics from adjacent layered walls. At d3 in FIG. 1, a multilayer shell microcapsule having four layered walls 3 to 6 is shown.
本発明の多層外殻マイクロカプセルは、この多層外殻マ
イクロカプセルが存在づる状態におけるエネルギーの変
動、すなわち、具体的には外的あるいは内的な機械的応
力、物理的応力、化学的応力、熱応力、電気的応力、磁
気的応力および物理化学的応力等の変動に対応して層状
壁が崩壊し、若しくはその特性が変化する。そして、こ
の層状壁の崩壊若しくは変化に伴って、マイクロカプセ
ルの表面に表われていた特性が消失し、代わって崩壊若
しくは変化した層状壁よりも芯材側に位置していた他の
層状壁の特性が表在化する。The multilayer outer shell microcapsules of the present invention are susceptible to energy fluctuations in the state in which the multilayer outer shell microcapsules exist, that is, specifically, external or internal mechanical stress, physical stress, chemical stress, thermal stress, etc. The layered wall collapses or its properties change in response to changes in stress, electrical stress, magnetic stress, physicochemical stress, etc. As this layered wall collapses or changes, the characteristics that appeared on the surface of the microcapsule disappear, and in its place, other layered walls located closer to the core material than the collapsed or changed layered wall. Characteristics become external.
たとえば第１図において、層状壁３および５が色剤を含
む層状壁であり、かつ層状壁３に含まれる色剤と層状壁
５に含まれる色剤とが異なり、層状壁４および６が不透
明樹脂層状壁であり、かつ層状壁４を構成する樹脂の機
械的強度が層状壁６を構成する樹脂の機械的強度よりも
高い場合、使用する前における多層外殻マイクロカプセ
ルの色は、層状壁６の樹脂の色である。For example, in FIG. 1, layered walls 3 and 5 are layered walls containing a coloring agent, and the coloring agent contained in layered wall 3 and the coloring agent contained in layered wall 5 are different, and layered walls 4 and 6 are opaque. If the wall is a resin layered wall and the mechanical strength of the resin constituting the layered wall 4 is higher than the mechanical strength of the resin constituting the layered wall 6, the color of the multilayer outer shell microcapsules before use will be different from that of the layered wall. 6 resin color.
このような多層外殻マイクロカプセルに外部から機械的
応力を付与すると、まず層状壁６が破壊され、色剤を含
む層状壁５の色が多層外殻マイクロカプセルの表面に表
在化する。この色彩の変化によって、本発明の多層外殻
マイクロカプセルに一定の機械的応力が付与されたこと
を認識層ることができる。他方、層状壁６を破壊した後
にさらに強い機械的応力を加えることにより層状壁４も
破壊される。こうして層状壁６と層状壁４とが破壊され
ることより表在化するのは、層状壁３と層状壁５とに含
まれる色剤の混合色である。したがって、表在化した邑
を分析することにより、加えられた機械的応力の強さを
測定することができる。When external mechanical stress is applied to such a multilayer outer shell microcapsule, the layered wall 6 is first destroyed, and the color of the layered wall 5 containing the coloring agent is exposed on the surface of the multilayer outer shell microcapsule. This color change allows one to recognize that a certain mechanical stress has been applied to the multilayer outer shell microcapsules of the present invention. On the other hand, by applying stronger mechanical stress after destroying the layered wall 6, the layered wall 4 is also destroyed. As the layered wall 6 and the layered wall 4 are destroyed in this way, the mixed color of the colorants contained in the layered wall 3 and the layered wall 5 is brought to the surface. Therefore, by analyzing the surfaced eaves, the strength of the applied mechanical stress can be measured.
また、付与する機械的応力を調整することにより、層状
壁６のみを選択的に破壊することができ、ざらに層状壁
６および層状壁４の両者を選択的に破壊することもでき
る。そして、層状壁６のみを選択的に破壊した場合には
層状壁５の色が表在化し、層状壁６および層状壁４の両
者を破壊した場合には層状壁５および層状壁３に含まれ
る２種類の色材の混合色が表在化する。したがって、付
与する機械的応力等を予め設定することにより、所望の
色彩のパターンを形成することができる。Further, by adjusting the applied mechanical stress, only the layered wall 6 can be selectively destroyed, or even both the layered wall 6 and the layered wall 4 can be selectively destroyed. When only the layered wall 6 is selectively destroyed, the color of the layered wall 5 becomes visible, and when both the layered wall 6 and the layered wall 4 are destroyed, the color is included in the layered wall 5 and the layered wall 3. A mixed color of two types of color materials becomes visible. Therefore, by setting the applied mechanical stress and the like in advance, a pattern of a desired color can be formed.
さらに、たとえば、本発明の多層外殻マイクロカプセル
を溶媒に分散させ、との分散液の水素イオン濃度、溶存
酸素濃度等を変化させて多層外殻マイクロカプセルに化
学的応力を加えることができる。この化学的応力に対応
させて多層外殻マイクロカプセルの層状壁を段階的に溶
解若しくは分解させることにより、この層状壁よりも芯
材側にある層状壁の特性を表在化させ、溶媒の水素イオ
ン濃度あるいは溶存酸素濃度などの変化聞を測定するこ
とができる。Furthermore, for example, the multilayer outer shell microcapsules of the present invention can be dispersed in a solvent, and chemical stress can be applied to the multilayer outer shell microcapsules by changing the hydrogen ion concentration, dissolved oxygen concentration, etc. of the dispersion. By gradually dissolving or decomposing the layered wall of the multilayered outer shell microcapsule in response to this chemical stress, the characteristics of the layered wall on the core material side are exposed, and the hydrogen of the solvent Changes in ion concentration or dissolved oxygen concentration can be measured.
また、同様に、たとえば、ガラス転移点の異なる複数の
樹脂を異なる色剤を含む層状壁を介して積層して多層外
殻を形成することにより、熱応力の変化に対応させて段
階的に層状壁を溶融状態にして選択的に色剤を含む層状
壁の特性を表在化させることができ、この表在化した特
性を測定することにより変化した熱応力を測定すること
ができる。Similarly, for example, by laminating multiple resins with different glass transition points through layered walls containing different coloring agents to form a multilayer outer shell, layers can be layered in stages in response to changes in thermal stress. The characteristics of the layered wall containing the coloring agent can be selectively brought to the surface by melting the wall, and by measuring the surfaced characteristics, the changed thermal stress can be measured.
さらに、たとえば、顔料を有する層状壁と、この顔料の
上に特定の溶媒に可溶性を示す樹脂を用いて形成した層
状壁とを有する多層外殻マイクロカプセルを、上記の特
定の溶媒を含む溶液中に投入して層状壁に物理化学的応
力を付与して溶解させることにより、顔料を有する層状
壁の特性を表在化させて、上記特定の溶媒を検出するこ
とができる。Furthermore, for example, a multilayer outer shell microcapsule having a layered wall having a pigment and a layered wall formed using a resin that is soluble in a specific solvent on the pigment is placed in a solution containing the above-mentioned specific solvent. By applying physicochemical stress to the layered wall and dissolving it, the characteristics of the layered wall containing the pigment can be brought to the surface, and the specific solvent can be detected.
また、たとえば樹脂中に導電性発熱粒子を混合し、通電
による内部からの発熱によってり層状壁を段階的に溶融
状態にすることにより、あるいは本発明の多層外殻マイ
クロカプセルを電磁波が照射されている環境下に置いて
照射された電磁波によって層状壁を加熱して段階的に溶
融状態にプることにより、電気的応力あるいは磁気的応
力を利用して、他の層状壁の特性を表在化させることが
できる。Further, for example, by mixing conductive heating particles in a resin and gradually melting the layered wall by heat generation from inside by energizing, or by irradiating the multilayer outer shell microcapsule of the present invention with electromagnetic waves. By placing the layered wall in an environment where it is heated by irradiated electromagnetic waves and gradually bringing it to a molten state, the characteristics of other layered walls are brought to the surface using electrical or magnetic stress. can be done.
本発明の多層外殻マイクロカプセルにおいては、上述の
ように用途および利用する応力の種類などに対応させて
層状壁を形成する素材を適宜選択することができる。In the multilayer outer shell microcapsule of the present invention, the material forming the layered wall can be appropriately selected depending on the application and the type of stress to be used, as described above.
たとえば、熱応力、電気的応力あるいは磁気的応力等に
より、層状壁を段階的に溶融状態にし、色彩の変化によ
り加えられた応力の測定などを行なう場合、層状壁は、
ガラス転移点の異なる樹脂を用いて形成することができ
る。この場合、芯材側から最外層側に向かってガラス転
移点が段階的に低くなるように層状壁を構成する。そし
て、この層状壁の間に色材を含む層状壁を介在される。For example, when a layered wall is melted step by step by thermal stress, electrical stress, or magnetic stress, etc., and the stress applied is measured by the change in color, the layered wall is
It can be formed using resins having different glass transition points. In this case, the layered wall is configured such that the glass transition point decreases stepwise from the core side to the outermost layer side. A layered wall containing a coloring material is interposed between the layered walls.
この場合に使用することができる樹脂としては、組成あ
るいは重合度等を変えることによりガラス転移点を任意
に変え得る樹脂を用いることができ、具体的には、ポリ
メチル（メタ）アクリレート、トルメチルアクリレート
／ブチルメタクリレート共重合体、（メタ）アクリル酸
アルキルエステル／スチレン共重合体、メタクリル酸メ
チル／（メタ）アクリル酸アルキルエステル共重合体、
スチレン−アクリロニトリル共重合体、ポリスチレン、
アクリロニトリルおよびポリエチレン、ポリプロピレン
、エチレン−酢酸ビニル共重合体、エチレン−アクリル
酸エチル共重合体、アクリロニトリル−ブタジェン−ス
チレン共重合体、塩素化ポリエチレン、ポリフッ化ビニ
リデン、ポリテトラフルオロエチレン等のビニル重合体
、ナイロン、ポリエステル樹脂、ポリアミド樹脂等の縮
合系ポリマー等を挙げることができる。As the resin that can be used in this case, resins whose glass transition point can be arbitrarily changed by changing the composition or degree of polymerization, etc. can be used. Specifically, polymethyl (meth)acrylate, tolumethyl acrylate, etc. /butyl methacrylate copolymer, (meth)acrylic acid alkyl ester/styrene copolymer, methyl methacrylate/(meth)acrylic acid alkyl ester copolymer,
Styrene-acrylonitrile copolymer, polystyrene,
Acrylonitrile and vinyl polymers such as polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, acrylonitrile-butadiene-styrene copolymer, chlorinated polyethylene, polyvinylidene fluoride, polytetrafluoroethylene, Examples include condensation polymers such as nylon, polyester resins, and polyamide resins.
また、この場合に使用することができる色材としては、
キナクリドン系顔料、スレン系顔料等の縮合多環系顔料
、アゾ系顔料、フタロシアニン顔料等の有機顔料、複合
酸化物顔料、クロム酸塩顔料等の無機顔料、金属顔料、
ｉ性染料、塩基性染料、媒染染料、建染染料、不溶性ア
ゾ染料等の通常用いられている染料および顔料を挙げる
ことができる。In addition, coloring materials that can be used in this case include:
Condensed polycyclic pigments such as quinacridone pigments and thren pigments, organic pigments such as azo pigments and phthalocyanine pigments, inorganic pigments such as complex oxide pigments and chromate pigments, metal pigments,
Examples include commonly used dyes and pigments such as i-based dyes, basic dyes, mordant dyes, vat dyes, and insoluble azo dyes.
これらの色剤を含む層状壁の配列順序は、芯材側から最
外層側に向かって明度が高くなるように色剤を含む層状
壁を配列することが好ましい。Regarding the arrangement order of the layered walls containing these coloring agents, it is preferable that the layered walls containing the coloring agents are arranged such that the brightness increases from the core material side to the outermost layer side.
なお、上記の染料おるいは顔料を含む層状壁は樹脂から
なる層状壁と別に設けられていることを必要とするもの
ではなく、たとえば異なる特性の樹脂からなる層状壁中
に染料あるいは顔料が含まれていてもよい。Note that the layered wall containing the dye or pigment described above does not need to be provided separately from the layered wall made of resin. It may be
また、上記のように染料あるいは顔料を用いることなく
、最外層を透明熱硬化性樹脂を用いて形成し、この最外
層と芯材との間に段階的に溶融状態になる樹脂を用いて
複数の層状壁を形成し、反応性染料成分と他の反応性成
分あるいは触媒成分等とをこの層状壁で区画して積層し
、層状壁を溶融状態にして反応性染料成分と他の反応性
成分あるいは触媒成分などとを接触させることにより発
色させることもできる。In addition, as described above, without using dyes or pigments, the outermost layer is formed using a transparent thermosetting resin, and a resin that becomes molten in stages is used between this outermost layer and the core material. The reactive dye component and other reactive components or catalyst components are separated and laminated using this layered wall, and the layered wall is melted to separate the reactive dye component and other reactive components. Alternatively, color can be developed by contacting with a catalyst component or the like.
機械的応力あるいは物理的応力等の変動に対応させて層
状壁を崩壊させる本発明の多層外殻マイクロカプセルは
、最外Ｎ側から芯材側に向かって弾性率が高くなるよう
に樹脂を選択して層状壁を形成することが望ましい。こ
のように弾性率を変化させる方法としてはＪポリマー、
プレポリマー、七ツマ−を橋かけ剤、触媒とともに液状
、溶液状、塊状で混合し、これを重合・硬化させること
により橋かけとともにからみ合いを形成する方法（通常
乳化重合や懸濁重合で達成できる。）およびポリメチル
メタクリレート、ポリスチレン、ポリカーボネート等の
ように硬度が高くもろい樹脂と、ポリプロピレン、ポリ
エチレン、ＡＢＳ、エチレン−酢酸ビニル共重合体、エ
チレン−アクリル酸エチル共重合体、アクリロニトリル
−ブタジェン−スチレン共重合体およびナイロン、フッ
素樹脂、シリコーン樹脂、ポリエステル樹脂、ボリアミ
ド樹脂等のような弾性率の高い樹脂とを組合わせ１弾性
率の高い樹脂の配合率を調整する方法、ポリメチルメタ
クリレート、ポリスチレン等の硬度の高い共重合体を製
造する際に、ブタジェン、イソプレン、クロロプレン、
エヂレン、プロピレン等の弾性を付与し得る七ツマー成
分を配合する方法などを挙げることができる。In the multilayer outer shell microcapsule of the present invention whose layered walls collapse in response to changes in mechanical stress or physical stress, a resin is selected so that the elastic modulus increases from the outermost N side toward the core material side. It is desirable to form a layered wall. Methods for changing the elastic modulus in this way include J polymer,
A method in which a prepolymer and a 7-mer are mixed together with a cross-linking agent and a catalyst in liquid, solution, or bulk form, and then polymerized and cured to form cross-linking and entanglement (usually achieved by emulsion polymerization or suspension polymerization). ) and highly hard and brittle resins such as polymethyl methacrylate, polystyrene, polycarbonate, etc., polypropylene, polyethylene, ABS, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, acrylonitrile-butadiene-styrene. A method of combining a copolymer and a resin with high elastic modulus such as nylon, fluororesin, silicone resin, polyester resin, polyamide resin, etc. 1. Adjusting the blending ratio of resin with high elastic modulus, polymethyl methacrylate, polystyrene, etc. When producing copolymers with high hardness, butadiene, isoprene, chloroprene,
Examples include a method of blending a 7-mer component capable of imparting elasticity such as ethylene or propylene.
ざらに、化学的応力あるいは物理化学的応力の変動によ
り層状壁を崩壊させ、若しくはその特性を変化させる方
法としては、酸基、カルボキシル基等の官能基の含有率
を変化させて溶媒に対する溶解度を変えた樹脂を用いて
層状壁を形成する方法、酸化触媒および水素化触媒等の
触媒凹を調整することにより、分解速度あるいは崩壊速
度が制御された樹脂を用いて層状壁を形成する方法等を
挙げることができる。Broadly speaking, methods for collapsing layered walls or changing their properties by changes in chemical stress or physicochemical stress include changing the content of functional groups such as acid groups and carboxyl groups to increase their solubility in solvents. A method of forming a layered wall using a different resin, a method of forming a layered wall using a resin whose decomposition rate or disintegration rate is controlled by adjusting the catalyst recesses of an oxidation catalyst and a hydrogenation catalyst, etc. can be mentioned.
また、電気的応力あるいは磁気的応力の変動により層状
壁を崩壊若しくはその特性を変化させる方法としては、
ニッケル、クロム、鉄クロム、炭化硅素、硅化モリブデ
ン、ジルコニアおよび導電性樹脂等の導電性発熱粉体を
ガラス転移点の異なる樹脂に混入して層状壁を通電量に
対応した発熱により崩壊させる方法、上記の導電性発熱
粉体の添加量を変えて発熱量を変化させて選択的に層状
壁を崩壊させる方法、および樹脂に金属粉を添加し、こ
の金属粉の添加量を調整することにより高周波を照射し
た際の発熱量を調整して層状壁を高周波等の照射最に対
応させて崩壊させる方法などを挙げることができる。In addition, as a method of collapsing the layered wall or changing its properties by changing electrical stress or magnetic stress,
A method in which conductive heating powders such as nickel, chromium, iron chromium, silicon carbide, molybdenum silicide, zirconia, and conductive resin are mixed with resins having different glass transition points, and the layered wall is collapsed by heat generation corresponding to the amount of current applied; The method of selectively collapsing the layered wall by changing the amount of heat generated by changing the amount of conductive heat-generating powder added, and the method of adding metal powder to the resin and adjusting the amount of this metal powder to generate high-frequency An example of this method is to adjust the amount of heat generated when irradiated with irradiation to cause the layered wall to collapse in response to the irradiation of high frequency waves or the like.
このような多層外殻マイクロカプセルは、芯材を水など
に分散させ、この芯材上に層状壁を構成する成分を順次
析出させてマイクロカプセルを製造する湿式方法を利用
して調製することもできるが、本発明においては、以下
に示す乾式法を採用することが好ましい。乾式法は、ま
ず、芯材１の外周面に静電電荷を生じさせ、この静電電
荷を利用して顔料あるいは樹脂等の粉体を付着・固定化
させた後にマイクロカプセル化して芯材の外周面に第１
の層状壁３を形成し、次いで同様にして静電電荷を利用
してこの層状壁３の周囲に他の顔料あるいは樹脂の粉体
を付着・固定化させた後にマイクロカプセル化して第２
の層状壁４を形成し、同様にして第３の層状壁５および
第４の層状壁６を形成する方法である。芯材１の外周面
に静電電荷を生じさせるには、たとえば芯材１と第１の
層状壁３を構成する粉体等とを乾燥状態で混合して攪拌
する方法を挙げることができる。この際、芯材１に第１
の層状壁を構成する粉体を良好に付着させるためには、
芯材の粒子径と付着する粉体の粒子径とが１／１０：〜
１／２０の範囲内にあることが好ましい。Such multilayer outer shell microcapsules can also be prepared using a wet method in which microcapsules are manufactured by dispersing a core material in water or the like and sequentially precipitating the components constituting the layered wall on the core material. However, in the present invention, it is preferable to employ the dry method shown below. In the dry method, first, an electrostatic charge is generated on the outer circumferential surface of the core material 1, and this electrostatic charge is used to attach and fix powder such as pigment or resin, and then it is microencapsulated to form the core material. 1st on the outer circumferential surface
A layered wall 3 is formed, and then other pigment or resin powder is adhered and fixed around this layered wall 3 using electrostatic charge in the same manner, and then micro-encapsulated to form a second layered wall 3.
In this method, a layered wall 4 is formed, and a third layered wall 5 and a fourth layered wall 6 are formed in the same manner. In order to generate an electrostatic charge on the outer circumferential surface of the core material 1, for example, a method may be used in which the core material 1 and powder or the like constituting the first layered wall 3 are mixed in a dry state and stirred. At this time, the first
In order to ensure good adhesion of the powder that makes up the layered wall of
The particle size of the core material and the particle size of the attached powder are 1/10: ~
It is preferably within the range of 1/20.
このようにして外周面に粉体が付着した芯材１を気流中
で互いに衝突させるか、あるいは機械的衝撃を加え、こ
の衝突あるいは衝撃によって芯材１の外周面に付着した
粉末を層状に固定することにより第１の層状壁３を形成
することができる。In this way, the core materials 1 with powder attached to the outer circumferential surface are collided with each other in an air flow or mechanical impact is applied, and the powder attached to the outer circumferential surface of the core material 1 is fixed in a layer by this collision or impact. By doing so, the first layered wall 3 can be formed.
また、第２の層状壁４、第３の層状壁５および第４の層
状壁６も、上記の方法と同様にして形成することができ
る。Further, the second layered wall 4, the third layered wall 5, and the fourth layered wall 6 can also be formed in the same manner as the above method.
本発明の多層外殻マイクロカプセルにおいて、上記のよ
うにして調製される層状壁の厚さを、それぞれ０．０５
〜４０μｍにすることが好ましい。In the multilayer shell microcapsules of the present invention, the thickness of the layered walls prepared as described above is 0.05.
It is preferable to set it to 40 micrometers.
また、層状壁が積層された多層外殻の厚さは、通常は、
０．０５〜４０μｍである。In addition, the thickness of the multilayer outer shell in which layered walls are laminated is usually
It is 0.05 to 40 μm.
上記のような層状壁は、市販の乾式表面改質装置（たと
えば、■奈良機械製作断裂、乾式表面改質装置ＮＨ３−
１＞を利用して形成することができる。The layered wall as described above can be produced using commercially available dry surface modification equipment (for example,
1>.
本発明に係る多層外殻マイクロカプセルは、機械的応力
に対応して段階的に破壊させる複数の層状壁を有する多
層外殻マイクロカプセルを支持体上に塗布することによ
り、圧力センサーあるいは衝撃センサー等として使用す
ることができる。また、赤色顔料、青色顔料および黄色
顔料をそれぞれ独立に含む３層の層状壁を上記の層状壁
により区画した多層外殻マイクロカプセルを用いてイン
クリボンを製造し、これを用いることにより、印字圧を
変えることにより多色印字が可能になる。The multilayer outer shell microcapsule according to the present invention can be used as a pressure sensor or an impact sensor by coating a multilayer outer shell microcapsule on a support body, which has a plurality of layered walls that break down in stages in response to mechanical stress. It can be used as In addition, an ink ribbon is manufactured using a multilayer outer shell microcapsule in which three layered walls each independently containing a red pigment, a blue pigment, and a yellow pigment are partitioned by the layered walls. By changing the , multicolor printing becomes possible.
ざらに、ｐＨ値あるいは酸素濃度等の変動によって崩壊
する層状壁と色材を含む層状壁とを交互に設けることに
より、ｐＨセンサーおるいは溶存酸素濃度センサー等と
して使用することができる。In other words, by alternately providing layered walls that collapse due to changes in pH value or oxygen concentration and layered walls containing a coloring material, it can be used as a pH sensor, a dissolved oxygen concentration sensor, or the like.
また、化学的応力に対応させて、層状壁が段階的に崩壊
する多層外殻マイクロカプセルは、たとえば芯材上に整
腸剤を含む層状壁、アルカリ性で崩壊する層状壁、制酸
剤を含む層状壁および酸性で崩壊する層状壁をこの順序
に設けることにより、健胃作用と整腸作用とを有する医
薬として利用することができ、また、この制酸剤の代わ
りに即効性医薬を用い整腸剤の代わりに遅効性医薬を用
いることにより、従来の医薬よりも即効性に優れ、薬効
維持時間の長い医薬として利用することができる。In addition, multilayer outer microcapsules whose layered walls disintegrate in stages in response to chemical stress include, for example, a layered wall containing an intestinal regulator on a core material, a layered wall that disintegrates in alkalinity, and a layered wall containing an antacid. By providing a layered wall that disintegrates with acidity in this order, it can be used as a medicine that has stomachic and intestinal regulation effects, and it is also possible to use a quick-acting medicine instead of this antacid and to replace an intestinal regulation agent. By using a slow-acting drug, it can be used as a drug that has better immediate effect than conventional drugs and maintains its efficacy for a longer time.
さらに、電気的応力あるいは磁気的応力により段階的に
崩壊する層状壁を有する多層外殻マイクロカプセルは、
絶縁センサー等として利用プることができ、また電気的
応力あるいは磁気的応力を加えて分子の配向性等を制御
することにより、層状壁の光透過性などの特性を段階的
に変えて、層状壁を崩壊さゼることなく、他の層状壁の
特性を表在化させることもできる。Furthermore, multilayer outer shell microcapsules with layered walls that collapse in stages due to electrical or magnetic stress,
It can be used as an insulated sensor, etc., and by controlling the orientation of molecules by applying electrical or magnetic stress, the properties such as light transmittance of the layered wall can be changed in stages. It is also possible to expose other layered wall properties without collapsing the wall.
また、たとえば、色剤を含む層状壁と特性の溶媒に対し
て溶解性を示す層状壁とを繰返し積層した多層マイクロ
カプセルは、上記特定の溶媒の検出剤として利用するこ
とができる。Further, for example, a multilayer microcapsule in which a layered wall containing a coloring agent and a layered wall exhibiting solubility in a specific solvent are repeatedly laminated can be used as a detection agent for the above-mentioned specific solvent.
なお、本発明に係る多層外殻マイクロカプセルは、上記
の用途の外に、層状壁の特性を変えることにより、たと
えば緩効性肥料、緩効性殺虫剤、徐放性芳香剤、多機能
粘着剤・接着剤等としても使用することが可能である。In addition to the above-mentioned uses, the multilayer shell microcapsules according to the present invention can be used, for example, as slow-release fertilizers, slow-release pesticides, sustained-release fragrances, and multifunctional adhesives by changing the properties of the layered walls. It can also be used as an agent, adhesive, etc.
発明の効果
本発明によれば、多層外殻マイクロカプセルが置かれた
環境のエネルギー状態の変化に伴って、外殻を構成する
２層以上の層状壁のうちの最外層側から段階的に層状壁
が崩壊し、若しくはその特性が変化し、その層状壁より
も芯材側に位置づる他の層状壁の特性が表在化するので
、層状壁の破壊状態を調べることにより、本発明の多層
外殻マイクロカプセルの置かれた環境における機械的応
力、化学的応力、熱応力、電気的応力、磁気的応力およ
び物理化学的応力等の変動、すなわちエネルギー状態の
変動を認識、あるいは測定することができる。Effects of the Invention According to the present invention, as the energy state of the environment in which the multilayer outer shell microcapsule is placed changes, the layered walls of the two or more layered walls constituting the outer shell gradually change from the outermost layer side. When a wall collapses or its characteristics change, the characteristics of other layered walls located closer to the core material than the layered wall become apparent. It is possible to recognize or measure fluctuations in mechanical stress, chemical stress, thermal stress, electrical stress, magnetic stress, physicochemical stress, etc. in the environment where the outer shell microcapsule is placed, that is, fluctuations in energy state. can.
また、エネルギーの変動幅を予め設定することにより、
多層外殻を所望の段階ま゛で破壊し、若しくは変化させ
て所望の特性を多層外殻マイクロカプセルの表面に表在
化させることができる。In addition, by setting the energy fluctuation range in advance,
The multilayer shell can be destroyed or changed at desired stages to bring desired properties onto the surface of the multilayer shell microcapsule.
以下本発明の実施例を示すが本発明はこれらにより限定
されるものではない。Examples of the present invention will be shown below, but the present invention is not limited thereto.
実施例１
芯材として平均粒子径が１０μｍのポリスチレン粉末を
用い、このポリスチレン粉末１００ｇと銅フタロシアニ
ン系青色顔料（平均粒子径：０．０５μｍ）１５９とを
乾式表面改質装置（■奈良機械製作新製、ＮＨ３−１＞
を用いて５分間処理することにより銅フタロシアニンで
表面被覆（第１層状壁）した青色粉末を得た。Example 1 Polystyrene powder with an average particle size of 10 μm was used as the core material, and 100 g of this polystyrene powder and a copper phthalocyanine blue pigment (average particle size: 0.05 μm) 159 were mixed in a dry surface modification device (Nara Kikai Seisaku Shin). manufactured by NH3-1>
A blue powder whose surface was coated (first layered wall) with copper phthalocyanine was obtained by treating the powder with copper phthalocyanine for 5 minutes.
次に、このようにして得られた第１層状壁を有する青色
粉末１００′ＩＪの表面に平均粒子径が０．４μｍのポ
リメチルメタクリレート１０９を用いて表面被覆（第２
層状壁）し、ざらにこの第２層状壁上にアゾ系黄色顔料
（平均粒子径：０．０５μｍ）１５ｇを用いて表面被覆
（第３層状壁）し、さらにこの第３層状壁土に平均粒子
径が０．４μｍのポリメチルメタクリレート１０ｇを用
いて表面被覆（第４層状壁）して、４層の層状壁を有す
る本発明の多層外殻マイクロカプセルを製造した。Next, the surface of the blue powder 100'IJ having the first layered wall thus obtained is coated with polymethyl methacrylate 109 having an average particle size of 0.4 μm (second layered wall).
Layered wall), then on this second layered wall, 15 g of azo yellow pigment (average particle size: 0.05 μm) is used to coat the surface (third layered wall), and then on this third layered wall soil, average particles are applied. The surface was coated (fourth layered wall) with 10 g of polymethyl methacrylate having a diameter of 0.4 μm to produce a multilayer outer shell microcapsule of the present invention having four layered walls.
得られた多層外殻マイクロカプセルは、青色をおびた黄
色であり、被覆重量から算出した第１層状壁の平均厚さ
は０．２２μｍ１第２層状壁の平均厚さは０．１５μｍ
、第３層状壁の平均厚さは０．２５μｍ、第４層状壁の
平均厚さは０．１８μｍであった。The obtained multilayer outer shell microcapsules have a bluish yellow color, and the average thickness of the first layer wall calculated from the coating weight is 0.22 μm1 The average thickness of the second layer wall is 0.15 μm
The average thickness of the third layered wall was 0.25 μm, and the average thickness of the fourth layered wall was 0.18 μm.
１ｑられた多層外殻マイクロカプセルをトルエンを含む
溶媒と混合することにより、このマイクロカプセルに物
理化学的応力が作用して層状壁が溶解し青色と黄色の中
間色を呈し、トルエンの検出に有効に使用することがで
きた。By mixing the multi-layer outer shell microcapsules with a toluene-containing solvent, physicochemical stress acts on the microcapsules, causing the layered walls to dissolve and exhibiting a color intermediate between blue and yellow, which is effective for toluene detection. I was able to use it.
亙塵五ｌ
実施例１において、芯材としてポリスチレン粉末の代わ
りに、平均粒子径を０．２〜２００μｍの範囲内で段階
的に変えた架橋ポリメチルメタクリレート粉末または架
橋ポリスチレン粉末を用い、層状壁を形成するための粉
末として、−次粒子径が１μｍ以下の顔料および一次粒
子径が３μｍのアクリル系樹脂粉末を用いて４層の層状
壁を有する多層外殻マイクロカプセルを製造した。In Example 1, instead of polystyrene powder as the core material, cross-linked polymethyl methacrylate powder or cross-linked polystyrene powder whose average particle diameter was changed in stages within the range of 0.2 to 200 μm was used to form a layered wall. A multilayer outer shell microcapsule having four layered walls was manufactured using a pigment having a primary particle diameter of 1 μm or less and an acrylic resin powder having a primary particle diameter of 3 μm as powders for forming the microcapsules.
この多層外殻マイクロカプセルは、実施例１における製
造条件とほぼ同様の条件で製造することができた。This multilayer outer shell microcapsule could be manufactured under substantially the same manufacturing conditions as in Example 1.
得られた多層外殻マイクロカプセルを実施例１と同様に
してトルエン溶媒と混合したところ、いずれの多層外殻
マイクロカプセルを用いた場合にも層状壁が良好に溶解
し、青色と黄色の中間色を呈し、トルエンを有効に検出
することができた。When the obtained multilayer outer shell microcapsules were mixed with toluene solvent in the same manner as in Example 1, the layered walls were well dissolved in any of the multilayer outer shell microcapsules, and an intermediate color between blue and yellow was obtained. It was possible to effectively detect toluene.
Ｘ凰■ユ
顔料としして青色顔料、赤色顔料、黄色顔料および白色
顔料の４種類の顔料を用意した。Four types of pigments, blue pigment, red pigment, yellow pigment, and white pigment, were prepared as X-X-Y pigments.
別に共重合比の異なる４種類のポリメチルメタクリレー
ト／ブチルメタクリレート共重合体を調製した。この４
種類のポリメタクリレート／ポリブチルメタクリレート
共重合体のガラス転移点は、３０°Ｃ（第１共重合体〉
、４５℃（第２共重合体）、６０℃（第３共重合体）、
７５℃（第４共重合体）である。Separately, four types of polymethyl methacrylate/butyl methacrylate copolymers having different copolymerization ratios were prepared. This 4
The glass transition point of the different types of polymethacrylate/polybutyl methacrylate copolymers is 30°C (first copolymer)
, 45°C (second copolymer), 60°C (third copolymer),
75° C. (fourth copolymer).
上記の４種類の顔料および４種類の共重合体を用い、実
施例１と同様に操作してポリスチレン粉末の外周に８層
の層状壁を有する多層外殻マイクロカプセルを製造した
。Using the above four types of pigments and four types of copolymers, multilayer shell microcapsules having eight layered walls around the outer periphery of polystyrene powder were manufactured in the same manner as in Example 1.
ただし、顔料を含む層状壁の配置順序は、芯材側から青
色顔料、赤色顔料、黄色顔料および白色顔料の順序にし
、また共重合体からなる層状壁は、同様に芯材側から第
１共重合体、第２共重合体、第３共重合体および第４共
重合体の順序に配置し、芯材表面には青色顔料を含む層
状壁を設け、顔料を含む層状壁と共重合体からなる層状
壁とを交互に配置し、最外層には第４共重合体からなる
層状壁を配置した。このようにすることにより白色の多
層外殻マイクロカプセルを（ｑた。However, the order in which the layered walls containing pigments are arranged is blue pigment, red pigment, yellow pigment, and white pigment from the core material side, and the layered walls made of a copolymer are similarly arranged in the order of blue pigment, red pigment, yellow pigment, and white pigment from the core material side. The polymer, the second copolymer, the third copolymer and the fourth copolymer are arranged in this order, a layered wall containing a blue pigment is provided on the surface of the core material, and a layered wall containing the pigment and the copolymer are arranged in this order. The layered walls made of the fourth copolymer were arranged alternately, and the layered wall made of the fourth copolymer was arranged as the outermost layer. By doing this, white multilayer outer shell microcapsules were obtained.
この多層外殻マイクロカプセルを徐々に加熱すると、層
状壁が加熱温度に対応して順次溶融状態になり、白色の
多層外殻マイクロカプセルは、次第に淡黄色になり、ざ
らに加熱を続けると、橙色から赤紫色に変色し、最後に
は灰色になった。When this multilayer outer shell microcapsule is gradually heated, the layered walls gradually become molten in response to the heating temperature, and the white multilayer outer shell microcapsule gradually turns pale yellow, and when the heating is continued roughly, it turns orange. The color changed from red to purple, and finally to gray.
また、上記の色彩の変化は、一定の機械的応力を付与し
ながら加熱を行なうことにより特に顕箸に変化すること
が判明した。Furthermore, it has been found that the above-mentioned color change occurs especially when heating the chopsticks while applying a certain mechanical stress.
第１図は、本発明の多層外殻マイクロカプセルの一例を
模式的に示す断面図である。
１・・・芯材、２・・・外殻、３．５・・・色剤を含有
する層状壁、４，５・・・樹脂からなる層状壁代 理
人 弁理士 鈴 木 俊一部第 １ 図FIG. 1 is a cross-sectional view schematically showing an example of a multilayer shell microcapsule of the present invention. 1...Core material, 2...Outer shell, 3.5...Layered wall containing colorant, 4,5...Layered wall substitute made of resin
Person Patent Attorney Shunichi Suzuki Figure 1
Claims (3)
積層されてなる外殻とを有するマイクロカプセルであっ
て、該外殼が、この外殻に加えられるエネルギーにより
、外殼の最外層側から芯材方向に層状壁が順次崩壊し若
しくはその特性が順次変化することにより、崩壊若しく
は特性が変化した該層状壁よりも芯材側に位置する他の
層状壁の特性が該外殼表面に表在化する２層以上の層状
壁から構成されていることを特徴とする多層外殼マイク
ロカプセル。(1) A microcapsule having a core material and an outer shell formed by laminating a plurality of layered walls provided around the outer periphery of the core material, wherein the outer shell is activated by energy applied to the outer shell. As the layered walls sequentially collapse or their properties change sequentially from the outermost layer side toward the core material, the characteristics of other layered walls located closer to the core material than the layered wall whose properties have collapsed or whose properties have changed change to the outer shell. A multilayer outer shell microcapsule characterized by being composed of two or more layered walls that are exposed on the surface.
にあることを特徴とする請求項第１項に記載の多層外殻
マイクロカプセル。(2) The multilayer outer shell microcapsule according to claim 1, wherein the average particle diameter of the core material is within the range of 0.2 to 200 μm.
有することを特徴とする請求項第１項に記載の多層外殻
マイクロカプセル。(3) The multilayer outer shell microcapsule according to claim 1, wherein each of the layered walls has a layer thickness of 0.05 to 40 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP84088A JPH01180244A (en) | 1988-01-06 | 1988-01-06 | Microcapsule having multilayered external shell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP84088A JPH01180244A (en) | 1988-01-06 | 1988-01-06 | Microcapsule having multilayered external shell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01180244A true JPH01180244A (en) | 1989-07-18 |
Family
ID=11484814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP84088A Pending JPH01180244A (en) | 1988-01-06 | 1988-01-06 | Microcapsule having multilayered external shell |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01180244A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008045745A (en) * | 2006-08-16 | 2008-02-28 | Samsung Electronics Co Ltd | Valve unit, reaction device with the same, and method of forming valve in channel |
| JP2008511736A (en) * | 2004-09-01 | 2008-04-17 | アップルトン ペーパーズ インコーポレイテッド | Encapsulated curing system |
| JP2011058912A (en) * | 2009-09-09 | 2011-03-24 | Railway Technical Res Inst | System and method for measuring earthquake impactive force |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4897769A (en) * | 1972-03-25 | 1973-12-12 | ||
| JPS4997769A (en) * | 1973-01-23 | 1974-09-17 |
-
1988
- 1988-01-06 JP JP84088A patent/JPH01180244A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4897769A (en) * | 1972-03-25 | 1973-12-12 | ||
| JPS4997769A (en) * | 1973-01-23 | 1974-09-17 |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008511736A (en) * | 2004-09-01 | 2008-04-17 | アップルトン ペーパーズ インコーポレイテッド | Encapsulated curing system |
| JP2008045745A (en) * | 2006-08-16 | 2008-02-28 | Samsung Electronics Co Ltd | Valve unit, reaction device with the same, and method of forming valve in channel |
| US8464760B2 (en) | 2006-08-16 | 2013-06-18 | Samsung Electronic Co., Ltd. | Valve unit, reaction apparatus with the same, and method of forming valve in channel |
| JP2011058912A (en) * | 2009-09-09 | 2011-03-24 | Railway Technical Res Inst | System and method for measuring earthquake impactive force |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4661388A (en) | Pad fragrance sampling device | |
| US8257980B2 (en) | Sensory pigments used on food, packaging, paper and pharmaceutical and electronic products | |
| KR0157628B1 (en) | Fragrance sampling device | |
| EP3237556B1 (en) | Microparticles and apparatus for smart ink production | |
| TW200400220A (en) | Composite material comprising core/shell particles | |
| JPH09267422A (en) | Reversible temperature-sensitive deformable laminate | |
| EP0232001B1 (en) | Encapsulated colorants | |
| JPH01180244A (en) | Microcapsule having multilayered external shell | |
| US20050275123A1 (en) | Encapsulation process | |
| US5244768A (en) | Manufacturing process for an electrophotographic toner | |
| Guo et al. | Delicate and Independent Manipulation of Dynamic Fluorescence Behavior of Polymer Nanoparticles Based on a Core–Shell Strategy | |
| CA1129261A (en) | Stilt capsules for pressure-sensitive record material | |
| US20080090942A1 (en) | Tamper evident paint having microcapsules containing signal indicators | |
| TW200416228A (en) | Moisture barrier resins | |
| US20020142241A1 (en) | Microencapsulated electrophotographic toner particles having colored shells | |
| Yu et al. | Fabrication of compact poly (methyl methacrylate-co-butyl methacrylate-co-acrylic acid) microcapsules for electrophoretic displays by using emulsion droplets as templates | |
| JP2004107601A (en) | Stimulus-responsive color-changing liquid composition, color-changing laminate and process for producing it | |
| KR102152408B1 (en) | A label for authenticating genuine having hidden image effect and manufacturing method tehreof | |
| JP2013091166A (en) | Thermal transfer sheet and printed matter with perfume | |
| JP2003113249A (en) | Temperature-sensitive fine particle composition and sheet of temperature-sensitive fine particle | |
| JP3921984B2 (en) | Optical element | |
| JP4559745B2 (en) | Method for forming single particle film and method for producing electrophoretic display device using the same | |
| JP2003290647A (en) | Method for producing microcapsule encapsulating electrophoretic particle dispersion and reversible display medium using the capsule | |
| KR101921059B1 (en) | Nanoparticle Comprising Double Coating Layer and Manufacturing Method Thereof | |
| CN117487536A (en) | Double-shell thermochromic microcapsule as well as preparation method and application thereof |