JP2017154087A - Method for producing hollow particle and hollow particle - Google Patents
Method for producing hollow particle and hollow particle Download PDFInfo
- Publication number
- JP2017154087A JP2017154087A JP2016040078A JP2016040078A JP2017154087A JP 2017154087 A JP2017154087 A JP 2017154087A JP 2016040078 A JP2016040078 A JP 2016040078A JP 2016040078 A JP2016040078 A JP 2016040078A JP 2017154087 A JP2017154087 A JP 2017154087A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- hollow
- liquid
- monomer
- metal oxide
- 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.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 169
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 239000007788 liquid Substances 0.000 claims abstract description 56
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 37
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000011164 primary particle Substances 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- NLCKLZIHJQEMCU-UHFFFAOYSA-N cyano prop-2-enoate Chemical class C=CC(=O)OC#N NLCKLZIHJQEMCU-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 239000006260 foam Substances 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 40
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 239000012798 spherical particle Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 230000008016 vaporization Effects 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000009834 vaporization Methods 0.000 description 6
- 229920001651 Cyanoacrylate Polymers 0.000 description 5
- -1 cyanoacrylate compound Chemical class 0.000 description 5
- FGBJXOREULPLGL-UHFFFAOYSA-N ethyl cyanoacrylate Chemical compound CCOC(=O)C(=C)C#N FGBJXOREULPLGL-UHFFFAOYSA-N 0.000 description 5
- 229940053009 ethyl cyanoacrylate Drugs 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000003570 air Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000007870 radical polymerization initiator Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910018503 SF6 Inorganic materials 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 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
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- YZFWTZACSRHJQD-UHFFFAOYSA-N ciglitazone Chemical compound C=1C=C(CC2C(NC(=O)S2)=O)C=CC=1OCC1(C)CCCCC1 YZFWTZACSRHJQD-UHFFFAOYSA-N 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000007771 core particle Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- JJJFUHOGVZWXNQ-UHFFFAOYSA-N enbucrilate Chemical compound CCCCOC(=O)C(=C)C#N JJJFUHOGVZWXNQ-UHFFFAOYSA-N 0.000 description 1
- 229950010048 enbucrilate Drugs 0.000 description 1
- 239000007863 gel particle Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- ZTYMNUBYYQNBFP-UHFFFAOYSA-N propyl 2-cyanoprop-2-enoate Chemical compound CCCOC(=O)C(=C)C#N ZTYMNUBYYQNBFP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Landscapes
- Manufacturing Of Micro-Capsules (AREA)
Abstract
Description
本開示は、中空粒子の製造方法及び中空粒子に関し、特に金属酸化物粒子が表面に付着した中空粒子の製造方法及び該製造方法により得られる中空粒子に関する。 The present disclosure relates to a method for producing hollow particles and hollow particles, and more particularly, to a method for producing hollow particles having metal oxide particles attached to the surface thereof and a hollow particle obtained by the production method.
内部が気体で外部が固体の構造を有する中空粒子は、密度が低く、音や熱の伝達を抑制することもできるため、材料の比重調整や防音材・断熱材等へ用いられているほか、液体中で浮上する特性を利用して液体表面の流れを可視化するトレーサ等にも用いられている。近年では、中空粒子の超音波に対する周波数応答性を利用して、超音波診断用造影剤やドラッグデリバリーの薬剤輸送担体等の医療材料として中空粒子を用いる先進医療の研究も行われている。 Hollow particles that have a gas structure inside and a solid outside structure are low in density and can also suppress the transmission of sound and heat, so they are used for adjusting the specific gravity of materials, soundproofing materials, heat insulating materials, etc. It is also used for tracers that visualize the flow of the liquid surface by utilizing the characteristics of floating in the liquid. In recent years, advanced medical research using hollow particles as a medical material such as a contrast agent for ultrasonic diagnosis and a drug transport carrier for drug delivery has been conducted using the frequency response of the hollow particles to ultrasonic waves.
従来の中空粒子としては、中空のシリカ粒子や、中空の樹脂粒子が知られている（例えば、特許文献１及び２）。 As conventional hollow particles, hollow silica particles and hollow resin particles are known (for example, Patent Documents 1 and 2).
本発明は、従来の中空粒子とは異なる構成を有する、新規な中空粒子を提供することを目的とする。 An object of this invention is to provide the novel hollow particle which has a structure different from the conventional hollow particle.
本発明は、中空を有する殻部を備える中空粒子の製造方法であって、金属酸化物粒子を含む液体中でモノマーを含む気泡を発生させ、気泡及び液体の界面において、液体及びモノマーの接触により、モノマー由来のポリマーを含む層及び該層表面に担持された金属酸化物粒子を備える殻部を形成する工程を備える、製造方法を提供する。 The present invention relates to a method for producing a hollow particle having a hollow shell, wherein a bubble containing a monomer is generated in a liquid containing metal oxide particles, and contacted between the liquid and the monomer at the interface between the bubble and the liquid. And a manufacturing method comprising a step of forming a shell including a layer containing a monomer-derived polymer and metal oxide particles supported on the surface of the layer.
本発明において、金属酸化物粒子がシリカ粒子であることが好ましい。 In the present invention, the metal oxide particles are preferably silica particles.
本発明において、金属酸化物粒子がコロイダル粒子であることが好ましい。 In the present invention, the metal oxide particles are preferably colloidal particles.
本発明において、金属酸化物粒子の平均一次粒子径が１〜２００ｎｍであることが好ましい。 In the present invention, the average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm.
本発明において、モノマーがシアノアクリレート系化合物を含むことが好ましい。 In the present invention, the monomer preferably contains a cyanoacrylate compound.
本発明において、液体が水であることが好ましい。 In the present invention, the liquid is preferably water.
本発明は、また、中空を有する殻部を備え、該殻部がポリマーを含む層及び該層表面に担持された金属酸化物粒子を備える、中空粒子を提供する。 The present invention also provides a hollow particle comprising a shell having a hollow, the shell comprising a layer containing a polymer and metal oxide particles supported on the surface of the layer.
本発明によれば、従来の中空粒子とは異なる構成を有する、新規な中空粒子を提供することができる。本発明の製造方法は、特に以下の特徴を有していると言える。
・液体や固体を芯とした粒子から内部の芯を除去あるいは気化することによる中空化工程を必要とせず、簡便に中空粒子を作製することができる。
・固体膜となるモノマーは気体として液体中に供給され気泡の主成分となるため、気液界面に効率よくモノマーを供給することができる。
・金属酸化物粒子を液体中に分散することで、金属酸化物粒子が気液界面に効率よく吸着し、モノマー重合体からなる固体膜表面に金属酸化物粒子が付着した中空粒子を簡便に作製することができる。
ADVANTAGE OF THE INVENTION According to this invention, the novel hollow particle which has a structure different from the conventional hollow particle can be provided. It can be said that the production method of the present invention has the following characteristics in particular.
-Hollow particles can be easily produced without the need for a hollowing step by removing or vaporizing the inner core from liquid or solid core particles.
-Since the monomer used as a solid film is supplied in the liquid as a gas, and becomes a main component of a bubble, a monomer can be efficiently supplied to a gas-liquid interface.
・ By dispersing metal oxide particles in the liquid, the metal oxide particles are efficiently adsorbed on the gas-liquid interface, and hollow particles with metal oxide particles attached to the surface of a solid film made of a monomer polymer are easily produced. can do.
以下、図面を参照しながら本発明の好適な実施形態について詳細に説明する。なお、図面中、同一又は相当部分には同一符号を付し、重複する説明は省略する。 Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are denoted by the same reference numerals, and redundant description is omitted.
＜中空粒子の製造方法＞
本実施形態の中空粒子の製造方法は、中空を有する殻部を備える中空粒子の製造方法であって、金属酸化物粒子を含む液体中でモノマーを含む気泡を発生させ、気泡及び液体の界面において、液体及びモノマーの接触により、モノマー由来のポリマーを含む層及び該層表面に担持された金属酸化物粒子を備える殻部を形成する工程を備える。以下、本実施形態の製造方法について、図１を参照して説明する。
<Method for producing hollow particles>
The method for producing a hollow particle according to the present embodiment is a method for producing a hollow particle having a hollow shell, in which a bubble containing a monomer is generated in a liquid containing metal oxide particles, and at the interface between the bubble and the liquid. And a step of forming a shell including a layer containing a monomer-derived polymer and metal oxide particles supported on the surface of the layer by contacting the liquid and the monomer. Hereinafter, the manufacturing method of this embodiment is demonstrated with reference to FIG.
図１は、中空粒子の製造工程を示す模式図である。まず、供給ガス発生装置１により供給される供給ガス１ａが、送気管３を通りモノマーの気化容器２に供給され、気化容器２内において供給ガス１ａと気化されたモノマー（モノマーガス）２ａとが混合される。この混合ガス４が、送気手段５を用いて、送気管３を通り気泡発生手段６に供給される。気泡発生手段６の気泡発生部分は、金属酸化物粒子９を分散させた液体７中に挿入されている（浸漬している）。そして、気泡発生手段６により、混合ガス４を含む気泡８が液体７中で発生する。その際、金属酸化物粒子９が、気泡８及び液体７の気液界面に吸着すると共に、当該界面において気泡８中のモノマー２ａと液体７が接触することにより、モノマー２ａが重合する。このようにして、モノマー２ａ由来のポリマーを含む層表面に金属酸化物粒子９が付着した状態の固体膜（殻部）が形成され、中空粒子１０が生成する。 FIG. 1 is a schematic view showing a process for producing hollow particles. First, the supply gas 1a supplied by the supply gas generator 1 is supplied to the monomer vaporization vessel 2 through the air supply pipe 3, and the supply gas 1a and the monomer (monomer gas) 2a vaporized in the vaporization vessel 2 are obtained. Mixed. This mixed gas 4 is supplied to the bubble generating means 6 through the air supply pipe 3 using the air supply means 5. The bubble generating part of the bubble generating means 6 is inserted (immersed) in the liquid 7 in which the metal oxide particles 9 are dispersed. Then, bubbles 8 containing the mixed gas 4 are generated in the liquid 7 by the bubble generating means 6. At that time, the metal oxide particles 9 are adsorbed on the gas-liquid interface between the bubbles 8 and the liquid 7, and the monomer 2 a in the bubbles 8 and the liquid 7 come into contact with each other at the interface, whereby the monomer 2 a is polymerized. In this way, a solid film (shell) in which the metal oxide particles 9 are attached to the surface of the layer containing the polymer derived from the monomer 2a is formed, and the hollow particles 10 are generated.
図２は、中空粒子１０の生成機構を示す模式図である。まず、図２（ａ）に示すように、モノマー２ａを含む混合ガス４が、金属酸化物粒子９を分散させた液体７中に気泡８として供給される。次に、図２（ｂ）に示すように、金属酸化物粒子９が液体７と気泡８の気液界面に吸着すると共に、モノマー２ａの重合反応が気泡８内側から起こる。そして、図２（ｃ）に示すように、モノマー重合体からなる固体膜の表面（外表面）に金属酸化物粒子９が付着した、すなわち中空（中空部１０ｂ）を有する殻部１０ａを備える中空粒子１０を簡便に製造することができる。なお、殻部１０ａにおいて、金属酸化物粒子９は、モノマー由来のポリマーを含む層表面に静電的に付着しているのではなく、粒子の一部がポリマーの層に取り込まれ（埋まり）担持された状態である。 FIG. 2 is a schematic diagram showing a mechanism for generating the hollow particles 10. First, as shown in FIG. 2A, the mixed gas 4 containing the monomer 2 a is supplied as bubbles 8 in the liquid 7 in which the metal oxide particles 9 are dispersed. Next, as shown in FIG. 2B, the metal oxide particles 9 are adsorbed on the gas-liquid interface between the liquid 7 and the bubbles 8, and the polymerization reaction of the monomer 2 a occurs from inside the bubbles 8. And as shown in FIG.2 (c), the hollow provided with the shell part 10a which the metal oxide particle 9 adhered to the surface (outer surface) of the solid film which consists of a monomer polymer, ie, has a hollow (hollow part 10b). The particles 10 can be easily produced. In the shell portion 10a, the metal oxide particles 9 are not electrostatically attached to the surface of the layer containing the monomer-derived polymer, but a part of the particles are taken in (embedded) in the polymer layer. It is the state that was done.
このようにして得られる中空粒子１０の平均粒子径は特に制限されず、例えば０．０５〜５０μｍ程度とすることができる。 The average particle diameter of the hollow particles 10 thus obtained is not particularly limited, and can be, for example, about 0.05 to 50 μm.
供給ガス発生装置１としては特に制限されず、高圧ボンベ、ダイアフラムポンプ、ギアポンプ等が例示される。 The supply gas generator 1 is not particularly limited, and examples thereof include a high pressure cylinder, a diaphragm pump, and a gear pump.
供給ガス１ａについては限定的ではなく、空気、窒素、酸素、二酸化炭素、アルゴン、六フッ化硫黄等が例示されるが、モノマー２ａが反応することなくの液体７中に供給されるようにする観点から、空気、窒素、二酸化炭素、アルゴンであることが好ましい。なお、最終的に生成する、金属酸化物粒子が表面に付着した中空粒子１０に内包される（中空部１０ｂに含まれる）ガス成分については、これらの供給ガス１ａの種類に応じて変えることができる。 The supply gas 1a is not limited, and air, nitrogen, oxygen, carbon dioxide, argon, sulfur hexafluoride and the like are exemplified, but the monomer 2a is supplied into the liquid 7 without reacting. From the viewpoint, air, nitrogen, carbon dioxide, and argon are preferable. In addition, about the gas component (it is contained in the hollow part 10b) included in the hollow particle 10 which the metal oxide particle adhere | attached on the surface finally produced | generated, it can change according to the kind of these supply gas 1a. it can.
気化容器２としては、モノマー２ａを保持可能であり、公知の加熱または減圧手段によってモノマー２ａを沸点以上に加熱して、あるいは蒸気圧以下に減圧して、気化できる機能を有していれば特に制限はなく、例えばガラス製や金属製の容器が挙げられる。なお、気化容器２を用いた加熱又は減圧方法としては、容器をアルコールランプ、ガスバーナー、ホットプレート等で加熱する方法、あるいは真空ポンプ等で減圧する方法が例示される。気化容器２は、モノマー２ａが常温で気体の際には必須ではない。 The vaporization vessel 2 can hold the monomer 2a, and has a function capable of vaporizing by heating the monomer 2a to a boiling point or higher by a known heating or depressurizing means or reducing the vapor pressure to a vapor pressure or lower. There is no restriction | limiting, For example, the container made from glass or metal is mentioned. Examples of the heating or decompression method using the vaporization container 2 include a method of heating the container with an alcohol lamp, a gas burner, a hot plate, or the like, or a method of decompressing with a vacuum pump or the like. The vaporization container 2 is not essential when the monomer 2a is a gas at normal temperature.
モノマー２ａとしては、液体７あるいは液体７に溶解した成分と反応性を有していれば特に制限はない。モノマー２ａと液体７の組み合わせとしては、シリコーン系組成物と水、湿気硬化型ウレタン系組成物と水、アクリル系組成物とラジカル重合開始剤を含有していてもよい水、アクリル系組成物とラジカル重合開始剤を含有していてもよい有機溶剤等が例示される。これらの中でも、反応機構がシンプルであり、また室温で容易に反応が進むという観点から、シアノアクリレート系化合物と水の組み合わせが好ましい。シアノアクリレート系化合物としては特に制限されず、メチルシアノアクリレート、エチルシアノアクリレート、プロピルシアノアクリレート、イソプロピルシアノアクリレート、ブチルシアノアクリレート等が挙げられる。 The monomer 2a is not particularly limited as long as it has reactivity with the liquid 7 or a component dissolved in the liquid 7. The combination of the monomer 2a and the liquid 7 includes a silicone composition and water, a moisture-curable urethane composition and water, an acrylic composition and water that may contain a radical polymerization initiator, an acrylic composition, Examples thereof include an organic solvent that may contain a radical polymerization initiator. Among these, a combination of a cyanoacrylate compound and water is preferable from the viewpoint that the reaction mechanism is simple and the reaction proceeds easily at room temperature. The cyanoacrylate compound is not particularly limited, and examples thereof include methyl cyanoacrylate, ethyl cyanoacrylate, propyl cyanoacrylate, isopropyl cyanoacrylate, and butyl cyanoacrylate.
固体膜形成に要する時間は、目詰まりや反応界面消失の防止の観点から、気泡の発生に要する時間より長く、気泡が溶解又は浮上によって消失する時間より短いことが好ましい。膜形成時間の範囲についてより具体的には、２０ｋＨｚ超音波による気泡発生の基準時間である５０マイクロ秒以上、液体中で安定に気泡が存在可能な４時間以下が特に好ましい。ただし、気泡の発生に要する時間は気泡発生手段によって、そして気泡が溶解又は浮上によって消失する時間は気泡内包成分の液体に対する溶解度、液体の粘度等気泡周囲の環境によってそれぞれ大きく影響を受けるため、固体膜形成に要する時間は前記範囲に限定されるものではない。 The time required for forming the solid film is preferably longer than the time required for the generation of bubbles and shorter than the time required for the bubbles to disappear by dissolution or floating from the viewpoint of preventing clogging and disappearance of the reaction interface. More specifically, the range of the film formation time is particularly preferably 50 microseconds or more, which is a reference time for generating bubbles by 20 kHz ultrasonic waves, and 4 hours or less in which bubbles can stably exist in a liquid. However, the time required for the generation of bubbles is greatly affected by the bubble generating means, and the time for the bubbles to disappear due to dissolution or floating is greatly affected by the environment surrounding the bubbles, such as the solubility of the bubble inclusion component in the liquid and the viscosity of the liquid. The time required for film formation is not limited to the above range.
混合ガス４中のモノマー２ａの濃度は特に制限されない。また、混合ガス４中のモノマー２ａの濃度が１００体積％の場合には、供給ガス１ａは必須ではない。 The concentration of the monomer 2a in the mixed gas 4 is not particularly limited. When the concentration of the monomer 2a in the mixed gas 4 is 100% by volume, the supply gas 1a is not essential.
送気手段５としては、気泡発生手段６に供給ガス１ａとモノマー２ａの混合ガス４を供給できれば特に制限はなく、ダイアフラムポンプ、ギアポンプ、ロータリーポンプ、チューブポンプ等が例示される。供給ガス発生装置１を用いて供給ガス１ａを加圧して送気する場合には、送気手段５は必須ではない。 The air supply means 5 is not particularly limited as long as the mixed gas 4 of the supply gas 1a and the monomer 2a can be supplied to the bubble generating means 6, and examples thereof include a diaphragm pump, a gear pump, a rotary pump, and a tube pump. In the case where the supply gas 1a is pressurized using the supply gas generator 1 to supply air, the air supply means 5 is not essential.
気泡発生手段６としては、混合ガス４を液体７中に気泡として供給できるものであれば特に制限はない。このような手段としては、微小孔を有する管または多孔質体を通して気体を液体中に噴出させる手段、噴流や旋回流中で生じるせん断力を利用して気相を液相に巻き込む手段、超音波を用いて気液界面を振動させ微細な気泡を生成する手段等が例示される。好ましい例としては、超音波の周期で瞬間的に微細な気泡を発生することにより、膜形成反応による目詰まりが発生しない、超音波を用いて気液界面を振動させ微細な気泡を生成する手段が挙げられる。 The bubble generating means 6 is not particularly limited as long as the mixed gas 4 can be supplied as bubbles in the liquid 7. Examples of such means include means for ejecting a gas into a liquid through a tube having a micropore or a porous body, means for entraining a gas phase in a liquid phase using a shearing force generated in a jet flow or a swirling flow, ultrasonic waves A means for generating a fine bubble by oscillating the gas-liquid interface by using the above is exemplified. As a preferred example, means for generating fine bubbles by vibrating ultrasonically the gas-liquid interface, which does not cause clogging due to film formation reaction, by generating fine bubbles instantaneously in the cycle of ultrasonic waves. Is mentioned.
液体７としては、モノマー２ａと反応する成分または触媒が含まれていれば構成に特に制限はなく、水や有機溶媒が挙げられる。液体７は、反応成分又は触媒のみで構成された液体、反応成分又は触媒が溶解した溶液、反応成分又は触媒が乳化分散した溶液（エマルション）等いずれの状態でも良い。 The liquid 7 is not particularly limited in configuration as long as it contains a component or catalyst that reacts with the monomer 2a, and examples thereof include water and an organic solvent. The liquid 7 may be in any state such as a liquid composed only of the reaction component or catalyst, a solution in which the reaction component or catalyst is dissolved, or a solution (emulsion) in which the reaction component or catalyst is emulsified and dispersed.
液体７には、モノマー２ａの反応速度の制御のためにｐＨを調整するべく、必要に応じて酸又はアルカリを添加することができる。酸の種類としては、特に制限はなく、塩酸、硝酸、硫酸等の無機酸、酢酸、酒石酸、クエン酸、リンゴ酸等の有機酸を用いることができる。モノマー２ａと液体７との組み合わせが、シアノアクリレート系化合物と水の場合、シアノアクリレート系化合物の反応速度制御性の観点から、酒石酸を用いることが好ましい。また、アルカリとしては、炭酸ナトリウム、炭酸カリウム、水酸化ナトリウム、水酸化カリウム、アンモニア等の無機アルカリ、テトラメチルアンモニウムヒドロキシド、イミダゾール系化合物等の有機アルカリを用いることできる。 An acid or an alkali can be added to the liquid 7 as necessary in order to adjust the pH in order to control the reaction rate of the monomer 2a. There is no restriction | limiting in particular as a kind of acid, Organic acids, such as inorganic acids, such as hydrochloric acid, nitric acid, a sulfuric acid, acetic acid, tartaric acid, a citric acid, malic acid, can be used. When the combination of the monomer 2a and the liquid 7 is a cyanoacrylate compound and water, it is preferable to use tartaric acid from the viewpoint of reaction rate controllability of the cyanoacrylate compound. As the alkali, inorganic alkalis such as sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and ammonia, and organic alkalis such as tetramethylammonium hydroxide and imidazole compounds can be used.
液体７には、モノマー２ａを含む気泡の微細化及び安定化のために、必要に応じて界面活性剤を添加することができる。界面活性剤としては、気泡８及び液体７の気液界面に吸着し、表面張力を下げる働きをするものであれば特に制限はなく、ポリビニルアルコール、メチルセルロース、ゼラチン、一価アルコール、ポリオキシエチレンソルビタンモノラウレート、ドデシル硫酸ナトリウム、セチルトリメチルアンモニウムブロミド等が例示される。 If necessary, a surfactant can be added to the liquid 7 in order to refine and stabilize the bubbles containing the monomer 2a. The surfactant is not particularly limited as long as it is adsorbed on the gas-liquid interface between the bubbles 8 and the liquid 7 and functions to lower the surface tension. Polyvinyl alcohol, methyl cellulose, gelatin, monohydric alcohol, polyoxyethylene sorbitan Examples include monolaurate, sodium dodecyl sulfate, cetyltrimethylammonium bromide and the like.
金属酸化物粒子９を構成する金属酸化物としては、特に制限はなく、例えばシリカ、アルミナ、チタニア、ジルコニア、セリア、酸化鉄、酸化銅などが挙げられる。これらの中でも、入手や表面処理の容易性の観点から、シリカ粒子であることが好ましい。 There is no restriction | limiting in particular as a metal oxide which comprises the metal oxide particle 9, For example, a silica, an alumina, a titania, a zirconia, a ceria, iron oxide, copper oxide etc. are mentioned. Among these, silica particles are preferable from the viewpoint of availability and surface treatment.
金属酸化物粒子の製法から分類される種類としては、特に制限はなく、例えばコロイダル粒子、ゾルゲル粒子、ヒュームド粒子等が挙げられる。これらの中でも、液体中での分散安定性の観点から、コロイダル粒子であることが好ましい。 There are no particular restrictions on the type classified from the method for producing metal oxide particles, and examples include colloidal particles, sol-gel particles, and fumed particles. Among these, colloidal particles are preferable from the viewpoint of dispersion stability in a liquid.
金属酸化物粒子の平均一次粒子径としては、モノマー２ａを含む気泡と、液体７との反応により生成する中空粒子の粒子径よりも、小さければ特に制限はないが、中空粒子に効率よく付着させる観点から、１〜２００ｎｍであることが好ましく、１〜１５０ｎｍであることがより好ましく、１〜１００ｎｍであることがさらに好ましい。 The average primary particle size of the metal oxide particles is not particularly limited as long as it is smaller than the particle size of the hollow particles produced by the reaction between the bubbles containing the monomer 2a and the liquid 7, but it is efficiently attached to the hollow particles. From the viewpoint, it is preferably 1 to 200 nm, more preferably 1 to 150 nm, and further preferably 1 to 100 nm.
次に、下記の実施例により本開示をさらに詳しく説明するが、これらの実施例は本開示を制限するものではない。 Next, the present disclosure will be described in more detail with reference to the following examples, but these examples do not limit the present disclosure.
（実施例１）
エチルシアノアクリレート４．０ｇを空気吸入口および混合ガス放出口を設けた５０ｍＬ三角フラスコに封入し、ホットスターラによって２５０℃で加熱しエチルシアノアクリレート蒸気を発生させた。また、三角フラスコに吸入される空気にはオゾナイザーによって一部オゾン化され８０ｐｐｍの濃度でオゾンガスを混入させた。加熱によって発生したエチルシアノアクリレート蒸気を、オゾンガスが混入した空気と共に流量計によって流量７５０ｍＬ／ｍｉｎに調整して中空超音波ホーンに送気した。そして、この混合ガスを、５００ｍＬビーカー中で冷却水循環装置によって１２℃に維持された、酒石酸０．２ｇ、コロイダルシリカとしてスノーテックスＺＬ（日産化学工業株式会社製、製品名、粒子径７０〜１００ｎｍ、シリカ粒子濃度４０％）２．０ｇを含む純水４００ｍＬの混合液中に中空超音波ホーンから放出することによって微細な気泡を発生させた。中空超音波ホーンの出口径は内径６．０ｍｍであり、共振周波数１４．４５ｋＨｚ、振幅６０μｍで振動することにより、混合ガスが瞬時に１ｍｍ以下の気泡に微細化された。このようにして発生させた気泡と水との界面において、エチルシアノアクリレートが水と接触して重合反応が開始され、その際水に分散しているシリカ粒子を取り込みながら固体膜が形成されることにより、微細な中空粒子が生成した。中空粒子の生成、分散により、透明な水相は時間と共に白濁した。白濁した水中より採取した、実施例１の中空粒子の電子顕微鏡画像を図３に示す。同図により、７０〜１００ｎｍのシリカ粒子が表面に付着した大きさ６００〜８００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含んだナノオーダーの中空粒子の作製が確認された。
Example 1
4.0 g of ethyl cyanoacrylate was sealed in a 50 mL Erlenmeyer flask provided with an air inlet and a mixed gas outlet, and heated at 250 ° C. with a hot stirrer to generate ethyl cyanoacrylate vapor. The air sucked into the Erlenmeyer flask was partially ozonized by an ozonizer and mixed with ozone gas at a concentration of 80 ppm. The ethyl cyanoacrylate vapor generated by heating was adjusted to a flow rate of 750 mL / min with a flow meter together with air mixed with ozone gas and sent to a hollow ultrasonic horn. And this mixed gas was maintained at 12 ° C. by a cooling water circulating device in a 500 mL beaker, 0.2 g of tartaric acid, Snowtex ZL (product name, particle size 70-100 nm, manufactured by Nissan Chemical Industries, Ltd.) Fine bubbles were generated by discharging from a hollow ultrasonic horn into a mixed solution of 400 mL of pure water containing 2.0 g of silica particle concentration 40%). The exit diameter of the hollow ultrasonic horn was 6.0 mm in inner diameter, and the mixed gas was instantly refined into bubbles of 1 mm or less by vibrating at a resonance frequency of 14.45 kHz and an amplitude of 60 μm. At the interface between the bubbles and water generated in this way, ethyl cyanoacrylate comes into contact with water to initiate the polymerization reaction, and a solid film is formed while capturing silica particles dispersed in water. As a result, fine hollow particles were produced. Due to the formation and dispersion of the hollow particles, the transparent aqueous phase became cloudy with time. FIG. 3 shows an electron microscope image of the hollow particles of Example 1 collected from the cloudy water. According to the figure, since particles having a size of 600 to 800 nm with silica particles of 70 to 100 nm adhering to the surface can be confirmed, it was confirmed that nano-order hollow particles containing air taken in from the air suction port were produced. .
（実施例２）
実施例１のスノーテックスＺＬ２．０ｇ添加をスノーテックス５０（日産化学工業株式会社製、製品名、粒子径２０〜２５ｎｍ、粒子濃度４８％）１．０ｇ添加に変えたこと以外は実施例１と同じ手順によって、中空粒子を作製した。図４は、実施例２の中空粒子の電子顕微鏡画像を示す。同図に示すように２０〜２５ｎｍのシリカ粒子が表面に付着した大きさ６００〜８００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含むナノオーダーの中空粒子の作製が確認された。
(Example 2)
Example 1 with the exception that 2.0 g of Snowtex ZL in Example 1 was changed to 1.0 g of Snowtex 50 (manufactured by Nissan Chemical Industries, Ltd., product name, particle size 20 to 25 nm, particle concentration 48%). Hollow particles were made by the same procedure. FIG. 4 shows an electron microscope image of the hollow particles of Example 2. As shown in the figure, since particles having a size of 600 to 800 nm with silica particles of 20 to 25 nm attached to the surface can be confirmed, it was confirmed that nano-order hollow particles containing air taken in from the air suction port were produced. It was.
（実施例３）
実施例１のスノーテックスＺＬ２．０ｇ添加をスノーテックスＸＳ（日産化学工業株式会社製、製品名、粒子径４〜６ｎｍ、粒子濃度２０％）０．５ｇ添加に変えたこと以外は実施例１と同じ手順によって、中空粒子を作製した。図５は、実施例３の中空粒子の電子顕微鏡画像を示す。同図に示すように４〜６ｎｍの球形粒子が表面に付着した大きさ４００〜６００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含むナノオーダーの中空粒子の作製が確認された。
(Example 3)
Example 1 except that the addition of 2.0 g of Snowtex ZL in Example 1 was changed to 0.5 g of Snowtex XS (manufactured by Nissan Chemical Industries, product name, particle size 4-6 nm, particle concentration 20%). Hollow particles were made by the same procedure. FIG. 5 shows an electron microscope image of the hollow particles of Example 3. As shown in the figure, since a particle having a size of 400 to 600 nm in which spherical particles of 4 to 6 nm are attached to the surface can be confirmed, the production of nano-order hollow particles containing air taken in from the air inlet is confirmed. It was.
（実施例４）
実施例１のスノーテックスＺＬ２．０ｇ添加をスノーテックス５０（日産化学工業株式会社製、製品名、粒子径２０〜２５ｎｍ、粒子濃度４８％）１．０ｇ添加に変え、さらに供給気体の流量７５０ｍＬ／ｍｉｎを１１００ｍＬ／ｍｉｎに変えたこと以外は実施例１と同じ手順によって、中空粒子を作製した。図６は、実施例４の中空粒子の電子顕微鏡画像を示す。同図に示すように２０〜２５ｎｍの球形粒子が表面に付着した大きさ６００〜８００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含むナノオーダーの中空粒子の作製が確認された。
Example 4
The addition of 2.0 g of Snowtex ZL in Example 1 was changed to 1.0 g of Snowtex 50 (manufactured by Nissan Chemical Industries, Ltd., product name, particle size 20 to 25 nm, particle concentration 48%), and the flow rate of the supply gas was 750 mL / Hollow particles were produced by the same procedure as in Example 1 except that min was changed to 1100 mL / min. FIG. 6 shows an electron microscope image of the hollow particles of Example 4. As shown in the figure, since particles having a size of 600 to 800 nm in which spherical particles of 20 to 25 nm are adhered to the surface can be confirmed, the production of nano-order hollow particles containing air taken in from the air inlet is confirmed. It was.
（実施例５）
実施例１のスノーテックスＺＬ２．０ｇ添加をスノーテックス５０（粒子径２０〜２５ｎｍ、粒子濃度４８％）１．０ｇ添加に変え、さらに供給気体の流量７５０ｍＬ／ｍｉｎを５００ｍＬ／ｍｉｎに変えたこと以外は実施例１と同じ手順によって、中空粒子を作製した。図７は、実施例５の中空粒子の電子顕微鏡画像を示す。同図に示すように２０〜２５ｎｍの球形粒子が表面に付着した大きさ６００〜８００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含むナノオーダーの中空粒子の作製が確認された。
(Example 5)
The addition of 2.0 g of Snowtex ZL in Example 1 was changed to 1.0 g of Snowtex 50 (particle size 20 to 25 nm, particle concentration 48%), and the flow rate of the supplied gas was changed to 500 mL / min. Produced hollow particles by the same procedure as in Example 1. FIG. 7 shows an electron microscope image of the hollow particles of Example 5. As shown in the figure, since particles having a size of 600 to 800 nm in which spherical particles of 20 to 25 nm are adhered to the surface can be confirmed, the production of nano-order hollow particles containing air taken in from the air inlet is confirmed. It was.
（実施例６）
実施例１のスノーテックスＺＬ２．０ｇ添加をスノーテックスＯ−４０（日産化学工業株式会社製、製品名、粒子径２０〜２５ｎｍ、粒子濃度４０％、酸性タイプ）１．１ｇ添加に変えたこと以外は実施例１と同じ手順によって、中空粒子を作製した。図８は、実施例６の中空粒子の電子顕微鏡画像を示す。同図に示すように２０〜２５ｎｍの球形粒子が表面に付着した大きさ６００〜８００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含むナノオーダーの中空粒子の作製が確認された。
(Example 6)
Except for changing the addition of 2.0 g of Snowtex ZL in Example 1 to 1.1 g of Snowtex O-40 (manufactured by Nissan Chemical Industries, Ltd., product name, particle size 20 to 25 nm, particle concentration 40%, acidic type) Produced hollow particles by the same procedure as in Example 1. FIG. 8 shows an electron microscopic image of the hollow particles of Example 6. As shown in the figure, since particles having a size of 600 to 800 nm in which spherical particles of 20 to 25 nm are adhered to the surface can be confirmed, the production of nano-order hollow particles containing air taken in from the air inlet is confirmed. It was.
（実施例７）
実施例１のスノーテックスＺＬ２．０ｇ添加をスノーテックス５０（粒子径２０〜２５ｎｍ、粒子濃度４８％）１．０ｇ添加に変え、中空超音波ホーン出口の内径６．０ｍｍ単一穴形状を内径３．５ｍｍ３つ穴形状に変えたこと以外は実施例１と同じ手順によって、中空粒子を作製した。図９は、実施例７の中空粒子の電子顕微鏡画像を示す。同図に示すように２０〜２５ｎｍの球形粒子が表面に付着した大きさ６００〜８００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含むナノオーダーの中空粒子の作製が確認された。
(Example 7)
The addition of 2.0 g of Snowtex ZL in Example 1 was changed to 1.0 g of Snowtex 50 (particle size 20 to 25 nm, particle concentration 48%), and the inner diameter of the hollow ultrasonic horn outlet 6.0 mm was changed to a single hole shape 3 Hollow particles were produced by the same procedure as in Example 1 except that the shape was changed to a 3 mm 3 hole shape. FIG. 9 shows an electron microscopic image of the hollow particles of Example 7. As shown in the figure, since particles having a size of 600 to 800 nm in which spherical particles of 20 to 25 nm are adhered to the surface can be confirmed, the production of nano-order hollow particles containing air taken in from the air inlet is confirmed. It was.
（実施例８）
実施例１のスノーテックスＺＬ２．０ｇ添加をスノーテックス５０（粒子径２０〜２５ｎｍ、粒子濃度４８％）１．０ｇ添加に変え、中空超音波ホーン出口の内径６．０ｍｍ単一穴形状を内径２．３ｍｍ７つ穴形状に変えたこと以外は実施例１と同じ手順によって、中空粒子を作製した。図１０は、実施例８の中空粒子の電子顕微鏡画像を示す。同図に示すように２０〜２５ｎｍの球形粒子が表面に付着した大きさ６００〜８００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含むナノオーダーの中空粒子の作製が確認された。
(Example 8)
The addition of 2.0 g of Snowtex ZL in Example 1 was changed to 1.0 g of Snowtex 50 (particle size 20 to 25 nm, particle concentration 48%), and the inner diameter of the hollow ultrasonic horn outlet 6.0 mm was changed to a single hole shape of 2 Hollow particles were produced by the same procedure as in Example 1 except that the shape was changed to a 3 mm 7 hole shape. FIG. 10 shows an electron microscopic image of the hollow particles of Example 8. As shown in the figure, since particles having a size of 600 to 800 nm in which spherical particles of 20 to 25 nm are adhered to the surface can be confirmed, the production of nano-order hollow particles containing air taken in from the air inlet is confirmed. It was.
（実施例９）
実施例１のスノーテックスＺＬ２．０ｇ添加をスノーテックス５０（粒子径２０〜２５ｎｍ、粒子濃度４８％）１．０ｇ添加に変え、中空超音波ホーン出口の内径６．０ｍｍ単一穴形状を内径２．０ｍｍ９つ穴形状に変えたこと以外は実施例１と同じ手順によって、中空粒子を作製した。図１１は、実施例９の中空粒子の電子顕微鏡画像を示す。同図に示すように２０〜２５ｎｍの球形粒子が表面に付着した大きさ６００〜８００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含むナノオーダーの中空粒子の作製が確認された。
Example 9
The addition of 2.0 g of Snowtex ZL in Example 1 was changed to 1.0 g of Snowtex 50 (particle size 20 to 25 nm, particle concentration 48%), and the inner diameter of the hollow ultrasonic horn outlet 6.0 mm was changed to a single hole shape of 2 Hollow particles were produced by the same procedure as in Example 1 except that the hole shape was changed to 0.0 mm and 9 holes. FIG. 11 shows an electron microscopic image of the hollow particles of Example 9. As shown in the figure, since particles having a size of 600 to 800 nm in which spherical particles of 20 to 25 nm are adhered to the surface can be confirmed, the production of nano-order hollow particles containing air taken in from the air inlet is confirmed. It was.
（実施例１０）
実施例１のスノーテックスＺＬ２．０ｇ添加をスノーテックスＯ−４０（粒子径２０〜２５ｎｍ、粒子濃度４０％）１．１ｇ添加に変え、供給気体の流量７５０ｍＬ／ｍｉｎを１１００ｍＬ／ｍｉｎに変えたこと以外は実施例１と同じ手順によって、中空粒子を作製した。図１２は、実施例１０の中空粒子の電子顕微鏡画像を示す。同図に示すように２０〜２５ｎｍの球形粒子が表面に付着した大きさ６００〜８００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含むナノオーダーの中空粒子の作製が確認された。
(Example 10)
The addition of 2.0 g of Snowtex ZL in Example 1 was changed to 1.1 g of Snowtex O-40 (particle size 20 to 25 nm, particle concentration 40%), and the flow rate of the supply gas was changed to 1100 mL / min. Except for the above, hollow particles were produced by the same procedure as in Example 1. FIG. 12 shows an electron microscopic image of the hollow particles of Example 10. As shown in the figure, since particles having a size of 600 to 800 nm in which spherical particles of 20 to 25 nm are adhered to the surface can be confirmed, the production of nano-order hollow particles containing air taken in from the air inlet is confirmed. It was.
（実施例１１）
実施例１のスノーテックスＺＬ２．０ｇ添加をスノーテックスＯ−４０（粒子径２０〜２５ｎｍ、粒子濃度４０％）１．１ｇ添加に変え、供給気体の流量７５０ｍＬ／ｍｉｎを１１００ｍＬ／ｍｉｎに変え、供給気体の乾燥空気を二酸化炭素に変えたこと以外は実施例１と同じ手順によって、中空粒子を作製した。図１３は、実施例１１の中空粒子の電子顕微鏡画像を示す。同図に示すように２０〜２５ｎｍの球形粒子が表面に付着した大きさ４００〜７００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含むナノオーダーの中空粒子の作製が確認された。
(Example 11)
The addition of 2.0 g of Snowtex ZL in Example 1 was changed to 1.1 g of Snowtex O-40 (particle size 20 to 25 nm, particle concentration 40%), the supply gas flow rate was changed to 750 mL / min, and the supply was performed. Hollow particles were produced by the same procedure as in Example 1 except that the gaseous dry air was changed to carbon dioxide. FIG. 13 shows an electron microscopic image of the hollow particles of Example 11. As shown in the figure, since particles having a size of 400 to 700 nm with spherical particles of 20 to 25 nm attached to the surface can be confirmed, the production of nano-order hollow particles containing air taken in from the air inlet is confirmed. It was.
（実施例１２）
実施例１のスノーテックスＺＬ２．０ｇ添加をスノーテックスＯ−４０（粒子径２０〜２５ｎｍ、粒子濃度４０％）１．１ｇ添加に変え、供給気体の流量７５０ｍＬ／ｍｉｎを１１００ｍＬ／ｍｉｎに変え、供給気体の乾燥空気をアルゴンに変えたこと以外は実施例１と同じ手順によって、中空粒子を作製した。図１４は、実施例１２の中空粒子の電子顕微鏡画像を示す。同図に示すように２０〜２５ｎｍの球形粒子が表面に付着した大きさ４００〜７００ｎｍの粒子が確認できることから、内部に空気吸入口から取り込んだ空気を含むナノオーダーの中空粒子の作製が確認された。
(Example 12)
The addition of 2.0 g of Snowtex ZL in Example 1 was changed to 1.1 g of Snowtex O-40 (particle size 20 to 25 nm, particle concentration 40%), the supply gas flow rate was changed to 750 mL / min, and the supply was performed. Hollow particles were produced by the same procedure as in Example 1 except that the gaseous dry air was changed to argon. FIG. 14 shows an electron microscopic image of the hollow particles of Example 12. As shown in the figure, since particles having a size of 400 to 700 nm with spherical particles of 20 to 25 nm attached to the surface can be confirmed, the production of nano-order hollow particles containing air taken in from the air inlet is confirmed. It was.
本発明で提供する製造方法では、モノマーを液体中に溶解させるのではなく、モノマーガスを含む気泡を液体中に供給するため、反応場である気液界面に選択的に材料を供給することができる。また、あらかじめ金属酸化物粒子を液体中に分散させることによって、金属酸化物粒子を気液界面に吸着させることができるため、モノマー重合により生じる固体膜表面に効率よく金属酸化物粒子を付着させることができる。このようにして得られた、モノマー重合体を固体膜として備える、表面に金属酸化物粒子が付着した中空粒子は、断熱材、防音材、感熱材、緩衝材、軽量化材料、衝撃吸収剤、光学材料、塗料、化粧品、医薬品等様々な用途に有効である。 In the production method provided by the present invention, instead of dissolving the monomer in the liquid, the bubbles containing the monomer gas are supplied into the liquid. Therefore, the material can be selectively supplied to the gas-liquid interface as a reaction field. it can. Moreover, since the metal oxide particles can be adsorbed to the gas-liquid interface by dispersing the metal oxide particles in the liquid in advance, the metal oxide particles can be efficiently attached to the surface of the solid film generated by the monomer polymerization. Can do. The thus obtained hollow particles having a monomer polymer as a solid film and having metal oxide particles attached to the surface are heat insulating materials, soundproofing materials, heat-sensitive materials, buffer materials, weight-reducing materials, shock absorbers, It is effective for various applications such as optical materials, paints, cosmetics, and pharmaceuticals.
１…供給ガス発生装置、１ａ…供給ガス、２…気化容器、２ａ…モノマー（モノマーガス）、３…送気管、４…混合ガス、５…送気手段、６…気泡発生手段、７…液体、８…気泡、９…金属酸化物粒子、１０…中空粒子、１０ａ…殻部、１０ｂ…中空部。
DESCRIPTION OF SYMBOLS 1 ... Supply gas generator 1a ... Supply gas, 2 ... Vaporization container, 2a ... Monomer (monomer gas), 3 ... Air supply pipe, 4 ... Mixed gas, 5 ... Air supply means, 6 ... Bubble generation means, 7 ... Liquid 8 ... bubbles, 9 ... metal oxide particles, 10 ... hollow particles, 10a ... shell parts, 10b ... hollow parts.
Claims (7)
金属酸化物粒子を含む液体中でモノマーを含む気泡を発生させ、前記気泡及び前記液体の界面において、前記液体及び前記モノマーの接触により、前記モノマー由来のポリマーを含む層及び該層表面に担持された前記金属酸化物粒子を備える前記殻部を形成する工程を備える、製造方法。 A method for producing a hollow particle comprising a shell having a hollow,
A bubble containing a monomer is generated in a liquid containing metal oxide particles, and is supported on the layer containing the monomer-derived polymer and the surface of the layer by contact of the liquid and the monomer at the interface between the bubble and the liquid. A manufacturing method comprising the step of forming the shell portion including the metal oxide particles.
A hollow particle comprising a shell having a hollow, the shell comprising a layer containing a polymer and metal oxide particles supported on the surface of the layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016040078A JP6677018B2 (en) | 2016-03-02 | 2016-03-02 | Method for producing hollow particles and hollow particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016040078A JP6677018B2 (en) | 2016-03-02 | 2016-03-02 | Method for producing hollow particles and hollow particles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017154087A true JP2017154087A (en) | 2017-09-07 |
| JP6677018B2 JP6677018B2 (en) | 2020-04-08 |
Family
ID=59807656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016040078A Expired - Fee Related JP6677018B2 (en) | 2016-03-02 | 2016-03-02 | Method for producing hollow particles and hollow particles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6677018B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210106364A (en) | 2020-02-20 | 2021-08-30 | 아지노모토 가부시키가이샤 | Resin composition |
-
2016
- 2016-03-02 JP JP2016040078A patent/JP6677018B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210106364A (en) | 2020-02-20 | 2021-08-30 | 아지노모토 가부시키가이샤 | Resin composition |
| US11884814B2 (en) | 2020-02-20 | 2024-01-30 | Ajinomoto Co., Inc. | Resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6677018B2 (en) | 2020-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kudo et al. | Effect of ultrasonic frequency on size distributions of nanosized mist generated by ultrasonic atomization | |
| JP3051945B2 (en) | Inorganic uniform microsphere and method for producing the same | |
| JP4931001B2 (en) | Method for accelerating cavitation reaction and method for producing metal nanoparticles using the same | |
| JP2007021315A (en) | Method for producing hollow microcapsule | |
| JP2017029876A (en) | Hollow particle made from bubbles and method for producing the same | |
| JP2006187757A (en) | High-speed centrifugal type ozone water producing method and system | |
| JP6677018B2 (en) | Method for producing hollow particles and hollow particles | |
| JP5709130B2 (en) | Method and apparatus for producing crystalline fine particles with excellent mixing efficiency | |
| JP5590666B2 (en) | Hollow particles made from bubbles and method for producing the same | |
| JP6629828B2 (en) | Method of generating mechanical and electrochemical cavitation, method of changing surface geometry and electrochemical properties of material, method of stripping rare metal, and apparatus for generating mechanical and electrochemical cavitation | |
| JP6212537B2 (en) | Products and methods for producing uniform spherical acrylic polymer beads | |
| Kobayashi et al. | Microbubble generation with rapid dissolution of ammonia (NH3)-hydrogen (H2) mixed gas fed from a nozzle into water | |
| JP2009062321A (en) | Method and device for reducing carbon dioxide | |
| JP2015085251A (en) | Hollow particle made from air bubble and production device therefor | |
| JP6525137B2 (en) | Method of manufacturing dispersion liquid and manufacturing apparatus of dispersion liquid | |
| JP4300291B2 (en) | Method and apparatus for generating microbubbles with uniform diameter | |
| JP2002113340A (en) | Method and device for generating micro air bubble using ultrasonic wave | |
| JP2019094226A (en) | Method for producing hollow particles | |
| KAJIHARA et al. | Preparation of Hollow Silica Nanoparticles Using Ultrasonically Generated Microbubbles as a Template | |
| JP5508854B2 (en) | Method for producing inorganic spherical body and emulsifying device | |
| JP2020138168A (en) | Method for producing hollow particle | |
| Koda et al. | Sonochemical Engineering Processes | |
| JP2016159291A (en) | Production method of polymer nanoparticle, polymer nanoparticle, and formation method of nanobubble | |
| YUYAMA et al. | Fabrication of Cyanoacrylate Hollow Particles using Microbubble Generation Technique | |
| JP2005097420A (en) | Method for surface modification of fine particle |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190204 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20191129 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200107 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200127 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200212 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200225 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 6677018 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| LAPS | Cancellation because of no payment of annual fees |