JP5693187B2 - Aqueous dispersion of inorganic oxide fine particles - Google Patents
Aqueous dispersion of inorganic oxide fine particles Download PDFInfo
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- JP5693187B2 JP5693187B2 JP2010271014A JP2010271014A JP5693187B2 JP 5693187 B2 JP5693187 B2 JP 5693187B2 JP 2010271014 A JP2010271014 A JP 2010271014A JP 2010271014 A JP2010271014 A JP 2010271014A JP 5693187 B2 JP5693187 B2 JP 5693187B2
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- 239000010419 fine particle Substances 0.000 title claims description 197
- 239000006185 dispersion Substances 0.000 title claims description 169
- 229910052809 inorganic oxide Inorganic materials 0.000 title claims description 136
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 150
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 96
- 239000000377 silicon dioxide Substances 0.000 claims description 71
- 235000019441 ethanol Nutrition 0.000 claims description 67
- 239000002245 particle Substances 0.000 claims description 52
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000007787 solid Substances 0.000 claims description 28
- 229910052783 alkali metal Inorganic materials 0.000 claims description 18
- 150000001340 alkali metals Chemical class 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims 1
- 230000008014 freezing Effects 0.000 description 21
- 238000007710 freezing Methods 0.000 description 21
- 238000010257 thawing Methods 0.000 description 21
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 239000011734 sodium Substances 0.000 description 17
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 239000002612 dispersion medium Substances 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000003456 ion exchange resin Substances 0.000 description 4
- 229920003303 ion-exchange polymer Polymers 0.000 description 4
- 230000002427 irreversible effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011859 microparticle Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
Description
本発明は無機酸化物微粒子の水分散液に関し、特に、凍結・解凍後の再分散性に優れた無機酸化物微粒子の水分散液に関するものである。 The present invention relates to an aqueous dispersion of inorganic oxide fine particles, and more particularly to an aqueous dispersion of inorganic oxide fine particles having excellent redispersibility after freezing and thawing.
シリカゾルやシリカアルミナゾル、あるいはチタニアゾルなどの無機酸化物微粒子の分散液は、研磨剤、塗料、ハードコート剤など様々な用途に使用されている。
このような水分散液の一例として、特許文献１に記載されるようなシリカ系ゾルが知られている。
しかし、このような分散液のうち分散媒が水である水分散液は、例えば氷点下のような低温条件下で保管または輸送、使用した場合に、該水分散液が凍結してゲル化する場合があり、再分散させることが困難な場合があるという問題があった。
Dispersions of inorganic oxide fine particles such as silica sol, silica alumina sol, and titania sol are used in various applications such as abrasives, paints, and hard coat agents.
As an example of such an aqueous dispersion, a silica-based sol as described in Patent Document 1 is known.
However, an aqueous dispersion in which the dispersion medium is water among such dispersions, for example, when the aqueous dispersion freezes and gels when stored, transported, or used under low temperature conditions such as below freezing. There is a problem that it may be difficult to redisperse.
本発明者らは、このような課題を鑑みて、鋭意研究した結果、水を分散媒とした無機酸化物微粒子の分散液に少量のアルコールを添加することで、該分散液を凍結後解凍させた際の不可逆的凝集が著しく抑制されることを見出し、本発明を完成させるに到った。
すなわち本発明では、低温条件下で凍結させても、解凍させた際には再分散が容易で、品質の低下しにくい無機酸化物微粒子の水分散液を提供することを目的としている。
As a result of diligent research in view of such problems, the inventors of the present invention added a small amount of alcohol to a dispersion of inorganic oxide fine particles using water as a dispersion medium, so that the dispersion was thawed after freezing. As a result, it was found that irreversible aggregation during the process was significantly suppressed, and the present invention was completed.
That is, an object of the present invention is to provide an aqueous dispersion of inorganic oxide fine particles that are easily redispersed and hardly deteriorate in quality when thawed even if frozen under low temperature conditions.
本発明の無機酸化物微粒子の水分散液は、平均粒子径１〜５００ｎｍの無機酸化物微粒子と、アルコールとを含む水分散液であって、該アルコールの含有量が該無機酸化物微粒子の単位表面積あたりに１×１０-8〜２０ｍｏｌ／ｍ2の範囲にあり、該水分散液に含まれる該無機酸化物微粒子の固形分濃度が０．００１〜６０重量％の範囲にあることを特徴とする。 The aqueous dispersion of inorganic oxide fine particles of the present invention is an aqueous dispersion containing inorganic oxide fine particles having an average particle diameter of 1 to 500 nm and alcohol, and the content of the alcohol is a unit of the inorganic oxide fine particles. It is in the range of 1 × 10 −8 to 20 mol / m 2 per surface area, and the solid content concentration of the inorganic oxide fine particles contained in the aqueous dispersion is in the range of 0.001 to 60% by weight. To do.
前記アルコールがメチルアルコール、エチルアルコール、イソプロピルアルコールから選ばれた１種以上であることが好ましい。
前記水分散液に含まれるアルコール濃度が０．５〜８重量％の範囲にあることが好ましい。
前記水分散液に含まれるアルカリ金属含有量がＭ2Ｏ換算基準（ただしＭはアルカリ金属元素とする）の固形分濃度で０．４５重量％未満の範囲にあることが好ましい。
The alcohol is preferably at least one selected from methyl alcohol, ethyl alcohol, and isopropyl alcohol.
The concentration of alcohol contained in the aqueous dispersion is preferably in the range of 0.5 to 8% by weight.
The alkali metal content contained in the aqueous dispersion is preferably in the range of less than 0.45 wt% in terms of solid content concentration based on M 2 O conversion (where M is an alkali metal element).
前記無機酸化物微粒子がケイ素とアルミニウムとを含むことが好ましい。
前記無機酸化物微粒子がシリカ微粒子であることが好ましい。
前記無機酸化物微粒子の平均粒子径が１００〜２００ｎｍの範囲にあることが好ましい。
前記水分散液に含まれる前記無機酸化物微粒子の固形分濃度が０．００１〜２０重量％の範囲にあることが好ましい。
The inorganic oxide fine particles preferably contain silicon and aluminum.
The inorganic oxide fine particles are preferably silica fine particles.
The average particle diameter of the inorganic oxide fine particles is preferably in the range of 100 to 200 nm.
It is preferable that the solid content concentration of the inorganic oxide fine particles contained in the aqueous dispersion is in the range of 0.001 to 20% by weight.
本発明に係る無機酸化物微粒子の水分散液は、該無機酸化物微粒子の単位表面積あたりに対して所定の範囲のアルコールを含んでいるために、該水分散液が凍結した場合にも、これを解凍した際に該分散液中に含まれる該無機酸化物微粒子を再分散させることが容易である。
また再分散後の分散性や透明性が、凍結前と比べて低下することも少ない。
このような無機酸化物微粒子の水分散液は凍結によってその品質が低下することが非常に少ないため寒冷地や低温条件下でも輸送および保管または使用することができる。また、該水分散液に含まれるアルコールの量は、無機酸化物微粒子の固形分濃度にもよるが、比較的少ないため、危険物の法的取り扱い制限を受けることも少なく、必要以上にアルコール成分を含まず、分散媒の主成分を水とすることができるため、安全性も高く、また使用する用途が制限されることが少なく様々な目的に使用することができる。
Since the aqueous dispersion of inorganic oxide fine particles according to the present invention contains a predetermined range of alcohol with respect to the unit surface area of the inorganic oxide fine particles, it can be used even when the aqueous dispersion is frozen. It is easy to re-disperse the inorganic oxide fine particles contained in the dispersion when the thawing is thawed.
In addition, the dispersibility and transparency after redispersion are less likely to be lower than before freezing.
Such an aqueous dispersion of inorganic oxide fine particles can be transported, stored, or used even in a cold region or under a low temperature condition because the quality of the aqueous dispersion is hardly reduced by freezing. In addition, the amount of alcohol contained in the aqueous dispersion is relatively small depending on the solid content concentration of the inorganic oxide fine particles. In addition, since the main component of the dispersion medium can be water, the safety is high, and the use is not limited and can be used for various purposes.
以下に、本発明を実施するための形態について具体的に述べる。
無機酸化物微粒子の水分散液
本発明に係る無機酸化物微粒子の水分散液は、平均粒子径１〜５００ｎｍの無機酸化物微粒子と、アルコールとを含む水分散液であって、該アルコールの含有量が該無機酸化物微粒子の単位表面積あたりに１．０×１０-8〜２０ｍｏｌ／ｍ2の範囲にあり、該水分散液に含まれる該無機酸化物微粒子の固形分濃度が０．００１〜６０重量％の範囲にあることを特徴としている。
前記水分散液に含まれるアルコールの含有量が、上記の範囲にあることによって、必要最小限のアルコール添加量で、該水分散液を凍結、解凍させたのちの再分散性を著しく向上させることができる。
その理由としては、定かではないものの、少なくとも水分散液が凍結する際に、アルコール分子が無機酸化物微粒子の表面の一部を被覆することにより、不可逆的な凝集が抑制されるためであると考えられる。
Below, the form for implementing this invention is described concretely.
Aqueous dispersion of inorganic oxide fine particles An aqueous dispersion of inorganic oxide fine particles according to the present invention is an aqueous dispersion containing inorganic oxide fine particles having an average particle diameter of 1 to 500 nm and an alcohol, and containing the alcohol The amount is in the range of 1.0 × 10 −8 to 20 mol / m 2 per unit surface area of the inorganic oxide fine particles, and the solid content concentration of the inorganic oxide fine particles contained in the aqueous dispersion is 0.001 to 0.001. It is characterized by being in the range of 60% by weight.
When the content of the alcohol contained in the aqueous dispersion is within the above range, the redispersibility after the aqueous dispersion is frozen and thawed can be remarkably improved with the minimum amount of alcohol added. Can do.
The reason for this is that although it is not clear, at least when the aqueous dispersion freezes, alcohol molecules cover a part of the surface of the inorganic oxide fine particles, thereby suppressing irreversible aggregation. Conceivable.
前記アルコールの含有量は、前記無機酸化物微粒子の単位表面積あたりに１．０×１０-8〜２０ｍｏｌ／ｍ2、より好ましくは１．０×１０-6〜１．０×１０-3ｍｏｌ／ｍ2、さらに好ましくは３．０×１０-6〜５．０×１０-4ｍｏｌ／ｍ2の範囲にあることが好ましい。
前記アルコールの含有量が１．０×１０-8ｍｏｌ／ｍ2未満の場合には、前記水分散液の凍結解凍後の再分散性が向上する効果が低いため好ましくない。
前記アルコールの含有量が２０ｍｏｌ／ｍ2を超えると、前記水分散液の凍結解凍後の再分散性を向上させる効果が、それ以上増加しなくなり、かつ、水分散液が不要なアルコールを含むとその使用用途が制限される場合があったり、用途にもよるがその安全性が低下する場合があるので好ましくない。
The content of the alcohol is 1.0 × 10 −8 to 20 mol / m 2 , more preferably 1.0 × 10 −6 to 1.0 × 10 −3 mol / per unit surface area of the inorganic oxide fine particles. m 2 , more preferably in the range of 3.0 × 10 −6 to 5.0 × 10 −4 mol / m 2 .
If the alcohol content is less than 1.0 × 10 −8 mol / m 2 , the effect of improving the redispersibility of the aqueous dispersion after freezing and thawing is low, such being undesirable.
When the content of the alcohol exceeds 20 mol / m 2 , the effect of improving the redispersibility after freezing and thawing of the aqueous dispersion no longer increases, and the aqueous dispersion contains an unnecessary alcohol. This is not preferable because the use application may be limited or the safety may be reduced depending on the application.
前記水分散液に含まれる前記無機酸化物微粒子の固形分濃度は０．００１〜６０重量％、より好ましくは０．００１〜４０重量％、さらに好ましくは０．００１〜２０重量％の範囲にあることが好ましい。
前記固形分濃度が０．００１重量％未満の場合には、そもそも、無機酸化物微粒子の水分散液の特徴が発現しにくいので好ましくない。前記固形分濃度が６０重量％の場合には、前記水分散液の分散安定性が低下するので好ましくない。
固形分濃度が０．００１〜２０重量％の範囲にある前記水分散液は、安定性が高く、凍結解凍したのちの再分散性が特に高いため好ましい。
The solid content concentration of the inorganic oxide fine particles contained in the aqueous dispersion is in the range of 0.001 to 60% by weight, more preferably 0.001 to 40% by weight, and still more preferably 0.001 to 20% by weight. It is preferable.
When the solid content concentration is less than 0.001% by weight, the characteristics of the aqueous dispersion of inorganic oxide fine particles are hardly exhibited in the first place, which is not preferable. When the solid content concentration is 60% by weight, the dispersion stability of the aqueous dispersion is lowered, which is not preferable.
The aqueous dispersion having a solid content in the range of 0.001 to 20% by weight is preferable because of its high stability and particularly high redispersibility after freeze-thawing.
前記アルコールは特に制限されるものではなく、公知のものを使用することができる。
中でも、メチルアルコール、エチルアルコール、イソプロピルアルコールを用いることが好ましい。特に、エチルアルコールは安全性が高いため特に好ましい。
The alcohol is not particularly limited, and a known alcohol can be used.
Of these, methyl alcohol, ethyl alcohol, and isopropyl alcohol are preferably used. In particular, ethyl alcohol is particularly preferable because of its high safety.
本発明に係る無機酸化物微粒子の水分散液は、殆どの場合、凍結させ解凍したのちに特殊な再分散工程を行わなくても、自発的に再分散する。また、アルコール含有量や無機酸化物微粒子の固形分濃度などの条件によって擬似的な凝集が起こった場合であっても、超音波処理などの簡単な再分散処理によって容易にこれを再分散させることができる。
このように水分散液に含まれる無機酸化物微粒子の凍結解凍後の再分散性が向上する理由としては定かではないものの、水分散液の分散時、もしくは凍結時に、無機酸化物微粒子の表面にアルコール分子が存在することにより、またはアルコール分子が該微粒子の表面を部分的または全体的に被覆または吸着することにより、凍結時の該微粒子の不可逆的な凝集が抑制され、解凍後に水分子が溶解すれば無機酸化物微粒子は再び分散するものと推察される。
In most cases, the aqueous dispersion of fine inorganic oxide particles according to the present invention is spontaneously redispersed without being subjected to a special redispersion step after being frozen and thawed. In addition, even if pseudo-aggregation occurs due to conditions such as alcohol content and solid content concentration of inorganic oxide fine particles, it can be easily redispersed by simple redispersion treatment such as ultrasonic treatment. Can do.
Although the reason why the re-dispersibility of the inorganic oxide fine particles contained in the aqueous dispersion is improved after freezing and thawing is not clear, the surface of the inorganic oxide fine particles is dispersed when the aqueous dispersion is dispersed or frozen. The presence of alcohol molecules, or the alcohol molecules partially or entirely covering or adsorbing the surface of the microparticles, suppresses irreversible aggregation of the microparticles during freezing, and the water molecules dissolve after thawing. In this case, it is assumed that the inorganic oxide fine particles are dispersed again.
本発明に係る水分散液に含まれる前記アルコール濃度は０．５〜８重量％、より好ましくは０．９〜３．５重量％の範囲にあることが好ましい。
前記アルコール濃度が０．５重量％未満の場合には、水分散液を凍結解凍したのちの再分散性が低下する場合があるので好ましくない。前記アルコール濃度が８重量％を超えると、水分散液の安全性および加工性や取り扱いの面、および使用する用途によっては好ましくない場合がある。
The concentration of the alcohol contained in the aqueous dispersion according to the present invention is preferably 0.5 to 8% by weight, more preferably 0.9 to 3.5% by weight.
When the alcohol concentration is less than 0.5% by weight, the redispersibility after freezing and thawing the aqueous dispersion may be lowered, which is not preferable. If the alcohol concentration exceeds 8% by weight, it may not be preferable depending on the safety and processability of the aqueous dispersion, the handling aspect, and the application to be used.
無機酸化物微粒子
本発明に係る水分散液の無機酸化物微粒子について詳述する。
前記無機酸化物微粒子としては、特に制限されるものではないが、例えば遷移金属、貴金属、アルカリ金属、アルカリ土類金属などをはじめとする金属の酸化物微粒子、複合酸化物微粒子などが挙げられる。
またこれらの金属酸化物微粒子や金属酸化物微粒子は有機ケイ素化合物やアミンなどの公知の表面処理剤によって少なくともその表面の一部を処理または修飾されたものであってもよい。
Inorganic oxide fine particles The inorganic oxide fine particles of the aqueous dispersion according to the present invention will be described in detail.
The inorganic oxide fine particles are not particularly limited, and examples thereof include metal oxide fine particles such as transition metals, noble metals, alkali metals, alkaline earth metals, and composite oxide fine particles.
Further, these metal oxide fine particles and metal oxide fine particles may be those obtained by treating or modifying at least a part of the surface with a known surface treating agent such as an organosilicon compound or an amine.
さらに具体的に述べれば、前記無機酸化物微粒子はケイ素、アルミニウム、チタニウム、マグネシウム、ジルコニウム、アンチモン、鉄、タングステンより選ばれた１種または１種以上の金属元素を含む酸化物微粒子および／または複合酸化物微粒子であることが好ましい。
また前記酸化物微粒子または複合酸化物微粒子は、さらにリン、ホウ素、セリウム、アルカリ金属、アルカリ土類金属より選ばれる１種以上を含むものであってもよい。
前記無機酸化物微粒子は、コアシェル型微粒子であってもよく、中空型微粒子であってもよい。また前記無機酸化物微粒子は副成分として有機基や樹脂などの有機物を含んでいてもかまわない。
More specifically, the inorganic oxide fine particles are oxide fine particles and / or composites containing one or more metal elements selected from silicon, aluminum, titanium, magnesium, zirconium, antimony, iron, and tungsten. Oxide fine particles are preferable.
The oxide fine particles or composite oxide fine particles may further contain one or more selected from phosphorus, boron, cerium, alkali metals, and alkaline earth metals.
The inorganic oxide fine particles may be core-shell fine particles or hollow fine particles. The inorganic oxide fine particles may contain an organic substance such as an organic group or a resin as a subcomponent.
前記無機酸化物微粒子は、平均粒子径１〜５００ｎｍの範囲にあることを特徴としている。
前記平均粒子径は、より好ましくは、５〜３００ｎｍ、さらに好ましくは、１００〜２００ｎｍの範囲にあることが好ましい。
前記平均粒子径が１ｎｍ未満の場合には、無機酸化物微粒子の安定性が低いので好ましくない。
また、前記平均粒子径が５００ｎｍを超えると、無機酸化物微粒子を含む水分散液の分散安定性が低下するので好ましくない。
The inorganic oxide fine particles are characterized by having an average particle diameter in the range of 1 to 500 nm.
The average particle diameter is more preferably 5 to 300 nm, and still more preferably 100 to 200 nm.
When the average particle diameter is less than 1 nm, the stability of the inorganic oxide fine particles is low, which is not preferable.
On the other hand, when the average particle diameter exceeds 500 nm, the dispersion stability of the aqueous dispersion containing inorganic oxide fine particles decreases, which is not preferable.
前記無機酸化物微粒子の形状は特に制限されるものではなく、球状、繊維状、針状、棒状、鎖状、金平糖状などを含むあらゆる形状の微粒子を使用することができる。
ただし、前記無機酸化物微粒子が、鎖状など、複数の一次粒子が結合した二次粒子を形成している形状にある場合には、前記平均粒子径は二次粒子径を意味するものとする。
The shape of the inorganic oxide fine particles is not particularly limited, and fine particles having any shape including spherical, fibrous, needle-like, rod-like, chain-like, and confetti shape can be used.
However, when the inorganic oxide fine particles are in the form of secondary particles in which a plurality of primary particles are bonded, such as a chain, the average particle diameter means the secondary particle diameter. .
前記無機酸化物微粒子は、粉末状の微粒子であっても良いが、より好ましくはゾルやコロイドなどの分散液状の微粒子であることが好ましい。分散液状の無機酸化物微粒子を用いると、本発明に係る無機酸化物微粒子の水分散液の安定性や透明性が向上するので好ましい。
分散液状の無機酸化物微粒子を用いる場合には、水を分散媒とする無機酸化物微粒子を用いることが好ましい。
The inorganic oxide fine particles may be powdery fine particles, but more preferably dispersed fine particles such as sol and colloid. Use of dispersed inorganic oxide fine particles is preferable because stability and transparency of the aqueous dispersion of inorganic oxide fine particles according to the present invention are improved.
In the case of using dispersed liquid inorganic oxide fine particles, it is preferable to use inorganic oxide fine particles containing water as a dispersion medium.
前記無機酸化物微粒子は、例えばアルコキシド法、ゾルゲル法、金属塩や金属アルコキシドを加水分解し必要に応じて中和する方法、水熱合成法などをはじめとする公知の方法で製造することができる。
また、分散液状の前記無機酸化物微粒子としては、市販品（例えば、日揮触媒化成（株）のカタロイド、ファインカタロイド、アトミーボール(AB)等）を用いてもよい。
The inorganic oxide fine particles can be produced by a known method including, for example, an alkoxide method, a sol-gel method, a method of hydrolyzing a metal salt or a metal alkoxide and neutralizing it if necessary, a hydrothermal synthesis method, and the like. .
In addition, as the inorganic oxide fine particles in a dispersed liquid form, commercially available products (for example, cataloid, fine cataloid, atomy ball (AB), etc. of JGC Catalysts & Chemicals Co., Ltd.) may be used.
さらに、前記水分散液に含まれるアルカリ金属含有量は、Ｍ2Ｏ換算基準（ただしＭはアルカリ金属元素とする）の固形分重量で０．４５重量％未満の範囲にあることが好ましい。
前記アルカリ金属含有量が固形分濃度で０．４５重量％を超える場合には、無機酸化物微粒子の種類にもよるが、凍結解凍後の水分散液の再分散性が低下する場合があるので好ましくない。
Further, the alkali metal content contained in the aqueous dispersion is preferably in the range of less than 0.45% by weight based on the solid content of M 2 O conversion standard (where M is an alkali metal element).
When the alkali metal content exceeds 0.45% by weight in terms of solid content, the redispersibility of the aqueous dispersion after freezing and thawing may decrease, depending on the type of inorganic oxide fine particles. It is not preferable.
例えば、シリカゾルやシリカアルミナゾルなどは製法によってはアルカリ金属を含む場合があるが、このようなゾルを無機酸化物微粒子として使用する場合に、最終的な水分散液のアルカリ金属含有量が上記範囲を超えるような場合には、必要に応じて、イオン交換樹脂や、限外ろ過膜などを用いて該水分散液中のアルカリ金属元素を除去してもよい。 For example, silica sol and silica alumina sol may contain an alkali metal depending on the production method, but when such a sol is used as inorganic oxide fine particles, the alkali metal content of the final aqueous dispersion falls within the above range. In such a case, if necessary, the alkali metal element in the aqueous dispersion may be removed using an ion exchange resin, an ultrafiltration membrane or the like.
また、前記無機酸化物微粒子のより好ましい形態の一つとして、ケイ素とアルミニウムとを含む無機酸化物微粒子が挙げられる。
また、前記ケイ素とアルミニウムとを含む無機酸化物微粒子のうち、分散液状のものは特に好ましい。
ケイ素とアルミニウムとを含む無機酸化物微粒子を本発明に係る水分散液に用いると、該無機酸化物微粒子の分散安定性が非常に高く、水分散液を凍結、解凍させたのちの再分散性に優れるため、好ましい。
Moreover, as one of the more preferable forms of the said inorganic oxide fine particle, the inorganic oxide fine particle containing silicon and aluminum is mentioned.
Further, among the inorganic oxide fine particles containing silicon and aluminum, a dispersion liquid is particularly preferable.
When inorganic oxide fine particles containing silicon and aluminum are used in the aqueous dispersion according to the present invention, the dispersion stability of the inorganic oxide fine particles is very high, and the redispersibility after the aqueous dispersion is frozen and thawed. Is preferable.
ケイ素とアルミニウムとを含む無機酸化物微粒子の一例としては、例えば特開昭６３−１２３８０７号公報に記載の酸性シリカゾルや、特開平０６−１９９５１５号公報に記載の酸性シリカゾルなどが挙げられる。
なお、前記無機酸化物微粒子が、ケイ素とアルミニウム以外の元素、例えばチタニウム、ジルコニウム、亜鉛などをさらに含むものであってもよい。
Examples of the inorganic oxide fine particles containing silicon and aluminum include, for example, an acidic silica sol described in JP-A No. 63-123807, an acidic silica sol described in JP-A No. 06-199515, and the like.
The inorganic oxide fine particles may further contain an element other than silicon and aluminum, such as titanium, zirconium, and zinc.
また、前記無機酸化物微粒子はシリカ微粒子であることが好ましい。
より好ましくは、前記シリカ微粒子は、シリカゾルに含まれるシリカ微粒子であることが好ましい。シリカゾルは、水硝子やケイ酸液を縮重合させる方法や、アルコキシド法などにより製造することができる。
The inorganic oxide fine particles are preferably silica fine particles.
More preferably, the silica fine particles are preferably silica fine particles contained in a silica sol. Silica sol can be produced by a method of condensation polymerization of water glass or silicic acid solution or an alkoxide method.
前記シリカゾルにアルカリ金属が含まれる場合には、該アルカリ金属を必要に応じてイオン交換樹脂や限外ろ過膜などにより除去してもよい。
このとき、前記シリカゾルに含まれるアルカリ金属含有量がＭ2O換算基準（ただし、Ｍはアルカリ金属元素）の固形分濃度で０．４重量％未満となるようにすればよい。
前記シリカゾルのアルカリ金属含有量が０．４重量％を超える場合には、該ゾルを含む水分散液を凍結させ、解凍させたのちの再分散性が低下する場合がある。
また、前記無機酸化物微粒子としてシリカ微粒子を用いる場合には、該シリカ微粒子の平均粒子径が１００〜２００ｎｍの範囲にあるものが好ましい。
平均粒子径が前記範囲にあるシリカ微粒子は、凍結解凍後の再分散性が高いため好ましい。
When an alkali metal is contained in the silica sol, the alkali metal may be removed with an ion exchange resin or an ultrafiltration membrane as necessary.
At this time, the alkali metal content contained in the silica sol may be less than 0.4 wt% in terms of the solid content concentration of M 2 O conversion standard (where M is an alkali metal element).
When the alkali metal content of the silica sol exceeds 0.4% by weight, the redispersibility after the aqueous dispersion containing the sol is frozen and thawed may be lowered.
When silica fine particles are used as the inorganic oxide fine particles, those having an average particle diameter of 100 to 200 nm are preferable.
Silica fine particles having an average particle diameter in the above range are preferred because of their high redispersibility after freezing and thawing.
前記無機酸化物微粒子の水分散液は、さらに、界面活性剤、分散剤、アロマ成分、各種添加剤その他、本発明を損なわない範囲において、公知の添加成分を含んでいても良い。
このように本発明に係る無機酸化物微粒子の水分散液は、凍結解凍後も不可逆的な凝集が起こらず、分散性、透明性、安定性、均一性を長期間高い品質で維持する効果に優れ、寒冷地や低温条件下で輸送または保管もしくは使用しても、品質の低下を招くことがない。
The aqueous dispersion of inorganic oxide fine particles may further contain a surfactant, a dispersant, an aroma component, various additives, and other known additive components as long as the present invention is not impaired.
Thus, the aqueous dispersion of inorganic oxide fine particles according to the present invention does not cause irreversible aggregation even after freezing and thawing, and is effective in maintaining dispersibility, transparency, stability, and uniformity for a long period of time with high quality. Even if it is transported, stored, or used in cold or low-temperature conditions, it does not cause quality degradation.
また前記水分散液は、無機酸化物微粒子の固形分濃度にもよるが、アルコール含有量が必要最小限ですむため、生体への安全性が高く、取り扱いが容易で、安価であり、また加工や他成分との混合が容易であり、簡便かつ安価な方法で製造することができ、その使用用途について制限されたり、規制されることが少ない。
本発明に係る水分散液は、研磨剤、各種被膜形成用塗料、各種の樹脂組成物製品、化粧料、日用品、歯科材料、各種繊維製品、衣料、化学品、建設材料などをはじめとしたあらゆる用途に使用することができる。
Although the aqueous dispersion depends on the solid content concentration of the inorganic oxide fine particles, the alcohol content is minimal, so it is safe for the living body, easy to handle, inexpensive, and processed. It can be easily mixed with other components and can be produced by a simple and inexpensive method, and its usage is not limited or regulated.
The aqueous dispersion according to the present invention can be used for various kinds including abrasives, various coating-forming coatings, various resin composition products, cosmetics, daily necessities, dental materials, various textile products, clothing, chemicals, construction materials, etc. Can be used for applications.
無機酸化物微粒子の分散液の製造方法
本発明に係る無機酸化物微粒子の水分散液の製造方法の一例としては、無機酸化物微粒子を含み、アルコールを含まない水分散液に、該無機酸化物微粒子の単位表面積あたりに１．０×１０-8〜２０ｍｏｌ／ｍ2の範囲となるようにアルコールを添加する方法が挙げられる。
前記アルコールの添加量が１．０×１０-8ｍｏｌ／ｍ2未満の場合には、該水分散液の凍解凍後に再分散性がほとんど得られない、もしくは得られないため好ましくない。
前記アルコールの添加量が２０ｍｏｌ／ｍ2を超えると、それ以上アルコールを添加しても効果はほとんど向上しなくなり、また不要に多くのアルコールを含むと用途によっては使用規制を受けたり、取り扱いや加工上での問題が生じる場合があるので、好ましくない。
Method for Producing Dispersion of Inorganic Oxide Fine Particles As an example of a method for producing an aqueous dispersion of inorganic oxide fine particles according to the present invention, the inorganic oxide is added to an aqueous dispersion containing inorganic oxide fine particles and no alcohol. An example is a method in which alcohol is added so as to be in the range of 1.0 × 10 −8 to 20 mol / m 2 per unit surface area of the fine particles.
When the amount of the alcohol added is less than 1.0 × 10 −8 mol / m 2 , it is not preferable because redispersibility is hardly obtained or not obtained after freeze-thawing of the aqueous dispersion.
If the amount of the alcohol added exceeds 20 mol / m 2 , the effect will hardly improve even if more alcohol is added, and if it contains an excessive amount of alcohol, it may be subject to usage restrictions, handling or processing depending on the application. Since the above problem may occur, it is not preferable.
無機酸化物微粒子およびアルコールについては、上述した無機酸化物微粒子およびアルコールを用いることができる。
具体的な製造方法としては、無機酸化物微粒子の水分散液を公知の液相法により合成するか、粉末状の無機酸化物微粒子を水に分散させて分散液とするか、または市販の無機酸化物微粒子の水分散液を用意し、これを必要に応じて水で希釈するか、あるいは濃縮させて所望の濃度に調整したのち、上記範囲のアルコールを添加し、攪拌等により混合することにより、本発明に係る無機酸化物微粒子の水分散液を調製することができる。
As the inorganic oxide fine particles and alcohol, the above-described inorganic oxide fine particles and alcohol can be used.
As a specific production method, an aqueous dispersion of inorganic oxide fine particles is synthesized by a known liquid phase method, or powdered inorganic oxide fine particles are dispersed in water to form a dispersion, or a commercially available inorganic oxide Prepare an aqueous dispersion of oxide fine particles, dilute it with water as necessary, or concentrate it to the desired concentration, add alcohol in the above range, and mix by stirring, etc. An aqueous dispersion of inorganic oxide fine particles according to the present invention can be prepared.
このとき、前記水分散液に含まれる無機酸化物微粒子の固形分濃度は０．００１〜６０重量％の範囲となるようにすることが好ましい。
前記無機酸化物微粒子の固形分濃度が０．００１重量％未満の場合には、そもそも、無機酸化物微粒子の水分散液の特徴が発現しにくく、６０重量％を超えると、前記水分散液の安定性が低下し、凍結解凍後の再分散性が低下するので好ましくない。
さらにこのようにして得られた水分散液に所望の添加成分を混合してもよい。
At this time, the solid content concentration of the inorganic oxide fine particles contained in the aqueous dispersion is preferably in the range of 0.001 to 60% by weight.
When the solid content concentration of the inorganic oxide fine particles is less than 0.001% by weight, the characteristics of the aqueous dispersion of inorganic oxide fine particles are hardly expressed in the first place. It is not preferable because stability is lowered and redispersibility after freezing and thawing is lowered.
Furthermore, you may mix a desired additional component with the aqueous dispersion obtained in this way.
［測定方法および評価試験方法］
次に、本発明の実施例その他で使用された測定方法および評価試験方法を具体的に述べれば、以下の通りである。
（１）比表面積の測定方法
無機酸化物微粒子の比表面積は窒素吸着法（ＢＥＴ法）により下記の方法で求めた。
無機酸化物微粒子の水分散液を１１０℃で１時間乾燥させたのち、得られた無機酸化物微粒子の粉末に含まれる無機酸化物微粒子の比表面積をＢＥＴ比表面積測定装置（（株）マウンテック製、Macsorb HM model-1220）によりＢＥＴ１点法を用いて測定した。
[Measurement method and evaluation test method]
Next, the measurement methods and evaluation test methods used in the examples and others of the present invention will be specifically described as follows.
(1) Measuring method of specific surface area The specific surface area of the inorganic oxide fine particles was determined by the following method using a nitrogen adsorption method (BET method).
After drying the aqueous dispersion of inorganic oxide fine particles at 110 ° C. for 1 hour, the specific surface area of the inorganic oxide fine particles contained in the obtained powder of the inorganic oxide fine particles is determined by a BET specific surface area measuring device (manufactured by Mountec Co., Ltd.). , Macsorb HM model-1220) using the BET one-point method.
（２）平均粒子径の測定方法
無機酸化物微粒子の水分散液に含まれる無機酸化物微粒子の平均粒子径をマイクロトラック(日機装（株）製、NPA150-1-000-0-10N)を用いて測定した。
(2) Measuring method of average particle diameter The average particle diameter of the inorganic oxide fine particles contained in the aqueous dispersion of inorganic oxide fine particles was measured using a microtrack (Nikkiso Co., Ltd., NPA150-1-000-0-10N). Measured.
（３）金属元素含有量の測定方法
無機酸化物微粒子に含まれる金属元素の組成分析については、誘導結合プラズマ発光分光分析装置（島津製作所（株）製、ＩＣＰＳ−８１００）を用いて行った。
ただし、アルカリ金属含有量（本実施例においては、ナトリウム）については、原子吸光分光法により、原子吸光分光光度計（（株）日立製作所製、Ｚ−５３００、測定モード；原子吸光、測定波長範囲；１９０〜９００ｎｍ）を用いて測定した。
(3) Measuring method of metal element content The composition analysis of the metal element contained in the inorganic oxide fine particles was performed using an inductively coupled plasma emission spectroscopic analyzer (ICPS-8100, manufactured by Shimadzu Corporation).
However, for the alkali metal content (sodium in this example), atomic absorption spectrophotometer (manufactured by Hitachi, Ltd., Z-5300, measurement mode; atomic absorption, measurement wavelength range) ; 190 to 900 nm).
（４）分散性の評価
凍結解凍後の無機酸化物微粒子の分散性を下記の通り評価した。
「良好」・・・特に分散工程に処さずとも分散する。目視にて透明でゲル化が確認されず、凍結解凍前後で平均粒子径に殆ど変化が見られない。
「不可」・・・抗菌消臭性無機酸化物微粒子が凝集沈降しており、超音波照射などの分散処理に処しても再分散しない。目視にて不透明でゲル化している部分がある。
(4) Evaluation of dispersibility The dispersibility of the inorganic oxide fine particles after freezing and thawing was evaluated as follows.
“Good”: Dispersed without being subjected to a dispersion process. It is transparent and gelation is not confirmed visually, and almost no change is observed in the average particle size before and after freezing and thawing.
“No”: Antibacterial and deodorant inorganic oxide fine particles are agglomerated and settled and do not re-disperse even when subjected to a dispersion treatment such as ultrasonic irradiation. There is a part that is opaque and gelled by visual inspection.
以下、本発明を実施例に基づき具体的に説明する。しかし、本発明は、これらの実施例に記載された範囲に限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples. However, the present invention is not limited to the scope described in these examples.
[実施例１]
シリカ微粒子を含むシリカゾル（製品名：カタロイドSI-30、日揮触媒化成（株）、シリカ微粒子の平均粒子径：10.6nm、シリカ微粒子の比表面積：257m2/g、ＳｉＯ2濃度；30.3重量％、Na2O含有量；0.4重量％、分散媒；水）40ｇ にエチルアルコール(林純薬工業、99％以上)1.2ｇを添加して、エチルアルコールを3重量％含むシリカ微粒子の水分散液を得た。
この水分散液に含まれるシリカ微粒子の平均粒子径は10.6nmで比表面積は257m2/gであり、該水分散液に含まれるシリカ微粒子の固形分濃度は２９．８重量％であった。
また、この水分散液に含まれるエチルアルコールは、該水分散液に含まれるシリカ微粒子の単位表面積当りに対して8.49×10-6mol/m2であった。
この水分散液を−2℃で凍結させた後、常温で解凍させたところ、シリカ微粒子は容易に再分散した。
解凍させた水分散液に含まれるシリカ微粒子の平均粒子径は約10.8nmで該水分散液は透明であった。
[Example 1]
Silica sol containing silica fine particles (Product name: Cataloid SI-30, JGC Catalysts & Chemicals Co., Ltd., average particle size of silica fine particles: 10.6 nm, specific surface area of silica fine particles: 257 m 2 / g, SiO 2 concentration: 30.3% by weight, Add 1.2 g of ethyl alcohol (Hayashi Junyaku Kogyo Co., Ltd., 99% or more) 1.2 g to 40 g of Na 2 O content: 0.4 wt%, dispersion medium: water, and prepare an aqueous dispersion of silica fine particles containing 3 wt% of ethyl alcohol. Obtained.
The average particle size of the silica fine particles contained in the aqueous dispersion was 10.6 nm and the specific surface area was 257 m 2 / g. The solid content concentration of the silica fine particles contained in the aqueous dispersion was 29.8% by weight.
The ethyl alcohol contained in the aqueous dispersion was 8.49 × 10 −6 mol / m 2 per unit surface area of the silica fine particles contained in the aqueous dispersion.
When this aqueous dispersion was frozen at −2 ° C. and then thawed at room temperature, the silica fine particles were easily redispersed.
The average particle diameter of the silica fine particles contained in the thawed water dispersion was about 10.8 nm, and the water dispersion was transparent.
[実施例２]
シリカ微粒子を含むシリカゾル（製品名：カタロイドSI-40、日揮触媒化成（株）、シリカ微粒子の平均粒子径：18.1nm、シリカ微粒子の比表面積：151m2/g、ＳｉＯ2濃度：40.5重量％、Na2O含有量：0.42重量％、分散媒；水）40ｇ にエチルアルコール(林純薬工業、99％以上)1.2ｇを添加して、エチルアルコールを3重量％含むシリカ微粒子の水分散液を得た。
この水分散液に含まれるシリカ微粒子の平均粒子径は18.1nmで比表面積は約151m2/gであり、該水分散液に含まれるシリカ微粒子の固形分濃度は３９．７重量％であった。
また、この水分散液に含まれるエチルアルコールは、該水分散液に含まれるシリカ微粒子の単位表面積当りに対して1.08×10-5mol/m2であった。
この水分散ゾルを−2℃で凍結させた後、常温で解凍させたところ、容易に再分散した。
解凍させた水分散液に含まれるシリカ微粒子の平均粒子径は約18.5nmで該水分散液は透明であった。
[Example 2]
Silica sol containing silica fine particles (Product name: Cataloid SI-40, JGC Catalysts & Chemicals Co., Ltd., average particle size of silica fine particles: 18.1 nm, specific surface area of silica fine particles: 151 m 2 / g, SiO 2 concentration: 40.5% by weight, Na 2 O content: 0.42 wt%, dispersion medium; water) 1.2 g of ethyl alcohol (Hayashi Junyaku Kogyo, 99% or more) is added to 40 g, and an aqueous dispersion of silica fine particles containing 3 wt% of ethyl alcohol is added. Obtained.
The average particle size of the silica fine particles contained in this aqueous dispersion was 18.1 nm, the specific surface area was about 151 m 2 / g, and the solid content concentration of the silica fine particles contained in the aqueous dispersion was 39.7% by weight. .
The ethyl alcohol contained in the aqueous dispersion was 1.08 × 10 −5 mol / m 2 per unit surface area of the silica fine particles contained in the aqueous dispersion.
When this water-dispersed sol was frozen at −2 ° C. and then thawed at room temperature, it was easily redispersed.
The average particle size of the silica fine particles contained in the thawed water dispersion was about 18.5 nm, and the water dispersion was transparent.
[実施例３]
シリカ微粒子を含むシリカゾル（製品名：SS(スフェリカスラリー)-120、日揮触媒化成（株）、シリカ微粒子の平均粒子径：120nm、シリカ微粒子の比表面積：23m2/g、ＳｉＯ2濃度：18.6重量％、Na2O含有量：0.07重量％、分散媒；水）40ｇ にエチルアルコール(林純薬工業、99％以上)1.2ｇを添加して、エチルアルコールを3重量％含むシリカ微粒子の水分散液を得た。
この水分散液に含まれるシリカ微粒子の平均粒子径は120nm、比表面積は約23m2/gであり、該水分散液に含まれるシリカ微粒子の固形分濃度は１８．１重量％であった。
また、この水分散液に含まれるエチルアルコールは、該水分散液に含まれるシリカ微粒子の単位表面積当りに対して1.56×10-4mol/m2であった。
この水分散ゾルを−2℃で凍結させた後、常温で解凍させたところ、容易に再分散した。
解凍させた水分散液に含まれるシリカ微粒子の平均粒子径は約122nmで該水分散液は透明であった。
[Example 3]
Silica sol containing silica fine particles (Product name: SS (Spherica slurry) -120, JGC Catalysts & Chemicals Co., Ltd., average particle size of silica fine particles: 120 nm, specific surface area of silica fine particles: 23 m 2 / g, SiO 2 concentration: 18.6 Silica fine particle water containing 3% by weight of ethyl alcohol by adding 1.2g of ethyl alcohol (Hayashi Junyaku Kogyo, 99% or more) to 40g of 40% by weight, Na 2 O content: 0.07% by weight, dispersion medium; water) A dispersion was obtained.
The average particle size of the silica fine particles contained in the aqueous dispersion was 120 nm, the specific surface area was about 23 m 2 / g, and the solid content concentration of the silica fine particles contained in the aqueous dispersion was 18.1% by weight.
The ethyl alcohol contained in the aqueous dispersion was 1.56 × 10 −4 mol / m 2 per unit surface area of the silica fine particles contained in the aqueous dispersion.
When this water-dispersed sol was frozen at −2 ° C. and then thawed at room temperature, it was easily redispersed.
The average particle size of the silica fine particles contained in the thawed water dispersion was about 122 nm, and the water dispersion was transparent.
[実施例４]
特開昭６３−１２３８０７号公報に記載された方法、即ち、ケイ酸ソーダの水溶液を加熱しながらこれにケイ酸液とアルミン酸ナトリウム溶液とを添加したのちイオン交換する方法により、ケイ素とアルミニウムとを含む無機酸化物微粒子の水分散液を製造した。この無機酸化物微粒子の平均粒子径は7.2nm、比表面積は378m2/g、該水分散液のＳｉＯ2濃度は16.6重量％、Al2O3濃度:0.07重量％,Na2O含有量：0.07重量％であった。この水分散液40ｇ にエチルアルコール(林純薬工業、99％以上)1.2ｇを添加して、エチルアルコールを3重量％含む無機酸化物微粒子の水分散液を得た。
この水分散液に含まれる無機酸化物微粒子の平均粒子径は7.2nmで比表面積は約378m2/gであり、該水分散液に含まれる無機酸化物微粒子の固形分濃度は１５．８重量％であった。
また、この水分散液に含まれるエチルアルコールは、該水分散液に含まれる無機酸化物微粒子の単位表面積当りに対して1.09×10-5mol/m2であった。
この水分散液を−2℃で凍結させた後、常温で解凍させたところ、容易に再分散した。
解凍させた水分散液に含まれる無機酸化物微粒子の平均粒子径は約7.4nmで該水分散液は透明であった。
[Example 4]
According to the method described in JP-A-63-123807, that is, an aqueous solution of sodium silicate is heated and an ion exchange is performed after adding a silicate solution and a sodium aluminate solution thereto, and then silicon and aluminum are exchanged. An aqueous dispersion of inorganic oxide fine particles containing was produced. The average particle diameter of the inorganic oxide fine particles is 7.2 nm, the specific surface area is 378 m 2 / g, the SiO 2 concentration of the aqueous dispersion is 16.6% by weight, Al 2 O 3 concentration: 0.07% by weight, Na 2 O content: 0.07% by weight. To 40 g of this aqueous dispersion, 1.2 g of ethyl alcohol (Hayashi Junyaku Kogyo, 99% or more) was added to obtain an aqueous dispersion of fine inorganic oxide particles containing 3% by weight of ethyl alcohol.
The average particle diameter of the inorganic oxide fine particles contained in the aqueous dispersion is 7.2 nm and the specific surface area is about 378 m 2 / g. The solid content concentration of the inorganic oxide fine particles contained in the aqueous dispersion is 15.8 wt. %Met.
The ethyl alcohol contained in the aqueous dispersion was 1.09 × 10 −5 mol / m 2 per unit surface area of the inorganic oxide fine particles contained in the aqueous dispersion.
When this aqueous dispersion was frozen at −2 ° C. and then thawed at room temperature, it was easily redispersed.
The average particle diameter of the inorganic oxide fine particles contained in the thawed water dispersion was about 7.4 nm, and the water dispersion was transparent.
[実施例５]
ケイ素とアルミニウムと銀を含む無機酸化物微粒子の水分散液（製品名：ATOMY BALL-(UA)、日揮触媒化成（株）、無機酸化物微粒子の平均粒子径：15nm、比表面積：143m2/g、ＳｉＯ2濃度：1.03重量％、Al2O3濃度:0.37重量％,Na2O含有量:0.01重量％,Ag2O濃度:0.07重量％）40ｇにエチルアルコール(林純薬工業、99％以上)1.2ｇを添加して、エチルアルコールを3重量％含む無機酸化物微粒子の水分散液を得た。
この水分散液に含まれる無機酸化物微粒子の平均粒子径は15nmで表面積は約143m2/gであり、該水分散液に含まれる無機酸化物微粒子の固形分濃度は、１．４４重量％であった。
また、この水分散液に含まれるエチルアルコールは、該水分散液に含まれる無機酸化物微粒子の単位表面積当りに対して3.16×10-4mol/m2であった。
この水分散液を−2℃で凍結させた後、常温で解凍させたところ、容易に再分散した。
解凍させた水分散液に含まれる無機酸化物微粒子の平均粒子径は約15nmで該水分散液は透明であった。
[Example 5]
Water dispersion of inorganic oxide fine particles containing silicon, aluminum and silver (Product name: ATOMY BALL- (UA), JGC Catalysts & Chemicals Co., Ltd., average particle size of inorganic oxide fine particles: 15 nm, specific surface area: 143 m 2 / g, SiO 2 concentration: 1.03% by weight, Al 2 O 3 concentration: 0.37% by weight, Na 2 O content: 0.01% by weight, Ag 2 O concentration: 0.07% by weight) to 40 g of ethyl alcohol (Hayashi Junyaku Kogyo, 99 1.2 g or more) was added to obtain an aqueous dispersion of inorganic oxide fine particles containing 3% by weight of ethyl alcohol.
The average particle diameter of the inorganic oxide fine particles contained in the aqueous dispersion is 15 nm and the surface area is about 143 m 2 / g. The solid content concentration of the inorganic oxide fine particles contained in the aqueous dispersion is 1.44% by weight. Met.
The ethyl alcohol contained in this aqueous dispersion was 3.16 × 10 −4 mol / m 2 per unit surface area of the inorganic oxide fine particles contained in the aqueous dispersion.
When this aqueous dispersion was frozen at −2 ° C. and then thawed at room temperature, it was easily redispersed.
The average particle diameter of the inorganic oxide fine particles contained in the thawed water dispersion was about 15 nm, and the water dispersion was transparent.
[実施例６]
チタニウムとケイ素と亜鉛を含む無機酸化物微粒子が分散した水分散液（製品名：ATOMY BALL-(20NTZ)20、日揮触媒化成（株）、平均粒子径：20nm、比表面積：100m2/g、ＴｉＯ2濃度：18.0重量％、ＳｉＯ2濃度：1.6重量％、ＺｎＯ濃度；０．４重量％、Ｎａ2Ｏ濃度０．０４重量％）40ｇ にエチルアルコール(林純薬工業、99％以上)1.2ｇを添加して、エチルアルコールを3重量％含む無機酸化物微粒子の水分散液を得た。
この水分散液に含まれる無機酸化物微粒子の平均粒子径は約20nmで比表面積は約100m2/gであり、該水分散液に含まれる無機酸化物微粒子の固形分濃度は１９．４重量％であった。
また、この水分散液に含まれるエチルアルコールは、該水分散液に含まれる無機酸化物微粒子の単位表面積当りに対して3.35×10-5mol/m2であった。
この水分散ゾルを−2℃で凍結させた後、常温で解凍させたところ、容易に再分散した。
解凍させた水分散液に含まれる無機酸化物微粒子の平均粒子径は約20nmで該水分散液は透明であった。
[Example 6]
An aqueous dispersion in which inorganic oxide fine particles containing titanium, silicon and zinc are dispersed (Product name: ATOMY BALL- (20NTZ) 20, JGC Catalysts & Chemicals Co., Ltd., average particle size: 20 nm, specific surface area: 100 m 2 / g, TiO 2 concentration: 18.0 wt%, SiO 2 concentration: 1.6 wt%, ZnO concentration: 0.4 wt%, Na 2 O concentration 0.04 wt%) 40 g and ethyl alcohol (Hayashi Junyaku Kogyo, 99% or more) 1.2 Then, an aqueous dispersion of inorganic oxide fine particles containing 3% by weight of ethyl alcohol was obtained.
The average particle diameter of the inorganic oxide fine particles contained in the aqueous dispersion is about 20 nm and the specific surface area is about 100 m 2 / g. The solid content concentration of the inorganic oxide fine particles contained in the aqueous dispersion is 19.4 wt. %Met.
The ethyl alcohol contained in this aqueous dispersion was 3.35 × 10 −5 mol / m 2 per unit surface area of the inorganic oxide fine particles contained in the aqueous dispersion.
When this water-dispersed sol was frozen at −2 ° C. and then thawed at room temperature, it was easily redispersed.
The average particle diameter of the inorganic oxide fine particles contained in the thawed water dispersion was about 20 nm, and the water dispersion was transparent.
[実施例７]
チタニウムとケイ素と亜鉛を含む無機酸化物微粒子が分散した水分散液（製品名：ATOMY BALL-(20NTZ)20、日揮触媒化成（株）、平均粒子径：20nm、比表面積：100m2/g、ＴｉＯ2濃度：18.0重量％、ＳｉＯ2濃度：1.6重量％、ＺｎＯ濃度；０．４重量％、Ｎａ2Ｏ濃度０．０４重量％）40ｇ にエチルアルコール(林純薬工業、99％以上)2.8ｇを添加して、エチルアルコールを7重量％含む無機酸化物微粒子の水分散液を得た。
この水分散液に含まれる無機酸化物微粒子の平均粒子径は約20nmで比表面積は約100m2/gであり、該水分散液に含まれる無機酸化物微粒子の固形分濃度は１８．７重量％であった。
また、この水分散液に含まれるエチルアルコールは、該水分散液に含まれる無機酸化物微粒子の単位表面積当りに対して７．８６×10-5mol/m2であった。
この水分散液を−2℃で凍結させた後、常温で解凍させたところ、容易に再分散した。
解凍させた水分散液に含まれる無機酸化物微粒子の平均粒子径は約20nmで該水分散液は透明であった。
[Example 7]
An aqueous dispersion in which inorganic oxide fine particles containing titanium, silicon and zinc are dispersed (Product name: ATOMY BALL- (20NTZ) 20, JGC Catalysts & Chemicals Co., Ltd., average particle size: 20 nm, specific surface area: 100 m 2 / g, TiO 2 concentration: 18.0 wt%, SiO 2 concentration: 1.6 wt%, ZnO concentration: 0.4 wt%, Na 2 O concentration 0.04 wt%) 40 g and ethyl alcohol (Hayashi Junyaku Kogyo, 99% or more) 2.8 g was added to obtain an aqueous dispersion of inorganic oxide fine particles containing 7% by weight of ethyl alcohol.
The average particle diameter of the inorganic oxide fine particles contained in the aqueous dispersion is about 20 nm and the specific surface area is about 100 m 2 / g. The solid content concentration of the inorganic oxide fine particles contained in the aqueous dispersion is 18.7 wt. %Met.
The ethyl alcohol contained in the aqueous dispersion was 7.86 × 10 −5 mol / m 2 with respect to the unit surface area of the inorganic oxide fine particles contained in the aqueous dispersion.
When this aqueous dispersion was frozen at −2 ° C. and then thawed at room temperature, it was easily redispersed.
The average particle diameter of the inorganic oxide fine particles contained in the thawed water dispersion was about 20 nm, and the water dispersion was transparent.
[実施例８]
シリカ微粒子を含むシリカゾル（製品名：カタロイドSI-50、日揮触媒化成（株）、シリカ微粒子の平均粒子径：27.3nm、シリカ微粒子の比表面積：100m2/g、ＳｉＯ2濃度：48.3重量％、Na2O含有量：0.49重量％、分散媒；水）を純水で希釈し、（ＳｉＯ2濃度：9.7重量％、Na2O含有量：0.1重量％）としたもの40ｇにエチルアルコール(林純薬工業、99％以上)1.2ｇを添加して、エチルアルコールを3重量％含むシリカ微粒子の水分散液を得た。
この水分散液に含まれるシリカ微粒子の平均粒子径は27.3nmで比表面積は約100m2/gであり、固形分濃度は９．５１重量％であった。
また、この水分散液に含まれるエチルアルコールは、該水分散液に含まれるシリカ微粒子の単位表面積当りに対して6.83×10-5mol/m2であった。
この水分散ゾルを−2℃で凍結させた後、常温で解凍させたところ容易に再分散した。
解凍させた水分散液に含まれるシリカ微粒子の平均粒子径は約27.2nmで該水分散液は透明であった。
[Example 8]
Silica sol containing silica fine particles (Product name: Cataloid SI-50, JGC Catalysts & Chemicals Co., Ltd., average particle size of silica fine particles: 27.3 nm, specific surface area of silica fine particles: 100 m 2 / g, SiO 2 concentration: 48.3 wt%, Na 2 O content: 0.49% by weight, dispersion medium; water) diluted with pure water (SiO 2 concentration: 9.7% by weight, Na 2 O content: 0.1% by weight) (Pure drug industry, 99% or more) 1.2 g was added to obtain an aqueous dispersion of silica fine particles containing 3% by weight of ethyl alcohol.
The average particle diameter of the silica fine particles contained in this aqueous dispersion was 27.3 nm, the specific surface area was about 100 m 2 / g, and the solid content concentration was 9.51% by weight.
The ethyl alcohol contained in the aqueous dispersion was 6.83 × 10 −5 mol / m 2 per unit surface area of the silica fine particles contained in the aqueous dispersion.
This water-dispersed sol was frozen at −2 ° C. and then thawed at room temperature, so that it was easily redispersed.
The average particle diameter of the silica fine particles contained in the thawed water dispersion was about 27.2 nm, and the water dispersion was transparent.
[実施例９]
シリカ微粒子を含むシリカゾル（製品名：カタロイドSI-50、日揮触媒化成（株）、シリカ微粒子の平均粒子径：27.3nm、比表面積：100m2/g、ＳｉＯ2濃度：48.3重量％、Na2O含有量：0.49重量％、分散媒；水）にイオン交換樹脂を添加して、Na2O含有量が0.39重量％となるまでナトリウムイオンを除去したのち、イオン交換樹脂を分離して、得られたシリカゾル40ｇにエチルアルコール(林純薬工業、99％以上)1.2ｇを添加して、エチルアルコールを3重量％含むシリカ微粒子の水分散液を得た。
また、この水分散液に含まれるエチルアルコールは、該水分散液に含まれるシリカ微粒子の単位表面積当りに対して1.38×10-5mol/m2であった。
この水分散液に含まれるシリカ微粒子の平均粒子径は27.3nmで比表面積は約100m2/gであり、固形分濃度は４７．４重量％であった。
この水分散ゾルを−2℃で凍結させた後、常温で解凍させたところ、容易に再分散した。
解凍させた水分散液に含まれるシリカ微粒子の平均粒子径は約27.4nmで該水分散液は透明であった。
[Example 9]
Silica sol containing silica fine particles (Product name: Cataloid SI-50, JGC Catalysts & Chemicals Co., Ltd., average particle size of silica fine particles: 27.3 nm, specific surface area: 100 m 2 / g, SiO 2 concentration: 48.3 wt%, Na 2 O Content: 0.49% by weight, dispersion medium; water) is obtained by adding the ion exchange resin, removing sodium ions until the Na 2 O content is 0.39% by weight, and then separating the ion exchange resin. 1.2 g of ethyl alcohol (Hayashi Junyaku Kogyo, 99% or more) was added to 40 g of silica sol to obtain an aqueous dispersion of silica fine particles containing 3% by weight of ethyl alcohol.
The ethyl alcohol contained in this aqueous dispersion was 1.38 × 10 −5 mol / m 2 per unit surface area of the silica fine particles contained in the aqueous dispersion.
The average particle size of the silica fine particles contained in this aqueous dispersion was 27.3 nm, the specific surface area was about 100 m 2 / g, and the solid content concentration was 47.4% by weight.
When this water-dispersed sol was frozen at −2 ° C. and then thawed at room temperature, it was easily redispersed.
The average particle diameter of the silica fine particles contained in the thawed water dispersion was about 27.4 nm, and the water dispersion was transparent.
[比較例１]
シリカ微粒子を含むシリカゾル（製品名：カタロイドSI-30、日揮触媒化成（株）、平均粒子径：10.6nm、比表面積：257m2/g、SiO2濃度：30.3重量％、Na2O含有量：0.4重量％、分散媒；水）40ｇを−2℃で凍結させた後、常温で解凍させたところ、解凍後のシリカゾルは、シリカ微粒子が凝集体を形成し、沈殿した。
[Comparative Example 1]
Silica sol containing silica fine particles (Product name: Cataloid SI-30, JGC Catalysts & Chemicals Co., Ltd., average particle size: 10.6 nm, specific surface area: 257 m 2 / g, SiO 2 concentration: 30.3 wt%, Na 2 O content: When 40 g of 0.4 wt%, dispersion medium (water) was frozen at −2 ° C. and then thawed at room temperature, silica fine particles formed aggregates and precipitated in the thawed silica sol.
[比較例２]
シリカ微粒子を含むシリカゾル（製品名：SS-120、日揮触媒化成（株）、平均粒子径：120nm、比表面積：23m2/g、ＳｉＯ2濃度：18.6重量％、Na2O含有量：0.07重量％、分散媒；水）40ｇを−2℃で凍結させた後、常温で解凍させたところ、解凍後の水分散液は、シリカ微粒子が凝集体を形成し、沈殿した。
[Comparative Example 2]
Silica sol containing silica fine particles (Product name: SS-120, JGC Catalysts & Chemicals Co., Ltd., average particle size: 120 nm, specific surface area: 23 m 2 / g, SiO 2 concentration: 18.6 wt%, Na 2 O content: 0.07 wt. %, Dispersion medium; water) was frozen at −2 ° C. and then thawed at room temperature. In the thawed water dispersion, silica fine particles formed aggregates and precipitated.
[比較例３]
ケイ素とアルミニウムと銀を含む無機酸化物微粒子の水分散液（製品名：ATOMY BALL-(UA)、日揮触媒化成（株）、平均粒子径：15nm、比表面積：143m2/g、ＳｉＯ2濃度：1.03重量％、Al2O3濃度:0.37重量％,Na2O含有量:0.01重量％,Ag2O濃度:0.07重量％）40ｇを−2℃で凍結させた後、常温で解凍させたところ、解凍後の水分散液は、無機酸化物微粒子が凝集体を形成し、沈殿した。
[Comparative Example 3]
Aqueous dispersion of inorganic oxide fine particles containing silicon, aluminum and silver (Product name: ATOMY BALL- (UA), JGC Catalysts & Chemicals Co., Ltd., average particle size: 15 nm, specific surface area: 143 m 2 / g, SiO 2 concentration : 1.03% by weight, Al 2 O 3 concentration: 0.37% by weight, Na 2 O content: 0.01% by weight, Ag 2 O concentration: 0.07% by weight) 40 g was frozen at −2 ° C. and then thawed at room temperature. However, in the aqueous dispersion after thawing, the inorganic oxide fine particles formed aggregates and precipitated.
[比較例４]
チタニウムとケイ素と亜鉛を含む無機酸化物微粒子の水分散液（製品名：ATOMY BALL-(20NTZ)20、日揮触媒化成（株）、平均粒子径：20nm、比表面積：100m2/g、ＴｉＯ2濃度：18.0重量％、ＳｉＯ2濃度：1.6重量％、ZnO濃度：0.4重量％、Ｎａ2Ｏ濃度；０．０４重量％）40ｇを−2℃で凍結させた後、常温で解凍させたところ、解凍後の水分散液は、無機酸化物微粒子が凝集体を形成し、沈殿した。
[Comparative Example 4]
Aqueous dispersion of inorganic oxide fine particles containing titanium, silicon and zinc (Product name: ATOMY BALL- (20NTZ) 20, JGC Catalysts & Chemicals Co., Ltd., average particle size: 20 nm, specific surface area: 100 m 2 / g, TiO 2 (Concentration: 18.0 wt%, SiO 2 concentration: 1.6 wt%, ZnO concentration: 0.4 wt%, Na 2 O concentration; 0.04 wt%) After freezing 40 g at −2 ° C., it was thawed at room temperature. In the aqueous dispersion after thawing, the inorganic oxide fine particles formed aggregates and precipitated.
[比較例５]
シリカ微粒子を含むシリカゾル（製品名：カタロイドSI-50、日揮触媒化成（株）、平均粒子径：27.3nm、比表面積：100m2/g、ＳｉＯ2濃度：48.3重量％、Na2O含有量：0.49重量％、分散媒；水）40ｇを−2℃で凍結させた後、常温で解凍させたところ、解凍後の水分散液は、シリカ微粒子が凝集体を形成し、沈殿した。
[Comparative Example 5]
Silica sol containing silica fine particles (Product name: Cataloid SI-50, JGC Catalysts & Chemicals Co., Ltd., average particle size: 27.3 nm, specific surface area: 100 m 2 / g, SiO 2 concentration: 48.3 wt%, Na 2 O content: After freezing 40 g of 0.49 wt%, dispersion medium; water) at −2 ° C. and then thawing at room temperature, silica fine particles formed aggregates and precipitated in the aqueous dispersion after thawing.
実施例および比較例で調製した無機酸化物微粒子の水分散液の性状、および該水分散液の凍結、解凍後の性状を表１に示す。
表１より、無機酸化物微粒子の単位表面積当りのアルコール含有量が所定量範囲内にある水分散液、すなわち、実施例で調製した水分散液は、凍結および解凍を経た後でも透明で、無機酸化物微粒子の平均粒子径は凍結前と同じか、ほとんど変わらず、高い再分散性を発現することが示された。
Table 1 shows the properties of the aqueous dispersion of inorganic oxide fine particles prepared in Examples and Comparative Examples, and the properties of the aqueous dispersion after freezing and thawing.
From Table 1, the aqueous dispersion in which the alcohol content per unit surface area of the inorganic oxide fine particles is within a predetermined amount range, that is, the aqueous dispersion prepared in the examples is transparent and inorganic even after freezing and thawing. The average particle diameter of the oxide fine particles was the same as that before freezing, or almost the same, indicating that high redispersibility was exhibited.
Claims (8)
The aqueous dispersion of silica-based inorganic oxide fine particles according to claim 1 or 2 , wherein the silica-based inorganic oxide fine particles are silica fine particles.
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