JPS62283817A - Titania sol and its production - Google Patents
Titania sol and its productionInfo
- Publication number
- JPS62283817A JPS62283817A JP12536786A JP12536786A JPS62283817A JP S62283817 A JPS62283817 A JP S62283817A JP 12536786 A JP12536786 A JP 12536786A JP 12536786 A JP12536786 A JP 12536786A JP S62283817 A JPS62283817 A JP S62283817A
- Authority
- JP
- Japan
- Prior art keywords
- titania
- sol
- particles
- present
- gel
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 327
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000002245 particle Substances 0.000 claims abstract description 71
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002612 dispersion medium Substances 0.000 claims abstract description 12
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910001853 inorganic hydroxide Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 abstract description 7
- 238000004090 dissolution Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 20
- 239000000499 gel Substances 0.000 description 16
- 239000011248 coating agent Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000002244 precipitate Substances 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000003608 titanium Chemical class 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 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 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000001935 peptisation Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- -1 chlorine ions Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
発明の技術分野
本発明は、チタニアゾルおよびその製造方法に関し、ざ
らに詳しくは、特定の形状粒子が分散されてなるチタニ
アゾルおよびそのようなチタニアゾルの製造方法に関す
る。Detailed Description of the Invention 3. Detailed Description of the Invention Technical Field of the Invention The present invention relates to a titania sol and a method for producing the same. Regarding the manufacturing method.
発明の技術的背景ならびにその問題点
近年、酸化チタン粒子は、その化学的特性を利用した用
途が広がりつつある。たとえば酸化チタンは、酸素と適
当な結合力を有するとともに耐酸性をも有するため、酸
化還元触媒として用いられたり、あるいは紫外線の遮断
力を利用して化粧材またはプラスチックの表面コート材
として用いられたり、また高屈折率を利用して反射防止
コート材として用いられたり、ざらにはこれらの効果を
組み合せて機能性ハードコート材などとして用いられて
いる。Technical background of the invention and its problems In recent years, titanium oxide particles have been increasingly used in applications that take advantage of their chemical properties. For example, titanium oxide has an appropriate bonding strength with oxygen and is also acid resistant, so it is used as a redox catalyst, or it is used as a surface coating material for decorative materials or plastics due to its ability to block ultraviolet rays. It is also used as an anti-reflection coating material by taking advantage of its high refractive index, and it is also used as a functional hard coating material by combining these effects.
上記のように酸化チタンは多くの用途に用いられている
が、いずれの場合であっても酸化チタンには多くの機能
が要求される。たとえば、触媒として酸化チタンを用い
る場合には、主反応に対する活性だけでなく、選択性、
機械的強度、耐熱性、耐酸性あるいは耐久性が求められ
、また化粧材として酸化チタンを用いる場合には、紫外
線の遮蔽効果だけではなく、円滑性、肌ざわり、透明性
などが求められている。ざらにコート材として酸化チタ
ンを用いる場合には、透明性、高屈折率に加えて、ざら
に優れた被膜形成性、密着性、被膜硬度、機械的強度、
耐摩耗性などが求められている。As mentioned above, titanium oxide is used for many purposes, but in each case, titanium oxide is required to have many functions. For example, when using titanium oxide as a catalyst, not only the activity for the main reaction but also the selectivity and
Mechanical strength, heat resistance, acid resistance, and durability are required, and when titanium oxide is used as a cosmetic material, it is required not only to have a UV shielding effect but also to have smoothness, texture, and transparency. . When using titanium oxide as a coating material, in addition to transparency and high refractive index, it has excellent film formation properties, adhesion, film hardness, mechanical strength,
Abrasion resistance is required.
このように酸化チタン粒子を種々の用途に用いるには、
酸化チタン粒子は、それぞれの用途に応じて種々の特性
を有することが求められるが、どのような用途に用いる
にしても、高い比表面積を有する超微粒子であることが
好ましい。しかも酸化チタン粒子に透明性が要求される
場合には、この粒子は粒子形状および大きざが揃ってい
るばかりでなく、配合時に媒体中に高分散することが求
められる。これらの特性を満たすような酸化チタン粒子
を製造するには、高分散したコロイド状チタニア（チタ
ニアゾル）を用いることが特に好ましい。In order to use titanium oxide particles for various purposes,
Titanium oxide particles are required to have various properties depending on the application, but no matter what application they are used for, it is preferable that they be ultrafine particles with a high specific surface area. Furthermore, when titanium oxide particles are required to have transparency, the particles are required not only to have a uniform particle shape and size, but also to be highly dispersed in a medium during blending. In order to produce titanium oxide particles that satisfy these characteristics, it is particularly preferable to use highly dispersed colloidal titania (titania sol).
チタニアゾルの製造方法としては、従来チタン塩水溶液
を加水分解してｊｑられるメタチタン酸を中和した後洗
浄して得られるゲル、あるいはチタン塩水溶液をイオン
交換樹脂などで脱イオンして得られるゲルなどを、酸で
解膠することによって得る方法が知られている。Conventional methods for producing titania sol include gels obtained by hydrolyzing an aqueous titanium salt solution and neutralizing the metatitanic acid produced by jq, and then washing, or gels obtained by deionizing an aqueous titanium salt solution with an ion exchange resin, etc. is obtained by peptizing it with acid.
しかしながら、上記のようなチタニアゾルの製造方法に
は、以下のような問題点がおる。However, the method for producing titania sol as described above has the following problems.
■ゾルの分散粒子は、球状あるいは擬球状をした凝集体
であり、粒径も不均一でおるため、白濁し透明性に劣る
。(2) The dispersed particles of the sol are spherical or pseudo-spherical aggregates and have non-uniform particle sizes, resulting in cloudiness and poor transparency.
■ゾルの生成条件によっては粒径の小さい透明性に優れ
たゾルを得ることは可能でおるが、この場合には安定剤
として多量の酸を必要とする。(2) Depending on the sol production conditions, it is possible to obtain a sol with small particle size and excellent transparency; however, in this case, a large amount of acid is required as a stabilizer.
■ゾルは酸性領［（ｐＨ３以下〉でしか安定でなく、中
性やアルカリ性では沈殿が生じたりおるいはゲル化を起
こすため、使用範囲が限定される。。(2) Sols are stable only in acidic conditions (pH 3 or less), and in neutral or alkaline conditions, precipitation or gelation occurs, so the range of use is limited.
■ゾルをアルコールなどの有機溶媒と混合したり、有機
溶媒で溶媒置換を行なうとしても、不安定となって沈殿
が生成するため、プラスチックなどの表面へのハードコ
ート剤などとして用いにくい。■Even if the sol is mixed with an organic solvent such as alcohol, or if the solvent is replaced with an organic solvent, it becomes unstable and a precipitate forms, making it difficult to use as a hard coating agent on the surfaces of plastics, etc.
■ゾルの粒子は球状あるいは擬球状であるため、たとえ
ばベース樹脂に混合して塗膜として用いた場合、塗膜中
のチタニア粒子は密には存在ぜずチタニア粒子間に空隙
が残存して、密度を高めることはできず、塗膜としての
特性あるいは塗膜強度に劣る。■Since the particles of the sol are spherical or pseudo-spherical, for example, when mixed with a base resin and used as a coating film, the titania particles in the coating film are not densely packed and voids remain between the titania particles. It is not possible to increase the density, and the properties and strength of the coating film are poor.
本発明者らは、上記のような問題点を解決すべく鋭意研
究したところ、特定の方法によってチタニアゾルを製造
すれば、従来のチタニアゾルの製造方法では得られなか
ったような特定形状のチタニア粒子が分散媒中に分散さ
れてなるチタニアゾルが得られ、このチタニアゾルから
１ｑられるチタニア粒子は種々の優れた特性を有してい
ることを見出して、本発明を完成するに至った。The present inventors conducted intensive research to solve the above problems and found that if titania sol is produced by a specific method, titania particles with a specific shape that cannot be obtained by conventional titania sol production methods can be obtained. The present invention was completed based on the discovery that a titania sol dispersed in a dispersion medium was obtained, and that 1q of titania particles produced from this titania sol had various excellent properties.
発明の目的
本発明は、上記のような従来技術に伴なう問題点を解決
しようとするものであっそ、分散性に優れるとともに広
いｐＨ領域で安定であって凝集することがなく、しかも
有機溶媒と混合しても沈澱が生ずることなく塗布性に優
れているような、特定形状のチタニア粒子が分散媒中に
高分散してなるチタニアゾルおよびその製造方法を提供
することを目的としている。Purpose of the Invention The present invention aims to solve the above-mentioned problems associated with the prior art. It is an object of the present invention to provide a titania sol in which titania particles of a specific shape are highly dispersed in a dispersion medium, which does not cause precipitation even when mixed with a solvent and has excellent coating properties, and a method for producing the titania sol.
発明の概要
本発明に係るチタニアゾルは、分散媒中に分散されてい
るチタニア粒子の長軸の長さをＬとし短軸の長さをＤと
したとき、Ｌ／Ｄ≧２でおるようなチタニア粒子が６０
％以上の量で存在していることを特徴としている。Summary of the Invention The titania sol according to the present invention is a titania sol in which L/D≧2, where L is the length of the major axis and D is the length of the minor axis of titania particles dispersed in a dispersion medium. 60 particles
% or more.
また本発明に係るチタニアゾルの製造方法は、チタニア
ゾルまたはチタニアゲルに、過酸化水素を加えてチタニ
アゾルまたはチタニアゲルを溶解し、次いで得られた溶
液に無機酸化物ゾルまたは無微水酸化物ゾルを混合した
後加熱することを特徴としている。Further, the method for producing titania sol according to the present invention includes adding hydrogen peroxide to titania sol or titania gel to dissolve the titania sol or titania gel, and then mixing the obtained solution with an inorganic oxide sol or a fine hydroxide sol. It is characterized by heating.
本発明に係るチタニアゾルは、特定の形状を有するチタ
ニア超微粒子が分散媒に分散されているため、分散性に
少れるとともに広いｐＨ領域で安定であって凝集するこ
とかなく、しかも有機溶媒と混合しても沈澱が生ずるこ
とがない。したがって本発明に係るチタニアゲルを用い
て、たとえば表面コート材を製造すると、基材との密着
性に優れ、しかも耐久性にも優れた紫外線遮断効果およ
び高屈折率を有する塗膜が得られる。The titania sol according to the present invention has ultrafine titania particles having a specific shape dispersed in a dispersion medium, so that it has low dispersibility, is stable in a wide pH range, does not aggregate, and can be mixed with an organic solvent. No precipitate will form. Therefore, when the titania gel according to the present invention is used to produce, for example, a surface coating material, a coating film having excellent adhesion to a substrate, excellent durability, ultraviolet blocking effect, and high refractive index can be obtained.
また本発明に係るチタニアゾルの製造方法によれば、特
定の形状を有するチタニア超微粒子が分散媒に分散され
てなる上記のような優れた特性を有するチタニアゾルを
製造することができる。Further, according to the method for producing a titania sol according to the present invention, it is possible to produce a titania sol having the above-mentioned excellent properties in which ultrafine titania particles having a specific shape are dispersed in a dispersion medium.
発明の詳細な説明
以下本発明に係るチタニアゾルについてより具体的に説
明する。DETAILED DESCRIPTION OF THE INVENTION The titania sol according to the present invention will be described in more detail below.
本発明に係るチタニアゾル中のチタニア粒子は、その長
軸の長さをＬとし、短軸の長さをＤとすると、一般に長
軸の長さＬは約３０〜５００ｍμであり、短軸の長ざＤ
は約１０〜３０ｙｒｔμであり、個々のチタニア粒子は
、凝集体ではなく６０〜３００人の大きざのアナターゼ
結晶粒子が細長く成長した形状となっている。チタニア
粒子の具体的形状としては、電子顕微鏡で観察すると、
円柱状、角柱状、繊維状、針状、紡錘状、楕円状、偏平
板状などの種々の形状をなしている。The titania particles in the titania sol according to the present invention generally have a length L of about 30 to 500 mμ, where the length of the long axis is L and the length of the short axis is D. ZaD
is about 10 to 30 yrtμ, and the individual titania particles are not aggregates but have the shape of elongated anatase crystal particles of 60 to 300 particles grown. When observed with an electron microscope, the specific shape of titania particles is as follows.
It has various shapes such as cylindrical, prismatic, fibrous, needle, spindle, elliptical, and flat plate.
チタニア粒子の長軸の長さしおよび短軸の長ざＤは、以
下のようにして決定される。すなわちチタニアゾル中の
チタニア粒子を電子顕微鏡で観察して、その最も長い長
手方向の艮ざをＬとする。The length of the major axis and the length of the minor axis D of the titania particles are determined as follows. That is, the titania particles in the titania sol are observed with an electron microscope, and the longest length of the particles is defined as L.
また長手方向の長さのＬ／２の個所での長手方向と直交
する方向の長さを短軸の長ざＤとする。Further, the length in the direction perpendicular to the longitudinal direction at a point corresponding to L/2 of the length in the longitudinal direction is defined as the length D of the short axis.
本発明に係るチタニアゾルにおいて、水などの分散媒中
に分散されているチタニア粒子の長手方向の長軸の長さ
しと短軸の長さＤとの比Ｌ／Ｄは、後述するようにチタ
ニアゾルの製造条件に応じて変化するが、本発明で規定
する製造条件に従えば、いずれの条件を採用しても、得
られるチタニアゾル中のチタニア粒子はＬ／Ｄの値が２
以上である粒子が６０％以上好ましくは７０％以上の量
で存在する。In the titania sol according to the present invention, the ratio L/D of the length of the long axis in the longitudinal direction of the titania particles dispersed in a dispersion medium such as water to the length D of the short axis is determined as described below. However, if the manufacturing conditions specified in the present invention are followed, the titania particles in the obtained titania sol will have an L/D value of 2, regardless of which conditions are adopted.
Particles that are
ざらに詳しく述べると、後述する本発明に係るチタニア
ゾルの製造方法によれば、得られるチタニアゾル中のチ
タニア粒子のＬ／Ｄ値の平均値を（Ｌ／Ｄ）Ａとすると
、［１±０．３］（Ｌ／Ｄ）ＡＴｒＬμの値を有するよ
うなチタニア粒子は、全体の粒子の６０％以上好ましく
は６５％以上ざらに好ましくは７０％以上の量で存在す
る。To explain in more detail, according to the titania sol manufacturing method according to the present invention, which will be described later, when the average L/D value of titania particles in the obtained titania sol is (L/D)A, [1±0. 3] The titania particles having the value of (L/D)ATrLμ are present in an amount of 60% or more, preferably 65% or more, and preferably 70% or more of the total particles.
なおチタニア粒子の（Ｌ／Ｄ）Ａは、後述するように製
造条件に応じて変化する。このように本発明に係るチタ
ニアゾルは極めて粒径の揃ったチタニア粒子を含んで構
成されている。Note that (L/D)A of the titania particles changes depending on manufacturing conditions as described later. As described above, the titania sol according to the present invention includes titania particles having extremely uniform particle sizes.
上記のように本発明に係るチタニアゾルは、その長軸の
長さをＬそして短軸の長さをＤとすると、Ｌ／Ｄ≧２と
なる粒子が全体粒子の６０％以上好ましくは７０％以上
の開で存在し、細長い特有の形状を有している。このた
め本発明に係るチタニアゾルを下記のような各分野に用
いれば、以下のような効果が得られる。As mentioned above, in the titania sol according to the present invention, where the length of the major axis is L and the length of the minor axis is D, the particles with L/D≧2 account for 60% or more of the total particles, preferably 70% or more. It exists in the open and has a unique elongated shape. Therefore, if the titania sol according to the present invention is used in the following fields, the following effects can be obtained.
たとえば、触媒担体などの成型体に用いる場合には、成
型時に加えられる力により粒子は規則正しく配列し非常
に成型性が向上するとともに、１ｑられる成型体は乾燥
あるいは焼成時にクラックが発生することがなく、圧縮
強度、摩耗強度が向上する。また本発明に係るチタニア
ゾルを予め別のチタニア、シリカ、アルミナなどのゾル
あるいは液で処理して、これらを凝集させた原料を用い
ると、細孔容積が大きく、軽質であるにもかかわらず圧
縮強度、摩耗強度、衝撃強度ににれだ成型体を得ること
ができる。一般に本発明に係るチタニアゾルを成型体形
成用に用いる場合には、し／Ｄ≧７のチタニア粒子を含
むゾルを単独で、あるいは２種以上の形状のゾルを用い
ると、その効果は大きい。For example, when used in molded bodies such as catalyst carriers, the force applied during molding causes the particles to be arranged regularly, greatly improving moldability, and the molded body produced by 1q does not crack during drying or firing. , compressive strength and abrasion strength are improved. Furthermore, if the titania sol according to the present invention is treated in advance with another sol or liquid of titania, silica, alumina, etc., and a raw material is used which is agglomerated, the pore volume is large and the compressive strength is increased even though it is light. It is possible to obtain a molded body with excellent abrasion strength and impact strength. Generally, when the titania sol according to the present invention is used for forming a molded object, the effect is great if a sol containing titania particles with /D≧7 is used alone, or two or more types of sols are used.
ざらに本発明に係るチタニアゾルを各種のコート剤とし
て用いる場合には、形状の効果が特に顕著である。すな
わち、従来公知の方法により得られる球状チタニアゾル
の場合には、粒子は３次元配列を示し、球と球との間に
空間が構成されることは避けられず、そのためコート部
の強度、基材との密着強度が低く、チタニア密度が低い
ため、紫外線反射能力に劣る。ところが、本発明に係る
チタニアゾルでは、粒子は特定の形状を有するため、基
材に密に２次元的に配列し、このため基材がチタニアの
密な膜で覆われることになり、密着訃、耐久性に富んだ
膜が得られるばかりか、紫外線遮蔽効果にもすぐれ、高
屈折率の膜が得られる。In general, when the titania sol according to the present invention is used as various coating agents, the effect of the shape is particularly remarkable. In other words, in the case of a spherical titania sol obtained by a conventionally known method, the particles exhibit a three-dimensional arrangement, and it is inevitable that spaces are formed between the spheres. Due to the low adhesion strength and low titania density, the UV reflecting ability is poor. However, in the titania sol according to the present invention, since the particles have a specific shape, they are densely arranged two-dimensionally on the base material, resulting in the base material being covered with a dense film of titania, resulting in poor adhesion. Not only can a highly durable film be obtained, but also a film with an excellent ultraviolet shielding effect and a high refractive index can be obtained.
ざらにまた、透明性が要求される場合には、Ｌ≦１００
ｍμの粒子のゾルを用いると極めて透明な膜が得られる
。なお、本発明のゾルは、アルコールなどの有機溶媒と
混合するか、これらと溶媒置換しても沈澱を生成せず安
定であるので、コート材としての用途が従来のチタニア
ゾルに比べて飛躍的に増大する。Furthermore, when transparency is required, L≦100
Very transparent films can be obtained using mμ particle sols. The sol of the present invention does not form precipitates and is stable even when mixed with organic solvents such as alcohol or replaced with these solvents, so its use as a coating material is dramatically greater than that of conventional titania sol. increase
本発明に係るチタニアゾルは、一般に５〜９のｐＨを有
しているが、このチタニアゾルに酸あるいはアルカリを
加えても、チタニア粒子がゲル化したりあるいは沈澱が
生ずることはなく、ｐＨ３〜１１という広範囲のｐＨ＠
域において安定である。The titania sol according to the present invention generally has a pH of 5 to 9, but even if an acid or alkali is added to the titania sol, the titania particles do not gel or precipitate, and the pH ranges from 3 to 11. pH of
stable within the range.
またチタニアゾル中のチタニア粒子の濃度は、目的に応
じて広範囲の濃度のものが安定に得られるが、一般に、
Ｔ ｉ Ｏ２に換算して２０重量％程度という高濃度に
濃縮しても安定に存在し、共存塩濃度も約０．０５重量
％以下と極めて少なくすることができる。In addition, the concentration of titania particles in titania sol can be stably obtained in a wide range of concentrations depending on the purpose, but in general,
It remains stable even when concentrated to a high concentration of about 20% by weight in terms of T i O2, and the concentration of coexisting salts can be extremely reduced to about 0.05% by weight or less.
なお、チタニアゾル中のチタニア粒子のＬ／Ｄが１０以
上でおるチタニアゾルは、極端なチキソトロピー性を示
す。Incidentally, a titania sol in which the L/D of titania particles in the titania sol is 10 or more exhibits extreme thixotropy.
次に本発明に係るチタニアゾルの製造方法について説明
する。Next, a method for producing titania sol according to the present invention will be explained.
まず、常法に従って従来公知の方法によってチタニアゾ
ルあるいはチタニアゲルを調製する。チタニアゲルは、
たとえば塩化チタン、硫酸チタンなどのチタン塩の水溶
液にアルカリを加えて中和することによって得られる。First, titania sol or titania gel is prepared by a conventionally known method. Titania gel is
For example, it can be obtained by adding an alkali to an aqueous solution of a titanium salt such as titanium chloride or titanium sulfate to neutralize it.
またチタニアゾルは、チタン塩の水溶液をイオン交換樹
脂に通して陰イオンを除去することによって得られる。Titania sol can also be obtained by passing an aqueous solution of titanium salt through an ion exchange resin to remove anions.
チタニアゾルあるいはチタニアゲルを調製するには、上
記のような方法に限らず、従来公知の方法が広く用いら
れうる。In order to prepare titania sol or titania gel, not only the above method but also a wide variety of conventionally known methods can be used.
次に上記のようにして得られたチタニアゾルまたはチタ
ニアゲルあるいはこれらの混合物に、過酸化水素を加え
てチタニアを溶解して均一な水溶液を調製する。この際
、必要に応じて加熱あるいは攪拌することが好ましい。Next, hydrogen peroxide is added to the titania sol, gel, or mixture thereof obtained as described above to dissolve titania and prepare a uniform aqueous solution. At this time, it is preferable to heat or stir as necessary.
またこの際チタニアの濃度が高くなりすぎると、チタニ
アの溶解に長時間を必要とし、ざらに未溶解状態のゲル
が沈澱したり、あるいは得られる水溶液が粘稠になりす
ぎるため好ましくない。このためチタニア濃度としては
約１０ｆｆｉ量％以下好ましくは約５重量％以下である
ことが望ましい。In addition, if the titania concentration is too high, it will take a long time to dissolve the titania, and undissolved gel will precipitate, or the resulting aqueous solution will become too viscous, which is not preferable. Therefore, it is desirable that the titania concentration be about 10% by weight or less, preferably about 5% by weight or less.
加えるべき過酸化水素の量はｌ−＋２０□／Ｔ ｉ ｏ
２重量比で１以上であれば、チタニアを完全に溶解する
ことができる。ト１２０２／Ｔ！０２比が１未満である
と、チタニアが完全に溶解せず、未反応のゲルまたはゾ
ルが残存するため好ましくない。またト１２０２／Ｔ！
０２比は大きいほど、チタニアの溶解速度は大きく反応
は短時間で終了するが、あまり過剰に過酸化水素を用い
ると、未反応の過酸化水素が系内に大量に残存すること
となり、次の工程に悪影響を与えるため好ましくない。The amount of hydrogen peroxide to be added is l-+20□/Tio
If the weight ratio of 2 is 1 or more, titania can be completely dissolved. T1202/T! If the 02 ratio is less than 1, titania is not completely dissolved and unreacted gel or sol remains, which is not preferable. Matata 1202/T!
The larger the 02 ratio is, the faster the titania dissolution rate is and the reaction is completed in a shorter time. However, if too much hydrogen peroxide is used, a large amount of unreacted hydrogen peroxide will remain in the system, which will lead to the next reaction. This is not preferable because it has a negative impact on the process.
したがって、Ｈ２Ｏ２／Ｔ！０２比が１〜６好ましくは
２〜６程度となるような量で過酸化水素を用いることが
好ましく、このような量で過酸化水素を用いると、チタ
ニアは２〜２０時間程度で完全に溶解する。Therefore, H2O2/T! It is preferable to use hydrogen peroxide in an amount such that the 02 ratio is about 1 to 6, preferably about 2 to 6. If hydrogen peroxide is used in such an amount, titania will be completely dissolved in about 2 to 20 hours. do.
この際の反応温度は５０’Ｃ以上好ましくは７０’Ｃ以
上であることが望ましい。The reaction temperature at this time is desirably 50'C or higher, preferably 70'C or higher.
上記のようにして得られたチタニア水溶液は、これをそ
のまま再び加熱すると加水分解し、チタニアの沈澱が生
ずるため好ましくない。しかし、低濃度たとえば約０．
１重量％以下のものであれば、一応ゾルの形で存在し得
るがゾルとしては 不安定でこれを濃縮してＴ ｉ
Ｏ２の濃度をあげていくと、もはやゾルとして存在す
ることができず沈澱が生成する。If the aqueous titania solution obtained as described above is heated again as it is, it will be hydrolyzed and titania will precipitate, which is not preferable. However, at low concentrations, for example about 0.
If it is less than 1% by weight, it may exist in the form of a sol, but as a sol it is unstable and it is concentrated and used as Ti.
When the concentration of O2 is increased, it can no longer exist as a sol and a precipitate is formed.
次に、上記のようにして得られたチタニア水溶液に、シ
リカゾル、チタニアゾル、ジルコニアゾルなどの無機酸
化物ゾルあるいは無機酸化物ゾルを加えて加熱しながら
加水分解する。このようにすると、上述のような特定形
状のチタニア粒子が水などの分散媒中に分散されてなる
チタニアゾルが得られる。Next, an inorganic oxide sol or inorganic oxide sol such as silica sol, titania sol, zirconia sol, etc. is added to the titania aqueous solution obtained as described above, and hydrolyzed while heating. In this way, a titania sol can be obtained in which titania particles having a specific shape as described above are dispersed in a dispersion medium such as water.
本発明で用いられる無Ｂ１ｆｆ１化物ゾルあるいは無機
水酸化物ゾルとしては、通常、ゾルとして安定に存在す
るものであればいかなるゾルでも使用可能であるが、特
に周期律表第１Ｖ族の金属酸化物ゾルが好ましい。これ
らの無機酸化物ゾルの平均粒径は、３０ｍμ以下好まし
くは１５ｍμ以下であることが好ましい。これらの無機
酸化物ゾルのうち、たとえばシリカゾルなどは通常安定
剤とてアルカリ金属イオンなどが共存しているが、この
ような場合には、あらかじめ、イオン交換などによりこ
れらのイオンを除去して用いる方が好ましい。As the B1ff1 compound-free sol or inorganic hydroxide sol used in the present invention, any sol can be used as long as it exists stably as a sol, but in particular metal oxides of Group 1V of the periodic table can be used. Sol is preferred. The average particle size of these inorganic oxide sols is preferably 30 mμ or less, preferably 15 mμ or less. Among these inorganic oxide sols, for example, silica sol usually coexists with alkali metal ions as stabilizers, but in such cases, these ions must be removed by ion exchange etc. before use. is preferable.
無機酸化物の添加法には特に制限なく、所定のチタニア
溶液と無機酸化物ゾルを一時に混合して加熱しても良く
、最初無機酸化物ゾルにチタニア溶液の一部を加えたの
ち、加熱し、加水分解が進むに従って順次加えていく方
法もとり得る。There are no particular restrictions on the method of adding the inorganic oxide, and a predetermined titania solution and inorganic oxide sol may be mixed at once and heated; first, a portion of the titania solution is added to the inorganic oxide sol, and then heated However, it is also possible to add them sequentially as the hydrolysis progresses.
チタニア溶液中のＴｉＯ２と、これに添加される無機酸
化物ゾル中の酸化物（ＭＯｘ）の重量比であるＴ ｉ
Ｏ２／ Ｍ ＯＸは、その値が大きくなればなるほど、
得られるチタニアゾル中のチタニア粒子は大きくなる傾
向か認められる。たとえば、Ｔ ！ ０２ ／ Ｍ Ｏ
ｘ ＝ １０〜３０ではＬ／Ｄ＝３〜６でおるチタニア
粒子のゾルが得られ、丁１０２／ＭＯｘ＝５０〜１００
ではＬ／Ｄ＝１０〜２０の長いチタニア粒子のゾルが得
られる。なお、Ｔ ｉ Ｏ２／ Ｍ ＯＸが１以下では
、本発明で特定するような形状のチタニア粒子は得られ
ず、また一方Ｔｉ○２／ＭＯｘ比が２００以上であると
、得られるチタニア粒子のＬ／Ｄの不均一な粒子になっ
たり、粒子同士の凝集が起こるなどの問題が生じるため
、Ｔ ＋ ０２ ／ Ｍ Ｏｘの１１よ、５〜２００の
範囲でおることが好ましい。T i which is the weight ratio of TiO2 in the titania solution and oxide (MOx) in the inorganic oxide sol added to it
The larger the value of O2/MOX, the more
It is observed that the titania particles in the obtained titania sol tend to become larger. For example, T! 02/MO
When x = 10-30, a sol of titania particles with L/D = 3-6 is obtained, and when x = 102/MOx = 50-100
In this case, a sol of long titania particles with L/D=10 to 20 is obtained. Note that if T i O2 / M OX is 1 or less, titania particles having the shape specified in the present invention cannot be obtained, and on the other hand, if the Ti○2 / MOx ratio is 200 or more, L of the titania particles obtained is Since problems such as nonuniform particles with /D and agglomeration of particles occur, it is preferable that T + 02 / M Ox be in the range of 11, 5 to 200.
加熱温度は、高いほど加水分解速度は速くなるため、６
０’Ｃ以上、好ましくは８０’Ｃ以上であることか望ま
しい。The higher the heating temperature, the faster the hydrolysis rate, so 6
It is desirable that the temperature is 0'C or higher, preferably 80'C or higher.
本発明において、無機酸化物ゾルとしてチタニアゾルを
用いる場合には、従来公知の、チタニアゲルの酸解膠法
で得られたチタニアゾルを用いることもできるが、本発
明による過酸化水素でゲルを溶解したチタニア溶液を希
釈したのち加熱し、加水分解して得られたＦａａチタニ
アゾルを用いることもできる。In the present invention, when titania sol is used as the inorganic oxide sol, titania sol obtained by the conventionally known acid peptization method for titania gel can be used, but titania sol obtained by dissolving the gel with hydrogen peroxide according to the present invention can also be used. Faa titania sol obtained by diluting the solution and then heating and hydrolyzing it can also be used.
さらに、本発明の方法で得られたチタニアゾルを、チタ
ニア溶液と混合し、加熱、７］０水分解すればざらに大
きなＬ／Ｄ値を有する粒子のチタニアゾルが得られる。Furthermore, if the titania sol obtained by the method of the present invention is mixed with a titania solution, heated, and subjected to 7]0 water decomposition, a titania sol with particles having a significantly larger L/D value can be obtained.
λ哩五四男
本発明に係るチタニアゾルは、特定の形状を有するチタ
ニア超微粒子が分散媒に分散されているため、分散性に
優れるとともに広いｏｈ領領域安定であって凝集するこ
とかなく、しかも有機溶媒と混合しても沈澱が生ずるこ
とない。したがって本発明に係るチタニアゾルを用いて
、たとえば表面コート材を製造すると、基材との密着性
に（至）れ、しかも耐久性にも例れた紫外線遮蔽効果お
よび高屈折率を有する塗膜が得られる。The titania sol according to the present invention has ultrafine titania particles having a specific shape dispersed in a dispersion medium, so it has excellent dispersibility and is stable in a wide oh region, and does not aggregate. No precipitation occurs even when mixed with organic solvents. Therefore, when the titania sol according to the present invention is used to manufacture, for example, a surface coating material, a coating film that has excellent adhesion to the base material, has a durable ultraviolet shielding effect, and has a high refractive index is produced. can get.
また本発明に係るチタニアゾルの製造方法によれば、特
定の形状を有するチタニア超微粒子が分散媒に分散され
てなる上記のような優れた特性を有するチタニアゾルを
製造することができる。Further, according to the method for producing a titania sol according to the present invention, it is possible to produce a titania sol having the above-mentioned excellent properties in which ultrafine titania particles having a specific shape are dispersed in a dispersion medium.
以下本発明を実施例により説明するが、本発明はこれら
実施例に限定されるものではない。EXAMPLES The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.
実施例 １
硫酸チタンをイオン交換水に溶解し、ＴｉＯ２として、
０．４重量％を含む水溶液を１ｑだ。この水溶液を攪拌
しながら、この水溶液に１５％アンモニア水を徐々に添
加し、ｐＨ８，５の白色スラリー液を得た。このスラリ
ーを濾過した後洗浄し、固形分濃度が９重量％であるチ
タニアゲルのケーキを得た。Example 1 Titanium sulfate was dissolved in ion-exchanged water to form TiO2.
1 q of an aqueous solution containing 0.4% by weight. While stirring this aqueous solution, 15% aqueous ammonia was gradually added to the aqueous solution to obtain a white slurry liquid with a pH of 8.5. This slurry was filtered and washed to obtain a titania gel cake having a solid content concentration of 9% by weight.
このケーキ５．５５Ｋｇに、３３％過酸化水素水６．０
６Ｋｇと水１３．４Ｋｇとの混合物を加えた後、８０’
Ｃで５時間加熱し、ＴｉＯ２として２．０重量％の溶液
２５Ｋｙを得た。このチタニア溶液は、黄褐色透明で、
ｐＨは８．１でめった。Add 6.0 kg of 33% hydrogen peroxide to 5.55 kg of this cake.
After adding a mixture of 6 Kg and 13.4 Kg of water, 80'
C for 5 hours to obtain 25Ky of a 2.0% by weight solution as TiO2. This titania solution is yellowish-brown and transparent.
The pH was 8.1.
次に、粒子径が７ｍμであり濃度が１５重量９６である
シリカゾル１３０３と、上記のチタニア）８液９ Ｋ’
ｊと、水１９１ ＫＳとを混合した後、９５°Ｃで６０
時間加熱した。溶液は最初黄褐色液であったが、６０時
間後には乳白色透明なコロイド液となった。Next, silica sol 1303 with a particle size of 7 mμ and a concentration of 15 weight 96, and the above titania) 8 liquid 9 K'
After mixing J and water 191 KS, the mixture was heated at 95°C for 60°C.
heated for an hour. The solution was initially a yellowish brown liquid, but after 60 hours it became a milky white transparent colloidal liquid.
このようにして得られたコロイド液を真空蒸発法で濃縮
したところ、表１に示すようなゾルを得た。When the colloidal liquid thus obtained was concentrated by vacuum evaporation, a sol as shown in Table 1 was obtained.
表１には、ゾルの性状および分散粒子の性状を示す。ま
た第１図にゾルから１ｑられたチタニア粒子の透過型電
子顕微鏡写真を示す。Table 1 shows the properties of the sol and the properties of the dispersed particles. Furthermore, FIG. 1 shows a transmission electron micrograph of titania particles 1q removed from the sol.
実施例 ２
実施例１で得られたチタニア溶液１．０Ｋｇと水２００
Ｋ’ｊを混合したのち、９５°Ｃで２時間加熱し、Ｔ
ｉｏ２として０．０１重量％のチタニアゾルを得た。Example 2 1.0 kg of titania solution obtained in Example 1 and 200 kg of water
After mixing K'j, heat at 95°C for 2 hours, and
A titania sol containing 0.01% by weight as io2 was obtained.
このゾルを実施例１のシリカゾルの代りに用いた以外は
、実施例１と同じ条件で加水分解し子顕微鏡写真を示す
。Hydrolysis was carried out under the same conditions as in Example 1, except that this sol was used in place of the silica sol in Example 1, and microscopic photographs are shown.
実施例 ３
酸化ジルコニウムとして０．０３６重量％を含む塩化ジ
ルコニウム水溶液５０に９を還流器付きフラスコに入れ
、よく撹拌しながら０．１Ｎのアンモニア水２．９に５
を徐々に添加した。ざらにこの液を９５°Ｃで５０時間
加熱したところ、酸化ジルコニウム濃度が０．０３４重
量％であり、ｐＨ１，８の薄い乳白色ゾル液が得られた
。Example 3 Add 9 to 50% of an aqueous solution of zirconium chloride containing 0.036% by weight as zirconium oxide to a flask equipped with a reflux device, and add 5 to 2.9% of 0.1N ammonia water while stirring well.
was added gradually. When this liquid was roughly heated at 95°C for 50 hours, a thin milky sol liquid with a zirconium oxide concentration of 0.034% by weight and a pH of 1.8 was obtained.
ざらにこの液に０．１Ｎのアンモニア水を混合し、ｐＨ
４，８とした後、イオン交換水で濾液に塩素イオンが検
出されなくなるまで洗浄した。Mix 0.1N ammonia water with this solution and adjust the pH.
4 and 8, the filtrate was washed with ion-exchanged water until no chloride ions were detected.
上記で得られたジルコニアゾルと実施例１のチタニア溶
液を、Ｔ ｉ ０２ ／ＭＯＸ＝１０となるように混合
し、さらに固形分濃度（ＴｉＯ２＋ＺｒＯ２＞が０．１
重量％になるように水を加えて９５°Ｃ１６０時間加熱
した。得られたゾルを濃縮したところ、表１に示すよう
なゾルを得た。The zirconia sol obtained above and the titania solution of Example 1 were mixed so that T i 02 /MOX = 10, and the solid content concentration (TiO2 + ZrO2 > 0.1
Water was added to the mixture to make the same weight percent, and the mixture was heated at 95°C for 160 hours. When the obtained sol was concentrated, the sol shown in Table 1 was obtained.
実施例 ４〜６
実施例１においてＴ ｉ ０２ ／ＭＯｘ重量比がそれ
ぞれ２０（実施例４）、３０（実施例５）、８０（実施
例６）となるようにチタニア溶液を添加して加水分解を
行なった以外は、実施例１と同様にしたところ、表１に
示すようなチタニアゾルを得た。Examples 4 to 6 In Example 1, titania solution was added and hydrolyzed so that the T i 02 /MOx weight ratio was 20 (Example 4), 30 (Example 5), and 80 (Example 6), respectively. The same procedure as in Example 1 was carried out except that the titania sols shown in Table 1 were obtained.
第３図に実施例５で得られたチタニア粒子の透過型電子
類＠鏡写真を示す。FIG. 3 shows a transmission electron type photograph of the titania particles obtained in Example 5.
実施例 ７
実施例５で得られた濃縮前のチタニアゾルに、実施例１
で１ｑられたチタニア溶液を、Ｔ ｉ ０２ ／ＭＯ，
＝’１３０、固形分濃度０．１重量％となるように加え
たのち、１００’Ｃで８４時間加熱して濃縮したところ
、表１に示すようなゾルを得た。Example 7 Example 1 was added to the titania sol obtained in Example 5 before concentration.
1 q of titania solution, T i 02 /MO,
='130, and the solid content was added to give a solid content concentration of 0.1% by weight, and then heated and concentrated at 100'C for 84 hours to obtain a sol as shown in Table 1.
実施例 ８
実施例１のシリカゾルおよびチタニア溶液を、Ｔ ｉ
Ｏ２／ Ｍ ＯＸ ＝ ３０、固形分濃度（Ｔｉ○２＋
３ｉ０．２）−１，０重量％になるように）昆合し、オ
ートクレーブ中で１３０°Ｃで２時間加熱して得られた
乳白色ゾルを濃縮したところ、表１に示すようなゾルを
（ｑだ。Example 8 The silica sol and titania solution of Example 1 were
O2/ M OX = 30, solid content concentration (Ti○2+
3i0.2)-1.0% by weight) and heated in an autoclave at 130°C for 2 hours to concentrate the resulting milky white sol, resulting in a sol as shown in Table 1 ( It's q.
比較例 コ
実施例１で得られたチタニアゲルをイオン交換水で希釈
し、Ｔ ： ０２温度が２．０重量％であるような懸濁
液を得た。これに０．１Ｎの塩酸をゾル状となるまで徐
々に添加した。得られたゾルを８０’Ｃで１時間加熱安
定させた後、減圧下水弁を蒸発させて解膠法により濃縮
ゾルを胃だ。このゾルは、２０ｕｆｆ１％まで濃縮可能
であったが、ｐＨは１．７と低く、また塩素イオンを２
．１１ｍ％も含んだゾルでめった。Comparative Example The titania gel obtained in Example 1 was diluted with ion-exchanged water to obtain a suspension having a T:02 temperature of 2.0% by weight. To this, 0.1N hydrochloric acid was gradually added until it became a sol. After the obtained sol was stabilized by heating at 80'C for 1 hour, the concentrated sol was evaporated using a reduced pressure sewage valve and the concentrated sol was injected into the stomach using the peptization method. Although this sol could be concentrated to 20uf1%, the pH was as low as 1.7, and the chlorine ions were
．． I met it with a sol containing 11m%.
このゾルの特性を表１に示す。The properties of this sol are shown in Table 1.
また第４図にこのゾルから得られたチタニア粒子の透過
型電子顕微鏡写真を示す。FIG. 4 shows a transmission electron micrograph of titania particles obtained from this sol.
第１図、第２図および第３図は本発明に係るチタニアゾ
ル中のチタニア粒子の電子顕微鏡写真であり、第４図は
比較例で得られたチタニアゾル中のチタニア粒子の電子
顕微鏡写真である。
代理人 弁理士 銘木 俊一部
！゛
００Ａ
リー＾覧Ｖ内島Ｖ−＾＾（Ｖ＾＾νＩ−手続補正書（蛙
）
特許庁長官 黒 １）明 雄 殿
１、事件の表示
昭和６１年特 許 願 第１２５．３６７月−２、発明
の名称
ヂタニアゾルおよびその製造方法
６６補正の内容
１）明細書第８頁第８〜１３行において、「変化するが
、・・・７０％以上の量で存在する。」と必るを、「変
化する。」と補正する。
２）明細書第８頁第１８行において、
３）明細書第１５頁第９行〜１０行において、「無１Ｍ
酸化物ゾルにチタニア溶液の一部を加えたのち、」とあ
るを「無機酸化物ゾルとチタニア溶液の一部を混合した
のち、」と補正する。
４）明細書第１５頁第１１行において、「に従って順次
加えていく方法もとり得る。」とあるを、「に従って残
りのチタニア溶液を順次加えていく方法もとり得る。」
と補正します。
５）明細書第１７頁第１２行と第１３行との間に、改行
して以下の文を挿入します。
「さらに、本発明に係る酸化チタンゾルは、化粧品配合
剤としてもすぐれた効果をもっている。1, 2, and 3 are electron micrographs of titania particles in a titania sol according to the present invention, and FIG. 4 is an electron micrograph of titania particles in a titania sol obtained in a comparative example. Agent Patent Attorney Shunbetsu Meiki!゛00A Lee^view V Uchijima V-^^ (V^^νI- Procedural amendment (Frog) Commissioner of the Patent Office Kuro 1) Akio Tono 1, Indication of the case 1985 Patent application No. 125.367- 2. Title of the invention Ditania sol and its manufacturing method Contents of amendment 66 1) In lines 8 to 13 of page 8 of the specification, it must be stated that "Although it varies, it is present in an amount of 70% or more." , correct it as "change." 2) In the specification, page 8, line 18, 3) In the specification, page 15, lines 9 to 10, “No 1M
"After adding a portion of the titania solution to the oxide sol," should be corrected to "After mixing a portion of the inorganic oxide sol and titania solution." 4) In line 11 of page 15 of the specification, the phrase "a method of sequentially adding the titania solution according to the following is also possible" is replaced with "a method of sequentially adding the remaining titania solution according to the following."
I will correct it. 5) Insert the following sentence between page 17, line 12 and line 13 of the statement on a new line. "Furthermore, the titanium oxide sol according to the present invention has excellent effects as a cosmetic compounding agent.
Claims (1)
さをＬとし短軸の長さをＤとしたとき、Ｌ／Ｄ≧２であ
るようなチタニア粒子が６０％以上の量で存在している
ことを特徴とするチタニアゾル。 ２）チタニアゾルまたはチタニアゲルに過酸化水素を加
えてチタニアゾルまたはチタニアゲルを溶解し、次いで
得られた溶液に無機酸化物ゾルまたは無機水酸化物ゾル
を混合した後加熱することを特徴とするチタニアゾルの
製造方法。[Claims] 1) When the length of the major axis of titania particles dispersed in the dispersion medium is L and the length of the minor axis is D, titania particles such that L/D≧2 are A titania sol characterized by being present in an amount of 60% or more. 2) A method for producing titania sol, which comprises adding hydrogen peroxide to titania sol or titania gel to dissolve the titania sol or titania gel, and then mixing the resulting solution with an inorganic oxide sol or inorganic hydroxide sol, followed by heating. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61125367A JPH0811693B2 (en) | 1986-05-30 | 1986-05-30 | Titania sol and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61125367A JPH0811693B2 (en) | 1986-05-30 | 1986-05-30 | Titania sol and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62283817A true JPS62283817A (en) | 1987-12-09 |
| JPH0811693B2 JPH0811693B2 (en) | 1996-02-07 |
Family
ID=14908377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61125367A Expired - Lifetime JPH0811693B2 (en) | 1986-05-30 | 1986-05-30 | Titania sol and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0811693B2 (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63229139A (en) * | 1986-10-29 | 1988-09-26 | Catalysts & Chem Ind Co Ltd | Titanium oxide sol and preparation of same |
| JPS643020A (en) * | 1986-09-22 | 1989-01-06 | Ishihara Sangyo Kaisha Ltd | Titania sol and production thereof |
| EP0770579A1 (en) | 1995-10-26 | 1997-05-02 | Asahi Glass Company Ltd. | Modified titanium oxide sol, photocatalyst composition and photocatalyst composition-forming agent |
| JPH09262481A (en) * | 1996-03-29 | 1997-10-07 | Tao:Kk | Photocatalyst and its production |
| JPH10237353A (en) * | 1997-02-24 | 1998-09-08 | Tao:Kk | Hydrophilic coating agent and surface hydrophilic substrate |
| JPH10237352A (en) * | 1997-02-24 | 1998-09-08 | Tao:Kk | Polyfunctional coating agent |
| EP1031538A1 (en) * | 1999-02-26 | 2000-08-30 | Saga Prefecture | Processes of producing a titanium oxide-forming solution and a dispersion with crystalline titanium oxide particles |
| JP2004043304A (en) * | 1996-08-30 | 2004-02-12 | Showa Denko Kk | Method for forming titanium dioxide membrane and catalyst or the like having the titanium dioxide membrane |
| US6774147B2 (en) | 1996-08-30 | 2004-08-10 | Showa Denko K.K. | Particles, aqueous dispersion and film of titanium oxide, and preparation thereof |
| JP2005068001A (en) * | 2003-08-01 | 2005-03-17 | Catalysts & Chem Ind Co Ltd | Fibrous titanium oxide particle, production method therefor, and application of the particle |
| JP2007047605A (en) * | 2005-08-11 | 2007-02-22 | Toyo Ink Mfg Co Ltd | Composition for light scattering film and light scattering film using the same |
| US7431903B2 (en) | 2001-10-30 | 2008-10-07 | Catalysts & Chemicals Industries Co., Ltd. | Tubular titanium oxide particles and process for preparing same |
| US7611688B2 (en) | 2004-11-19 | 2009-11-03 | Korea Research Institute Of Chemical Technology | Rutile titania nano sols and process for manufacturing the same |
| US7659226B2 (en) | 2007-02-26 | 2010-02-09 | Envont Llc | Process for making photocatalytic materials |
| JP2011178633A (en) * | 2010-03-03 | 2011-09-15 | Sekisui Chem Co Ltd | Method for producing amorphous titanium peroxide |
| JP2013203578A (en) * | 2012-03-28 | 2013-10-07 | Osaka Gas Co Ltd | Titanium oxide structure having high crystallinity and high specific surface area |
| CN114105193A (en) * | 2021-11-30 | 2022-03-01 | 重庆英诺维节能环保科技有限公司 | Preparation method of ultraviolet shielding nano titanium dioxide material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55113624A (en) * | 1979-02-26 | 1980-09-02 | Kyushu Refract Co Ltd | Titanium dioxide fibrous substance and manufacture thereof |
-
1986
- 1986-05-30 JP JP61125367A patent/JPH0811693B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55113624A (en) * | 1979-02-26 | 1980-09-02 | Kyushu Refract Co Ltd | Titanium dioxide fibrous substance and manufacture thereof |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS643020A (en) * | 1986-09-22 | 1989-01-06 | Ishihara Sangyo Kaisha Ltd | Titania sol and production thereof |
| JPH0587446B2 (en) * | 1986-10-29 | 1993-12-16 | Catalysts & Chem Ind Co | |
| JPS63229139A (en) * | 1986-10-29 | 1988-09-26 | Catalysts & Chem Ind Co Ltd | Titanium oxide sol and preparation of same |
| EP0770579A1 (en) | 1995-10-26 | 1997-05-02 | Asahi Glass Company Ltd. | Modified titanium oxide sol, photocatalyst composition and photocatalyst composition-forming agent |
| US6107241A (en) * | 1996-03-29 | 2000-08-22 | Tao Inc. | Photocatalytic body and method for making same |
| JPH09262481A (en) * | 1996-03-29 | 1997-10-07 | Tao:Kk | Photocatalyst and its production |
| WO1997036677A1 (en) * | 1996-03-29 | 1997-10-09 | Tao Inc. | Photocatalyst body and method of production thereof |
| US6429169B1 (en) | 1996-03-29 | 2002-08-06 | Saga-Ken | Photocatalytic body and method for making same |
| US7368183B2 (en) | 1996-08-30 | 2008-05-06 | Showa Denko K.K. | Particles, aqueous dispersion and film of titanium oxide, and preparation thereof |
| JP2004043304A (en) * | 1996-08-30 | 2004-02-12 | Showa Denko Kk | Method for forming titanium dioxide membrane and catalyst or the like having the titanium dioxide membrane |
| US6774147B2 (en) | 1996-08-30 | 2004-08-10 | Showa Denko K.K. | Particles, aqueous dispersion and film of titanium oxide, and preparation thereof |
| JPH10237352A (en) * | 1997-02-24 | 1998-09-08 | Tao:Kk | Polyfunctional coating agent |
| JPH10237353A (en) * | 1997-02-24 | 1998-09-08 | Tao:Kk | Hydrophilic coating agent and surface hydrophilic substrate |
| KR100394695B1 (en) * | 1999-02-26 | 2003-08-14 | 사가껭 | Processes of producing a titanium oxide-forming solution and a dispersion with crystalline titanium oxide particles |
| US6602918B1 (en) | 1999-02-26 | 2003-08-05 | Saga Prefecture | Processes of producing a titanium oxide-forming solution and a dispersion with crystalline titanium oxide particles |
| EP1031538A1 (en) * | 1999-02-26 | 2000-08-30 | Saga Prefecture | Processes of producing a titanium oxide-forming solution and a dispersion with crystalline titanium oxide particles |
| US7431903B2 (en) | 2001-10-30 | 2008-10-07 | Catalysts & Chemicals Industries Co., Ltd. | Tubular titanium oxide particles and process for preparing same |
| EP2223895A1 (en) | 2001-10-30 | 2010-09-01 | JGC Catalysts and Chemicals Ltd. | Tubular titanium oxide particles and use of the same |
| JP2005068001A (en) * | 2003-08-01 | 2005-03-17 | Catalysts & Chem Ind Co Ltd | Fibrous titanium oxide particle, production method therefor, and application of the particle |
| US7611688B2 (en) | 2004-11-19 | 2009-11-03 | Korea Research Institute Of Chemical Technology | Rutile titania nano sols and process for manufacturing the same |
| JP2007047605A (en) * | 2005-08-11 | 2007-02-22 | Toyo Ink Mfg Co Ltd | Composition for light scattering film and light scattering film using the same |
| US7659226B2 (en) | 2007-02-26 | 2010-02-09 | Envont Llc | Process for making photocatalytic materials |
| JP2011178633A (en) * | 2010-03-03 | 2011-09-15 | Sekisui Chem Co Ltd | Method for producing amorphous titanium peroxide |
| JP2013203578A (en) * | 2012-03-28 | 2013-10-07 | Osaka Gas Co Ltd | Titanium oxide structure having high crystallinity and high specific surface area |
| CN114105193A (en) * | 2021-11-30 | 2022-03-01 | 重庆英诺维节能环保科技有限公司 | Preparation method of ultraviolet shielding nano titanium dioxide material |
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|---|---|
| JPH0811693B2 (en) | 1996-02-07 |
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