JPH0645451B2 - Titania / silica composite and its manufacturing method - Google Patents
Titania / silica composite and its manufacturing methodInfo
- Publication number
- JPH0645451B2 JPH0645451B2 JP3376986A JP3376986A JPH0645451B2 JP H0645451 B2 JPH0645451 B2 JP H0645451B2 JP 3376986 A JP3376986 A JP 3376986A JP 3376986 A JP3376986 A JP 3376986A JP H0645451 B2 JPH0645451 B2 JP H0645451B2
- Authority
- JP
- Japan
- Prior art keywords
- titania
- aqueous solution
- titanium
- silica composite
- silica
- 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.)
- Expired - Lifetime
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- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Paints Or Removers (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
【発明の詳細な説明】 ＜産業上の利用分野＞ 本発明は新規なチタニア／シリカ複合体及びその製法に
関する。特に紙、塗料、プラスチックゴムへ内填又はコ
ートして不透明性を要求される充填剤として優れた性状
を有するチタニア／シリカ複合体を提供するものであ
る。DETAILED DESCRIPTION OF THE INVENTION <Industrial field of application> The present invention relates to a novel titania / silica composite and a method for producing the same. In particular, the present invention provides a titania / silica composite having excellent properties as a filler required to be opaque by filling or coating on paper, paint or plastic rubber.
＜従来技術＞ 従来、不透明性を付与する充填剤として酸化チタンが使
用されている。しかし酸化チタンは吸油量が１５〜３０
ｍｌ／１００ｇ程度である。このため酸化チタンを紙に
充填すると紙の印刷性が悪くなり、塗料に混合すると沈
降安定性が悪くなるため、酸化チタン単独で十分な充填
効果を発揮する場合が少ない。従って、一般には微粉シ
リカと併用される場合が多い。しかし、微粉シリカの屈
折率は１．４〜１．６と小さいため微粉シリカを充填剤
として紙に併用して充填した場合はインペイ性が小さく
実用的に難点となる。<Prior Art> Titanium oxide has been conventionally used as a filler for imparting opacity. However, titanium oxide has an oil absorption of 15 to 30.
It is about 100 ml / ml. For this reason, when the titanium oxide is filled in the paper, the printability of the paper is deteriorated, and when it is mixed with the paint, the sedimentation stability is deteriorated, so that the titanium oxide alone rarely exhibits a sufficient filling effect. Therefore, in general, it is often used in combination with finely divided silica. However, since the fine silica powder has a small refractive index of 1.4 to 1.6, when the fine silica powder is used as a filler in combination with paper, the in-pay property is small, which is a practical difficulty.
＜発明が解決しようとする問題点と解決手段＞ 本発明は上記従来技術の欠点を改良することにあり、特
に不透明性を付与し、吸油量が１００ｍｌ／１００ｇ以
上で且つ屈折率が１．６以上の充填剤を提供することを
目的とする。<Problems to be Solved by the Invention and Means for Solving the Problems> The present invention is to improve the above-mentioned drawbacks of the prior art. In particular, it imparts opacity, oil absorption is 100 ml / 100 g or more, and refractive index is 1.6. It is intended to provide the above-mentioned filler.
上記目的を達成すべく本発明者は鋭意研究を重ねて来
た。その結果、特定の製法によって得られるチタニア／
シリカ複合体が優れた充填剤の性状を有することを確認
し、更に研究を続けて本発明を完成し提供するに至っ
た。The present inventor has conducted extensive studies to achieve the above object. As a result, titania obtained by a specific manufacturing method /
It was confirmed that the silica composite had excellent filler properties, and further research was conducted to complete and provide the present invention.
即ち本発明は一次粒子径が１０〜１００ｎｍ、容積法に
よって測定した不透明度が０．５〜３０、吸油量が１０
０ｍｌ／１００ｇ〜３００ｍｌ／１００ｇ及び比表面積
が５０〜４００m2／ｇで且つチタニアがシリカに対して
０．５〜３０重量％含まれてなる非晶質のチタニア／シ
リカ複合体である。That is, the present invention has a primary particle size of 10 to 100 nm, an opacity of 0.5 to 30 as measured by a volume method, and an oil absorption of 10
It is an amorphous titania / silica composite having 0 ml / 100 g to 300 ml / 100 g, a specific surface area of 50 to 400 m 2 / g, and a titania content of 0.5 to 30 wt% with respect to silica.
また本発明は酸化チタンの存在下又は不存在下、珪酸ア
ルカリ水溶液にpHが１〜７になるようにチタンの酸性不
溶液を少くとも３０分以上の時間を費やして添加し、８
０℃〜該水溶液の沸点の温度に加熱することを特徴とす
るチタニア／シリカの複合体の製法をも提供する。In the present invention, an acidic non-solution of titanium is added to an aqueous alkali silicate solution in the presence or absence of titanium oxide so as to have a pH of 1 to 7 by spending at least 30 minutes or more.
Also provided is a process for producing a titania / silica composite, which comprises heating to a temperature of 0 ° C. to the boiling point of the aqueous solution.
本発明において容積法によって測定した不透明度とは、
内容積１００ｍｌのメスシリンダーの底部に白紙に黒点
を書いた紙を敷き、ラッカー塗料（木材用クリヤーラッ
カー）１００ｍｌに充填剤試料２ｇを混合し、この試料
を分散させた塗料を少しづつメスシリンダー内に投入
し、黒点が見えなくなった時の、投入塗料の合計容積
（ｍｌ）を測定し、この容積を表示したものである。従
って、本発明における容積法によって測定した不透明度
はその数値が小さい程、その充填剤試料は不透明性を付
与する性状を有することになる。In the present invention, the opacity measured by the volume method,
Spread a paper with black dots on the bottom of a graduated cylinder with an internal volume of 100 ml, mix 2 g of the filler sample with 100 ml of lacquer paint (clear lacquer for wood), and gradually add the paint in which the sample is dispersed into the graduated cylinder. The total volume (ml) of the coating material is measured when the black spots are no longer visible, and this volume is displayed. Therefore, the smaller the value of the opacity measured by the volumetric method in the present invention, the more the opacity of the filler sample is imparted.
本発明で提供するチタニア／シリカ複合体は容積法によ
って測定した不透明度は０．５〜３０の範囲にあること
が必要である。上記不透明度を０．５より小さくしよう
とするとチタニア／シリカ複合体を工業的に製造するこ
とが難しくあるか、可能であっても著しいコストアップ
になるので、工業的な観点から好ましくない。また前記
不透明度が３０を越えると本発明で目的とする不透明性
の付与が満されないので好ましくない。The titania / silica composite provided by the present invention needs to have an opacity measured by a volumetric method in the range of 0.5 to 30. If the opacity is set to be less than 0.5, it is difficult to industrially produce the titania / silica composite, or even if it is possible, the cost is significantly increased, which is not preferable from an industrial viewpoint. If the opacity exceeds 30, the opacity which is the object of the present invention cannot be satisfied, which is not preferable.
また本発明で提供するチタニア／シリカ複合体は一次粒
子径が１０〜１００ｎｍで凝集性を有する固体状物であ
る。上記一次粒子径は、後述する吸油量及び比表面積に
影響を与えるもので、専らチタニア／シリカ複合体の製
造工程に於ける諸条件によって制御されるものである。
該一次粒子径が１０ｎｍより小さい場合は後述する吸油
量が１００ｍｌ／１００ｇ以上の該複合体にするのが難
しいし、１００ｎｍより大きくなると該複合体の比表面
積が５０m2／ｇより小さくなり、該複合体の沈降安定性
が劣るので好ましくない。Further, the titania / silica composite provided in the present invention is a solid substance having a primary particle diameter of 10 to 100 nm and having a cohesive property. The primary particle size affects the oil absorption amount and the specific surface area described later, and is controlled exclusively by various conditions in the process of producing the titania / silica composite.
When the primary particle size is smaller than 10 nm, it is difficult to form the composite having an oil absorption amount of 100 ml / 100 g or more described later, and when it is larger than 100 nm, the specific surface area of the composite becomes smaller than 50 m 2 / g. It is not preferable because the sedimentation stability of the complex is poor.
更に本発明に提供するチタニア／シリカ複合体は吸油量
が１００ｍｌ／１００ｇ〜３００ｍｌ／１００ｇの範囲
であることが好ましい。該吸油量が１００ｍｌ／１００
ｇより小さい場合は印刷性が十分でなく、塗料に混合し
たとき沈降安定性を良好に保つことが出来ない。また逆
に吸油量が３００ｍｌ／１００ｇを越えるチタニア／シ
リカ複合体は製造することが難しく技術的に困難を伴う
のでコストアップになり好適ではない。Further, the titania / silica composite provided in the present invention preferably has an oil absorption of 100 ml / 100 g to 300 ml / 100 g. The oil absorption is 100 ml / 100
When it is less than g, the printability is not sufficient and the sedimentation stability cannot be kept good when mixed with a paint. On the contrary, a titania / silica composite having an oil absorption of more than 300 ml / 100 g is not suitable because it is difficult to manufacture and technically difficult, resulting in an increase in cost.
更に本発明で提供するチタニア／シリカ複合体はその比
表面積が５０〜４００m2／ｇの範囲であることが好まし
い。該比表面積が５０m2／ｇより小さいときは吸油量が
小さくなり印刷性が悪くなるし、ゴムに充填するときは
補助性が十分でなくなる。また逆に該比表面積が４００
m2／ｇより大きくなると吸油量が低下し粒子間の凝集力
が強くなりシリカの分散性が悪くなるので好ましくな
い。Further, the titania / silica composite provided in the present invention preferably has a specific surface area of 50 to 400 m 2 / g. When the specific surface area is less than 50 m 2 / g, the oil absorption amount becomes small and the printability deteriorates, and when the rubber is filled, the auxiliary property becomes insufficient. On the contrary, the specific surface area is 400
When it is larger than m 2 / g, the oil absorption amount decreases, the cohesive force between particles becomes strong, and the dispersibility of silica deteriorates, which is not preferable.
更に本発明で提供するチタニア／シリカ複合体の屈折率
は１．６６５以上〜２．６の間の特定の屈折率を有して
いる。しかしながら現在の屈折率の測定方法では適当な
測定溶媒がないので該複合体の屈折率を特定することは
出来ない。該屈折率が１．６６５より大きいことは溶媒
として１−ブロムナフタリン溶液を使用し、アッベの屈
折計で、温度と屈折率を測定する測定方法で確認出来、
また屈折率が２．６より小さいときは酸化チタンの屈折
率と比較することによって確認出来る。Furthermore, the refractive index of the titania / silica composite provided by the present invention has a specific refractive index of 1.665 or more and 2.6. However, the present method for measuring the refractive index cannot specify the refractive index of the complex because there is no suitable measuring solvent. The fact that the refractive index is larger than 1.665 can be confirmed by a measuring method in which 1-bromonaphthalene solution is used as a solvent and Abbe refractometer measures temperature and refractive index.
When the refractive index is smaller than 2.6, it can be confirmed by comparing with the refractive index of titanium oxide.
更に本発明のチタニア／シリカ複合体はチタニアがシリ
カに対して０．５〜３０重量％の範囲の組成である。該
チタニアが０．５重量％より小さいと不透明性がなくな
り、３０重量％以上では不透明性において大差なくまた
コストアップになるので経済的に好ましくない。Further, the titania / silica composite of the present invention has a composition of titania in the range of 0.5 to 30% by weight based on silica. When the titania is less than 0.5% by weight, the opacity disappears, and when it is 30% by weight or more, the opacity is not significantly different and the cost is increased, which is not economically preferable.
本発明に於ける複合体はＸ線測定のチャートによって非
晶質であることが確認出来る。しかしながら該複合体を
構成するチタニアとシリカとがどのような形態で相互に
存在しているのか明らかではない。一般にチタニアとシ
リカとの混合物はブフナーで濾過すると下層にチタニア
がまた上層にシリカが来るように層分離で区別出来る
が、本発明の複合体はこのような区別は出来ない。しか
も屈折率は唯一の特定のものが存在することが確認出来
る。このような観察から本発明の複合体のチタニアとシ
リカは相互に結合して単一の化合物を形成しているか、
上記性状を有するミクロブレンドとなっているかあるい
はこの両方の形態で混在するかのいずれかであろうと推
定される。It can be confirmed from the chart of X-ray measurement that the complex in the present invention is amorphous. However, it is not clear in what form the titania and the silica constituting the composite exist mutually. Generally, a mixture of titania and silica can be separated by layer separation such that titania is in the lower layer and silica is in the upper layer by filtering with a Buchner, but the composite of the present invention cannot make such a distinction. Moreover, it can be confirmed that there is only one specific refractive index. From such observation, whether the titania and silica of the complex of the present invention are bonded to each other to form a single compound,
It is presumed to be either a microblend having the above properties or a mixture of both forms.
本発明のチタニア／シリカ複合体の製造方法の代表的な
態様を例示すれば次の通りである。A typical embodiment of the method for producing the titania / silica composite of the present invention is as follows.
即ち、酸化チタンの存在下又は不存在下、珪酸アルカリ
水溶液にpHが１〜７になるようにチタンの酸性水溶液を
少くとも３０分以上の時間を費やして添加し、８０℃〜
該水溶液の沸点の温度に加熱することによって製造する
ことが出来る。That is, in the presence or absence of titanium oxide, an acidic aqueous titanium solution is added to the alkaline silicate aqueous solution at a temperature of 80 ° C.
It can be produced by heating to the boiling temperature of the aqueous solution.
該酸化チタンは特に限定されず、ルチル型、アナターゼ
型のどちらでも良い。また存在量はまた珪酸アルカリ水
溶液は特に限定的ではないが一般には珪酸ソーダ水溶液
又は珪酸カリ水溶液が好適に使用される。該珪酸アルカ
リ水溶液のモル濃度は特に限定的ではないが一般にはモ
ル比２．０〜３．４の範囲から選ぶのが好適である。The titanium oxide is not particularly limited and may be either rutile type or anatase type. The amount of the alkali silicate aqueous solution is not particularly limited, but generally a sodium silicate aqueous solution or a potassium silicate aqueous solution is preferably used. The molar concentration of the aqueous alkali silicate solution is not particularly limited, but it is generally preferable to select it from the molar ratio range of 2.0 to 3.4.
更にまた本発明の使用するチタンの酸性水溶液は公知の
ものが特に制限されず用いうる。一般には例えばチタン
の塩酸酸性水溶液、チタンの硫酸酸性水溶液、四塩化チ
タンの水溶液等が好適に使用される。また一般にはチタ
ンの濃度を１〜８％好ましくは３〜５％、酸性濃度を１
０〜３０％好ましくは２０〜２４％の範囲で使用すると
好適である。Furthermore, as the acidic aqueous solution of titanium used in the present invention, known ones can be used without particular limitation. Generally, for example, an acidic aqueous solution of titanium with hydrochloric acid, an acidic aqueous solution of titanium with sulfuric acid, an aqueous solution of titanium tetrachloride, and the like are preferably used. Generally, the titanium concentration is 1 to 8%, preferably 3 to 5%, and the acidic concentration is 1%.
It is suitable to use in the range of 0 to 30%, preferably 20 to 24%.
本発明のチタニア／シリカ複合体を製造するとき最も重
要なことは予め酸化チタンの存在又は不存在の珪酸アル
カリ水溶液を用意しておき、該珪酸アルカリ水溶液にチ
タンの酸性水溶液を加えていくことである。該チタンの
酸性水溶液の添加時間も重要な要件で、一般には少くと
も３０分以上の時間を費やして、珪酸アルカリ水溶液の
pHが１〜７になるように加える必要がある。更に該珪酸
アルカリ水溶液、珪酸アルカリ水溶液へチタンの酸性水
溶液を加えるとき或いは該チタンの酸性水溶液の添加後
の水溶液を８０℃〜該水溶液の沸点の温度下に加熱す
る。When manufacturing the titania / silica composite of the present invention, the most important thing is to prepare an alkali silicate aqueous solution in the presence or absence of titanium oxide in advance, and add an acidic aqueous solution of titanium to the alkali silicate aqueous solution. is there. The addition time of the acidic aqueous solution of titanium is also an important requirement, and generally, at least 30 minutes or more is spent to prepare the aqueous solution of alkali silicate.
It must be added so that the pH is 1-7. Furthermore, when the acidic aqueous solution of titanium is added to the alkaline silicate aqueous solution or the alkaline silicate aqueous solution, or after the acidic aqueous solution of titanium is added, the aqueous solution is heated at a temperature of 80 ° C. to the boiling point of the aqueous solution.
上記製造方法の態様は具体的には次ぎのような態様とす
れば好適である。Specifically, the aspect of the above-mentioned manufacturing method is preferably the following aspect.
（イ） 珪酸アルカリ水溶液にpHが１〜７好ましくは
２．５〜５．５となるに必要なチタンの酸性水溶液を８
０℃以上の該珪酸アルカリ水溶液に保持して３０分〜１
２０分程度の時間好ましくは出来るだけゆっくり添加す
る方法。(A) The acidic aqueous solution of titanium necessary for the pH to be 1 to 7, preferably 2.5 to 5.5 is added to the alkaline silicate aqueous solution.
Keeping in the alkali silicate aqueous solution at 0 ° C or higher for 30 minutes to 1
Method of adding for about 20 minutes, preferably as slowly as possible.
（ロ） ２０〜５０℃の珪酸アルカリ水溶液に該珪酸ア
ルカリ水溶液の２５〜５０％を中和するに必要な量のチ
タンの酸性水溶液を５〜２０分あるいはそれ以上の時間
で添加する。この状態ではシリカ、チタニア或いはチタ
ニア／シリカ複合体の粒子の沈澱はない。勿論予め酸化
チタンの存在下に上記反応を実施するときは該酸化チタ
ンは分散した状態である。次いで上記水溶液に最終の水
溶液pHが１〜７好ましくは２．５〜５．５となるように
残余のチタンの酸性水溶液を４０分〜１２０分あるいは
それ以上の時間を費やして、８０℃以上の温度下に加え
る方法。(B) An acidic aqueous solution of titanium necessary for neutralizing 25 to 50% of the alkaline silicate aqueous solution at 20 to 50 ° C. is added for 5 to 20 minutes or longer. In this state, there is no precipitation of particles of silica, titania or titania / silica composite. Of course, when the above reaction is carried out in the presence of titanium oxide in advance, the titanium oxide is in a dispersed state. Then, the remaining acidic aqueous solution of titanium is added to the above aqueous solution for 40 minutes to 120 minutes or longer so that the final pH of the aqueous solution is 1 to 7, preferably 2.5 to 5.5, and the temperature is kept at 80 ° C. or higher. How to add at temperature.
前記方法に於ける８０℃以上〜水溶液の沸点の温度での
加熱は好ましくは反応時に上記温度に保持するのが好適
であるが、前記（ロ）に示したように該反応の前段では
該温度に加熱せず実施する場合が良好なケースもある。
従ってチタニア／シリカ複合体の製造条件に応じて予め
決定して実施するのがよい。In the above method, heating at a temperature of 80 ° C. or higher to the boiling point of the aqueous solution is preferably maintained at the above temperature during the reaction, but as shown in the above (b), the temperature may be increased before the reaction. In some cases, it is preferable to carry out heating without heating.
Therefore, it is preferable to determine in advance according to the manufacturing conditions of the titania / silica composite, and to carry out.
上記方法で得られたチタニア／シリカ複合体は前記した
ような性状を有する固体状物として得られる。これらの
固体状物は必要に応じて粉砕して使用するとよい。The titania / silica composite obtained by the above method is obtained as a solid substance having the above-mentioned properties. These solid substances may be crushed as needed before use.
＜効 果＞ 本発明のチタニア／シリカ複合体は前記のようにすぐれ
た不透明度を付与するだけでなく、吸油量が大きくしか
も屈折率が大きい充填剤となる。従って、従来シリカ及
びチタニアが使用されている分野例えば紙用充填剤、塗
料用充填、ゴム用補強充填剤等として好適に使用され
る。<Effect> The titania / silica composite of the present invention not only imparts excellent opacity as described above, but also serves as a filler having a large oil absorption and a large refractive index. Therefore, it is preferably used in fields where silica and titania have been conventionally used, for example, as fillers for papers, fillers for paints, reinforcing fillers for rubbers, and the like.
＜実施例＞ 本発明を更に具体的に説明するために以下実施例を挙げ
て説明するが本発明はこれらの実施例に限定されるもの
ではない。<Examples> In order to more specifically describe the present invention, examples will be described below, but the present invention is not limited to these examples.
尚実施例において測定した種々の性状の測定方法は次ぎ
の通りである。The methods for measuring various properties measured in the examples are as follows.
（ｉ）一粒子径 透過型電子顕微鏡により測定した。(I) Single particle diameter Measured with a transmission electron microscope.
（ii）比表面積 簡易型ＢＥＴ法により測定した。(Ii) Specific surface area Measured by a simple BET method.
（iii）吸油量 ＪＩＳ Ｋ５１０１顔料試験方法により測定した。(Iii) Oil absorption amount Measured by the JIS K5101 pigment test method.
（iv）不透明度 内容積１００ｍｌのメスシリンダーの底部に、白紙に黒
点を書いた紙を敷き、ラッカー塗料（木材用クリヤーラ
ッカ（関西ペイント（株）製、セルバNo.６１）に試料
２ｇを分散させ、このラッカー塗料を少しづつメスシリ
ンダー内に投入し、黒点が見えなくなる時の、投入塗料
の合計容積（ｍｌ）を計った。(Iv) Opacity On the bottom of a graduated cylinder with an internal volume of 100 ml, lay a piece of white paper with black dots on it and disperse 2 g of the sample in lacquer paint (clear lacquer for wood (Kansai Paint Co., Ltd., Selva No. 61)). Then, this lacquer paint was gradually put into the graduated cylinder, and the total volume (ml) of the put paint when the black dots disappeared was measured.
（ｖ）屈折率 試料１〜２ｇを試験管へ入れ、１ブロムナフタリン溶液
を５〜１０ｍｌ添加し、スラリー化する。次ぎに試験管
へ温度計を入れ、軽く撹拌した後、温度を５〜５０℃ま
で変化させ、溶液が赤色に変色した時の温度を測定し
た。この温度より屈折率を算出した。(V) Refractive index Samples 1 to 2 g are put into a test tube, and 5 to 10 ml of 1 bromonaphthalene solution is added to form a slurry. Next, a thermometer was put in the test tube, and after lightly stirring, the temperature was changed to 5 to 50 ° C., and the temperature when the solution turned red was measured. The refractive index was calculated from this temperature.
（vi）非晶質の確認 Ｘ線回析装置により結晶ピーク位置の有無により確認し
た。(Vi) Confirmation of Amorphousness The presence or absence of a crystal peak position was confirmed by an X-ray diffractometer.
実施例１ 市販の珪酸ソーダSiO2４８．９９％、Na2O２２．３２
％、７１０ｍｌと水５２９０ｍｌを８の外部加熱方式
の反応槽へ投入し撹拌する。次に酸化チタン１７ｇと硫
酸濃度２３％（TiO2濃度４０％）の硫酸チタン３８２ｍ
ｌを添加する。添加後昇温し反応温度を９５℃とし、こ
の状態で５分間撹拌した後、前記硫酸チタン６６４ｍｌ
を９０分で添加し反応液のpHを３．０とし反応を終了す
る。この反応液を濾過水洗した後、乾燥、粉砕しチタニ
ア／シリカの複合体を得た。結果を第１表に示した。Example 1 Commercially available sodium silicate SiO 2 48.99%, Na 2 O 22.32
%, 710 ml and 5290 ml of water are charged into an external heating type reaction tank of 8 and stirred. Next, 17 g of titanium oxide and 382 m of titanium sulfate having a sulfuric acid concentration of 23% (TiO 2 concentration of 40%).
l is added. After the addition, the temperature is raised to a reaction temperature of 95 ° C., and the mixture is stirred for 5 minutes in this state, and then 664 ml of titanium sulfate is added.
Is added in 90 minutes to adjust the pH of the reaction solution to 3.0 and the reaction is completed. The reaction solution was filtered, washed with water, dried and pulverized to obtain a titania / silica composite. The results are shown in Table 1.
実施例２ 実施例１においてNa2O濃度１．９％のボウ硝3157ｍｌ、
水２１３３ｍｌにした以外は同様にして製造した。その
結果を第１表に示した。Example 2 3157 ml of Glauber's salt having a Na 2 O concentration of 1.9% in Example 1,
It was manufactured in the same manner except that 2133 ml of water was used. The results are shown in Table 1.
実施例３ 市販の珪酸ソーダSiO2２４．８７％、Na2O７．６３％１
３９９ｍｌとNa2O濃度１．９％のボウ硝３１５７ｍｌ、
水１４４４ｍｌを外部加熱方式の反応槽へ投入し、第１
硫酸チタン２５７ｍｌ、第２硫酸チタン４４０ｍｌとし
た以外は実施例１と同様にして製造した。結果を第１表
に示した。Example 3 Commercially available sodium silicate SiO 2 24.87%, Na 2 O 7.63% 1
399 ml and 3157 ml of Glauber's salt with Na 2 O concentration of 1.9%,
Add 1444 ml of water to the external heating type reaction tank and
The procedure of Example 1 was repeated except that 257 ml of titanium sulfate and 440 ml of second titanium sulfate were used. The results are shown in Table 1.
実施例４ 市販の珪酸ソーダSiO2２８．２６％、Na2O９．５０％、
１２３１ｍｌとボウ硝３１５７ｍｌ、水１６１２ｍｌを
外部加熱方式の反応槽へ投入し、撹拌しながら、前記硫
酸チタン１６１ｍｌを添加し、９５℃まで昇温し、この
温度で５分間撹拌した後、２２％硫酸６５０ｍｌを９０
分で添加し、反応液のpHを３．４とし反応を終了した。Example 4 Commercially available sodium silicate SiO 2 28.26%, Na 2 O 9.50%,
1231 ml, Glauber's salt 3157 ml, and water 1612 ml were charged into an external heating type reaction tank, 161 ml of the titanium sulfate was added with stirring, the temperature was raised to 95 ° C., and the mixture was stirred for 5 minutes at this temperature, then 22% sulfuric acid was added. 650 ml to 90
The pH of the reaction solution was adjusted to 3.4 and the reaction was completed.
以下は実施例１と同様にした。The subsequent steps were the same as in Example 1.
結果を第１表に示した。The results are shown in Table 1.
実施例５ 市販の珪酸ソーダSiO2４８．９９％、Na2O２２．３２
％、７１０ｍｌと水５２９０ｍｌを８の外部加熱方式
の反応槽へ投入し撹拌する。次に酸化チタン１７ｇを投
入し、良く分散させる。その後昇温し、反応温度９５℃
とした後硫酸濃度２３％（TiO2濃度４．０％）の硫酸チ
タン１０４６ｍｌを１２０分で添加し反応液のpHを３．
１として反応を終了した。この反応液を濾過・水洗した
後乾燥・粉砕し、チタニア／シリカ複合体を得た。Example 5 Commercially available sodium silicate SiO 2 48.99%, Na 2 O 22.32
%, 710 ml and 5290 ml of water are charged into an external heating type reaction tank of 8 and stirred. Next, 17 g of titanium oxide is added and well dispersed. After that, the temperature is raised and the reaction temperature is 95 ° C.
After that, 1046 ml of titanium sulfate having a sulfuric acid concentration of 23% (TiO 2 concentration of 4.0%) was added in 120 minutes to adjust the pH of the reaction solution to 3.
The reaction was terminated as 1. The reaction solution was filtered, washed with water, dried and pulverized to obtain a titania / silica composite.
結果を第１表に示した。The results are shown in Table 1.
比較例１ 市販の含水珪酸であるトクシールＰ、ファインシールＸ
−４０（徳山曹達製）ミズカシールP526（水沢化学製）
サイカイド２４４（富士デビソンＫ．Ｋ．製）について
不透明度を測定した結果を第１表に示した。Comparative Example 1 Tokuseal P and Fineseal X, which are commercially available hydrous silicates
-40 (manufactured by Tokuyama Soda) Mizuka Seal P526 (manufactured by Mizusawa Chemical)
Table 1 shows the results of measuring the opacity of CYCIDE 244 (manufactured by Fuji Devison KK).
比較例２ 市販の酸化チタン（チタン工業製）について実施例１と
同様に測定した結果を第１表に示した。Comparative Example 2 Table 1 shows the measurement results of commercially available titanium oxide (manufactured by Titanium Industry Co., Ltd.) in the same manner as in Example 1.
比較例３ 実施例５において、反応温度を５０℃にした以外は同様
にして製造した。その結果を第１表に示した。Comparative Example 3 Production was carried out in the same manner as in Example 5, except that the reaction temperature was 50 ° C. The results are shown in Table 1.
比較例４ 市販の珪酸ソーダSiO2２４．８７％、Na2O７．６３％１
９３０ｍｌと試薬のNa2OSO4６８７ｇを水４０７０ｍｌ
に溶解した溶液を外部加熱方式の反応槽へ投入し、第１
段硫酸チタン２０２ｍｌ、第２段硫酸チタン７９０ｍｌ
とした以外は実施例１と同様にして製造した。結果を第
１表に示した。Comparative Example 4 Commercially available sodium silicate SiO 2 24.87%, Na 2 O 7.63% 1
930 ml and reagent Na 2 OSO 4 687 g in water 4070 ml
The solution dissolved in is put into a reaction tank of external heating system,
Stage titanium sulfate 202ml, 2nd stage titanium sulfate 790ml
Was manufactured in the same manner as in Example 1 except that The results are shown in Table 1.
比較例５ 実施例５において、硫酸チタンの添加時間を１５分とし
た以外は同様に実施した。その結果を第１表に示した。Comparative Example 5 The same procedure as in Example 5 was carried out except that the addition time of titanium sulfate was changed to 15 minutes. The results are shown in Table 1.
Claims (2)
よって測定した不透明度が０．５〜３０、吸油量が１０
０ｍｌ／１００ｇ〜３００ｍｌ／１００ｇ及び比表面積
が５０〜４００m2／ｇで且つチタニアがシリカに対して
０．５〜３０重量％含まれてなる非晶質のチタニア／シ
リカ複合体。1. A primary particle size of 10 to 100 nm, an opacity of 0.5 to 30 measured by a volume method, and an oil absorption of 10.
An amorphous titania / silica composite having 0 ml / 100 g to 300 ml / 100 g, a specific surface area of 50 to 400 m 2 / g and 0.5 to 30% by weight of titania based on silica.
ルカリ水溶液にpHが１〜７になるようにチタンの酸性水
溶液を少くとも３０分以上の時間を費やして添加し、８
０℃〜該水溶液の沸点の温度に加熱することを特徴とす
るチタニア／シリカの複合体の製法。2. An acidic aqueous solution of titanium is added to an alkaline silicate aqueous solution in the presence or absence of titanium oxide so as to have a pH of 1 to 7, spending at least 30 minutes or more, and 8
A process for producing a titania / silica composite, which comprises heating to a temperature of 0 ° C. to the boiling point of the aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3376986A JPH0645451B2 (en) | 1986-02-20 | 1986-02-20 | Titania / silica composite and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3376986A JPH0645451B2 (en) | 1986-02-20 | 1986-02-20 | Titania / silica composite and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62197309A JPS62197309A (en) | 1987-09-01 |
| JPH0645451B2 true JPH0645451B2 (en) | 1994-06-15 |
Family
ID=12395654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3376986A Expired - Lifetime JPH0645451B2 (en) | 1986-02-20 | 1986-02-20 | Titania / silica composite and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0645451B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0778319A1 (en) * | 1995-12-08 | 1997-06-11 | Oji Paper Company Limited | Titania/silica composite particles and process for producing the same |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3557747B2 (en) * | 1995-08-23 | 2004-08-25 | 日板パッケージ株式会社 | Corrugated cardboard and deodorizing element using titanium oxide containing paper |
| FR2773167A1 (en) * | 1997-12-30 | 1999-07-02 | Rhodia Chimie Sa | PROCESS FOR THE PREPARATION OF MIXED MINERAL FLOCKS BASED ON TIO2, COMPOSITION BASED ON TIO2 AND SIO2 AND ITS USE AS AN OPACIFYING AGENT IN PARTICULAR IN THE PAPER INDUSTRY |
| JP3110011B2 (en) | 1998-01-28 | 2000-11-20 | ジーイー横河メディカルシステム株式会社 | MRI apparatus and mobile table |
| FR2782520B1 (en) * | 1998-08-20 | 2002-04-05 | Rhodia Chimie Sa | USE OF TITANIUM DIOXIDE AS AN ANTI-UV AGENT IN A RUBBER COMPOSITION |
| TWI292322B (en) * | 2000-09-25 | 2008-01-11 | Shiseido Co Ltd | Metal oxide/silica complex and cosmetics containing the same |
| DE10062449A1 (en) * | 2000-12-14 | 2002-06-20 | Degussa | Doped precipitated silica |
| DE102006004344B4 (en) * | 2006-01-30 | 2008-11-13 | Kronos International, Inc. | High-opacity titanium dioxide pigment and method of preparation |
| JP7031229B2 (en) * | 2017-10-31 | 2022-03-08 | 住友ゴム工業株式会社 | Golf club grips and golf clubs |
-
1986
- 1986-02-20 JP JP3376986A patent/JPH0645451B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0778319A1 (en) * | 1995-12-08 | 1997-06-11 | Oji Paper Company Limited | Titania/silica composite particles and process for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62197309A (en) | 1987-09-01 |
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