JPS63123815A - Neutral titania sol and production thereof - Google Patents
Neutral titania sol and production thereofInfo
- Publication number
- JPS63123815A JPS63123815A JP26686186A JP26686186A JPS63123815A JP S63123815 A JPS63123815 A JP S63123815A JP 26686186 A JP26686186 A JP 26686186A JP 26686186 A JP26686186 A JP 26686186A JP S63123815 A JPS63123815 A JP S63123815A
- Authority
- JP
- Japan
- Prior art keywords
- titania sol
- sol
- acid
- acidic
- neutral
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 230000007935 neutral effect Effects 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 230000002378 acidificating effect Effects 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000012670 alkaline solution Substances 0.000 claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229940106681 chloroacetic acid Drugs 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract 6
- 229960000583 acetic acid Drugs 0.000 claims abstract 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 claims abstract 2
- 229940005991 chloric acid Drugs 0.000 claims abstract 2
- 229960000443 hydrochloric acid Drugs 0.000 claims abstract 2
- 229940074355 nitric acid Drugs 0.000 claims abstract 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 8
- 239000010419 fine particle Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 5
- 238000001935 peptisation Methods 0.000 abstract description 5
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 abstract description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 abstract description 3
- 229920000642 polymer Polymers 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001879 gelation Methods 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 4
- 239000002537 cosmetic Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000010413 gardening Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、中性チタニアゾル及びその製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a neutral titania sol and a method for producing the same.
本発明の中性チタニアゾルは、種々の用途に適しており
、例えば、その紫外線遮断効果を利用した化粧品などの
原料として有用なものである。The neutral titania sol of the present invention is suitable for various uses, and is useful, for example, as a raw material for cosmetics that utilize its ultraviolet blocking effect.
一般に、大部分の粒子の大きさが０．１μｍ以下のチタ
ニア微粉末は、例えば樹脂の膜或は成型物に配合された
とき可視光線を透過させ、一方、紫外線を遮断して紫外
線によって変色、変質する物質を保護するので、食品や
医薬品などのプラスチック包装材、施設Ｓ園芸用プラス
チック被覆材、化粧品などに利用されている。このよう
なチタニア微粉末は、硫酸チタン水溶液を加熱加水分解
して析出する水酸化チタン凝集物を中和、洗浄し、塩酸
、硝酸などの酸を添加して該凝集物を解膠してｐＨ１〜
３のチタニアゾルを生成させ、次にこのゾルを中和した
後濾過、洗浄、乾燥、粉砕して得られるのが普通である
。Generally, fine titania powder, most of which has a particle size of 0.1 μm or less, transmits visible light when incorporated into a resin film or molded product, while blocking ultraviolet rays and discoloring due to ultraviolet rays. Because it protects substances that deteriorate, it is used in plastic packaging materials for foods and medicines, plastic covering materials for gardening facilities, cosmetics, etc. Such fine titania powder is produced by heating and hydrolyzing an aqueous titanium sulfate solution, neutralizing and washing the precipitated titanium hydroxide aggregates, and adding an acid such as hydrochloric acid or nitric acid to peptize the aggregates to a pH of 1. ~
It is usually obtained by producing the titania sol of No. 3, and then neutralizing this sol, followed by filtration, washing, drying, and pulverization.
一般にチタニアゾルは、前記のように塩酸、硝酸などの
酸性物質によって分散の安定化が達成されてｐＨ１〜３
の酸性を示すために、このままでは各種の用途に適さな
い。Generally, the dispersion of titania sol is stabilized by acidic substances such as hydrochloric acid and nitric acid as mentioned above, and the pH range is 1 to 3.
Because of its acidic nature, it is unsuitable for various uses as it is.
酸性物質を除去するために、中和−洗浄、イオン交換、
限外濾過などを行なうことが考えられるが、このような
方法で酸性物質を除去するとチタニアゾルのゲル化が起
こる。To remove acidic substances, neutralization-washing, ion exchange,
Ultrafiltration or the like may be considered, but if acidic substances are removed by such a method, gelation of the titania sol will occur.
そこで、一般には酸性チタニアゾルを中和、洗浄、乾燥
、粉砕して乾燥粉末として利用せざるを得ないが、この
場合ゾルの様な分散状態を再現できず、微粒子としての
特徴を十分に引き出すことができない現状である。Therefore, acidic titania sol generally has to be neutralized, washed, dried, and pulverized to be used as a dry powder, but in this case, it is not possible to reproduce the dispersion state like that of a sol, and it is difficult to fully bring out the characteristics of fine particles. The current situation is that this is not possible.
本発明者等は、上記問題点の解決策について幅広く検討
するなかで、酸性チタニアゾルの分散性を保持した状態
で酸性物質を除去できれば、ゾル本来の物性をその＊主
各種の用途に利用できることに着目して種々研究した。While extensively considering solutions to the above problems, the present inventors realized that if the acidic substances could be removed while maintaining the dispersibility of the acidic titania sol, the original physical properties of the sol could be utilized for various purposes. We focused on this and conducted various research.
その結果、（イ）上記酸性チタニアゾル中の酸性物質を
除去したり、中和したりすると直ちにゲル化を起こし、
チタニア微粒子が凝集するが、（ロ）ポリビニルアルコ
ールなどの水溶性高分子化合物を酸性チタニアゾルに添
加した後アルカリ溶液を加えて中和するとゲル化が起こ
らず、均一に分散した安定な状態の中性チタニアゾルが
得られ、（ハ）このチタニアゾルは容易に塗膜化でき、
その塗膜は紫外線吸収能をもつものであるなどの知見が
得られた。本発明はこれらの知見に基づくものである。As a result, (a) gelation occurs immediately when the acidic substance in the acidic titania sol is removed or neutralized;
Titania fine particles aggregate, but (b) If a water-soluble polymer compound such as polyvinyl alcohol is added to an acidic titania sol and then neutralized by adding an alkaline solution, gelation does not occur, and a neutral, uniformly dispersed state is created. A titania sol is obtained, and (c) this titania sol can be easily formed into a coating film.
Findings such as that the coating film has ultraviolet absorption ability were obtained. The present invention is based on these findings.
本願の第一の発明は、チタニア微粒子の酸性水分散液に
分散安定化剤としての水溶性高分子化合物及び中和剤と
してのアルカリ溶液を配合したことを特徴とする中性チ
タニアゾルであり、第二の発明は、水酸化チタンを一塩
基酸またはその塩で解膠して得られる酸性チタニアゾル
と水溶性高分子化合物とを混合した後膣ゾル中にアルカ
リ溶液を加えることを特徴とする中性チタニアゾルの製
造方法である。The first invention of the present application is a neutral titania sol, which is characterized in that a water-soluble polymer compound as a dispersion stabilizer and an alkaline solution as a neutralizing agent are blended into an acidic water dispersion of fine titania particles. The second invention is a neutral titania sol obtained by peptizing titanium hydroxide with a monobasic acid or a salt thereof, and an alkaline solution is added to the vaginal sol after mixing the acidic titania sol and a water-soluble polymer compound. This is a method for producing titania sol.
本発明の中性チタニアゾルは、チタニア微粒子が分散安
定化剤によって水中に均一に分散しているものであり、
このものを必要に応じて希釈し、塗布、乾燥することに
より分散状態が保持された透明な塗膜が得られるので、
例えば食料品包装材の表面に塗布する紫外線遮断用樹脂
組成物として使用することができ石。また、液状の化粧
材に配合して紫外線遮断用化粧品として使用することも
できる。The neutral titania sol of the present invention has titania fine particles uniformly dispersed in water by a dispersion stabilizer,
By diluting this material as necessary, applying it, and drying it, a transparent coating film that maintains its dispersed state can be obtained.
For example, stone can be used as a UV blocking resin composition applied to the surface of food packaging materials. It can also be used as a UV-blocking cosmetic by blending it into a liquid cosmetic material.
本発明のチタニアゾルの成分であるチタニア微粒子とし
ては、例えば、チタニアゾルを紫外線遮断用樹脂姐成物
の原料として使用する場合は、その大部分が普通８０％
以上が０．０１〜０．１μｍの範囲内の大外さのものが
望ましい。As for the titania fine particles that are a component of the titania sol of the present invention, for example, when the titania sol is used as a raw material for an ultraviolet blocking resin composition, most of the titania particles are usually 80%
It is desirable that the diameter is within the range of 0.01 to 0.1 μm.
これより大きくなり過ぎると可視光線の光散乱能が増大
して透明性が損なわれる。一方、小さくなり過ぎると紫
外線の透過度が大きくなり好ましくない。なお、チタニ
アの結晶形には大別してルチル型とアナタース型がある
が、いずれの結晶形のものも、また両型の混合物も使用
で軽る。If it is too large, the light scattering ability of visible light will increase and transparency will be impaired. On the other hand, if it becomes too small, the transmittance of ultraviolet rays increases, which is not preferable. Incidentally, the crystal forms of titania can be roughly divided into rutile type and anatase type, but either crystal form or a mixture of both types can be used.
分散安定化剤としては水溶性高分子化合物が適当であ１
）、具体的には例えばポリビニルアルコール、カルボキ
シメチルセルロース、メチルセルロースなどが挙げられ
る。これらは各種の重合度のものがあるが、例えばポリ
ビニルアルコールの場合、重合度１９００〜２１００の
ものよりも重合度５００程度のものの方がＴｉＯ□濃度
の大きいチタニアゾルが得られ易いので低重合度のもの
が望ましい。A water-soluble polymer compound is suitable as a dispersion stabilizer.
), specific examples include polyvinyl alcohol, carboxymethyl cellulose, and methyl cellulose. These have various degrees of polymerization, but for example, in the case of polyvinyl alcohol, it is easier to obtain titania sol with a higher concentration of TiO□ with a degree of polymerization of about 500 than with a degree of polymerization of 1900-2100. Something is desirable.
チタニアゾルにおけるチタニア微粒子及び水溶性高分子
化合物の濃度は、安定な分散状態のゾルを形成する観点
からチタニア微粒子は、ＴｉＯ□として１〜１００ｇ／
（１、水溶性高分子化合物は、固形分として１〜１００
ｇ／ρが適当である。The concentration of titania fine particles and water-soluble polymer compound in titania sol is from 1 to 100 g/TiO□ from the viewpoint of forming a stable dispersed sol.
(1. The water-soluble polymer compound has a solid content of 1 to 100
g/ρ is appropriate.
中和剤としてのアルカリ溶液はアンモニア水溶液、水酸
化ナトリウム水溶液など酸の中和剤として普通に使用さ
れているものでよい。The alkaline solution as a neutralizing agent may be one commonly used as an acid neutralizing agent, such as an ammonia aqueous solution or a sodium hydroxide aqueous solution.
本発明のチタニアゾルには、必要に応じ樹脂、着色剤な
どを配合させてもよい。The titania sol of the present invention may be blended with a resin, a coloring agent, etc., if necessary.
本願の第二の発明は、中性チタニアゾルの製造法を提供
するものである。The second invention of the present application provides a method for producing a neutral titania sol.
本製造法においては、まず、水酸化チタンを一塩基酸ま
たはその塩で解膠処理して酸性のチタニアゾルを生ｒ＃
、させる。水酸化チタンは、例えば硫酸チタン溶液を加
熱加水分解して得られる。普通、このものをアンモニア
水などのアルカリ性物質で中和し、濾過、洗浄、親水し
て、内部に残存している硫酸根をできるだけ除去した後
この脱水物に塩酸、硝酸、酢酸、塩素酸、クロル酢酸な
どの一塩基酸を加えて解膠処理する。別法として、前記
の中和による脱硫酸根処理を行なうことなく、水酸化チ
タンに、硫酸根と反応して不溶性の硫酸塩を形成すると
同時に一価の酸を形成するような塩、例えば塩化バリウ
ムを添加して解膠処理することもできる。解膠処理で生
成するチタニアゾルは、一塩基酸を安定剤として含有し
ており、ｐＨ１〜３の酸性を示す。In this production method, titanium hydroxide is first peptized with a monobasic acid or its salt to produce acidic titania sol.
, let. Titanium hydroxide can be obtained, for example, by heating and hydrolyzing a titanium sulfate solution. Normally, this product is neutralized with an alkaline substance such as aqueous ammonia, filtered, washed, and hydrophilized to remove as much of the sulfuric acid groups remaining inside. Peptize by adding a monobasic acid such as chloroacetic acid. Alternatively, without carrying out the desulfation treatment by neutralization described above, titanium hydroxide may be treated with a salt that reacts with the sulfate radicals to form an insoluble sulfate salt and at the same time forms a monovalent acid, such as barium chloride. It is also possible to perform peptization treatment by adding . The titania sol produced by the peptization treatment contains a monobasic acid as a stabilizer and exhibits acidity with a pH of 1 to 3.
次に、上記の酸性チタニアゾルと水溶性高分子化合物溶
液を混合し、その後アルカリ溶液を加えて酸性ゾルを中
和する。水溶性高分子化合物溶液は、普通１〜ＳＯｇ／
ｌのＴｉＯ２濃度の酸性チタニアゾルに対して１〜１０
０ｇ／ｇの固形分濃度のものをＴｉＯ□／固形分（重量
比）が０．１〜５の範囲内の値になるように混合するの
が望ましい。混合の際、酸性チタニアゾルのＴ ｉ Ｏ
２濃度が前記範囲より高くなり過ぎると水溶性高分子化
合物溶液の固形分濃度に関係なく、安定な分散状態のゾ
ルが得られ難くなるので避けるべきである。Next, the acidic titania sol and the water-soluble polymer compound solution are mixed, and then an alkaline solution is added to neutralize the acidic sol. The water-soluble polymer compound solution is usually 1 to SOg/
1 to 10 for acidic titania sol with a TiO2 concentration of
It is desirable to mix those having a solid content concentration of 0 g/g so that the TiO□/solid content (weight ratio) is within the range of 0.1 to 5. During mixing, T i O of acidic titania sol
If the concentration of 2 is too high above the above range, it will be difficult to obtain a sol in a stable dispersed state, regardless of the solid content concentration of the water-soluble polymer compound solution, and should be avoided.
中和剤としてのアルカリ溶液は、酸性ゾルを中和するの
に必要な量添加すればよいが、目的とするｐＨ値に維持
するために適宜その量を調整できる。The alkaline solution as a neutralizing agent may be added in an amount necessary to neutralize the acidic sol, but the amount can be adjusted as appropriate to maintain the desired pH value.
本製造法は、酸性チタニアゾルと水溶性高分子化合物溶
液とを混合した後アルカリ溶液を加えて中和する方法で
あり、本方法によって酸性チタニアゾルはゲル化を起こ
すことなく、ｐＨ６〜８の領域の中性チタニアゾルを生
成させることができ、必要に応じて更にこのものにアン
モニア水などのアルカリ性物質或は酸性物質を適宜添加
することにより、アルカリ領域更には酸領域でのｐＨ調
整ができる。This production method is a method in which acidic titania sol and a water-soluble polymer compound solution are mixed and then neutralized by adding an alkaline solution.With this method, acidic titania sol can be produced in the pH range of 6 to 8 without causing gelation. A neutral titania sol can be produced, and by adding an alkaline substance such as aqueous ammonia or an acidic substance to this sol as necessary, the pH can be adjusted in an alkaline region or even an acid region.
水溶性高分子化合物を添加しなかったり、添加してもそ
の量が少なかったりすると、アルカリ溶液による中和に
よってゲル化が起こり、安定な分散状態の中性チタニア
ゾルが得られなくなる。If a water-soluble polymer compound is not added, or if it is added in a small amount, gelation will occur due to neutralization with an alkaline solution, making it impossible to obtain a neutral titania sol in a stable dispersed state.
本製造法で得られる中性チタニアゾルのＴ ； ０２濃
度は、一般に１〜４０ｇ／ｌ程度のものであるが、この
ものは、例えば沸点での加熱に対しても安定な分散状態
を保持しているので、用途、目的に応じて加熱してＴｉ
Ｏ２濃度を１００ｇ／１２程度まで濃縮してもよい。The neutral titania sol obtained by this production method generally has a T; Therefore, Ti can be heated depending on the use and purpose.
The O2 concentration may be concentrated to about 100 g/12.
また、本発明の中性チタニアゾルには中和反応によって
生成した塩化アンモニウム、塩化ナトリウム、硝酸アン
モニウム、硝酸ナトリウムなどの塩が含まれている。こ
れらの塩の存在はゾルの安定性を妨害するものでないが
、必要に応じて限外濾過、イオン交換などの手段で塩を
除去することができる。Further, the neutral titania sol of the present invention contains salts such as ammonium chloride, sodium chloride, ammonium nitrate, and sodium nitrate produced by the neutralization reaction. Although the presence of these salts does not interfere with the stability of the sol, the salts can be removed by means of ultrafiltration, ion exchange, etc., if necessary.
更に、本発明の中性チタニアゾルは中性域のｐＨを示す
ので製造面、用途面での取扱いが非常に容易である。Furthermore, since the neutral titania sol of the present invention exhibits a pH in the neutral range, it is very easy to handle in terms of production and use.
Ａ 酸性チタニアゾルの調製
チタン鉱石を硫酸と反応させ、得られる硫酸チタン溶液
を加熱加水分解して生成させた凝集メタチタン酸をＴｉ
０２３０重量％の水性スラリーとし、このスラリーをア
ンモニア水でｐＨ７に中和し、その後濾過、洗浄して硫
酸根を除去した。得られた脱水ケーキに３５％塩酸を加
えて解膠処理して、ＨＣＱとして１．５重量％含有する
ｐＨ１，５のチタニアゾルを得た。A. Preparation of acidic titania sol Ti
This slurry was neutralized to pH 7 with aqueous ammonia, and then filtered and washed to remove sulfate groups. The obtained dehydrated cake was peptized by adding 35% hydrochloric acid to obtain a titania sol having a pH of 1.5 and containing 1.5% by weight of HCQ.
Ｂ 中性チタニアゾルの製造
前記Ａ項で得られた酸性チタニアゾル（ＴｉＯｚ ＳＯ
ｇ／１２）２５０−に重合度５００のポリビニルアルコ
ール溶液（ＰＶＡ固形分５０ｇ／ｌ ）２５０＋１１１
２を添加した後攪拌しながらアンモニア水溶液を添加し
て中和し、ｐＨ７，２の中性チタニアゾル（ＴｉＯ２２
Ｓｇ／ｌ ）を得た。B Production of neutral titania sol Acidic titania sol (TiOz SO
g/12) 250- to polyvinyl alcohol solution with a degree of polymerization of 500 (PVA solid content 50 g/l) 250+111
After adding 2, it was neutralized by adding ammonia aqueous solution while stirring, and neutralized titania sol (TiO22) with pH 7.2 was added.
Sg/l) was obtained.
Ｃアルカリ性チタニアゾルの製造
Ｂ項で得られた中性チタニアゾルに更に１７％アンモニ
ア水を添加し、ｐＨ１０の安定なアルカリ性チタニアゾ
ル（ＴｉＯ２５ｇ／ρ）を得た。C. Production of alkaline titania sol 17% aqueous ammonia was further added to the neutral titania sol obtained in Section B to obtain a stable alkaline titania sol (TiO 25 g/ρ) with a pH of 10.
Ｄ 試験例
前記Ｂ項で得られたＴｉ０２２５ｇ／１２の中性チタニ
アゾル（ＰＶＡ固形分２５ｇ／ｆｆ）を０．０２５ｍｍ
の厚みを持つポリプロピレン透明フィルム（７ジタツク
、富士写真フィルム社製）上に２０番手バーコーダ（１
，８μの乾燥塗膜）で塗布し、自然乾燥して透明な塗膜
を形成させた。この塗膜を有するポリプロピレンフィル
ムの可視光線（５５０Ｉ◎μ）及び紫外線（３００ｍμ
）の透過率を島津ダブルビーム分光光度計ＵＶ−２４０
（島津製作所製）によって測定した結果それぞれ９７％
及び０％であった。（ブランクとしてポリプロピレンフ
ィルムにポリビニルアルコールＳＯｇ／（ｌを塗布しｊ
こものを使用した。このブランクのものは両者共に１０
０％であった。）主だ、この塗膜を有するポリプロピレ
ンフィルムを殺菌燈下で１０時間曝露したが、紫外線吸
収能は低下しなかった。D Test Example 0.025 mm of Ti0225g/12 neutral titania sol (PVA solid content 25g/ff) obtained in the above section B
A No. 20 barcoder (No. 1
A transparent coating film was formed by drying naturally. Visible light (550I◎μ) and ultraviolet light (300mμ) of the polypropylene film with this coating film
) Shimadzu double beam spectrophotometer UV-240
(manufactured by Shimadzu Corporation), each result was 97%.
and 0%. (As a blank, apply polyvinyl alcohol SOg/(l) to a polypropylene film.
I used small things. Both of these blanks are 10
It was 0%. ) Mainly, when a polypropylene film with this coating was exposed under germicidal light for 10 hours, the UV absorption capacity did not decrease.
従来のチタニアゾルはｐＨ１〜３の酸性を示すものであ
るが、本発明のものは、ｐＨ６〜８の中性域のチタニア
ゾルで、取扱いが容易であり゛、しがも用途が限定され
ることなく、幅広い利用が期待される。また、本発明の
中性チタニアゾルは過酷な条件下の使用においてもゲル
化することなく、安定した分散状態を保持している。更
に、本発明の中性チタニアゾルは加熱処理に対しても安
定であり、目的、用途に応じて適宜加熱して所望のＴ
！ ０２濃度に主で濃縮することができる。Conventional titania sol is acidic with a pH of 1 to 3, but the titania sol of the present invention is a neutral titania sol with a pH of 6 to 8, and is easy to handle, without limiting its uses. , is expected to be widely used. Further, the neutral titania sol of the present invention does not gel even when used under severe conditions and maintains a stable dispersion state. Furthermore, the neutral titania sol of the present invention is stable against heat treatment, and can be heated appropriately depending on the purpose and use to achieve the desired T.
! It can be mainly concentrated to 0.02 concentration.
Claims (1)
での水溶性高分子化合物及び中和剤としてのアルカリ溶
液を配合したことを特徴とする中性チタニアゾル。 ２、水溶性高分子化合物がポリビニルアルコールである
ことを特徴とする特許請求の範囲第１項に記載の中性チ
タニアゾル。 ３、チタニア微粒子をＴｉＯ＿２として１〜５０ｇ／ｌ
含有することを特徴とする特許請求の範囲第１項に記載
の中性チタニアゾル。 ４、水酸化チタンを一塩基酸またはその塩で解膠して得
られる酸性チタニアゾルと水溶性高分子化合物とを混合
した後該ゾル中にアルカリ溶液を加えることを特徴とす
る中性チタニアゾルの製造方法。 ５、一塩基酸が塩酸、硝酸、酢酸、塩素酸、クロル酢酸
から選択される少なくとも一種であることを特徴とする
特許請求の範囲第４項に記載の方法。 ６、酸性チタニアゾル中のチタニアの濃度がＴｉＯ＿２
として１〜１００ｇ／ｌであることを特徴とする特許請
求の範囲第４項に記載の方法。[Scope of Claims] 1. A neutral titania sol, characterized in that a water-soluble polymer compound as a dispersion stabilizer and an alkaline solution as a neutralizing agent are blended into an acidic water dispersion of fine titania particles. 2. The neutral titania sol according to claim 1, wherein the water-soluble polymer compound is polyvinyl alcohol. 3. Titania fine particles as TiO_2 from 1 to 50 g/l
The neutral titania sol according to claim 1, which contains the neutral titania sol according to claim 1. 4. Production of a neutral titania sol, which is characterized by mixing an acidic titania sol obtained by peptizing titanium hydroxide with a monobasic acid or a salt thereof and a water-soluble polymer compound, and then adding an alkaline solution to the sol. Method. 5. The method according to claim 4, wherein the monobasic acid is at least one selected from hydrochloric acid, nitric acid, acetic acid, chloric acid, and chloroacetic acid. 6. The concentration of titania in the acidic titania sol is TiO_2
5. The method according to claim 4, characterized in that the amount of 1 to 100 g/l is 1 to 100 g/l.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26686186A JPS63123815A (en) | 1986-11-10 | 1986-11-10 | Neutral titania sol and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26686186A JPS63123815A (en) | 1986-11-10 | 1986-11-10 | Neutral titania sol and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS63123815A true JPS63123815A (en) | 1988-05-27 |
Family
ID=17436677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26686186A Pending JPS63123815A (en) | 1986-11-10 | 1986-11-10 | Neutral titania sol and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63123815A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100383220B1 (en) * | 2000-06-15 | 2003-05-12 | 한국화학연구원 | A process for preparing of neutral TiO2 sols having transparence in visible range |
| KR100475687B1 (en) * | 2002-10-26 | 2005-03-10 | 한국과학기술원 | Preparation method of titania particles |
| GB2416164A (en) * | 2004-07-15 | 2006-01-18 | Wen-Chuan Liu | A method for synthesising a nanometre-scale titanium dioxide gel |
| WO2009133895A1 (en) | 2008-05-02 | 2009-11-05 | ポーラ化成工業株式会社 | Titania fine-particle composite and compositons coantining the titania fine-particle composite |
| KR101028506B1 (en) | 2008-12-17 | 2011-04-11 | 한국원자력연구원 | Manufacturing method of titanium dioxide using radioactive rays |
-
1986
- 1986-11-10 JP JP26686186A patent/JPS63123815A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100383220B1 (en) * | 2000-06-15 | 2003-05-12 | 한국화학연구원 | A process for preparing of neutral TiO2 sols having transparence in visible range |
| KR100475687B1 (en) * | 2002-10-26 | 2005-03-10 | 한국과학기술원 | Preparation method of titania particles |
| GB2416164A (en) * | 2004-07-15 | 2006-01-18 | Wen-Chuan Liu | A method for synthesising a nanometre-scale titanium dioxide gel |
| WO2009133895A1 (en) | 2008-05-02 | 2009-11-05 | ポーラ化成工業株式会社 | Titania fine-particle composite and compositons coantining the titania fine-particle composite |
| US8945520B2 (en) | 2008-05-02 | 2015-02-03 | Pola Chemical Industries Inc. | Titania fine-particle composite and compositions containing the titania fine-particle composite |
| US9144541B2 (en) | 2008-05-02 | 2015-09-29 | Pola Chemical Industries Inc. | Titania fine-particle composite and compositions containing the titania fine-particle composite |
| KR101028506B1 (en) | 2008-12-17 | 2011-04-11 | 한국원자력연구원 | Manufacturing method of titanium dioxide using radioactive rays |
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