JP3512838B2 - Method for producing flaky zinc oxide powder - Google Patents
Method for producing flaky zinc oxide powderInfo
- Publication number
- JP3512838B2 JP3512838B2 JP31339093A JP31339093A JP3512838B2 JP 3512838 B2 JP3512838 B2 JP 3512838B2 JP 31339093 A JP31339093 A JP 31339093A JP 31339093 A JP31339093 A JP 31339093A JP 3512838 B2 JP3512838 B2 JP 3512838B2
- Authority
- JP
- Japan
- Prior art keywords
- zinc
- flaky
- zinc oxide
- oxide powder
- solution
- 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 - Fee Related
Links
Description
【０００１】[0001]
【産業上の利用分野】本発明は薄片状酸化亜鉛粉末の製
造方法に関する。さらに詳細には任意の平均粒径で狭い
粒径分布を有する紫外線遮蔽能に優れた、例えば、化粧
料、樹脂、繊維、包材、塗料等への紫外線遮蔽用充填剤
として好適な薄片状酸化亜鉛粉末の製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing flaky zinc oxide powder. More specifically, flaky oxidization having a narrow particle size distribution with an arbitrary average particle size and excellent in UV screening ability, which is suitable as a UV screening filler for, for example, cosmetics, resins, fibers, packaging materials, paints, etc. The present invention relates to a method for producing zinc powder.
【０００２】近年、オゾンホールによる地表到達太陽光
の紫外線量の増加は、主としてＵＶＢ（２９０〜３２０
ｎｍ波長の紫外線）により生じる日焼けや雪焼けによる
皮膚の急性炎症、或いは主としてＵＶＡ（３２０〜４０
０ｎｍ波長の紫外線）の繰り返し照射により生じる皮膚
の老化、更にはメラノーマ等の皮膚癌増大等として生物
に悪影響を与えるのみならず、工業製品、衣料、食物、
住宅等に於いても紫外線劣化の増大を惹起するとして、
この問題解決が重要な課題となって来ている。In recent years, an increase in the amount of ultraviolet rays of sunlight reaching the surface due to ozone holes is mainly due to UVB (290 to 320).
Acute inflammation of the skin due to sunburn and snowburn caused by UV rays (nm wavelength UV) or mainly UVA (320-40)
Aging of the skin caused by repeated irradiation of (0 nm wavelength ultraviolet ray) and further increase of skin cancer such as melanoma not only adversely affect the organism, but also industrial products, clothing, food,
It is said that it causes an increase in ultraviolet deterioration even in houses, etc.
Solving this problem has become an important issue.
【０００３】[0003]
【従来の技術】従来より紫外線による影響を回避する目
的より紫外線を吸収、散乱する有機物や無機物、例えば
パラアミノ安息香酸やサリチル酸類等の有機物や、酸化
チタン、酸化亜鉛、酸化鉄等の無機化物を塗布、混合す
ることは広く行われている。しかし紫外線遮蔽用の有機
物質は肌への刺激性や光により分解したり又は性能が低
下する等の耐久性に問題がある。一方、無機物は材料自
身の安定性及び紫外線吸収能に優れており、中でも酸化
亜鉛は優れた紫外線吸収能を有する。ところで広く流通
している顔料用の酸化亜鉛は、粒径が大きく触感や透明
性に劣る為、化粧料等の用途では超微粒子の酸化亜鉛の
検討がされている。しかしながら超微粒子酸化亜鉛は、
良好な紫外線遮蔽能及び透明性は満足するものの、微粒
子であるが故に表面積が大きく活性に富むので有機物と
接触した場合有機物と反応したりその分解を促進すると
云う弊害があった。それ故、隠ぺい性、透明性に優れ且
つ有機物との反応性が激しくない酸化亜鉛の開発が希求
されている。2. Description of the Related Art Conventionally, organic substances and inorganic substances that absorb and scatter ultraviolet rays for the purpose of avoiding the influence of ultraviolet rays, for example, organic substances such as para-aminobenzoic acid and salicylic acid, and inorganic substances such as titanium oxide, zinc oxide and iron oxide. Coating and mixing are widely performed. However, organic substances for shielding ultraviolet rays have a problem in durability such as irritation to the skin, decomposition by light, or deterioration in performance. On the other hand, the inorganic material is excellent in stability and ultraviolet ray absorbing ability of the material itself, and among them, zinc oxide has excellent ultraviolet ray absorbing ability. By the way, zinc oxide for pigments, which is widely distributed, has a large particle size and is inferior in touch and transparency, and therefore ultrafine zinc oxide has been studied for use in cosmetics and the like. However, ultrafine zinc oxide
Although satisfactory ultraviolet ray shielding ability and transparency are satisfied, since they are fine particles, they have a large surface area and are highly active, so that they have the adverse effect of reacting with organic substances or promoting their decomposition when they come into contact with organic substances. Therefore, the development of zinc oxide, which is excellent in hiding property and transparency, and which does not have strong reactivity with organic substances, is desired.
【０００４】以上の要求を満たす材料の一つとして薄片
状酸化亜鉛が考えられ、その製造方法も公知である。例
えば特公昭５５−２５１３３号には「硫酸亜鉛を含む酸
性水溶液にアンモニアガスを接触吸収させることによ
り、酸性領域で結晶体を析出させる塩基性硫酸亜鉛板状
結晶体の製造方法」が教示されており、この用途として
白色顔料用の板状酸化亜鉛粉末が記載されている。しか
しながら該方法で得られたで得られた板状酸化亜鉛粉末
は粒径が最高数百μｍ、厚さ数μｍ以上に達するので、
触感に劣る上に単位重量当りの隠蔽面積が低く、従って
紫外線遮蔽能も低い。Flake-shaped zinc oxide is considered as one of the materials satisfying the above requirements, and its manufacturing method is also known. For example, Japanese Examined Patent Publication No. 55-25133 teaches "a method for producing a basic zinc sulfate plate-like crystal body in which a crystalline body is precipitated in an acidic region by contacting and absorbing ammonia gas in an acidic aqueous solution containing zinc sulfate". For this purpose, a plate-like zinc oxide powder for white pigment is described. However, the plate-shaped zinc oxide powder obtained by the method has a maximum particle size of several hundred μm and a thickness of several μm or more.
In addition to being inferior to the touch, the concealed area per unit weight is low, and therefore the ultraviolet shielding ability is also low.
【０００５】又、特公昭５４−１９２３５号及び５４−
４２９６０号には「特定の亜鉛塩を尿素と特定の条件下
にて混合反応して均一な粒径の板状水酸化亜鉛を製造す
る方法」が記載されている。しかし、これらの方法で作
られた水酸化亜鉛は均一な粒径を示すものの、１００μ
ｍの粒径で厚みも１０μｍに達するので、これを焼成し
て得た酸化亜鉛も単位重量当たりの隠蔽性が低くなり、
紫外線遮蔽能が劣る。又、特開平１−２３０４３１号に
は「平均粒子径０．１〜１μｍ、平均粒子厚さ０．０１
〜０．２μｍ、平均板状比３以上の薄片状酸化亜鉛粉末
を、当量以上の酸基を含有するｐＨ１１以上の亜鉛を含
む水溶液から、場合によっては水溶性有機物の共存下、
沈澱として得る製造方法」が教示されている。しかしな
がら該方法に於いて製造された酸化亜鉛は、平均粒径が
０．１〜１μｍと可視光と同等の大きさであるが為に散
乱により可視光の透過性に劣るとの欠点を有する。Further, Japanese Examined Patent Publications Nos. 54-19235 and 54-
No. 42960 describes "a method for producing a plate-shaped zinc hydroxide having a uniform particle size by mixing and reacting a specific zinc salt with urea under specific conditions". However, although zinc hydroxide produced by these methods shows a uniform particle size,
Since the particle size of m is 10 μm and the thickness is 10 μm, the zinc oxide obtained by firing this also has a low hiding property per unit weight.
Poor UV blocking ability. Further, JP-A 1-230431 discloses that "average particle diameter is 0.1 to 1 µm, average particle thickness is 0.01.
.About.0.2 μm, flaky zinc oxide powder having an average plate ratio of 3 or more, from an aqueous solution containing zinc having a pH of 11 or more containing an equivalent amount or more of acid groups, and optionally in the presence of a water-soluble organic substance,
"Preparation method obtained as a precipitate" is taught. However, the zinc oxide produced by this method has a defect that the average particle diameter is 0.1 to 1 μm, which is equivalent to that of visible light, and therefore the transmittance of visible light is poor due to scattering.
【０００６】[0006]
【発明が解決しようとする課題】かかる状況下におい
て、本発明者等は可視光線の透過性及び紫外線遮蔽能、
特にＵＶＡ領域に於ける紫外線遮蔽能に優れると共に、
隠ぺい性に優れた薄片状酸化亜鉛粉末を得るべく鋭意検
討した結果、特定物質の存在下に、亜鉛塩溶液の中和反
応を行い、これを焼成する場合には、上記の特性を全て
満足する薄片状酸化亜鉛粉末が得られることを見出し本
発明を完成するに至った。Under the circumstances, the present inventors have found that the visible light transmittance and the ultraviolet ray shielding ability are
In particular, it excels in UV blocking ability in the UVA range,
As a result of earnest studies to obtain flaky zinc oxide powder having excellent hiding property, as a result of performing a neutralization reaction of a zinc salt solution in the presence of a specific substance and firing this, all of the above properties are satisfied. The inventors have found that flaky zinc oxide powder can be obtained, and completed the present invention.
【０００７】[0007]
【課題を解決するための手段】即ち、本発明は亜鉛塩溶
液とアンモニウムイオン又は分解してアンモニウムイオ
ンを発生する化合物を含有する溶液を混合し、中和反応
により薄片状塩基性亜鉛塩の結晶又は薄片状水酸化亜鉛
の結晶を析出させ、ろ過、乾燥した後、焼成することに
より薄片状酸化亜鉛粉末を製造する方法に於いて、該中
和反応を水溶性有機物質の存在下に行うことを特徴とす
る薄片状酸化亜鉛粉末の製造方法を提供するにある。Means for Solving the Problems That is, according to the present invention, a zinc salt solution and a solution containing an ammonium ion or a compound which decomposes to generate an ammonium ion are mixed, and a flaky basic zinc salt crystal is formed by a neutralization reaction. or to deposit crystals of the flaky zinc hydroxide, filtration, and dried, in the method for producing the flaky zinc oxide powder by calcining, performs neutralization reaction in the presence of a water-soluble organic substances It is another object of the present invention to provide a method for producing flaky zinc oxide powder.
【０００８】更に本発明は亜鉛塩溶液とアンモニウムイ
オン又は分解してアンモニウムイオンを発生する化合物
を含有する溶液を混合し、中和反応により薄片状塩基性
亜鉛塩の結晶又は薄片状水酸化亜鉛の結晶を析出させ、
必要によりろ過、乾燥した後、焼成することにより薄片
状酸化亜鉛粉末を製造する方法に於いて、該中和反応
を、水溶性有機物質と該溶液中の亜鉛原子１モル当り
０．０００１モル〜０．５モルのアルミニウム及び／又
は鉄の金属原子の存在下に行うことを特徴とする薄片状
酸化亜鉛粉末の製造方法を提供するにある。Further, in the present invention, a zinc salt solution is mixed with a solution containing ammonium ions or a compound which decomposes to generate ammonium ions, and crystals of flaky basic zinc salt or flaky zinc hydroxide are formed by a neutralization reaction. Deposit crystals,
In the method for producing a flaky zinc oxide powder by filtering, drying and firing if necessary, the neutralization reaction is carried out in an amount of 0.0001 mol to 1 mol of zinc atom in the solution and the water-soluble organic substance. Another object of the present invention is to provide a method for producing flaky zinc oxide powder, which is characterized in that it is carried out in the presence of 0.5 mol of aluminum and / or iron metal atoms.
【０００９】以下、本発明方法を更に詳細に説明する。
本発明に於いて薄片状酸化亜鉛とは板状、薄片状、六角
板状、円板状、盤状、葉片状、雲母状、箔状等の形態で
あって、アスペクト比が３以上、好ましくは５〜４０
で、平均厚みが０．１μｍ〜１μ、平均直径が１μｍ〜
１００μｍの粉末を示す。本発明方法で得られた薄片状
酸化亜鉛は、１〜１００μｍの平均粒子径で粒径のバラ
ツキが７０％以下、好ましくは６０％以下、より好まし
くは５０％以下の粒径分布の狭い薄片状酸化亜鉛粉末で
ある。ここに於いて薄片の形状（大きさ）は一定ではな
いので、本発明に於いて平均直径は，百個の薄片の（最
大差渡し径＋最小差渡し径）／２の値の平均値で規定
し、又粒径分布のバラツキは、１００個の薄片の粒径の
（標準偏差／平均粒子径）×１００（％）値で示すもの
とする。また薄片の厚みは走査型電子顕微鏡写真の視野
内で読み取れる全ての薄片の厚みを読み、算術平均によ
り平均粒子厚さとした。The method of the present invention will be described in more detail below.
In the present invention, the flaky zinc oxide is in the form of plate, flakes, hexagonal plate, disc, disc, leaf, mica, foil, etc., and has an aspect ratio of 3 or more, Preferably 5-40
And the average thickness is 0.1 μm to 1 μ, and the average diameter is 1 μm to
100 μm powder is shown. The flaky zinc oxide obtained by the method of the present invention has a narrow flaky shape with an average particle size of 1 to 100 μm and a variation in particle size of 70% or less, preferably 60% or less, more preferably 50% or less. It is a zinc oxide powder. Since the shape (size) of the flakes is not constant here, the average diameter in the present invention is the average value of the values of (maximum difference diameter + minimum difference diameter) / 2 of 100 pieces. The variation of the particle size distribution is specified by (standard deviation / average particle size) × 100 (%) value of the particle size of 100 flakes. The thickness of each thin piece was the average particle thickness obtained by arithmetically averaging the thicknesses of all the thin pieces that can be read within the field of view of the scanning electron microscope.
【００１０】本発明方法は、亜鉛塩溶液とアンモニウム
イオン又は分解してアンモニウムイオンを発生する化合
物を含有する溶液を混合し、中和反応により薄片状塩基
性亜鉛塩の結晶又は薄片状水酸化亜鉛の結晶を析出さ
せ、必要によりろ過、乾燥した後、焼成することにより
薄片状酸化亜鉛粉末を製造する方法に於いて、該中和反
応を水溶性有機物質の存在下に行うことを特徴とするも
のである。この方法の実施に際し、使用される亜鉛塩溶
液は、硫酸亜鉛、硝酸亜鉛、塩化亜鉛、酢酸亜鉛等の有
機酸塩、或いは亜鉛アルコキシド等が挙げられる。In the method of the present invention, a solution of a zinc salt and a solution containing an ammonium ion or a compound which decomposes to generate an ammonium ion are mixed, and crystals of flaky basic zinc salt or flaky zinc hydroxide are subjected to a neutralization reaction. In the method for producing flaky zinc oxide powder by precipitating crystals of the above, filtering and drying if necessary, and then calcining, the neutralization reaction is carried out in the presence of a water-soluble organic substance. It is a thing. When carrying out this method, examples of the zinc salt solution used include organic acid salts such as zinc sulfate, zinc nitrate, zinc chloride and zinc acetate, and zinc alkoxide.
【００１１】また、アンモニウムイオン又は分解してア
ンモニウムイオンを発生する化合物を含有する溶液と
は、アンモニアガス、アンモニア水、尿素水溶液、ヘキ
サメチレンテトラミン水溶液等が挙げられる。Examples of the solution containing ammonium ion or a compound that decomposes to generate ammonium ion include ammonia gas, ammonia water, aqueous urea solution, and aqueous hexamethylenetetramine solution.
【００１２】本発明に於いては、亜鉛塩溶液とアンモニ
ウムイオン又は分解してアンモニウムイオンを発生する
化合物の中和反応時に、水溶性有機物質を存在せしめる
ことを必須とする。該中和反応を水溶性有機物質の存在
下に実施することにより得られる薄片状塩基性亜鉛塩結
晶又は薄片状水酸化亜鉛の粒径、粒径分布、結晶形等の
結晶性の制御が可能となる。かかる効果を有する水溶性
有機物質としてはアルコール類、ポリオール類、ケトン
類、ポリエーテル類、エステル類、カルボン酸類、ポリ
カルボン酸類、セルロース類、糖類、スルホン酸類、ア
ミノ酸類、アミン類であって、より具体的にはメタノー
ル、エタノール、プロパノール、ブタノール、ペンタノ
ール、ヘキサノール等の脂肪族アルコール、エチレング
リコール、プロパンジオール、ブタンジオール、グルセ
リン、ポリエチレングリコール、ポリプロピレングリコ
ール等の脂肪族多価アルコール、フェノール、カテコー
ル、クレゾール等の芳香族アルコール、フルフリルアコ
ール等の複素環を有するアルコール類、アセトン、メチ
ルエチルケトン、アセチルアセトン等のケトン類、エチ
ルエーテル、テトラヒドロフラン、ジオキサン、ポリオ
キシアルキレンエーテル、エチレンオキサイド付加物、
プロピレンオキサイド付加物等のエーテルあるいはポリ
エーテル類、酢酸エチル、アセト酢酸エチル、グリシン
エチルエステル等のエステル類、蟻酸、酢酸、プロピオ
ン酸、ブタン酸、酪酸、蓚酸、マロン酸、クエン酸、酒
石酸、グルコン酸、サリチル酸、安息香酸、アクリル
酸、マレイン酸、グリセリン酸、エレオステアリン酸、
ポリアクリル酸、ポリマレイン酸、アクリル酸ーマレイ
ン酸コポリマー等のカルボン酸、ポリカルボン酸、ある
いはヒドロキシカルボン酸やその塩類、カルボキシメチ
ルセルロース類、グルコース、ガラクトース等の単糖
類、蔗糖、ラクトース、アミロース、キチン、セルロー
ス等の多糖類、アルキルベンゼンスルホン酸、パラトル
エンスルホン酸、アルキルスルホン酸、α−オレフィン
スルホン酸、ポリオキシエチレンアルキルスルホン酸、
リグニンスルホン酸、ナフタレンスルホン酸等のスルホ
ン酸類やその塩類、グリシン、グルタミン酸、アスパラ
ギン酸、アラニン等のアミノ酸、モノエタノールアミ
ン、ジエタノールアミン、トリエタノールアミン、ブタ
ノールアミン等のヒドロキシアミン類、トリメチルアミ
ノエチルアルキルアミド、アルキルピリジニウム硫酸
塩、アルキルトリメチルアンモニウムハロゲン化物、ア
ルキルベタイン、アルキルジエチレントリアミノ酢酸等
を例とし挙げることができる。In the present invention, it is essential that a water-soluble organic substance be present during the neutralization reaction of the zinc salt solution and ammonium ion or a compound that decomposes to generate ammonium ion. Crystallinity such as particle size, particle size distribution and crystal form of flaky basic zinc salt crystals or flaky zinc hydroxide obtained by carrying out the neutralization reaction in the presence of a water-soluble organic substance is possible. Becomes Water-soluble organic substances having such effects include alcohols, polyols, ketones, polyethers, esters, carboxylic acids, polycarboxylic acids, celluloses, saccharides, sulfonic acids, amino acids, amines, More specifically, aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, etc., aliphatic polyhydric alcohols such as ethylene glycol, propanediol, butanediol, glycerin, polyethylene glycol, polypropylene glycol, phenol, catechol. , Aromatic alcohols such as cresol, alcohols having a heterocycle such as furfuryl acol, ketones such as acetone, methyl ethyl ketone, acetylacetone, ethyl ether, tetrahydrofuran, dioxane Polyoxyalkylene ethers, ethylene oxide adducts,
Ethers or polyethers such as propylene oxide adducts, esters such as ethyl acetate, ethyl acetoacetate, glycine ethyl ester, formic acid, acetic acid, propionic acid, butanoic acid, butyric acid, oxalic acid, malonic acid, citric acid, tartaric acid, glucon Acid, salicylic acid, benzoic acid, acrylic acid, maleic acid, glyceric acid, eleostearic acid,
Carboxylic acid such as polyacrylic acid, polymaleic acid, acrylic acid-maleic acid copolymer, polycarboxylic acid, or hydroxycarboxylic acid or salts thereof, carboxymethylcellulose, glucose, galactose and other monosaccharides, sucrose, lactose, amylose, chitin, cellulose Polysaccharides such as, alkylbenzene sulfonic acid, paratoluene sulfonic acid, alkyl sulfonic acid, α-olefin sulfonic acid, polyoxyethylene alkyl sulfonic acid,
Sulfonic acids such as ligninsulfonic acid and naphthalenesulfonic acid and salts thereof, amino acids such as glycine, glutamic acid, aspartic acid and alanine, hydroxyamines such as monoethanolamine, diethanolamine, triethanolamine and butanolamine, trimethylaminoethylalkylamide , Alkylpyridinium sulfate, alkyltrimethylammonium halide, alkylbetaine, alkyldiethylenetriaminoacetic acid and the like can be mentioned as examples.
【００１３】これら水溶性有機物の中でも水酸基、カル
ボキシル基及びアミノ基の何れか一種或いは二種以上の
官能基を有する水溶性有機物質が好ましく、水酸基とカ
ルボキシル基を有するヒドロキシカルボン酸やその塩類
が特に好ましい。これらは単独又は２種以上のものを混
合して共存させる事もできる。亜鉛塩溶液とアンモニウ
ムイオン又は分解してアンモニウムイオンを発生する化
合物の中和反応時に存在する水溶性有機物質は、中和反
応により析出する薄片状塩基性亜鉛塩結晶又は薄片状水
酸化亜鉛の表面に吸着して粒子の成長を制御しているも
のと思われ、結果として結晶形や平均粒子径、粒径分布
等の結晶性が制御できる。Among these water-soluble organic substances, water-soluble organic substances having one or more functional groups of hydroxyl group, carboxyl group and amino group are preferable, and hydroxycarboxylic acid having hydroxyl group and carboxyl group and salts thereof are particularly preferable. preferable. These may be used alone or in combination of two or more. The water-soluble organic substance present during the neutralization reaction of the zinc salt solution and ammonium ion or a compound that decomposes to generate ammonium ion is a flaky basic zinc salt crystal or flaky zinc hydroxide surface which is precipitated by the neutralization reaction. It is believed that the particles are adsorbed on and control the growth of particles, and as a result, the crystallinity such as the crystal form, average particle size, and particle size distribution can be controlled.
【００１４】水溶性有機物は、母液（亜鉛塩溶液とアン
モニウムイオン又は分解してアンモニウムイオンを発生
する化合物を含有する溶液）中に約０．００１重量％〜
約１０重量％の範囲で共存させるのが好ましく、その量
は所望粒径と粒径分布等により決定される。The water-soluble organic matter is contained in the mother liquor (a solution containing a zinc salt solution and ammonium ions or a compound which decomposes to generate ammonium ions) in an amount of about 0.001% by weight.
It is preferable to coexist in the range of about 10% by weight, and the amount thereof is determined by the desired particle size, particle size distribution and the like.
【００１５】この水溶性有機物は、薄片状塩基性亜鉛塩
又は薄片状水酸化亜鉛が析出する際に存在する事が肝要
であり、予め亜鉛塩水溶液やアンモニウムイオン又は分
解してアンモニウムイオンを発生する化合物を含有する
水溶液に溶解、混合してから反応析出に供したり、反応
析出時、別途溶解した水溶性有機物溶液を適宜添加する
事で達成できる。薄片の機械的強度を改善する為に、亜
鉛原子１モル当たり０．０００１〜０．５モル、好まし
くは亜鉛原子１モル当たり０．０００１〜０．４モルの
アルミニウム及び／又は鉄の金属原子の存在下で中和反
応を行う事は特に有効な方法である。It is essential that this water-soluble organic substance is present when the flaky basic zinc salt or flaky zinc hydroxide is deposited, and an aqueous zinc salt solution or ammonium ion or decomposes to generate ammonium ion in advance. It can be achieved by dissolving and mixing in an aqueous solution containing a compound, and then subjecting it to reaction precipitation, or by appropriately adding a separately dissolved water-soluble organic substance solution during reaction precipitation. In order to improve the mechanical strength of the flakes, 0.0001 to 0.5 mol per mol of zinc atom, preferably 0.0001 to 0.4 mol of metal atom of aluminum and / or iron per mol of zinc atom. Performing the neutralization reaction in the presence is a particularly effective method.
【００１６】亜鉛塩溶液とアンモニウムイオン又は分解
してアンモニウムイオンを発生する化合物を含有する溶
液を混合し、中和反応により薄片状塩基性亜鉛塩の結晶
又は薄片状水酸化亜鉛を析出させる方法は公知の方法を
適用できる。この中和反応に際して撹拌を行ったり温度
の制御を行う事は良好な薄片状塩基性亜鉛塩や水酸化亜
鉛を得るのに重要である。反応温度は用いるアンモニウ
ムイオン又は分解してアンモニウムイオンを発生する化
合物の種類により異なるが、通常約３０℃から溶液の沸
点の間で行う事ができ、反応性を高め生産性を高める為
に約６０℃〜約１００℃の温度がより好ましい。反応析
出後、反応温度又はそれより低い温度にて１０分以上、
好ましくは３０分以上保持する事は、得られた薄片状塩
基性亜鉛又は薄片状水酸化亜鉛の結晶性や形状、表面性
状等を改善するのに特に有効である。A method of precipitating flaky basic zinc salt crystals or flaky zinc hydroxide by a neutralization reaction by mixing a zinc salt solution with a solution containing ammonium ions or a compound which decomposes to generate ammonium ions Known methods can be applied. Stirring and temperature control during this neutralization reaction are important for obtaining good flaky basic zinc salt and zinc hydroxide. The reaction temperature varies depending on the type of ammonium ion used or the compound that decomposes to generate ammonium ion, but it can usually be carried out between about 30 ° C. and the boiling point of the solution, and about 60 to increase the reactivity and productivity. More preferred is a temperature of from 0 ° C to about 100 ° C. 10 minutes or more at the reaction temperature or lower after the reaction precipitation,
Preferably, holding for 30 minutes or more is particularly effective for improving the crystallinity, shape, surface properties and the like of the obtained flaky basic zinc or flaky zinc hydroxide.
【００１７】反応析出した或いは反応温度又はそれより
低い温度にて特定時間保持した溶液は次いで固液分離
し、洗浄、乾燥されるが、分散性の良好な酸化亜鉛を得
る為には、結晶性制御に用いた水溶性有機物の除去や母
液に残存したイオンを除去することが好ましく、例えば
母液に残存したイオンの洗浄については、析出した薄片
状塩基性亜鉛又は薄片状水酸化亜鉛スラリーの電導度が
約１０００μｓ以下、より好ましくは約５００μｓ以下
となる迄洗浄してイオンを取り除くことが推奨される。The solution precipitated by reaction or kept at a reaction temperature or lower for a specific time is then subjected to solid-liquid separation, washed and dried. In order to obtain zinc oxide having good dispersibility, crystalline It is preferable to remove the water-soluble organic substances used for control and to remove the ions remaining in the mother liquor.For example, for washing the ions remaining in the mother liquor, the conductivity of the precipitated flaky basic zinc or flaky zinc hydroxide slurry Is recommended to be depleted of ions for up to about 1000 μs or less, more preferably about 500 μs or less.
【００１８】又、更に分散性改良を目的として、洗浄処
理等を終えた固液分離の最終段階でメタノール、エタノ
ール、イソプロパノール等の低級アルコールやテトラヒ
ドロフラン、アセトン等の水溶性有機溶媒中に分散後、
場合によっては超音波分散処理後、スプレードライやド
ラムドライヤー等で乾燥する事が推奨される。Further, for the purpose of further improving the dispersibility, after dispersing in a water-soluble organic solvent such as tetrahydrofuran, acetone or a lower alcohol such as methanol, ethanol or isopropanol in the final stage of solid-liquid separation after washing treatment and the like,
In some cases, it is recommended to dry with a spray dryer or a drum dryer after the ultrasonic dispersion treatment.
【００１９】乾燥後の薄片は、次いで焼成されるが、焼
成は通常酸素含有雰囲気、具体的には空気中で行われ
る。焼成温度は約８５０〜約１２００℃の温度で約１０
分以上、通常３０分から約２時間焼成される。焼成温度
と時間は焼成した酸化亜鉛が用いられる物性により決定
される。焼成炉は管状炉、箱型炉等のバッチ炉やプッシ
ャー炉、ロータリーキルントンネル炉、ローラーハース
炉等の連続炉を用いる事ができ、熱源に関してもガス、
電気のいずれでもよく制限を受けない。The dried flakes are then calcined, usually in an oxygen-containing atmosphere, specifically air. The firing temperature is about 850 to about 1200 ° C and about 10
Min or more, usually 30 minutes to about 2 hours. The firing temperature and time are determined by the physical properties of the fired zinc oxide. The firing furnace may be a tubular furnace, a batch furnace such as a box furnace, a pusher furnace, a continuous kiln such as a rotary kiln tunnel furnace, a roller hearth furnace, or the like.
It is not restricted by electricity.
【００２０】焼成後の薄片物質は、必要ならば解砕処理
した後、所望粒度に分級して一般の樹脂充填剤、ゴム用
充填剤、顔料、化粧用顔料、更には化粧料、衣料、塗
料、食品包装材料等の各種用途の紫外線遮蔽剤等として
使用可能である。The flaked material after firing is, if necessary, crushed and then classified to a desired particle size to be used for general resin fillers, rubber fillers, pigments, cosmetic pigments, and further cosmetics, clothing, paints. It can be used as an ultraviolet shielding agent for various uses such as food packaging materials.
【００２１】[0021]
【発明の効果】以上詳述した本発明方法により得られた
薄片状酸化亜鉛粉末は、所望とする粒径に於いて、粒径
のバラツキが７０％以下、好ましくは６０％以下、より
好ましくは５０％以下の狭い粒径分布を有し、著しい微
粉や粗大粒がないために、優れた可視光線の透過性、紫
外線遮蔽能、隠蔽性、充填性を有し、且つ有機物との反
応性も穏やかであるとの特性を持つもので、その工業的
価値は頗る大である。INDUSTRIAL APPLICABILITY The flaky zinc oxide powder obtained by the method of the present invention described in detail above has a particle size variation of 70% or less, preferably 60% or less, more preferably, in a desired particle size. It has a narrow particle size distribution of 50% or less, and has no remarkable fine powder or coarse particles, so it has excellent visible light transmittance, ultraviolet ray shielding ability, hiding ability, filling ability, and reactivity with organic substances. It has the characteristic of being mild and its industrial value is enormous.
【００２２】[0022]
【実施例】以下、実施例により本発明を更に詳細に説明
する。EXAMPLES The present invention will be described in more detail below with reference to examples.
【００２３】実施例１
硫酸亜鉛７水和物（ＺｎＳＯ4 ・７Ｈ2 Ｏ／東邦亜鉛
製）５７．６ｇとグルコン酸ナトリウム（和光純薬製）
０．１５ｇを脱イオン水１００ｇに溶解した。この溶液
を５００ｍｌのセパラブルフラスコに入れ、マグネット
スターラーで攪拌しながら９０℃に加熱、溶解した。こ
の溶液を９０℃に保持しながら、２５％アンモニウム水
１６．３ｇをマイクロチューブポンプにて１５分かけて
滴下した。滴下終了後、９０℃にて４時間保持して熟成
を行った後、溶液を約５ｌｔの脱イオン水中に投入し、
静置した。静置後固液分離し、更に脱イオン水による洗
浄を３回行った所、スラリーの上澄みの電導度は７５μ
ｓとなった。このスラリーを濾過、乾燥して１８．５ｇ
の白色粉末を得た。この粉末の粒径を光学顕微鏡で視察
した所、平均４．５μｍ、バラツキ４０％であった。
又、厚みを走査電子顕微鏡で測定した所、０．２μｍで
あった。上記得られた粉末をマッフル炉で９００℃で３
０分焼成し、１６．０ｇの薄片状酸化亜鉛粉末を得た。
上記で得られた薄片状酸化亜鉛粉末０．１８ｇをシリコ
ンオイル（ＫＳ−６２Ｆ／信越化学社製）１．０２ｇと
めのう乳鉢で良く混合し、この混合物を脱脂ポリプロピ
レンフイルム（厚さ５０μｍ）にドクターブレード法に
て１０μｍの厚みで塗布して、その分光拡散透過率（５
０φ積分球付き／日立３３０分光光度計）を測定した
所、１２％／３７０ｎｍ、８１％／５００ｎｍであっ
た。また、同一試料を用い、３８０ｎｍに於ける直線透
過率（積分球無し）を測定したところ、吸光度は２．２
３であった。薄片の強度測定方法として、上記で得られ
た薄片状酸化亜鉛粉末０．５ｇを０．２％ヘキサメタリ
ン酸ナトリウム水溶液１００ｍｌにホモジナイザー（Ｕ
Ｓ−３００Ｔ：超音波分散器／リーズ＆ノ−スラップ社
製）で分散し、マイクロトラックＭＫII（リーズアンド
ノ−スラップ社製）により各々１分間と１０分間分散処
理し、次いで処理後の薄片の平均粒径を測定することに
より、（１０分間分散処理後の薄片の平均粒径／１分間
分散処理後の薄片の平均粒径）×１００％として薄片の
強度を求めた。その結果は６８％であった。Example 1 57.6 g of zinc sulfate heptahydrate (ZnSO 4 .7H 2 O / manufactured by Toho Zinc) and sodium gluconate (manufactured by Wako Pure Chemical Industries)
0.15 g was dissolved in 100 g deionized water. This solution was put into a 500 ml separable flask and heated to 90 ° C. while stirring with a magnetic stirrer to dissolve. While maintaining this solution at 90 ° C., 16.3 g of 25% ammonium water was added dropwise by a microtube pump over 15 minutes. After completion of dropping, the mixture was kept at 90 ° C. for 4 hours for aging, and then the solution was poured into about 5 liters of deionized water,
I let it stand. After standing, it was subjected to solid-liquid separation and further washed with deionized water three times, and the conductivity of the supernatant of the slurry was 75 μm.
It became s. This slurry was filtered and dried to 18.5 g.
Of white powder was obtained. When the particle size of this powder was observed with an optical microscope, the average was 4.5 μm and the variation was 40%.
The thickness was 0.2 μm as measured by a scanning electron microscope. The above-obtained powder was mixed in a muffle furnace at 900 ° C for 3
Firing was performed for 0 minutes to obtain 16.0 g of flaky zinc oxide powder.
0.18 g of the flaky zinc oxide powder obtained above was thoroughly mixed with 1.02 g of silicon oil (KS-62F / manufactured by Shin-Etsu Chemical Co., Ltd.) in an agate mortar, and this mixture was applied to a degreased polypropylene film (thickness 50 μm) by a doctor. The blade method is applied to a thickness of 10 μm, and its spectral diffusion transmittance (5
It was 12% / 370 nm and 81% / 500 nm when measured with a 0φ integrating sphere / Hitachi 330 spectrophotometer). The linear transmittance (without integrating sphere) at 380 nm was measured using the same sample, and the absorbance was 2.2.
It was 3. As a method for measuring the strength of the flakes, 0.5 g of the flaky zinc oxide powder obtained above was added to 100 ml of a 0.2% aqueous sodium hexametaphosphate homogenizer (U).
S-300T: Dispersed with an ultrasonic disperser / made by Leeds & No-Slap), and dispersed with Microtrac MKII (made by Leeds & No-Slap) for 1 minute and 10 minutes, respectively, and then the thin pieces after treatment By measuring the average particle size, the strength of the flakes was determined as (average particle size of flakes after 10 minutes dispersion treatment / average particle size of flakes after 1 minute dispersion treatment) × 100%. The result was 68%.
【００２４】実施例２
実施例１において、２５％アンモニウム水を２７．７ｇ
に、グルコン酸ナトリウムに代えて酒石酸１４ｍｇに、
反応温度を１００℃に代えた以外は同様にして薄片状塩
基性硫酸亜鉛の白色粉末を１９．５ｇ得た。この粉末の
粒径を光学顕微鏡にて観察した所、平均８μｍ、厚み
０．４μｍ、バラツキ３８％であった。Example 2 In Example 1, 27.7 g of 25% ammonium water was added.
To 14 mg tartaric acid instead of sodium gluconate,
19.5 g of white powder of flaky basic zinc sulfate was obtained in the same manner except that the reaction temperature was changed to 100 ° C. When the particle size of this powder was observed with an optical microscope, the average was 8 μm, the thickness was 0.4 μm, and the variation was 38%.
【００２５】実施例３〜５
実施例１において、グルコン酸ナトリウムに代えてエチ
レングリコール０．２ｇ（実施例３）、２，３−ブタン
ジオール０．３ｇ（実施例４）、ゼラチン０．１ｇ（実
施例５）の水溶性有機物をそれぞれ添加剤として添加
し、薄片状塩基性硫酸亜鉛の白色粉末を合成、この粒径
を光学顕微鏡にて観察した所、エチレングリコールにお
いては平均粒径６．１μｍ、厚み０．５μｍ、バラツキ
３７％であり、２，３−ブタンジオールにおいては平均
粒径５．８μｍ、厚み０．６μｍ、バラツキ４７％、ゼ
ラチンにおいては平均粒径３．１μｍ、厚み０．２μ
ｍ、バラツキ４２％であった。Examples 3 to 5 In Example 1, instead of sodium gluconate, 0.2 g of ethylene glycol (Example 3), 0.3 g of 2,3-butanediol (Example 4), and 0.1 g of gelatin ( The water-soluble organic substance of Example 5) was added as an additive to synthesize white powder of flaky basic zinc sulfate, and the particle size was observed with an optical microscope. The average particle size of ethylene glycol was 6.1 μm. , Thickness 0.5 μm, variation 37%, mean particle size 5.8 μm, thickness 0.6 μm, variation 47% in 2,3-butanediol, mean particle size 3.1 μm, thickness 0.2 μ in gelatin
The variation was 42%.
【００２６】比較例１
実施例１において、グルコン酸ナトリウムを添加しない
事以外は全て同一条件にて、薄片状塩基性硫酸亜鉛を合
成し、光学顕微鏡にて観察した所、平均粒径６．６μ
ｍ、厚み０．７μｍ、バラツキ９４％であった。Comparative Example 1 In Example 1, flaky basic zinc sulfate was synthesized under the same conditions except that sodium gluconate was not added, and when observed with an optical microscope, the average particle size was 6.6 μm.
m, the thickness was 0.7 μm, and the variation was 94%.
【００２７】実施例６
実施例１において硫酸アルミニウム水和物（Ａｌ2 （Ｓ
Ｏ4 ）3 ・１４〜１８Ｈ2 Ｏ／和光純薬製）０．６３ｇ
を追加した以外は同様にして、平均粒径４．１μｍ、厚
み０．２μｍ、バラツキ４３％の薄片状塩基性硫酸亜鉛
を得た。又、この粉末を９００℃で３０分焼成して得た
酸化亜鉛粉末の分光拡散透過率は８％／３７０ｎｍ、７
８％／５００ｎｍで、強度は７５％であった。Example 6 In Example 1, aluminum sulfate hydrate (Al 2 (S
O 4 ) 3・ 14-18H 2 O / Wako Pure Chemical Industries) 0.63 g
Flake basic zinc sulfate having an average particle size of 4.1 μm, a thickness of 0.2 μm and a variation of 43% was obtained in the same manner except that was added. The zinc oxide powder obtained by baking this powder at 900 ° C. for 30 minutes has a spectral diffusion transmittance of 8% / 370 nm, 7
At 8% / 500 nm, the intensity was 75%.
【００２８】比較例２
実施例２において、酒石酸を添加しない事以外は全て同
一条件にて、薄片状塩基性硫酸亜鉛を合成し、光学顕微
鏡にて観察した所、平均粒径２６μｍ、厚み２．５μ
ｍ、バラツキ７８％であった。Comparative Example 2 In Example 2, flaky basic zinc sulfate was synthesized under the same conditions except that tartaric acid was not added, and observed with an optical microscope. The average particle diameter was 26 μm and the thickness was 2. 5μ
The variation was 78%.
【００２９】比較例３
実施例２において、２５％アンモニウム水に代えてウロ
トロピン２８ｇを用い、グルコン酸ナトリウムを添加し
ない事以外は全て同一条件にて、薄片状塩基性硫酸亜鉛
を合成し、光学顕微鏡にて観察した所、平均粒径５．６
μｍ、厚み０．４μｍ、バラツキ７５％であった。Comparative Example 3 In Example 2, flaky basic zinc sulfate was synthesized under the same conditions except that 28 g of urotropin was used instead of 25% ammonium water and sodium gluconate was not added, and an optical microscope was used. The average particle size was 5.6.
The thickness was 0.4 μm and the variation was 75%.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 1/00 - 23/08 C09K 3/00 104 ─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. 7 , DB name) C01G 1/00-23/08 C09K 3/00 104
Claims (5)
解してアンモニウムイオンを発生する化合物を含有する
溶液を混合し、中和反応により薄片状塩基性亜鉛塩の結
晶又は薄片状水酸化亜鉛の結晶を析出させ、ろ過、乾燥
した後、焼成することにより薄片状酸化亜鉛粉末を製造
する方法に於いて、該中和反応を水溶性有機物質の存在
下に行うことを特徴とする薄片状酸化亜鉛粉末の製造方
法。1. A zinc salt solution and a solution containing an ammonium ion or a compound which decomposes to generate an ammonium ion are mixed, and flaky basic zinc salt crystals or flaky zinc hydroxide crystals are formed by a neutralization reaction. precipitation, filtration, and dried, in the method for producing the flaky zinc oxide powder by calcining, flaky zinc oxide and performing neutralization reaction in the presence of a water-soluble organic substances Powder manufacturing method.
アミノ基のいずれか一種又は二種以上の官能基を有する
事を特徴とする請求項１記載の薄片状酸化亜鉛粉末の製
造方法。2. The water-soluble organic substance is a hydroxyl group, a carboxyl group,
2. The method for producing flaky zinc oxide powder according to claim 1, which has one or more functional groups of amino groups.
亜鉛、酢酸亜鉛又は炭酸亜鉛の何れか一種であることを
特徴とする請求項１記載の薄片状酸化亜鉛粉末の製造方
法。3. The method for producing flaky zinc oxide powder according to claim 1, wherein the zinc salt solution is any one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate and zinc carbonate.
モニウムイオンを発生する化合物を含有する溶液が、ア
ンモニア水溶液、尿素水溶液またはヘキサメチレンテト
ラミンであることを特徴とする請求項１記載の薄片状酸
化亜鉛粉末の製造方法。4. The flaky zinc oxide powder according to claim 1, wherein the solution containing ammonium ions or a compound that decomposes to generate ammonium ions is an aqueous ammonia solution, an aqueous urea solution or hexamethylenetetramine. Manufacturing method.
中の亜鉛原子１モル当りアルミニウム及び／又は鉄の金
属原子０．０００１モル〜０．５モルの存在下に行うこ
とを特徴とする請求項１記載の薄片状酸化亜鉛粉末の製
造方法。5. The neutralization reaction is carried out in the presence of a water-soluble organic substance and 0.0001 to 0.5 mol of metal atoms of aluminum and / or iron per mol of zinc atoms in the solution. The method for producing the flaky zinc oxide powder according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31339093A JP3512838B2 (en) | 1993-12-14 | 1993-12-14 | Method for producing flaky zinc oxide powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31339093A JP3512838B2 (en) | 1993-12-14 | 1993-12-14 | Method for producing flaky zinc oxide powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07165422A JPH07165422A (en) | 1995-06-27 |
| JP3512838B2 true JP3512838B2 (en) | 2004-03-31 |
Family
ID=18040700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31339093A Expired - Fee Related JP3512838B2 (en) | 1993-12-14 | 1993-12-14 | Method for producing flaky zinc oxide powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3512838B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014007045A1 (en) | 2012-07-02 | 2014-01-09 | 日本碍子株式会社 | Zinc oxide powder and process for manufacturing same |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0893409B1 (en) * | 1994-06-06 | 2003-09-03 | Nippon Shokubai Co., Ltd. | Zinc oxide-based fine particles, process for producing the same, and use thereof |
| JP5136264B2 (en) * | 2008-07-28 | 2013-02-06 | 堺化学工業株式会社 | Method for producing nitrogen-containing zinc oxide powder |
| CN105960379B (en) * | 2014-02-07 | 2018-04-17 | 堺化学工业株式会社 | Six square plate shape Zinc oxide particles, its manufacture method, cosmetic preparation, filler, resin combination, infrared light reflecting material and coating composition |
| WO2019107304A1 (en) * | 2017-11-30 | 2019-06-06 | 堺化学工業株式会社 | Granular composite containing keratin and hexagonal plate-like zinc oxide |
-
1993
- 1993-12-14 JP JP31339093A patent/JP3512838B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014007045A1 (en) | 2012-07-02 | 2014-01-09 | 日本碍子株式会社 | Zinc oxide powder and process for manufacturing same |
| US9327994B2 (en) | 2012-07-02 | 2016-05-03 | Ngk Insulators, Ltd. | Zinc oxide powder and process for manufacturing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07165422A (en) | 1995-06-27 |
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