JPH05239376A - White rustproof pigment composition - Google Patents
White rustproof pigment compositionInfo
- Publication number
- JPH05239376A JPH05239376A JP7854792A JP7854792A JPH05239376A JP H05239376 A JPH05239376 A JP H05239376A JP 7854792 A JP7854792 A JP 7854792A JP 7854792 A JP7854792 A JP 7854792A JP H05239376 A JPH05239376 A JP H05239376A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- rust preventive
- zinc phosphate
- white
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、白色防錆顔料に係り、
更に言えばリン酸亜鉛系の改良された無公害の白色防錆
顔料組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a white rust preventive pigment,
More specifically, it relates to an improved non-polluting white rust preventive pigment composition based on zinc phosphate.
【０００２】[0002]
【従来の技術】従来、防錆顔料として最も代表的なもの
として鉛丹あるいはジンククロメートが広く使用されて
いる。これ等の防錆顔料は、極めて優れた防錆力を示す
が、着色顔料であることやその組成中における鉛、クロ
ムなどの成分に毒性が認められる。近時、これら毒性成
分を含有する顔料に対する使用制限が厳しくなってきて
いる現状から、これに対応する新たな低毒性あるいは無
公害性の白色防錆顔料が開発され、実用に供されてい
る。2. Description of the Related Art Hitantan or zinc chromate has been widely used as the most representative rust preventive pigment. Although these rust preventive pigments show extremely excellent rust preventive power, they are color pigments and the components such as lead and chromium in the composition are toxic. Due to the recent strict restrictions on the use of pigments containing these toxic components, new low-toxic or non-polluting white rust preventive pigments have been developed and put into practical use.
【０００３】これまでに無公害防錆顔料として、(a) 金
属縮合リン酸塩系、例えば縮合リン酸アルミニウム、
(b) 金属リン酸塩系、例えばリン酸亜鉛、リン酸ケイ
素、リン酸チタニウム、(c) 金属亜リン酸塩系、例えば
亜リン酸亜鉛、バリウム塩、マグネシウム塩、マンガン
塩、(d) 金属次亜リン酸塩系、例えば次亜リン酸カルシ
ウムまたは次亜リン酸鉄、(e) 金属モリブデン酸塩、例
えば亜鉛塩、カルシウム塩など数多くの提案がなされて
いる。Heretofore, as a pollution-free rust preventive pigment, (a) a metal condensed phosphate type, for example, condensed aluminum phosphate,
(b) a metal phosphate system such as zinc phosphate, silicon phosphate, titanium phosphate, (c) a metal phosphite system such as zinc phosphite, barium salt, magnesium salt, manganese salt, (d) Numerous proposals have been made for metal hypophosphite systems such as calcium or iron hypophosphite, (e) metal molybdates such as zinc salts and calcium salts.
【０００４】これらの無公害防錆顔料において、リン酸
亜鉛系のものは性能的及び経済性の面から実用性が高い
とされており、その製造法は例えば特公昭49−2005号公
報、特開昭52−69898 号公報、特開昭55−36267 号公
報、特開昭56−169113号公報、特開昭59−42297 号公
報、特開平１−308814号公報などに開示されている。こ
れらの方法は、いずれも微細なリン酸亜鉛を製造するこ
とにより防錆力の向上を図るものである。Among these pollution-free rust-preventive pigments, zinc phosphate-based pigments are said to be highly practical in terms of performance and economical efficiency, and the production method thereof is described, for example, in Japanese Patent Publication No. 49-2005. It is disclosed in JP-A-52-69898, JP-A-55-36267, JP-A-56-169113, JP-A-59-42297 and JP-A-1-308814. All of these methods are intended to improve the rust preventive power by producing fine zinc phosphate.
【０００５】一方、亜リン酸リン酸亜鉛カリウム系の特
殊な防錆顔料にキレート能のある有機ホスホン酸（塩）
を用いることが知られている（特開昭60−124660号公
報）。On the other hand, an organic phosphonic acid (salt) having a chelating ability for a special anticorrosive pigment based on zinc potassium phosphite
Is known to be used (JP-A-60-124660).
【０００６】[0006]
【発明が解決しようとする課題】しかしながら、これら
の無公害白色防錆顔料は防錆力が鉛丹やクロメート顔料
に比べて劣り、また使用に際して顔料特性に一長一短が
あって、改良すべきところが多い。とくに水系塗料とし
て用いる場合の防錆力が弱いため防錆顔料として満足す
べきものではない。However, these pollution-free white rust preventive pigments are inferior in rust preventive power as compared with red lead and chromate pigments, and have many merits and demerits in pigment characteristics when used, and there are many points to be improved. .. Especially when used as a water-based paint, it is not satisfactory as a rust preventive pigment because of its weak rust preventive power.
【０００７】とりわけリン酸亜鉛は、その性質上から板
状乃至鱗片状の粗大な一次粒子を形成し易いために微細
化し難く、そのうえ単に微細化した程度に過ぎないもの
では防錆力の改善には限度があり、余り期待できるもの
は得られない。また、キレート能を有する有機ホスホン
酸を用いた亜リン酸リン酸亜鉛カリウムは上記したよう
に特殊顔料であって顔料化および塗料化に種々の問題が
あり、実用に供するには多くの改善すべき点がある。In particular, zinc phosphate is difficult to be finely divided because it is easy to form plate-like or scale-like coarse primary particles due to its properties. Moreover, if it is merely finely divided, it improves the rust preventive power. There is a limit to what you can expect. In addition, zinc potassium phosphite phosphite using an organic phosphonic acid having a chelating ability is a special pigment as described above and has various problems in pigmentation and coating, and many improvements are required for practical use. There is a point.
【０００８】このように、従来提案されている多くの白
色防錆顔料のうち実用性のあるものは極く限られたもの
に過ぎず、加えて単独で使用されるものはなく、多くの
場合数種の複合により使用されている実情にある。As described above, among the many white rust preventive pigments proposed so far, the ones having practical utility are very limited, and there is no one used alone, and in many cases. It is actually used by several composites.
【０００９】本発明者らは、上記の実情に鑑み無公害性
の白色防錆顔料の研究を鋭意重ねている過程で、リン酸
亜鉛にキレート能を有する有機リン化合物を作用させた
ところ、優れた防錆機能を発揮することを解明した。本
発明は、かかる知見に基づいて開発されたもので、その
目的は優れた防錆能を有する無公害のリン酸亜鉛系白色
防錆顔料組成物を提供することにある。In view of the above situation, the inventors of the present invention have made an effort to make zinc phosphate an organic phosphorus compound having a chelating ability to act in the course of earnestly researching a pollution-free white rust-preventive pigment. It has been clarified that it exhibits a rust prevention function. The present invention was developed based on such findings, and an object thereof is to provide a pollution-free zinc phosphate-based white rust preventive pigment composition having excellent rust preventive ability.
【００１０】[0010]
【課題を解決するための手段】上記の目的を達成するた
めの本発明による白色防錆顔料組成物は、リン酸亜鉛と
キレート能を有する有機リン化合物を含有させてなるこ
を構成上の特徴とするものである。The white rust-preventive pigment composition according to the present invention for achieving the above object is characterized by containing zinc phosphate and an organophosphorus compound having a chelating ability. It is what
【００１１】本発明の白色防錆顔料を組成するリン酸亜
鉛は、微細な球状粒子であって、見掛けの粒子は可及的
に微細であることが望ましい。ここに微細な球状粒子と
いうのは、従来のような粗大な板状乃至鱗片状一次粒子
との相対的関係において、実質的にこれを含まず、また
必ずしも真球を意味するものではなく、電子顕微鏡観察
により容易に確認できる丸味を帯びた微細粒子をいう。The zinc phosphate constituting the white rust preventive pigment of the present invention is fine spherical particles, and it is desirable that the apparent particles are as fine as possible. Here, the fine spherical particles, in the relative relationship with the conventional coarse plate-like or scale-like primary particles, substantially does not include this, and does not necessarily mean a true sphere, electron It refers to fine rounded particles that can be easily confirmed by microscopic observation.
【００１２】また、リン酸亜鉛は電子顕微鏡観察によれ
ばアモルファス的な粒子の如くであるが、主として４水
塩〔 Zn3(PO4)2・4H2O〕および／または２水塩〔 Zn3(P
O4)2・2H2O〕の混合結晶粒子であり、Ｘ線回析分析によ
って容易にこれを確認することができる。なお、本発明
のリン酸亜鉛には、リン酸亜鉛自体のほかにカルシウ
ム、マグネシウム、バリウム、ストロンチウムのアルカ
リ土類金属を約10％まで置換させた固溶体または混合リ
ン酸塩も含まれる。Further, although zinc phosphate is as amorphous specific particles according to electron microscopy, mainly tetrahydrate [Zn 3 (PO 4) 2 · 4H 2 O ] and / or dihydrate [Zn 3 (P
O 4) is 2 · 2H 2 O mixed crystal particles], it is possible to easily confirm this by X-ray diffraction analysis. The zinc phosphate of the present invention includes not only zinc phosphate itself, but also a solid solution or a mixed phosphate in which an alkaline earth metal such as calcium, magnesium, barium, or strontium is replaced by about 10%.
【００１３】次に、本発明に係る白色防錆顔料において
キレート能を有する有機リン化合物は特に限定する必要
はないが、例えばアミノアルキレンホスホン酸、エチレ
ンジアミンテトラアルキレンホスホン酸、アルキルメタ
ン−１−ヒドロキシ−１，１−ジホスホン酸、２−ヒド
ロキシホスホノ酢酸およびそれらのアンモニウム塩、ア
ルカリ金属塩、亜鉛、カルシウム、マグネシウム、バリ
ウム、ストロンチウムのような二価金属塩が代表的な成
分となる。Next, the organophosphorus compound having a chelating ability in the white rust preventive pigment according to the present invention is not particularly limited. For example, aminoalkylenephosphonic acid, ethylenediaminetetraalkylenephosphonic acid, alkylmethane-1-hydroxy- Typical components are 1,1-diphosphonic acid, 2-hydroxyphosphonoacetic acid and their ammonium salts, alkali metal salts, divalent metal salts such as zinc, calcium, magnesium, barium and strontium.
【００１４】アミノアルキレンホスホン酸としては、例
えばニトリロトリスメチレンホスホン酸、ニトリロトリ
スエチレンホスホン酸、ニトリロトリスプロピレンホス
ホン酸、ニトリロジエチルメチレンホスホン酸、ニトリ
ロプロピルビスメチレンホスホン酸等が、エチレンジア
ミンテトラアルキレンホスホン酸としては、例えばエチ
レンジアミンテトラメチレンホスホン酸、エチレンジア
ミンテトラエチレンホスホン酸、エチレンジアミンテト
ラプロピレンホスホン酸等が、アルキルメタン−１−ヒ
ドロキシ−１，１−ジホスホン酸としては、例えばメタ
ン−１−ヒドロキシ−１，１−ジホスホン酸、エタン−
１−ヒドロキシ−１，１−ジホスホン酸、プロパン−１
−ヒドロキシ−１，１−ジホスホン酸等が挙げられ、そ
れらは１種又は２種以上であってもよい。As the aminoalkylenephosphonic acid, for example, nitrilotrismethylenephosphonic acid, nitrilotristrisethylenephosphonic acid, nitrilotristrisphosphonic acid, nitrilodiethylmethylenephosphonic acid, nitrilopropylbismethylenephosphonic acid and the like are used as ethylenediaminetetraalkylenephosphonic acid. Are, for example, ethylenediaminetetramethylenephosphonic acid, ethylenediaminetetraethylenephosphonic acid, ethylenediaminetetrapropylenephosphonic acid and the like, and as alkylmethane-1-hydroxy-1,1-diphosphonic acid, for example, methane-1-hydroxy-1,1- Diphosphonic acid, ethane-
1-hydroxy-1,1-diphosphonic acid, propane-1
-Hydroxy-1,1-diphosphonic acid and the like can be mentioned, and they may be one kind or two or more kinds.
【００１５】かかるキレート能を有する有機リン化合物
のリン酸亜鉛に対する含有量は、当該化合物の種類や後
記する顔料の調製法等によって異なるものであるが、顔
料組成物全重量当り 0.1〜30重量％、好ましくは１〜10
重量％の範囲にある。 0.1重量％未満ではリン酸亜鉛の
改質が実質的になされずに防錆力が不充分となり、一
方、30重量％を越えると顔料特性が悪化して塗料化に支
障が生じるのみならず、経済的に不利になる。The content of the organophosphorus compound having a chelating ability with respect to zinc phosphate varies depending on the type of the compound and the method for preparing the pigment described below, but is 0.1 to 30% by weight based on the total weight of the pigment composition. , Preferably 1-10
It is in the range of% by weight. If it is less than 0.1% by weight, the zinc phosphate is not substantially modified and the rust preventive power becomes insufficient, while if it exceeds 30% by weight, not only the pigment characteristics are deteriorated but the formation of a paint is hindered. It becomes economically disadvantageous.
【００１６】キレート能を有する有機リン化合物をリン
酸亜鉛に含有させる方法には湿式法と乾式法とが考えら
れるが、湿式法を適用することが好ましい。湿式法とい
うのは、リン酸亜鉛の製造の際にリン酸源の一部代替と
して上記有機リン化合物を使用する方法であり、これに
は例えば、次のような幾つかの態様がある。 (1) 酸化亜鉛（亜鉛華）のスラリー（Ａ液）とリン酸と
有機リン化合物の混合液を混合して反応させる方法。 (2) Ａ液とリン酸と有機リン化合物とを個別的に混合し
て反応させる方法。 (3) Ａ液の調製の際に有機リン化合物を添加して反応さ
せたスラリーとリン酸とを混合反応させる方法。 (4) 可溶性亜鉛塩（例えば硫酸亜鉛、硝酸亜鉛）とリン
酸アルカリおよび有機リン化合物との混合液を混合して
反応させる方法。A wet method and a dry method can be considered as a method of incorporating an organophosphorus compound having a chelating ability into zinc phosphate, but a wet method is preferably applied. The wet method is a method in which the above-mentioned organic phosphorus compound is used as a partial substitute for a phosphoric acid source in the production of zinc phosphate, and there are, for example, the following several modes. (1) A method in which a slurry (Liquid A) of zinc oxide (zinc white), a mixed solution of phosphoric acid and an organic phosphorus compound are mixed and reacted. (2) A method in which the solution A, phosphoric acid, and an organic phosphorus compound are individually mixed and reacted. (3) A method of mixing and reacting a slurry obtained by adding an organic phosphorus compound and reacting it with phosphoric acid when preparing the liquid A. (4) A method in which a mixed solution of a soluble zinc salt (eg, zinc sulfate, zinc nitrate), an alkali phosphate and an organic phosphorus compound is mixed and reacted.
【００１７】なお、上記の各反応においては、必要に応
じ酸化亜鉛または亜鉛塩の代りに一部、アルカリ土類金
属の酸化物、水酸化物あるいは可溶性塩を亜鉛量の約10
％まで配合使用することができる。また、酸化亜鉛を用
いる不均一系反応において、分散剤やシリカ、アルミ
ナ、ジルコニアなどのゾルを少量使用することもでき
る。In each of the above reactions, if necessary, instead of zinc oxide or zinc salt, a portion of an oxide, hydroxide or soluble salt of an alkaline earth metal may be used in an amount of about 10 parts of zinc.
It can be blended and used up to%. Further, in a heterogeneous reaction using zinc oxide, a small amount of a dispersant or a sol such as silica, alumina or zirconia can be used.
【００１８】反応時の温度は特に限定の必要はなく、常
温または加温のいずれの条件でもよい。しかし、固液の
不均一系の反応にあっては、多くの場合40〜80℃の温度
範囲に加温することが好ましい。反応時間は0.5 〜10時
間、好ましくは１〜６時間の範囲にある。反応終了後
は、要すれば湿式粉砕を施したのち、常法により濾過、
分離、洗浄、乾燥および粉砕して製品とする。The temperature at the time of reaction is not particularly limited and may be room temperature or heating. However, in the case of solid-liquid heterogeneous reaction, it is often preferable to heat to a temperature range of 40 to 80 ° C. The reaction time is in the range of 0.5 to 10 hours, preferably 1 to 6 hours. After the completion of the reaction, if necessary, wet pulverization is performed, and then filtration by a conventional method,
Separate, wash, dry and grind to make product.
【００１９】一方、乾式法は予め調製したリン酸亜鉛に
有機リン化合物溶液を添加して均一化とともに反応させ
る方法であり、この場合、酸化亜鉛と有機リン化合物と
の混合反応物を添加配合させてもよい。該乾式法での反
応は、強力セン断力を伴う混合機、例えばヘンシェルミ
キサー、ボールミルあるいは強力なブレンダー等でおこ
ない、これを製品とする。On the other hand, the dry method is a method in which a solution of an organic phosphorus compound is added to zinc phosphate prepared in advance and the reaction is carried out with homogenization. In this case, a mixed reaction product of zinc oxide and an organic phosphorus compound is added and blended. May be. The reaction in the dry method is carried out with a mixer accompanied by a strong shearing force, such as a Henschel mixer, a ball mill or a powerful blender, to obtain a product.
【００２０】本発明に係るリン酸亜鉛系防錆顔料組成物
は、必要に応じ使用時の取扱いを考慮して表面処理を施
すことができる。表面処理剤としては、シランカップリ
ング剤、高級脂肪酸、若しくはその金属塩の如き誘導
体、酸性リン酸エステルまたはその金属塩等が挙げられ
る。更に本発明に係る防錆顔料組成物は、必要に応じて
他の白色防錆顔料、例えば亜リン酸塩系、次亜リン酸塩
系、トリポリリン酸アルミニウム系、モリブデン酸塩系
の防錆顔料との配合物、またはシリカ、酸化チタン、亜
鉛華、硫酸バリウム、リン酸カルシウム、リン酸マグネ
シウム等の増量剤との配合物として使用することができ
る。The zinc phosphate-based rust preventive pigment composition according to the present invention can be subjected to a surface treatment, if necessary, in consideration of handling during use. Examples of the surface treatment agent include a silane coupling agent, a higher fatty acid, or a derivative such as a metal salt thereof, an acidic phosphoric acid ester or a metal salt thereof, and the like. Further, the anticorrosive pigment composition according to the present invention, if necessary, other white anticorrosive pigments, for example, phosphite-based, hypophosphite-based, aluminum tripolyphosphate-based, molybdate-based anticorrosion pigments. Or a filler with silica, titanium oxide, zinc white, barium sulfate, calcium phosphate, magnesium phosphate, or the like.
【００２１】[0021]
【作用】本発明に係る白色防錆顔料は、リン酸亜鉛にキ
レート能を有する有機リン化合物を含有させることによ
り、結晶発達に対する著しい抑制作用と障壁作用をもた
らして、板状乃至鱗片状の粗大な一次粒子を実質的に含
有しない微細な球状粒子を生成させる。他方、リン酸亜
鉛の生成において亜鉛の一部をアルカリ土類金属と置換
することにより同様に微細な粒子を生成させる作用を有
する。このような微細な粒子からなるリン酸亜鉛と共に
キレート能を有する有機リン化合物の存在がより一層の
防錆能を発揮させるために機能し、無公害の白色防錆顔
料組成物となる。The white rust-preventive pigment according to the present invention contains zinc phosphate having an organophosphorus compound having a chelating ability, thereby exerting a remarkable inhibitory effect and a barrier effect on the crystal development, resulting in plate-like or flaky coarse particles. To form fine spherical particles substantially free of such primary particles. On the other hand, in the production of zinc phosphate, a part of zinc is replaced with an alkaline earth metal, which also has an action of producing fine particles. The presence of an organophosphorus compound having a chelating ability together with zinc phosphate composed of such fine particles functions to exert further anticorrosive ability, resulting in a pollution-free white anticorrosive pigment composition.
【００２２】[0022]
【実施例】以下、本発明の実施例を比較例と対比して具
体的に説明する。なお、各例において「部」とあるのは
重量を示すものとする。EXAMPLES Examples of the present invention will be specifically described below in comparison with comparative examples. In addition, in each example, "part" means weight.
【００２３】実施例１ 亜鉛華(JIS 3号）11.1部を水 100部に加え、十分に撹拌
混合した。ついで、コロイドミルに通して機械的分散操
作を施し、亜鉛華スラリー（Ａ液）を得た。このＡ液を
撹拌しながら50℃に加温し、これに75％リン酸10.3部と
メタン−１−ヒドロキシ−１，１−ジホスホン酸の60％
水溶液 1.4部を水39.1部に溶解した混合液（Ｂ液）を0.
85部／分の添加速度で徐々に添加した。添加反応後もス
ラリー温度50℃を維持しながら約１時間撹拌を続けた。
ついで、常法により濾過、乾燥、粉砕の工程を経て防錆
顔料を得た。得られた顔料は白色を呈し、電子顕微鏡写
真で観察したところ球状の微粒子であった。Example 1 11.1 parts of zinc white (JIS No. 3) was added to 100 parts of water, and they were sufficiently stirred and mixed. Then, it was passed through a colloid mill and mechanically dispersed to obtain a zinc white slurry (Liquid A). The solution A was heated to 50 ° C. with stirring, to which 10.3 parts of 75% phosphoric acid and 60% of methane-1-hydroxy-1,1-diphosphonic acid were added.
A mixture of 1.4 parts of water and 39.1 parts of water (solution B) was added to 0.
Gradually added at an addition rate of 85 parts / min. After the addition reaction, stirring was continued for about 1 hour while maintaining the slurry temperature at 50 ° C.
Then, a rust preventive pigment was obtained through the steps of filtration, drying and pulverization by a conventional method. The obtained pigment was white and spherical particles were observed by an electron micrograph.
【００２４】実施例２ 亜鉛華(JIS 1号)11.1 部をヘキサメタリン酸ナトリウム
1.2部と水 100部の溶液に加え、混合撹拌した。ついで
ホモジナイザーに通して機械的分散操作を施して亜鉛華
スラリー（Ａ液）を得た。このＡ液を撹拌しながら50℃
に加温し、これに75％リン酸10.3部とメタン−１−ヒド
ロキシ−１，１−ジホスホン酸の60％水溶液 1.4部を水
39.1部に溶解した混合液（Ｂ液）を0.85部／分の添加速
度で徐々に添加した。添加反応後もスラリー温度50℃を
維持しながら約１時間撹拌を続けた。ついで、常法によ
り濾過、乾燥、粉砕の工程を経て防錆顔料を得た。得ら
れた顔料は白色で、電子顕微鏡写真観察したところ球状
微粒子であった。Example 2 11.1 parts of zinc white (JIS No. 1) was added to sodium hexametaphosphate.
A solution of 1.2 parts and 100 parts of water was added and mixed and stirred. Then, it was passed through a homogenizer and mechanically dispersed to obtain a zinc white slurry (Liquid A). 50 ℃ with stirring this liquid A
The mixture was heated to 10% with 75% phosphoric acid and 1.4 parts of a 60% aqueous solution of methane-1-hydroxy-1,1-diphosphonic acid.
The mixed solution (B solution) dissolved in 39.1 parts was gradually added at an addition rate of 0.85 part / min. After the addition reaction, stirring was continued for about 1 hour while maintaining the slurry temperature at 50 ° C. Then, a rust preventive pigment was obtained through the steps of filtration, drying and pulverization by a conventional method. The obtained pigment was white and was found to be spherical fine particles when observed by an electron micrograph.
【００２５】実施例３ 実施例１と同様にして得たＡ液を撹拌しながら50℃に加
温し、これに75％リン酸10.3部とニトリロトリスメチレ
ンホスホン酸の50％水溶液 1.7部を水39.1部に溶解した
混合液（Ｂ液）を0.85部／分の添加速度で徐々に添加し
た。添加反応後もスラリー温度50℃を維持しながら約１
時間撹拌を続けた。ついで、常法により濾過、乾燥、粉
砕の工程を経て防錆顔料を得た。得られた顔料は白色
で、電子顕微鏡写真観察により球状微粒子であることが
確認された。Example 3 Solution A obtained in the same manner as in Example 1 was heated to 50 ° C. with stirring, and 10.3 parts of 75% phosphoric acid and 1.7 parts of a 50% aqueous solution of nitrilotrismethylenephosphonic acid were added to water. The mixed solution (B solution) dissolved in 39.1 parts was gradually added at an addition rate of 0.85 part / min. Approximately 1 while maintaining the slurry temperature at 50 ° C after the addition reaction
Stirring was continued for hours. Then, a rust preventive pigment was obtained through the steps of filtration, drying and pulverization by a conventional method. The obtained pigment was white, and it was confirmed by electron micrograph observation that it was spherical fine particles.
【００２６】比較例 実施例１と同様にして得たＡ液を撹拌しながら50℃に加
温し、これに75％リン酸11.4を水63.6部に溶解した液
（Ｂ液）を1.25部／分の添加速度で徐々に添加した。そ
の後は実施例と同様の操作を経て白色防錆顔料を得た。
この顔料を電子顕微鏡写真観察したところ、板状の粗粒
子であった。Comparative Example Solution A obtained in the same manner as in Example 1 was heated to 50 ° C. with stirring, and 1.25 parts of a solution prepared by dissolving 75% phosphoric acid 11.4 in water 63.6 parts (solution B) was used. It was added gradually at the addition rate of minutes. After that, the same procedure as in the example was performed to obtain a white rust preventive pigment.
When this pigment was observed with an electron microscope photograph, it was found to be plate-like coarse particles.
【００２７】防錆能の評価 実施例と比較例で得た各防錆顔料および市販の無公害型
防錆顔料を対象とし、下記の条件により防錆試験をおこ
なった。 (1) 防錆塗料の調製 各防錆顔料５部とアルキッド系水性ワニス〔大日本イン
キ工業（株）製、ウォーターゾルCD-520〕112 部をペイ
ントシェーカーにて塗料化し、試験防錆塗料を調製し
た。 (2) 塗装鋼板の調製 上記の防錆試験塗料組成物 100部に対し１部のドライヤ
ー（５％ナフテン酸コバルトドライヤーＷタイプ：20％
ナフテン酸鉛ドライヤーＷタイプ＝１：１）を配合し、
250× 350×1.6 の日本テストパネル製、鉄板 SS400
（旧SS41) に乾燥塗装膜厚が20〜30μm になるようにバ
ーコーターにて塗布し、室温で１週間乾燥させて塗装鋼
板を得た。ついで、乾燥塗装鋼板を70×150 の大きさに
切断して１枚当たり６枚の試験鋼板を得た。Evaluation of Anticorrosion Ability of each antirust pigment obtained in Examples and Comparative Examples and a commercially available pollution-free antirust pigment were subjected to an antirust test under the following conditions. (1) Preparation of anti-corrosion paint 5 parts of each anti-corrosion pigment and 112 parts of alkyd water-based varnish [Dainippon Ink & Chemicals Co., Ltd., Watersol CD-520] were made into a paint using a paint shaker to prepare a test anti-corrosion paint. Prepared. (2) Preparation of coated steel sheet 1 part of a dryer (5% cobalt naphthenate dryer W type: 20% to 100 parts of the above-mentioned rustproof test coating composition)
Mix lead naphthenate dryer W type = 1: 1),
250 × 350 × 1.6 Japanese test panel, iron plate SS400
(Old SS41) was coated with a bar coater so that the dry coating film thickness was 20 to 30 μm, and dried at room temperature for 1 week to obtain a coated steel sheet. Then, the dry coated steel plate was cut into a size of 70 × 150 to obtain 6 test steel plates per one.
【００２８】(3) 防錆試験 (2) で調製した塗装鋼板をクロスカットして塩水噴霧試
験機にセットし、防錆試験をおこなった。 (4) 試験評価結果 塩水噴霧試験 400時間における結果を下記５段階評価法
により評価し、防錆顔料の防錆効果を判定した。 評点５：クロスカット部以外の錆発生が全くなく、ブリ
スターもない。 評点４：クロスカット部から片側２mm以内に錆が発生。
ブリスターはない。 評点３：クロスカット部から片側６mm以内に錆および部
分的にブリスターが発生。 評点２：クロスカット部から片側12mm以内に錆および部
分的にブリスターが発生。 評点１：鋼板全面に錆およびブリスターが発生。 得られた各防錆顔料の防錆能評価結果を表１に示した。
なお、表１のブランクとは防錆顔料を含有しないワニス
を用いた塗装鋼板である。(3) Rust prevention test The coated steel sheet prepared in (2) was cross-cut and set in a salt spray tester to perform a rust prevention test. (4) Test evaluation results The results of the salt spray test for 400 hours were evaluated by the following five-stage evaluation method to determine the rust preventive effect of the rust preventive pigment. Rating 5: No rust was generated except in the cross-cut portion, and there was no blister. Rating 4: Rust occurred within 2 mm on one side from the cross cut part.
There are no blister. Rating 3: Rust and partial blister occurred within 6 mm on one side from the cross cut part. Rating 2: Rust and partial blister occurred within 12 mm on one side from the cross cut part. Rating 1: Rust and blisters occurred on the entire surface of the steel sheet. Table 1 shows the results of evaluation of the rust preventive ability of the obtained rust preventive pigments.
The blank in Table 1 is a coated steel sheet using a varnish containing no rust preventive pigment.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【発明の効果】本発明に係る白色防錆顔料組成物は、微
細な球状粒子から構成されるリン酸亜鉛を主組成とし、
これにキレート能を有する有機リン化合物を含有したも
のであるが、従来の無公害白色防錆顔料に比べて著しく
優れた防錆能力を有している。この防錆能力は水性塗料
系において十分に発揮されるため、無公害の白色防錆顔
料として大いに実用性が期待できるものである。The white rust preventive pigment composition according to the present invention comprises zinc phosphate composed of fine spherical particles as a main composition,
Although it contains an organophosphorus compound having a chelating ability, it has a remarkably excellent rust preventive ability as compared with conventional non-polluting white rust preventive pigments. Since this rust preventive ability is sufficiently exerted in the water-based paint system, it can be expected to be highly practical as a pollution-free white rust preventive pigment.
フロントページの続き (72)発明者 横山 棯 東京都板橋区坂下３丁目36番５号 東邦顔 料工業株式会社研究部内Continuation of the front page (72) Inventor, Yoko Yoko Iso 3-6-5 Sakashita, Itabashi-ku, Tokyo Toho Kagaku Kogyo Co., Ltd. Research Department
Claims (5)
ン化合物を含有させてなることを特徴とする白色防錆顔
料組成物。1. A white rust preventive pigment composition comprising zinc phosphate containing an organic phosphorus compound having a chelating ability.
求項１記載の白色防錆顔料組成物。2. The white rust preventive pigment composition according to claim 1, wherein the zinc phosphate is fine spherical particles.
水塩の混合物である請求項１又は２記載の白色防錆顔料
組成物。3. Zinc phosphate is tetrahydrate and / or 2
The white rust preventive pigment composition according to claim 1 or 2, which is a mixture of hydrates.
アミノアルキレンホスホン酸、エチレンジアミンテトラ
アルキレンホスホン酸、アルキルメタン−１−ヒドロキ
シ−１，１−ジホスホン酸、２−ヒドロキシホスホノ酢
酸またはそれらの塩から選ばれた１種又は２種以上であ
る請求項１記載の白色防錆顔料組成物。4. An organophosphorus compound having a chelating ability,
One or more selected from aminoalkylenephosphonic acid, ethylenediaminetetraalkylenephosphonic acid, alkylmethane-1-hydroxy-1,1-diphosphonic acid, 2-hydroxyphosphonoacetic acid or salts thereof. The white rust preventive pigment composition described.
有量が、全重量当り0.1 〜30重量％である請求項１又は
４記載の白色防錆顔料組成物。5. The white rust preventive pigment composition according to claim 1, wherein the content of the organic phosphorus compound having a chelating ability is 0.1 to 30% by weight based on the total weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04078547A JP3131492B2 (en) | 1992-02-27 | 1992-02-27 | Method for producing white rust preventive pigment composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04078547A JP3131492B2 (en) | 1992-02-27 | 1992-02-27 | Method for producing white rust preventive pigment composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05239376A true JPH05239376A (en) | 1993-09-17 |
| JP3131492B2 JP3131492B2 (en) | 2001-01-31 |
Family
ID=13664948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04078547A Expired - Lifetime JP3131492B2 (en) | 1992-02-27 | 1992-02-27 | Method for producing white rust preventive pigment composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3131492B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006054593A1 (en) * | 2004-11-17 | 2006-05-26 | Dai Nippon Toryo Co., Ltd. | Anticorrosive coating compositions |
| JP2015199800A (en) * | 2014-04-04 | 2015-11-12 | パナソニックＩｐマネジメント株式会社 | Adhesive composition for metal member and thermoplastic resin-coated metal member prepared using the same |
| WO2016102265A1 (en) * | 2014-12-22 | 2016-06-30 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Method for producing anisotropic zinc phosphate particles and zinc metal mixed phosphate particles and use thereof |
-
1992
- 1992-02-27 JP JP04078547A patent/JP3131492B2/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006054593A1 (en) * | 2004-11-17 | 2006-05-26 | Dai Nippon Toryo Co., Ltd. | Anticorrosive coating compositions |
| US7658791B2 (en) | 2004-11-17 | 2010-02-09 | Dai Nippon Toryo Co., Ltd. | Anticorrosive coating compositions |
| JP2015199800A (en) * | 2014-04-04 | 2015-11-12 | パナソニックＩｐマネジメント株式会社 | Adhesive composition for metal member and thermoplastic resin-coated metal member prepared using the same |
| WO2016102265A1 (en) * | 2014-12-22 | 2016-06-30 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Method for producing anisotropic zinc phosphate particles and zinc metal mixed phosphate particles and use thereof |
| JP2018507153A (en) * | 2014-12-22 | 2018-03-15 | ライプニッツ−インスティトゥート フィア ノイエ マテリアーリエン ゲマインニュッツィゲ ゲゼルシャフト ミット ベシュレンクタ ハフトゥンク | Method for producing anisotropic zinc phosphate particles and anisotropic zinc metal mixed phosphate particles, and use thereof |
| US10774223B2 (en) | 2014-12-22 | 2020-09-15 | Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh | Method for producing anisotropic zinc phosphate particles |
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| Publication number | Publication date |
|---|---|
| JP3131492B2 (en) | 2001-01-31 |
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