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JP2968118B2 - Scale-like composite pigment having durability gloss and method for producing the same - Google Patents

Scale-like composite pigment having durability gloss and method for producing the same

Info

Publication number
JP2968118B2
JP2968118B2 JP4328892A JP4328892A JP2968118B2 JP 2968118 B2 JP2968118 B2 JP 2968118B2 JP 4328892 A JP4328892 A JP 4328892A JP 4328892 A JP4328892 A JP 4328892A JP 2968118 B2 JP2968118 B2 JP 2968118B2
Authority
JP
Japan
Prior art keywords
flaky
inorganic
powder
composite
pigment
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
Application number
JP4328892A
Other languages
Japanese (ja)
Other versions
JPH05239378A (en
Inventor
陸雄 荻野
賢輔 水野
憲之 鈴木
博志 伊藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NIPPON PAAKARAIJINGU KK
Original Assignee
NIPPON PAAKARAIJINGU KK
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by NIPPON PAAKARAIJINGU KK filed Critical NIPPON PAAKARAIJINGU KK
Priority to JP4328892A priority Critical patent/JP2968118B2/en
Publication of JPH05239378A publication Critical patent/JPH05239378A/en
Application granted granted Critical
Publication of JP2968118B2 publication Critical patent/JP2968118B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/06Treatment with inorganic compounds
    • C09C3/063Coating
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/0015Pigments exhibiting interference colours, e.g. transparent platelets of appropriate thinness or flaky substrates, e.g. mica, bearing appropriate thin transparent coatings
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40Compounds of aluminium
    • C09C1/405Compounds of aluminium containing combined silica, e.g. mica
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/10Interference pigments characterized by the core material
    • C09C2200/102Interference pigments characterized by the core material the core consisting of glass or silicate material like mica or clays, e.g. kaolin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2200/00Compositional and structural details of pigments exhibiting interference colours
    • C09C2200/40Interference pigments comprising an outermost surface coating
    • C09C2200/401Inorganic protective coating
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2220/00Methods of preparing the interference pigments
    • C09C2220/10Wet methods, e.g. co-precipitation
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C2220/00Methods of preparing the interference pigments
    • C09C2220/10Wet methods, e.g. co-precipitation
    • C09C2220/106Wet methods, e.g. co-precipitation comprising only a drying or calcination step of the finally coated pigment

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Powder Metallurgy (AREA)

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明が属する技術分野】本発明は、耐久性光沢を有す
る鱗片状複合顔料およびその製造方法に関するものであ
る。更に詳しく述べるならば、本発明は、ジルコニウム
化合物・クロム含有複合材料からなる複合皮膜層を有
し、耐水性、耐候性の優れた、耐久性光沢を有する鱗片
状複合顔料、およびその製造方法に関するものである。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flaky composite pigment having a durable gloss and a method for producing the same. More specifically, the present invention relates to a flaky composite pigment having a durable gloss, having a composite coating layer composed of a zirconium compound / chromium-containing composite material, having excellent water resistance and weather resistance, and a method for producing the same. Things.

【0002】[0002]

【従来の技術】自動車等の外装用塗膜に要求される品質
のうち、特に重要なことは、屋外の様々な気象環境条件
に長期間曝されても外観品質の低下が無いことである。
従来より、二酸化チタンを顔料として樹脂中に分散、含
有せしめた塗膜の場合、チョーキングと呼ばれる白亜化
現象が発生することが知られている。二酸化チタンの有
するこの様な性質を抑制する手段として、クロム化合
物、珪素化合物、りん化合物、ジルコニウム化合物等か
ら選ばれた少なくとも1種を、顔料用二酸化チタン中に
ドープしたり、或はその表面を被覆して安定化する方法
が提案されている。
2. Description of the Related Art Among the quality requirements for exterior coating films for automobiles and the like, it is particularly important that the appearance quality does not deteriorate even when exposed to various outdoor weather conditions for a long period of time.
It has been known that a chalking phenomenon called chalking occurs in a coating film in which titanium dioxide is dispersed and contained in a resin as a pigment. As means for suppressing such properties possessed by titanium dioxide, at least one selected from chromium compounds, silicon compounds, phosphorus compounds, zirconium compounds, etc. is doped into titanium dioxide for pigments or the surface thereof is Methods of coating and stabilizing have been proposed.

【0003】自動車用外面塗装に、アルミニウムフレー
ク顔料を樹脂中に分散、含有せしめた塗料が使用されて
いるが、このような顔料を含む塗膜も、様々な気象条件
に曝された場合に塗膜外観が劣化することが知られてい
る。この様な気象条件に対する耐久性を評価する方法と
しては屋外暴露試験が知られているが、その他に促進評
価法として促進耐候性試験、湿潤試験、高温水浸漬試験
等の試験が知られており、それによって塗膜表面の光
沢、色調等の劣化を評価することができる。
[0003] Paints in which aluminum flake pigments are dispersed and contained in a resin are used for exterior coating for automobiles, and coatings containing such pigments are also applied when exposed to various weather conditions. It is known that the film appearance deteriorates. An outdoor exposure test is known as a method for evaluating the durability against such weather conditions, but other accelerated evaluation methods such as an accelerated weather resistance test, a wet test, and a high-temperature water immersion test are also known. This makes it possible to evaluate the deterioration of the gloss and color tone of the coating film surface.

【0004】従来、雲母薄片、雲母状酸化鉄等(以下雲
母薄片等と称す)の鱗片状顔料粉末の表面に、酸化チタ
ン、酸化鉄等の金属酸化物を単独で、または酸化チタン
と酸化鉄とを組み合わせてコーティングを施し、真珠光
沢を有する顔料を調製すること、およびこのような光沢
顔料を塗料、インキ、プラスチック等の着色剤として使
用することが知られている。しかしながら、このような
雲母薄片等の表面に二酸化チタン等の金属酸化物をコー
ティングして得られる光沢顔料を使用した塗料を、自動
車等の外面塗装に適用した場合、その塗膜は、アルミニ
ウムフレーク顔料を樹脂中に分散、含有せしめた塗料か
らなる塗膜と同様に、高温水浸漬試験等の耐水性試験に
おいて塗膜の光沢劣化などが発生し到底実用に適さない
ものである。
Conventionally, metal oxides such as titanium oxide and iron oxide, or titanium oxide and iron oxide have been applied to the surface of flaky pigment powders such as mica flakes and mica-like iron oxide (hereinafter referred to as mica flakes and the like). It is known to apply a coating to prepare a pigment having pearl luster and to use such a luster pigment as a colorant for paints, inks, plastics and the like. However, when a paint using a glossy pigment obtained by coating the surface of such a mica flake with a metal oxide such as titanium dioxide is applied to the exterior coating of an automobile or the like, the coating film is made of aluminum flake pigment. In a water resistance test such as a high-temperature water immersion test, gloss deterioration of the coating film occurs, which is completely unsuitable for practical use, similarly to a coating film composed of a paint dispersed and contained in a resin.

【0005】塗膜表面の光沢、色調等の劣化の原因とし
て、水分子が塗膜を透過し顔料表面に到達することによ
り微細な膨れを形成し、その後、水が蒸発することによ
り、塗膜中に微細な空孔を形成し、この空孔部が著しく
光を散乱して、塗膜表面の光沢、色調を劣化すると考え
られている。この様な金属酸化物で被覆された雲母薄片
等を顔料として含有する塗膜において、その外観の劣化
を防止する方法として、通常の顔料用二酸化チタンに施
されている表面処理方法を応用することは容易に類推で
きる。しかし、金属酸化物被覆雲母薄片等からなる真珠
光沢顔料は、単なる顔料用二酸化チタンより遙かに複雑
な性状を有しており、従って顔料用二酸化チタンの表面
処理と同一の方法を、金属酸化物被覆雲母薄片からなる
真珠光沢顔料に応用しても、その耐水性向上効果が無い
か、または不十分である。
[0005] As a cause of deterioration of the gloss and color tone of the coating film surface, water molecules penetrate the coating film and reach the pigment surface to form fine blisters. It is considered that fine pores are formed therein, and the pores remarkably scatter light, thereby deteriorating the gloss and color tone of the coating film surface. As a method for preventing the deterioration of the appearance of a coating film containing a mica flake or the like coated with such a metal oxide as a pigment, a surface treatment method applied to titanium dioxide for a pigment is usually applied. Can be easily analogized. However, pearlescent pigments composed of metal oxide-coated mica flakes and the like have properties much more complicated than mere titanium dioxide for pigments. Even if applied to pearlescent pigments composed of flakes of mica flakes, the effect of improving water resistance is not available or is insufficient.

【0006】一方、二酸化チタン被覆雲母薄片に対する
耐水性付与方法として、特開昭47−34527号に
は、この顔料基体の表面をメタクリラートクロムクロラ
イドで処理して得られる顔料及びその製造方法が開示さ
れている。また、特開昭54−96534号には、クロ
ム(III)化合物水溶液に水酸化ナトリウムなどの塩基性
物質を添加し、中和沈澱反応を利用してクロム(III)水
酸化物被覆層を形成する方法が開示されている。また、
特開昭58−69258号および特開昭58−6925
9号には、クロム酸化物および(または)クロムホスフ
ェートにより保護層を形成し、得られた顔料を焼成して
真珠光沢顔料を製造する方法、およびそれにより得られ
る真珠光沢顔料が開示されている。これらの方法は二酸
化チタン被覆雲母薄片からなる真珠光沢顔料の耐水性向
上には、ある程度の効果が認められるものの、しかし充
分ではない。
On the other hand, as a method for imparting water resistance to titanium dioxide-coated mica flakes, JP-A-47-34527 discloses a pigment obtained by treating the surface of a pigment base with methacrylate chromium chloride and a method for producing the same. Have been. JP-A-54-96534 discloses that a chromium (III) hydroxide coating layer is formed by adding a basic substance such as sodium hydroxide to a chromium (III) compound aqueous solution and utilizing a neutralization precipitation reaction. A method for doing so is disclosed. Also,
JP-A-58-69258 and JP-A-58-6925
No. 9 discloses a method for producing a pearlescent pigment by forming a protective layer with chromium oxide and / or chromium phosphate and calcining the obtained pigment, and a pearlescent pigment obtained thereby. . These methods have some effects, but are not sufficient, to improve the water resistance of pearlescent pigments composed of titanium dioxide-coated mica flakes.

【0007】一方、特開昭58−174449号には、
塩基性のクロム化合物、またはアルミニウム化合物と、
分子中にカルボキシル基1個当り4個より多い炭素原子
を含有するカルボン酸を用いて疎水性の真珠光沢顔料を
製造する方法が開示されている。また、特開昭59−7
8265号には、メタアクリレート・クロム塩化物を沈
着させた真珠光沢顔料が開示されている。これらの方法
にはメタアクリレート・クロム化合物のような特殊な原
料が使用されているため、経済的に不利なだけでなく、
得られる耐久性向上効果も充分なものとはいい難い。更
に特開昭63−130673号、および特開平1−29
2067号には次亜リン酸塩の存在下でジルコニウム化
合物を加水分解し、顔料基材表面に含水酸化ジルコニウ
ムを付着させて真珠光沢顔料を製造する方法が開示され
ている。しかしこれらの方法は非常に複雑な工程と厳密
な工程管理を必要としているため、製造上の不利は否め
ない。
On the other hand, JP-A-58-174449 discloses that
A basic chromium or aluminum compound,
A method for producing a hydrophobic pearlescent pigment using a carboxylic acid containing more than 4 carbon atoms per carboxyl group in the molecule is disclosed. Also, JP-A-59-7
No. 8265 discloses a pearlescent pigment having methacrylate chromium chloride deposited thereon. These methods use special raw materials such as methacrylate and chromium compounds, which are not only economically disadvantageous, but also
It is difficult to say that the obtained durability improving effect is sufficient. Further, Japanese Patent Application Laid-Open Nos.
No. 2067 discloses a method for producing a pearlescent pigment by hydrolyzing a zirconium compound in the presence of hypophosphite and attaching hydrous zirconium oxide to the surface of a pigment substrate. However, these methods require a very complicated process and strict process control, so that a disadvantage in manufacturing cannot be denied.

【0008】一般に金属材料の表面は酸化物に覆われて
いるため、これに表面処理を施さずにそのまま塗装をお
こなった場合には、水分、温度などの影響によりブリス
ターと呼ばれる塗膜膨れを生ずるという問題を有するこ
とが知られている。非晶質合金を、例えば特開平1−2
87209号記載の方法によりフレーク状粉末としたも
のを顔料として用い、これを樹脂中に分散含有せしめた
塗料から形成された塗膜の場合にも、この顔料と樹脂と
の界面で同様の膨れが生じ、塗膜外観が著しく損なわれ
るため、これが実用上の大きな障害となっている。
Generally, since the surface of a metal material is covered with an oxide, if the metal material is directly coated without being subjected to a surface treatment, a blistered film called blister is generated due to the influence of moisture, temperature and the like. It is known to have the problem that Amorphous alloys are disclosed in, for example,
In the case of a coating film formed from a paint obtained by dispersing and containing flake-form powder in a resin according to the method described in Japanese Patent No. 87209, similar swelling occurs at the interface between the pigment and the resin. As a result, the appearance of the coating film is significantly impaired, and this is a serious obstacle in practical use.

【0009】また、雲母薄片等の鱗片状粉末を顔料基材
として用い、これを金属酸化物で被覆して得られる真珠
光沢顔料、雲母薄片を二酸化チタンで被覆し、更にこの
二酸化チタン被覆層を、特開平3−79673号に記載
の方法等により低次酸化チタンとして得られる有色雲母
チタン顔料、鱗片状薄片を顔料基材として用い、これに
水溶液中からの無電解めっき法もしくは蒸着めっき法
(スパッタリング、PVD,CVD等を含む)等を施し
て金属被覆を形成して得られる顔料、或は、例えば特開
平1−108267号、および特開平1−104673
号に記載の方法により、金属または合金を鱗片状粉末か
らなる顔料基体の表面の一部に付着して得られた顔料、
を樹脂中に分散含有させた場合にも、樹脂と顔料との界
面で上記と同様の現象が発生し、塗膜と長期的な外観品
質が劣化するという問題があり、これが上記顔料の実用
化の妨げになっている。
A pearlescent pigment obtained by using flaky powder such as mica flakes as a pigment base material and coating it with a metal oxide is coated with titanium dioxide. A colored mica titanium pigment or flaky flake obtained as a lower titanium oxide by the method described in JP-A-3-79673 or the like is used as a pigment substrate, and electroless plating or vapor deposition plating from an aqueous solution ( (Including sputtering, PVD, CVD, etc.) or the like to form a metal coating, or, for example, JP-A-1-108267 and JP-A-1-1044673.
Pigment obtained by adhering a metal or alloy to a part of the surface of a pigment substrate made of flaky powder,
When dispersed in the resin, the same phenomenon as described above occurs at the interface between the resin and the pigment, and there is a problem that the coating film and the long-term appearance quality are deteriorated. It is hindering.

【0010】[0010]

【発明が解決しようとする課題】本発明は、自動車車体
外面塗装など、屋外の様々な厳しい自然環境下に長期間
晒されても充分な耐久性、すなわち色調、光沢において
長期耐久性を有する、光沢を有する鱗片状複合顔料、お
よびその製造方法を提供しようとするものである。
DISCLOSURE OF THE INVENTION The present invention has sufficient durability even under long-term exposure to various harsh natural environments such as exterior coating of automobile bodies, that is, long-term durability in color tone and gloss. An object of the present invention is to provide a flaky composite pigment having gloss and a method for producing the same.

【0011】[0011]

【課題を解決するための手段】本発明者らは、上記課題
を解決すべく鋭意検討を重ねた結果、鱗片状無機顔料粉
粒の表面に、ジルコニウム・クロム含有複合材料からな
る複合皮膜層を形成することにより、耐湿性、光沢保持
性、分散性に優れた耐久性光沢を有する鱗片状複合顔料
が得られることを見出し、本発明を完成したものであ
る。
Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that a composite coating layer made of a zirconium-chromium-containing composite material is formed on the surface of the flaky inorganic pigment particles. It has been found that by forming such a pigment, a flaky composite pigment having a durable gloss having excellent moisture resistance, gloss retention and dispersibility can be obtained, and the present invention has been completed.

【0012】本発明に係る耐久性光沢を有する鱗片状複
合顔料は、鱗片状無機顔料粉粒からなる基体(A)、及
び、前記鱗片状無機顔料粉粒からなる基体(A)の表面
を被覆し、かつジルコニウム・クロム含有複合材料から
なる複合皮膜層(B)を含み、前記鱗片状無機顔料粉粒
からなる基体(A)が、 (1)無機鱗片状粉粒からなる芯体の表面が、金属、合
金及び金属酸化物から選ばれた少なくとも1種からなる
表面層により被覆されている粉末、 (2)無機鱗片状粉粒からなる芯体の表面が、少なくと
も1層の金属又は合金皮膜層、及び少なくとも1層の金
属酸化物皮膜層を任意の順序で積層して形成された表面
層により被覆されている粉末、並びに、 (3)(i)無機鱗片状粉粒からなる芯体、及び(ii)
無機鱗片状粉粒からなる芯体の表面が、金属酸化物皮膜
層により被覆されている複合芯体、から選ばれた少なく
とも1種の表面に、金属及び合金から選ばれた少なくと
も1種からなる複数の皮膜層が島状に点在して形成され
ている粉末、から選ばれた少なくとも1種からなり、前
記粉末(1),(2)及び(3)の各々において、前記
無機鱗片状粉粒からなる芯体が、 (a)雲母薄片、 (b)アルミニウムフレーク、 (c)非晶質合金フレーク、及び (d)雲母状酸化鉄(MIO)粉末 から選ばれた少なくとも1種からなる、ことを特徴とす
る、耐久性光沢を有する鱗片状複合顔料。
The scaly composite pigment having a durable luster according to the present invention covers the surface of a substrate (A) composed of scaly inorganic pigment particles and the surface of a substrate (A) composed of the scaly inorganic pigment particles. And a composite coating layer (B) comprising a zirconium / chromium-containing composite material, wherein the substrate (A) comprising the flaky inorganic pigment particles comprises: (1) a core body comprising the inorganic flaky particles; Powder coated with a surface layer made of at least one selected from metals, alloys and metal oxides; and (2) at least one metal or alloy coating on the surface of a core made of inorganic flaky powder. And a powder coated with a surface layer formed by laminating at least one metal oxide film layer in an arbitrary order; and (3) (i) a core body composed of inorganic flaky powder, And (ii)
The surface of the core made of inorganic flaky powder is at least one type selected from a composite core coated with a metal oxide film layer, and at least one type selected from metals and alloys. A powder in which a plurality of coating layers are formed in an island-like manner; and in each of the powders (1), (2) and (3), the inorganic flaky powder The core body composed of particles comprises at least one selected from the group consisting of (a) mica flakes, (b) aluminum flakes, (c) amorphous alloy flakes, and (d) mica-like iron oxide (MIO) powder. A flaky composite pigment having a durable gloss.

【0013】また、本発明に係る耐久性光沢を有する鱗
片状複合顔料の製造方法は、前記無機鱗片状無機顔料粉
粒からなる基体(A)を、少なくとも1種のジルコニウ
ムイオン供給化合物と、少なくとも1種のクロム3価イ
オン供給化合物とを含有し、かつ1.0〜5.0のpH値
を有する酸性処理水溶液中に懸濁し、この懸濁液を20
〜90℃の温度に加熱処理することによって、前記顔料
粉粒の表面上に、ジルコニウム・クロム含有複合材料か
らなる複合皮膜層を形成し、前記加熱処理によって得ら
れた鱗片状顔料粉末を捕集し、水洗し、乾燥することを
特徴とするものである。
Further, the method for producing a scale-like composite pigment having a durable luster according to the present invention is characterized in that the base (A) comprising the inorganic scale-like inorganic pigment powder is prepared by mixing at least one zirconium ion supplying compound with at least one zirconium ion supplying compound. Suspended in an acidic treatment aqueous solution containing one kind of chromium trivalent ion supplying compound and having a pH value of 1.0 to 5.0.
A composite coating layer made of a zirconium-chromium-containing composite material is formed on the surface of the pigment particles by heat treatment at a temperature of ~ 90 ° C, and the flaky pigment powder obtained by the heat treatment is collected. And then washed with water and dried.

【0014】[0014]

【発明の実施の形態】本発明の鱗片状複合顔料におい
て、その顔料基体(A)と、複合皮膜層(B)との重量
比(A)/(B)は、1000/0.2〜1000/2
0であることが好ましく、1000/1〜1000/1
0であることがより好ましい。また、複合皮膜層(B)
は、顔料基体の表面の全面を被覆していることが好まし
いが、この表面の一部を被覆するものであってもよく、
この場合、顔料基体(A)の表面積の10%以上を被覆
していることが好ましい。
BEST MODE FOR CARRYING OUT THE INVENTION In the scaly composite pigment of the present invention, the weight ratio (A) / (B) of the pigment base (A) to the composite coating layer (B) is 1000 / 0.2 to 1000. / 2
0, preferably 1000/1 to 1000/1
More preferably, it is 0. In addition, composite coating layer (B)
Preferably covers the entire surface of the pigment substrate, but may cover a part of this surface,
In this case, it is preferable that 10% or more of the surface area of the pigment substrate (A) is covered.

【0015】本発明において鱗片状複合顔料の基体
(A)として用いられる鱗片状無機顔料粉粒は、下記粉
末材料: (1)無機鱗片状粉粒からなる芯体の表面が金属、合金
および金属酸化物から選ばれた少なくとも1種からなる
表面層により被覆されている粉末、 (2)無機鱗片状粉粒からなる芯体の表面が、少なくと
も1層の金属又は合金皮膜層、および少なくとも1層の
金属酸化物皮膜層を、任意の順序で積層して形成された
表面層により被覆されている粉末、 (3)(i)無機鱗片状粉粒からなる芯体、および(i
i)無機鱗片状粉粒からなる芯体の表面が金属酸化物被
膜層により被覆されている複合芯体、から選ばれた少な
くとも1種の表面に、金属および合金から選ばれた少な
くとも1種からなる複数の皮膜層が島状に形成されてい
る粉末、から選ばれる。前記粉体(1),(2)及び
(3)の各々において、前記無機鱗片状粉粒からなる芯
体が、 (a)雲母薄片、 (b)アルミニウムフレーク、 (c)非晶質合金フレーク、 (d)雲母状酸化鉄(MIO)粉末、 から選ばれた1種からなるものである。これらの粉末材
料(1),(2),(3)の各々は、鱗片状の形状を有
するものであって、その厚さは0.2〜5μm、直径
(長径、および短径)は5〜500μmであることが好
ましい。
In the present invention, the scaly inorganic pigment particles used as the base (A) of the scaly composite pigment include the following powder materials: (1) The surface of a core composed of inorganic scaly particles is formed of a metal, an alloy or a metal. Powder coated with at least one surface layer selected from oxides, (2) at least one metal or alloy film layer, and at least one layer of a core body made of inorganic flaky powder. Powder coated with a surface layer formed by laminating the metal oxide film layers in any order; (3) (i) a core composed of inorganic flaky powder;
i) at least one surface selected from a composite core in which the surface of a core composed of inorganic flaky particles is coated with a metal oxide coating layer, and at least one surface selected from a metal and an alloy; Powder in which a plurality of coating layers are formed in an island shape. In each of the powders (1), (2) and (3), the core made of the inorganic flaky powder is (a) mica flake, (b) aluminum flake, (c) amorphous alloy flake And (d) mica-like iron oxide (MIO) powder. Each of these powder materials (1), (2), and (3) has a flaky shape, a thickness of 0.2 to 5 μm, and a diameter (major axis and minor axis) of 5 μm. It is preferably about 500 μm.

【0016】本発明に用いられる非晶質合金フレーク
(c)は、例えば、10%Ni、10%Cr、2%M
o、12%P、8%C、残Feの非晶質合金、又は5%
Ni、15%Cr、2%Mo、11%P、10%C、残
Feの非晶質合金からなるフレークから選ばれることが
好ましい。
The amorphous alloy flake (c) used in the present invention is, for example, 10% Ni, 10% Cr, 2% M
o, 12% P, 8% C, amorphous alloy of residual Fe, or 5%
It is preferable to be selected from flakes composed of an amorphous alloy of Ni, 15% Cr, 2% Mo, 11% P, 10% C, and the remaining Fe.

【0017】また、本発明において基体として用いられ
る粉末材料(1),(2)および(5)において、芯体
として用いられる無機鱗片状粉粒は、前述のように芯体
材料(a),(b),(c)、および(d)から選ばれ
たものである。
In the powder materials (1), (2) and (5) used as the substrate in the present invention, the inorganic flaky powder used as the core is composed of the core material (a), (B), (c), and (d).

【0018】更に、粉末材料(1)〜(3)において表
面層、皮膜層又は島状皮膜層を形成するために用いられ
る金属、又は合金は、例えば銀、金、銅、パラジウム、
コバルト、アルミニウム、ニッケル−リン合金、ニッケ
ル−ホウ素合金、ニッケル−コバルト−リン合金、ニッ
ケル−タングステン−リン合金、銀−金合金およびコバ
ルト−リン合金などから選ぶことができる。
Further, in the powder materials (1) to (3), the metal or alloy used for forming the surface layer, the coating layer or the island coating layer is, for example, silver, gold, copper, palladium, or the like.
It can be selected from cobalt, aluminum, nickel-phosphorus alloy, nickel-boron alloy, nickel-cobalt-phosphorus alloy, nickel-tungsten-phosphorus alloy, silver-gold alloy, cobalt-phosphorus alloy and the like.

【0019】更に、上記粉末材料(1),(2)および
(3)において、表面層、又は皮膜層を形成するために
用いられる金属酸化物は、例えば二酸化チタン、酸化
鉄、水酸化アルミニウム、二酸化ケイ素、二酸化ジルコ
ニウム、および二酸化スズなどから選ぶことができる。
Further, in the powder materials (1), (2) and (3), the metal oxide used for forming the surface layer or the coating layer is, for example, titanium dioxide, iron oxide, aluminum hydroxide, It can be selected from silicon dioxide, zirconium dioxide, tin dioxide and the like.

【0020】上記粉末材料(1)〜(3)において、そ
の芯体又は複合芯体と、表面層又は島状皮膜層との重量
比は99/1〜30/70であることが好ましい。ま
た、上記粉末材料(2)において、芯体上に、金属酸化
物皮膜層として、二酸化チタン皮膜層が形成されること
が好ましく、表面層の最外側表面には金属皮膜層として
銀皮膜層が形成されることが好ましく、金属、又は合金
皮膜層と、金属酸化物皮膜層との重量比は5/95〜5
0/50であることが好ましい。
In the powder materials (1) to (3), the weight ratio of the core or the composite core to the surface layer or the island-like coating layer is preferably 99/1 to 30/70. In the powder material (2), a titanium dioxide film layer is preferably formed as a metal oxide film layer on the core, and a silver film layer is formed as a metal film layer on the outermost surface of the surface layer. It is preferably formed, and the weight ratio of the metal or alloy coating layer to the metal oxide coating layer is 5/95 to 5
It is preferably 0/50.

【0021】上記粉末材料(3)において、複合芯体
(ii)中の無機鱗片状粉粒からなる芯体と、金属酸化物
皮膜層との重量比は95/5〜40/60であることが
好ましく、また島状皮膜層が、芯体(i)、又は複合芯
体(ii)の表面の0.05〜95%を被覆していること
が好ましく、島状皮膜層は、それぞれ0.01〜5μm
の平均粒径を有し、互いに離間して島状体に分布してい
ることが好ましい。
In the above powder material (3), the weight ratio of the core made of inorganic flaky powder in the composite core (ii) to the metal oxide film layer is 95/5 to 40/60. It is preferable that the island-shaped coating layer covers 0.05 to 95% of the surface of the core (i) or the composite core (ii). 01-5 μm
It is preferable that the particles have an average particle size of and are distributed in islands apart from each other.

【0022】本発明において、ジルコニウム・クロム含
有複合材料からなる複合皮膜層(B)は、基体を形成す
る鱗片状無機材料粉粒を、少なくとも1種のジルコニウ
ムイオン供給化合物と、少なくとも1種のクロム3価イ
オン供給化合物とを含有し、かつ1.0〜5.0のpHに
調整された酸性処理水溶液中に懸濁し、この懸濁液を2
0〜90℃において加熱処理することによって得られ
る。前記加熱処理温度は20℃〜90℃である。
In the present invention, the composite coating layer (B) made of a zirconium / chromium-containing composite material comprises a scaly inorganic material powder forming a substrate, at least one kind of zirconium ion supplying compound and at least one kind of chromium. The suspension was suspended in an aqueous acid treatment solution containing a trivalent ion-supplying compound and adjusted to a pH of 1.0 to 5.0.
It is obtained by heat treatment at 0 to 90 ° C. The heat treatment temperature is from 20C to 90C.

【0023】ジルコニウムイオン供給化合物に格別の限
定はないが、一般にフッ化ジルコニウム酸、フッ化ジル
コニウム酸アンモニウム塩、およびフッ化ジルコニウム
酸アルカリ金属塩から選ばれることが好ましい。
Although there is no particular limitation on the zirconium ion supplying compound, it is generally preferable to select from the compounds selected from fluorinated zirconic acid, ammonium fluorinated zirconate, and alkali metal fluorinated zirconate.

【0024】また、クロム3価イオン供給化合物にも格
別の限定はないが、リン酸3価クロム塩、フッ酸3価ク
ロム塩、硝酸3価クロム塩、硫酸3価クロム塩、塩酸3
価クロム塩、炭酸3価クロム塩およびクロム酸3価クロ
ム塩から選ばれることが好ましい。
The chromium trivalent ion supplying compound is not particularly limited, but trivalent chromium phosphate, trivalent fluoric acid salt, trivalent chromium nitrate, trivalent chromium sulfate, trivalent chromium sulfate, and the like.
It is preferably selected from chromium (IV) salts, trivalent chromium carbonate salts and trivalent chromium chromate salts.

【0025】クロム酸3価クロム塩は、例えば無水クロ
ム酸の水溶液を適当な還元剤をもちいて一部を還元する
ことにより製造することができる。このとき用いられる
還元剤としては、一般に知られる還元剤が使用可能であ
るが、好ましくは、メタノール、エタノール、プロパノ
ール等の1価アルコール、エチレングリコール、プロピ
レングリコール、グリセリン等の多価アルコール、グリ
コール酸、酒石酸、クエン酸、乳酸、アスコルビン酸等
のオキシカルボン酸類、ホルミアルデヒド等のアルデヒ
ド類、フェノール、ピロガロール、没食子酸等の芳香族
酸類、および分解して上記還元性化合物を生成するタン
ニン類、グルコース、サッカロース、および分解してそ
れらを生成するデキストリン、スターチ等の多糖類から
選ばれた1種または2種以上からなるものが使用でき
る。
The trivalent chromium chromate can be produced, for example, by partially reducing an aqueous solution of chromic anhydride using a suitable reducing agent. As the reducing agent used at this time, generally known reducing agents can be used, but preferably, monohydric alcohols such as methanol, ethanol and propanol, polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin, and glycolic acid , Tartaric acid, citric acid, lactic acid, oxycarboxylic acids such as ascorbic acid, aldehydes such as formaldehyde, phenol, pyrogallol, aromatic acids such as gallic acid, and tannins that decompose to form the reducing compound, It is possible to use one or more selected from glucose, saccharose, and polysaccharides such as dextrin and starch that are decomposed to produce them.

【0026】また、酸性処理水溶液のpH値を1.0〜
5.0に調整するためには、無機酸および有機酸から選
ばれた少なくとも1種が使用される。このような無機酸
および有機酸は、特に限定するものではないが、好まし
くはリン酸、硫酸、硝酸、フッ酸、塩酸等の無機酸、ギ
酸、酢酸、蓚酸、安息香酸等のカルボン酸類、酒石酸、
クエン酸、乳酸等のオキシカルボン酸類、および石炭
酸、タンニン酸等のフェノール類が使用できる、より好
ましくはリン酸、硫酸、硝酸、フッ酸、タンニン酸から
選ばれる1種または2種以上が使用できる。
Further, the pH value of the acidic treatment aqueous solution is adjusted to 1.0 to 1.0.
In order to adjust to 5.0, at least one selected from inorganic acids and organic acids is used. Such inorganic acids and organic acids are not particularly limited, but are preferably inorganic acids such as phosphoric acid, sulfuric acid, nitric acid, hydrofluoric acid, and hydrochloric acid, carboxylic acids such as formic acid, acetic acid, oxalic acid, and benzoic acid, and tartaric acid. ,
Oxycarboxylic acids such as citric acid and lactic acid, and phenols such as carboxylate and tannic acid can be used. More preferably, one or more selected from phosphoric acid, sulfuric acid, nitric acid, hydrofluoric acid, and tannic acid can be used. .

【0027】本発明方法において、酸性処理水溶液中の
ジルコニウムイオンとクロム3価イオンの重量比(Zr
/Cr)は、1/20〜10/1であることが好まし
い。Zr/Cr比が1/20未満では、得られる複合皮
膜層中のジルコニウム含有量が不足し、必要な耐久性向
上効果が得られない。またZr/Cr比が10/1超で
は、上記効果が飽和に達し、不経済である。
In the method of the present invention, the weight ratio of zirconium ion to chromium trivalent ion (Zr
/ Cr) is preferably 1/20 to 10/1. If the Zr / Cr ratio is less than 1/20, the zirconium content in the obtained composite coating layer will be insufficient, and the necessary effect of improving durability cannot be obtained. If the Zr / Cr ratio exceeds 10/1, the above effects reach saturation, which is uneconomical.

【0028】本発明方法において、酸性処理水溶液のpH
値は、上述のように1.0〜5.0に調整される。この
pH値が1.0未満では、顔料に対する皮膜形成反応が不
十分になり、また、pH値が5.0超では、不必要な沈澱
が生成し薬剤の浪費を招き経済的でない。
In the method of the present invention, the pH of the aqueous acidic treatment solution
The value is adjusted between 1.0 and 5.0 as described above. this
When the pH value is less than 1.0, the film-forming reaction to the pigment is insufficient, and when the pH value is more than 5.0, an unnecessary precipitate is formed, which leads to waste of the drug, which is not economical.

【0029】上記のようにして組成、およびpHを調整し
た酸性処理水溶液中に、鱗片状無機顔料粉粒を懸濁し、
これを攪拌しながら、20〜90℃の温度に加温して、
顔料粉粒の表面に複合皮膜を形成し、得られた複合顔料
を捕集し、更に水洗した後に、好ましくは300℃以下
で乾燥することにより、耐湿性、光沢保持性、分散性に
優れ、耐久光沢性にすぐれた鱗片状複合顔料を得ること
ができる。基体用鱗片状無機顔料粉粒を懸濁後に、必要
とする酸性処理水溶液による処理温度と処理時間は工業
的採算性により決められるべきであり、それによって必
要な処理温度と処理時間とを適宜に定めることができ
る。
The flaky inorganic pigment particles are suspended in the aqueous acidic solution adjusted in composition and pH as described above,
While stirring this, warm to a temperature of 20 to 90 ° C.
A composite film is formed on the surface of the pigment particles, the obtained composite pigment is collected, washed with water, and then dried at preferably 300 ° C. or less, so that it has excellent moisture resistance, gloss retention, and dispersibility. A flaky composite pigment having excellent durability gloss can be obtained. After suspending the scaly inorganic pigment particles for the substrate, the treatment temperature and treatment time with the required acidic treatment aqueous solution should be determined by industrial profitability, and accordingly the necessary treatment temperature and treatment time may be appropriately adjusted. Can be determined.

【0030】本発明方法による上記処理により基体用顔
料粉粒の表面に析出するジルコニウム・クロム複合材料
の皮膜層の組成は未だ明らかではないが、XPS(X線
光電子分光分析)によれば、ジルコニウム(IV)・クロ
ム(III)の酸化物もしくは水酸化物の複合形態をしてい
るものと推測される。
Although the composition of the coating layer of the zirconium-chromium composite material deposited on the surface of the pigment particles for the substrate by the above treatment according to the method of the present invention is not yet clear, according to XPS (X-ray photoelectron spectroscopic analysis), It is presumed that it is in a complex form of (IV) -chromium (III) oxide or hydroxide.

【0031】本発明方法において、上記処理によって得
られた複合顔料の濾過捕集、および水洗後の乾燥温度に
は特に規定するものではないが、300℃超では得られ
る複合顔料の色調に変化をもたらし好ましくない。
In the method of the present invention, there is no particular limitation on the drying temperature after filtration and collection of the composite pigment obtained by the above treatment and washing with water, but if it exceeds 300 ° C., the color tone of the obtained composite pigment may change. It is undesirable to bring.

【0032】この様にして得られた光沢を有する鱗片状
複合顔料は、公知の方法により熱硬化性樹脂、又はラッ
カー型樹脂等からなる塗料中に混合して用いるのに好適
であり、このような複合顔料含有樹脂によって、金属、
プラスチック、木材、コンクリート、硝子等の材料に施
された被覆層は屋外の条件下で満足すべき耐久性を示す
ものであり、特に自動車用の外装用塗料の着色剤として
十分満足すべき耐水性を保持し、しかも優れた分散性を
有し、該顔料の持つ色調、光沢をまったく損なう事なく
優れた意匠性を発揮する塗料として使用し得るものであ
る。
The scaly composite pigment having a luster obtained in this way is suitable for being mixed with a thermosetting resin or a lacquer type resin or the like by a known method and used. Metal,
The coating layer applied to materials such as plastic, wood, concrete, glass, etc. shows satisfactory durability under outdoor conditions, especially water resistance enough to be used as a coloring agent for exterior paints for automobiles. And has excellent dispersibility, and can be used as a paint exhibiting excellent design properties without impairing the color tone and gloss of the pigment at all.

【0033】[0033]

【実施例】下記実施例により本発明を具体的に説明する
が、本発明の範囲はこれらの実施例により限定されるも
のではない。
The present invention will be described in detail with reference to the following examples, but the scope of the present invention is not limited by these examples.

【0034】実施例1 雲母薄片の表面を、この雲母薄片重量に対し約20%の
二酸化チタンにより被覆して得られた粒度10〜50μ
mの金属酸化物被覆雲母薄片90gを、水610ml中に
懸濁させた。別にフッ化ジルコニウム酸をジルコニウム
換算で0.62g/リットル、およびタンニン酸還元法
により製造され、全クロムに対しクロム3価イオンを約
20%含有するクロム酸クロム水溶液であって、全クロ
ム換算で10g/リットルの濃度を有する水溶液とを含
む水溶液90mlを、攪拌下で290mlに希釈し、これに
リン酸を添加してpHを約2.0として酸性水溶液を調製
した。この酸性処理水溶液を上記金属被覆雲母薄片懸濁
液に加え攪拌を続けながら60℃に加温し、この温度を
約30分間保持した。次に、この水性懸濁液を濾過し、
固体生成物を濾取、水洗し、これを120℃で3時間乾
燥した。
Example 1 A particle size of 10 to 50 μm obtained by coating the surface of a mica flake with about 20% of titanium dioxide based on the weight of the mica flake.
90 g of m-metal oxide-coated mica flakes were suspended in 610 ml of water. Separately, it is an aqueous solution of chromium chromate, which is produced by a zirconium conversion of 0.62 g / liter of fluorinated zirconate and a tannic acid reduction method and contains about 20% of chromium trivalent ions with respect to total chromium. 90 ml of an aqueous solution containing an aqueous solution having a concentration of 10 g / liter was diluted to 290 ml with stirring, and phosphoric acid was added to adjust the pH to about 2.0 to prepare an acidic aqueous solution. This acidic treatment aqueous solution was added to the metal-coated mica flake suspension, and the mixture was heated to 60 ° C. with continued stirring, and this temperature was maintained for about 30 minutes. Next, the aqueous suspension was filtered,
The solid product was collected by filtration, washed with water, and dried at 120 ° C. for 3 hours.

【0035】実施例2 雲母薄片の表面を、この雲母薄片重量の約60%の酸化
鉄で被覆して得られた、粒度5〜20μmの金属酸化物
被覆雲母薄片90gを水400ml中に懸濁させた。別に
フッ化ジルコニウム酸アンモニウムをジルコニウム換算
で2g/リットル、およびクロム3価イオンをフッ化ク
ロムを用いてクロム換算で0.6g/リットル含有し、
リン酸により、pHを約1.5とした酸性水溶液の90ml
を攪拌下で500mlに希釈した。この水溶液を上記金属
被覆雲母薄片懸濁液に加え、攪拌を続けながら90℃に
加温し、この温度を約10分間保持した。次に、この水
性懸濁液を濾過し、固体生成物を濾取し、水洗し、これ
を150℃で2時間乾燥した。
Example 2 90 g of a metal oxide-coated mica flake having a particle size of 5 to 20 μm obtained by coating the surface of a mica flake with iron oxide at about 60% by weight of the mica flake was suspended in 400 ml of water. I let it. Separately, ammonium fluoride zirconate contains 2 g / l in terms of zirconium, and chromium trivalent ion contains 0.6 g / l in terms of chromium using chromium fluoride,
90 ml of an acidic aqueous solution adjusted to a pH of about 1.5 with phosphoric acid
Was diluted to 500 ml with stirring. This aqueous solution was added to the metal-coated mica flake suspension, and the mixture was heated to 90 ° C. while continuing to stir, and this temperature was maintained for about 10 minutes. Next, the aqueous suspension was filtered, and the solid product was collected by filtration, washed with water, and dried at 150 ° C. for 2 hours.

【0036】実施例3 雲母薄片の表面を、この雲母薄片重量の約40%の二酸
化チタンと低次酸化チタン約9%とにより被覆して得ら
れた粒度10〜50μmの二酸化チタン・低次酸化チタ
ン被覆雲母薄片90gを、水610ml中に懸濁させた。
別にフッ化ジルコニウム酸アンモニウムをジルコニウム
換算で1g/リットルと、クロム3価イオンを硫酸クロ
ムを用いてクロム換算で10g/リットルとを含有する
水溶液90mlを、攪拌下で290mlに希釈し、これをリ
ン酸でpH約1.7とした酸性水溶液を調製した。この酸
性水溶液を上記金属被覆雲母薄片懸濁液に加え攪拌を続
けながら75℃に加温し、この温度を約20分間保持し
た。次に、この水性懸濁液を濾過して固体生成物を濾取
し、水洗し、これを110℃で4時間乾燥した。
Example 3 Titanium dioxide having a particle size of 10 to 50 μm and obtained by coating the surface of mica flakes with about 40% by weight of the mica flakes of titanium dioxide and about 9% of low-order titanium oxide. 90 g of titanium-coated mica flakes were suspended in 610 ml of water.
Separately, 90 ml of an aqueous solution containing 1 g / l of ammonium fluoride zirconate in terms of zirconium and 10 g / l in terms of chromium using chromium trivalent ions using chromium sulfate is diluted to 290 ml with stirring, and this is diluted with phosphorus. An acidic aqueous solution adjusted to a pH of about 1.7 with an acid was prepared. This acidic aqueous solution was added to the above-mentioned metal-coated mica flake suspension, and the mixture was heated to 75 ° C. while stirring, and this temperature was maintained for about 20 minutes. Next, the aqueous suspension was filtered to collect a solid product, which was washed with water and dried at 110 ° C. for 4 hours.

【0037】実施例4 雲母薄片を芯体として用い、その表面の一部分にスパッ
タリング法によりアルミニウムを付着させて得られた、
粒度10〜60μmの金属被覆雲母薄片90gを、水6
10ml中に懸濁させた。別に、フッ化ジルコニウム酸を
ジルコニウム換算で1.3g/リットル、および、タン
ニン酸還元法により製造され、全クロムに対しクロム3
価イオンを約20%含有するクロム酸クロム水溶液を全
クロム換算で20g/リットル含有する水溶液90mlを
調製し、これを攪拌下で290mlに希釈し、リン酸でpH
を約1.8として酸性水溶液を調製した。この酸性水溶
液を上記金属被覆雲母薄片懸濁液に加え攪拌を続けなが
ら60℃に加温し、この温度を約30分間保持した。次
に、この水性懸濁液を濾過し、固体生成物を濾取、水洗
し、これを110℃で5時間乾燥した。
Example 4 A mica flake was used as a core body, and aluminum was adhered to a part of its surface by a sputtering method.
90 g of metal-coated mica flakes having a particle size of 10 to 60 μm
Suspended in 10 ml. Separately, fluorinated zirconic acid is produced at 1.3 g / l in terms of zirconium, and is produced by a tannic acid reduction method.
90 ml of an aqueous solution containing 20 g / l of a chromium chromate aqueous solution containing about 20% of valence ions in terms of total chromium was prepared, diluted with stirring with 290 ml, and adjusted to pH 290 with phosphoric acid.
Was adjusted to about 1.8 to prepare an acidic aqueous solution. This acidic aqueous solution was added to the above-mentioned metal-coated mica flake suspension, and the mixture was heated to 60 ° C while stirring, and this temperature was maintained for about 30 minutes. Next, the aqueous suspension was filtered, and the solid product was collected by filtration, washed with water, and dried at 110 ° C. for 5 hours.

【0038】実施例5 雲母薄片の表面を、その重量に対し約46%の二酸化チ
タンにより被覆し、更にその表面の一部をスパッタリン
グ法によりアルミニウムによって被覆して得られた、粒
度5〜20μmの、金属酸化物・金属二層被覆雲母薄片
90gを、水610ml中に懸濁させた。別に、フッ化ジ
ルコニウム酸アンモニウムをジルコニウム換算で5g/
リットルおよび、硝酸クロムを用いて得られたクロム3
価イオンを、クロム換算で0.4g/リットル含有する
水溶液90mlを、攪拌下で290mlに希釈して水溶液を
調製した。この水溶液を上記金属被覆雲母薄片懸濁液に
加え、さらにタンニン酸を加えてpHを約3.0とした。
この酸性懸濁液を攪拌しながら90℃に加温し、この温
度を約10分間保持した。次に、この水性懸濁液を濾過
し、固体生成物を濾取、水洗し、これを140℃で2時
間乾燥した。
Example 5 The surface of mica flakes was coated with about 46% by weight of titanium dioxide, and a part of the surface was further coated with aluminum by sputtering to obtain a particle size of 5 to 20 μm. 90 g of mica flakes coated with two layers of metal oxide and metal were suspended in 610 ml of water. Separately, ammonium fluoride zirconate is converted to zirconium in an amount of 5 g /
Liter and chromium 3 obtained using chromium nitrate
90 ml of an aqueous solution containing 0.4 g / l of valent ions in terms of chromium was diluted to 290 ml with stirring to prepare an aqueous solution. This aqueous solution was added to the above metal-coated mica flake suspension, and tannic acid was further added to adjust the pH to about 3.0.
The acidic suspension was heated to 90 ° C. with stirring, and this temperature was maintained for about 10 minutes. Next, the aqueous suspension was filtered, and the solid product was collected by filtration, washed with water, and dried at 140 ° C. for 2 hours.

【0039】実施例6 合金組成としてNi(10原子%)、Cr(10原子
%)、Mo(2原子%)、P(12原子%)、C(8原
子%)、残分Feおよび不可避不純物で構成され、形状
が粉末であって、厚さ1〜4μm、アスペクト比(厚さ
に対する長径の比)10〜100、短径と長径の比1〜
5、短径および長径の寸法10〜400μmである非晶
質合金フレーク90gを、水610ml中に懸濁させた。
別に、フッ化ジルコニウム酸をジルコニウム換算で0.
62g/リットルおよびタンニン酸還元法により製造さ
れたクロム3価イオンを全クロムに対し約20%含有す
るクロム酸クロム水溶液の、全クロム換算で10g/リ
ットルを含有する水溶液90mlを攪拌下で290mlに希
釈し、リン酸でpHを約2.0とした酸性水溶液を調製し
た。この酸性水溶液を上記非晶質合金粉末懸濁液に加
え、攪拌を続けながら60℃に加温し、この温度を約3
0分間保持した。次に、この水性懸濁液を濾過し、固体
生成物を濾取、水洗し、これを120℃で3時間乾燥し
た。
Example 6 Ni (10 atomic%), Cr (10 atomic%), Mo (2 atomic%), P (12 atomic%), C (8 atomic%), residual Fe and inevitable impurities And a powder having a thickness of 1 to 4 μm, an aspect ratio (ratio of major axis to thickness) of 10 to 100, and a ratio of minor axis to major axis of 1 to
5. 90 g of amorphous alloy flakes with minor and major dimensions of 10 to 400 μm were suspended in 610 ml of water.
Separately, fluorinated zirconate is converted to zirconium in an amount of 0.1.
An aqueous solution containing 62 g / liter and about 20% of chromium trivalent ion produced by the tannic acid reduction method and containing about 20% of the total chromium, and 90 ml of an aqueous solution containing 10 g / l in terms of total chromium was reduced to 290 ml with stirring. An acidic aqueous solution was prepared by diluting and adjusting the pH to about 2.0 with phosphoric acid. This acidic aqueous solution is added to the above-mentioned amorphous alloy powder suspension, and the mixture is heated to 60 ° C. while stirring is continued.
Hold for 0 minutes. Next, the aqueous suspension was filtered, and the solid product was collected by filtration, washed with water, and dried at 120 ° C. for 3 hours.

【0040】実施例7 雲母薄片の表面を、その重量に対し約46%の二酸化チ
タンにより被覆し、更に、その表面上に、無電解めっき
法により銀を島状に析出させて得られた、粒度5〜20
μmの鱗片状粉末90gを、水610ml中に懸濁させ
た。別に、フッ化ジルコニウム酸をジルコニウム換算で
0.62g/リットル、および、タンニン酸還元法によ
り製造され、クロム3価イオンを全クロムに対し約20
%含有するクロム酸クロム水溶液を、全クロム換算で1
0g/リットルを含有する水溶液90mlを、攪拌下で2
90mlに希釈し、リン酸でpHを約2.0として酸性水溶
液を調製した。この酸性水溶液を上記非晶質合金粉末懸
濁液に加え攪拌を続けながら60℃に加温し、この温度
を約30分間保持した。次に、この水性懸濁液を濾過
し、固体生成物を濾取、水洗し、これを120℃で3時
間乾燥した。
Example 7 The surface of a mica flake was coated with about 46% by weight of titanium dioxide by weight, and silver was deposited in an island shape on the surface by electroless plating. Particle size 5-20
90 g of a scaly powder of μm were suspended in 610 ml of water. Separately, fluorinated zirconate is produced at 0.62 g / liter in terms of zirconium and tannic acid reduction method, and trivalent chromium ions are added to the total chromium by about 20%.
% Chromate aqueous solution containing 1%
90 ml of an aqueous solution containing 0 g / l are
The solution was diluted to 90 ml, and the pH was adjusted to about 2.0 with phosphoric acid to prepare an acidic aqueous solution. This acidic aqueous solution was added to the above-mentioned amorphous alloy powder suspension and heated to 60 ° C. while continuing stirring, and this temperature was maintained for about 30 minutes. Next, the aqueous suspension was filtered, and the solid product was collected by filtration, washed with water, and dried at 120 ° C. for 3 hours.

【0041】実施例8 雲母薄片の表面を、その重量に対し約45%の二酸化チ
タンにより被覆し、更に、その表面にスパッタリング法
により約10%の金属チタンによって被覆して得られ
た、粒度10〜20μmの、金属酸化物・金属二層被覆
雲母薄片90gを、水610ml中に懸濁させた。別に、
フッ化ジルコニウム酸をジルコニウム換算で0.62g
/リットル、および、タンニン酸還元法により製造さ
れ、全クロムに対してクロム3価イオンを約20%含有
するクロム酸クロム水溶液であって、全クロム換算で1
0g/リットルの濃度を有する水溶液とを含む水溶液9
0mlを、攪拌下で290mlに希釈し、これにリン酸を添
加してでpHを約2.0として酸性水溶液を調製した。こ
の酸性処理水溶液を上記金属酸化物・金属二層被覆雲母
薄片懸濁液に加え攪拌を続けながら60℃に加温し、こ
の温度を約30分間保持した。次に、この水性懸濁液を
濾過し、固体生成物を濾取、水洗し、これを120℃で
3時間乾燥した。
Example 8 The surface of a mica flake was coated with about 45% by weight of titanium dioxide, and the surface was further coated with about 10% of titanium metal by sputtering to obtain a particle size of 10%. 90 g of 2020 μm metal oxide / metal bilayer coated mica flakes were suspended in 610 ml of water. Separately,
0.62 g of fluorinated zirconate in terms of zirconium
Per liter, and an aqueous solution of chromium chromate which is produced by a tannic acid reduction method and contains about 20% of trivalent chromium ions with respect to total chromium.
Aqueous solution containing an aqueous solution having a concentration of 0 g / liter 9
0 ml was diluted to 290 ml with stirring, and phosphoric acid was added to adjust the pH to about 2.0 to prepare an acidic aqueous solution. This aqueous solution of acidic treatment was added to the suspension of mica flakes coated with the metal oxide / metal bilayer, and the mixture was heated to 60 ° C. with continuous stirring, and this temperature was maintained for about 30 minutes. Next, the aqueous suspension was filtered, and the solid product was collected by filtration, washed with water, and dried at 120 ° C. for 3 hours.

【0042】比較例1 雲母薄片の表面を、その重量の約20%の二酸化チタン
により被覆して得られた、粒度10〜50μmの金属酸
化物被覆雲母薄片100gを、1700mlの蒸留水でス
ラリーとし、そのpHを2Nの硫酸を滴下して6.0に調
整した。別に、5%の塩化第二クロム(CrCl3 )溶
液32mlを100mlの蒸留水で希釈した。この溶液を一
定の割合で約30分間に上記スラリーに添加した。この
塩化第二クロムの添加の間、10%の水酸化ナトリウム
溶液の所要量を加えてそのpHを6.0に保持した。塩化
第二クロム溶液の全量を添加した後、スラリーを濾過、
水洗して得られた濾過物を110〜120℃で1時間乾
燥した。
COMPARATIVE EXAMPLE 1 100 g of a metal oxide-coated mica flake having a particle size of 10 to 50 μm obtained by coating the surface of a mica flake with about 20% by weight of titanium dioxide was slurried with 1700 ml of distilled water. The pH was adjusted to 6.0 by dropwise addition of 2N sulfuric acid. Separately, 32 ml of a 5% chromic chloride (CrCl 3 ) solution was diluted with 100 ml of distilled water. This solution was added at a constant rate to the slurry over a period of about 30 minutes. During the addition of chromic chloride, the pH was maintained at 6.0 by adding the required amount of 10% sodium hydroxide solution. After adding the entire amount of the chromic chloride solution, the slurry was filtered,
The filtrate obtained by washing with water was dried at 110 to 120 ° C for 1 hour.

【0043】比較例2 雲母薄片の表面を、その重量の約60%の酸化鉄で被覆
して得られた、粒度5〜20μmの金属酸化物被覆雲母
薄片100gを、1700mlの蒸留水でスラリーとし、
そのpHを2Nの硫酸を滴下して6.0に調整した。別
に、5%の塩化第二クロム(CrCl3 )溶液32mlを
100mlの蒸留水で希釈した。この溶液を一定の割合で
約30分間に上記スラリーに添加した。この塩化第二ク
ロムの添加の間、10%の水酸化ナトリウム溶液の所要
量を加えてそのpHを6.0に保持した。塩化第二クロム
溶液の全量を添加した後、スラリーを濾過、水洗して得
られた濾過物を110〜120℃で1時間乾燥した。
Comparative Example 2 100 g of a metal oxide-coated mica flake having a particle size of 5 to 20 μm obtained by coating the surface of a mica flake with about 60% by weight of iron oxide was slurried with 1700 ml of distilled water. ,
The pH was adjusted to 6.0 by dropwise addition of 2N sulfuric acid. Separately, 32 ml of a 5% chromic chloride (CrCl 3 ) solution was diluted with 100 ml of distilled water. This solution was added at a constant rate to the slurry over a period of about 30 minutes. During the addition of chromic chloride, the pH was maintained at 6.0 by adding the required amount of 10% sodium hydroxide solution. After the entire amount of the chromic chloride solution was added, the slurry was filtered and washed with water, and the obtained filtrate was dried at 110 to 120 ° C for 1 hour.

【0044】比較例3 実施例6に用いた顔料と同一の非晶質合金フレークを水
洗して120℃で3時間乾燥した。
Comparative Example 3 The same amorphous alloy flake as the pigment used in Example 6 was washed with water and dried at 120 ° C. for 3 hours.

【0045】比較例4 実施例5で用いた顔料と同一の金属酸化物・金属二層被
覆雲母薄片をそのまま120℃で1時間乾燥した。
Comparative Example 4 A mica flake coated with the same metal oxide and metal bilayer as the pigment used in Example 5 was directly dried at 120 ° C. for 1 hour.

【0046】比較例5 実施例3で用いた顔料と同一の粒度10〜50μmの二
酸化チタン・低次酸化チタン被覆雲母薄片を水洗して1
20℃で3時間乾燥した。
Comparative Example 5 A titanium dioxide / lower titanium oxide-coated mica flake having the same particle size of 10 to 50 μm as the pigment used in Example 3 was washed with water and
Dried at 20 ° C. for 3 hours.

【0047】上記実施例1〜8および比較例1〜5にお
いて得られた顔料について、下記のテストを行った。 (1)塗料の準備 (A)熱硬化型アクリルメラミン樹脂系ベース塗料 熱硬化性アクリルメラミン樹脂(大日本インキ製、商
標:アクリディクA−322、160重量部と大日本イ
ンキ製、商標:スーパーベッカミンL117−60、3
4重量部との混合物)の固形分85重量部に対し、実施
例1〜8および比較例1〜5の各々の顔料15重量部を
加えて13種類塗料を調製した。 (B)熱硬化型アクリルメラミン樹脂系クリヤー塗料 大日本インキ製、商標:アクリディクA−310(14
0重量部)と、大日本インキ製、商標:スーパーベッカ
ミンL117−60(50重量部)とを混合し、熱硬化
型アクリルメラミン樹脂系クリヤー塗料を調製した。 (C)2液硬化型アクリルウレタン樹脂系ベース塗料 2液硬化性アクリルウレタン樹脂(大日本インキ製、商
標:アクリディク54−480、100重量部と、三井
東圧製、商標:オレスターNP−1000、20重量部
との混合物)の固形分85重量部に対し、前記各顔料1
5重量部を加え13種類の塗料を調製した。 (D)2液硬化型アクリルウレタン樹脂系クリヤー塗料 大日本インキ製、商標:アクリディク54−480(1
00重量部)と、三井東圧製、商標:オレスターNP−
1000(20重量部)とを混合し、2液硬化性アクリ
ルウレタン樹脂クリヤー塗料を調製した。
The following tests were performed on the pigments obtained in Examples 1 to 8 and Comparative Examples 1 to 5. (1) Preparation of paint (A) Thermosetting acrylic melamine resin-based paint Thermosetting acrylic melamine resin (manufactured by Dainippon Ink, trademark: Acridic A-322, 160 parts by weight and Dainippon Ink, trademark: Super Becca Min L117-60, 3
15 parts by weight of each of the pigments of Examples 1 to 8 and Comparative Examples 1 to 5 were added to 85 parts by weight of the solid content (mixture with 4 parts by weight) to prepare 13 types of paints. (B) Thermosetting acrylic melamine resin clear paint, manufactured by Dainippon Ink, trademark: Acrydik A-310 (14
0 parts by weight) and Super Beckamine L117-60 (50 parts by weight) manufactured by Dainippon Ink, to prepare a thermosetting acrylic melamine resin-based clear paint. (C) Two-part curable acrylic urethane resin base paint Two-part curable acrylic urethane resin (manufactured by Dainippon Ink, trademark: Acrydik 54-480, 100 parts by weight, Mitsui Toatsu, trademark: Olester NP-1000) , 20 parts by weight) of the above pigment 1
13 parts of paints were prepared by adding 5 parts by weight. (D) Two-component curable acrylic urethane resin-based clear paint Dainippon Ink, trademark: Acrydik 54-480 (1
00 parts by weight) and Mitsui Toatsu, trademark: Olestar NP-
1000 (20 parts by weight) to prepare a two-part curable acrylic urethane resin clear coating.

【0048】(2)性能試験板の準備 冷延鋼板(サイズ=70×150mm)に、常法により自
動車用塗装前処理を施した後、カチオン電着、中塗り塗
装を順次施して52枚の中塗り塗装板を作製した。次
に、その中の26枚の板に、さらに上記の通りに塗料化
したアクリルメラミン樹脂系ベース塗料(A)をそれぞ
れ乾燥膜厚15μmとなるように塗装した。更にwet
−on−wet法によりアクリルメラミン樹脂系クリヤ
ー塗料(B)を乾燥膜厚35μmとなるように塗布し、
145℃、30分間加熱、硬化して試験板を各々2枚ず
つ作製した。同様に、アクリルウレタン樹脂系ベース塗
料(C)13種類をそれぞれ乾燥膜厚15μmとなるよ
うに塗装し、これにwet−on−wet法によりアク
リルウレタン樹脂系クリヤー塗料(D)を、乾燥膜厚3
5μmとなるように塗布し、80℃、30分間加熱、硬
化し13種類の試験板を各々2枚ずつ作製した。
(2) Preparation of performance test plate A cold-rolled steel plate (size = 70 × 150 mm) was subjected to an automotive coating pretreatment by a conventional method, and then was subjected to cation electrodeposition and intermediate coating sequentially to obtain 52 sheets. An intermediate coated plate was produced. Next, the acrylic melamine resin-based base paint (A), which was formed as described above, was further applied to 26 plates among them so as to have a dry film thickness of 15 μm. More wet
An acrylic melamine resin clear paint (B) is applied by an on-wet method so as to have a dry film thickness of 35 μm,
Heating and curing at 145 ° C. for 30 minutes produced two test plates each. Similarly, 13 kinds of acrylic urethane resin-based base paints (C) were applied so as to have a dry film thickness of 15 μm, respectively, and an acrylic urethane resin-based clear paint (D) was applied thereto by a wet-on-wet method. 3
The mixture was applied to a thickness of 5 μm, heated at 80 ° C. for 30 minutes, and cured to prepare two types of 13 types of test plates.

【0049】(3)性能試験条件 (A)高温耐水性試験 上記の通りに作製した26種類(塗装系A/B13種
類、塗装系C/D13種類)の試験板の各々の長手方向
の半分を、80℃の温水中に24時間浸漬した後、浸漬
部分と未浸漬部分の塗装面の変化を目視にて判定した。 (B)促進耐候性試験 上記と同様の試験板26種類の各々について、サンシャ
インウエザオーメーターにて促進耐候性試験を1000
時間行い、試験前後の光沢保持率(ΔG)、色差(Δ
E)を測定した。上記高温耐水性試験、および促進耐候
性試験の結果を表1に示す。
(3) Performance Test Conditions (A) High-Temperature Water Resistance Test Half of the lengthwise half of each of the 26 types of test plates (13 types of coating A / B, 13 types of coating C / D) prepared as described above were tested. After immersion in warm water at 80 ° C. for 24 hours, changes in the painted surface between the immersed portion and the unimmersed portion were visually determined. (B) Accelerated weathering test For each of the 26 types of test plates similar to the above, an accelerated weathering test was performed with a sunshine weatherometer at 1000 times.
After the test, the gloss retention (ΔG) before and after the test, the color difference (ΔG)
E) was measured. Table 1 shows the results of the high-temperature water resistance test and the accelerated weather resistance test.

【0050】[0050]

【表1】 [Table 1]

【0051】表1に示した通り、本発明の実施例1ない
し8において得られた光沢を有する鱗片状顔料はいずれ
も高温耐水性試験、促進耐候性試験において著しく良好
な結果を示したのに対し、比較例1ないし5は高温耐水
性試験、促進耐候性試験については実施例に比べ著しく
劣っており到底自動車車体外面塗装などの過酷な条件下
で使用し得ないことは容易に類推できる。さらに、製造
工程上も比較例1ないし5が煩雑な薬液管理を必要とす
るのに対し、本発明による実施例1ないし8は簡便な方
法で良好な製品が得られると云う利点があることは明ら
かである。
As shown in Table 1, the glossy flaky pigments obtained in Examples 1 to 8 of the present invention showed remarkably good results in the high-temperature water resistance test and the accelerated weather resistance test. On the other hand, Comparative Examples 1 to 5 are remarkably inferior to the Examples in the high-temperature water resistance test and the accelerated weather resistance test, and it can easily be inferred that they cannot be used under severe conditions such as painting the outer surface of an automobile body. Furthermore, the comparative examples 1 to 5 also require complicated chemical liquid management in the manufacturing process, while the examples 1 to 8 according to the present invention have the advantage that a good product can be obtained by a simple method. it is obvious.

【0052】[0052]

【発明の効果】本発明の鱗片状複合顔料は、きわめてす
ぐれた高温耐水性および耐候性を有する耐久性光沢を有
するものであって、自動車車体外面用塗料、その他の用
途に有用なものである。また、本発明の製造方法によ
り、耐久性光沢を有する鱗片状複合顔料を、効率よく製
造することができる。
Industrial Applicability The flaky composite pigment of the present invention has a durable luster having extremely excellent high-temperature water resistance and weather resistance, and is useful for paints for automobile body outer surfaces and other uses. . Further, according to the production method of the present invention, a flaky composite pigment having a durable gloss can be efficiently produced.

───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI C09C 1/64 C09C 1/64 (72)発明者 伊藤 博志 愛知県豊田市トヨタ町1番地 トヨタ自 動車株式会社内 (56)参考文献 特開 昭63−130673(JP,A) 特開 昭61−295234(JP,A) 特開 昭58−219266(JP,A) 特公 昭43−25644(JP,B1) (58)調査した分野(Int.Cl.6,DB名) C09C 3/06 C09C 1/24 C09C 1/40 C09C 1/62 C09C 1/64 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI C09C 1/64 C09C 1/64 (72) Inventor Hiroshi Ito 1 Toyota Town, Toyota City, Aichi Prefecture Inside Toyota Motor Corporation (56) References JP-A-63-130673 (JP, A) JP-A-61-295234 (JP, A) JP-A-58-219266 (JP, A) JP-B-43-25644 (JP, B1) (58) Survey Field (Int.Cl. 6 , DB name) C09C 3/06 C09C 1/24 C09C 1/40 C09C 1/62 C09C 1/64

Claims (5)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】 鱗片状無機顔料粉粒からなる基体
(A)、及び、前記鱗片状無機顔料粉粒からなる基体
(A)の表面を被覆し、かつジルコニウム・クロム含有
複合材料からなる複合皮膜層(B)を含み、 前記鱗片状無機顔料粉粒からなる基体(A)が、 (1)無機鱗片状粉粒からなる芯体の表面が、金属、合
金及び金属酸化物から選ばれた少なくとも1種からなる
表面層により被覆されている粉末、 (2)無機鱗片状粉粒からなる芯体の表面が、少なくと
も1層の金属又は合金皮膜層、及び少なくとも1層の金
属酸化物皮膜層を任意の順序で積層して形成された表面
層により被覆されている粉末、並びに、 (3)(i)無機鱗片状粉粒からなる芯体、及び(ii)
無機鱗片状粉粒からなる芯体の表面が、金属酸化物皮膜
層により被覆されている複合芯体、から選ばれた少なく
とも1種の表面に、金属及び合金から選ばれた少なくと
も1種からなる複数の皮膜層が島状に点在して形成され
ている粉末、 から選ばれた少なくとも1種からなり、 前記粉末(1),(2)及び(3)の各々において、前
記無機鱗片状粉粒からなる芯体が、 (a)雲母薄片、 (b)アルミニウムフレーク、 (c)非晶質合金フレーク、及び (d)雲母状酸化鉄(MIO)粉末 から選ばれた少なくとも1種からなる、 ことを特徴とする、耐久性光沢を有する鱗片状複合顔
料。
1. A substrate (A) composed of flaky inorganic pigment particles and a composite film covering the surface of the substrate (A) composed of the flaky inorganic pigment particles and comprising a zirconium / chromium-containing composite material A substrate (A) comprising a layer (B) and comprising the flaky inorganic pigment particles, wherein (1) a surface of a core comprising the inorganic flaky particles is at least selected from a metal, an alloy and a metal oxide; (2) The surface of a core body composed of inorganic flaky particles is formed of at least one metal or alloy film layer and at least one metal oxide film layer. A powder coated with a surface layer formed by laminating in any order; (3) (i) a core made of inorganic flaky powder; and (ii)
The surface of the core made of inorganic flaky powder is at least one type selected from a composite core coated with a metal oxide film layer, and at least one type selected from metals and alloys. A powder in which a plurality of coating layers are formed in an island-like manner; and in each of the powders (1), (2) and (3), the inorganic scaly powder The core body composed of particles comprises at least one selected from the group consisting of (a) mica flakes, (b) aluminum flakes, (c) amorphous alloy flakes, and (d) mica-like iron oxide (MIO) powder. A flaky composite pigment having a durable gloss.
【請求項2】 前記鱗片状無機顔料粉粒からなる基体
(A)と、前記複合皮膜層(B)との重量比(A)/
(B)が、1000/0.2〜1000/20である、
請求項1に記載の鱗片状複合顔料。
2. A weight ratio (A) / (base) of the substrate (A) comprising the flake-like inorganic pigment particles and the composite coating layer (B).
(B) is 1000 / 0.2 to 1000/20,
The flaky composite pigment according to claim 1.
【請求項3】 請求項1に記載の鱗片状無機顔料粉粒か
らなる基体(A)を、少なくとも1種のジルコニウムイ
オン供給化合物と少なくとも1種のクロム3価イオン供
給化合物とを含有し、かつ1.0〜5.0のpH値を有す
る酸性処理水溶液中に懸濁し、この懸濁液を20〜90
℃の温度に加熱処理することによって、前記鱗片状無機
顔料粉粒の表面上に、ジルコニウム・クロム含有複合材
料からなる複合皮膜層(B)を形成し、前記加熱処理に
より得られた鱗片状粉末を濾過捕集し、水洗し、乾燥す
ること、を特徴とする耐久性光沢を有する鱗片状複合顔
料の製造方法。
3. The substrate (A) comprising the flaky inorganic pigment particles according to claim 1, comprising at least one zirconium ion supplying compound and at least one trivalent chromium ion supplying compound, and Suspended in an aqueous acidic treatment solution having a pH value of 1.0 to 5.0, and suspending the suspension at 20 to 90.
C. to form a composite coating layer (B) made of a zirconium / chromium-containing composite material on the surface of the flaky inorganic pigment particles by heat treatment, and the flaky powder obtained by the heat treatment , Washing and drying, and drying the scaly composite pigment having a durable luster.
【請求項4】 前記酸性処理水溶液が、無機酸および有
機酸から選ばれた少なくとも1種によって、前記1.0
〜5.0のpH値に調整される、請求項3に記載の方法。
4. The method according to claim 1, wherein the acidic aqueous solution is treated with at least one selected from inorganic acids and organic acids.
4. The method according to claim 3, wherein the pH is adjusted to a pH value of ~ 5.0.
【請求項5】 前記乾燥が300℃以下の温度で行われ
る、請求項3に記載の方法。
5. The method according to claim 3, wherein the drying is performed at a temperature of 300 ° C. or less.
JP4328892A 1992-02-28 1992-02-28 Scale-like composite pigment having durability gloss and method for producing the same Expired - Fee Related JP2968118B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP4328892A JP2968118B2 (en) 1992-02-28 1992-02-28 Scale-like composite pigment having durability gloss and method for producing the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP4328892A JP2968118B2 (en) 1992-02-28 1992-02-28 Scale-like composite pigment having durability gloss and method for producing the same

Publications (2)

Publication Number Publication Date
JPH05239378A JPH05239378A (en) 1993-09-17
JP2968118B2 true JP2968118B2 (en) 1999-10-25

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ID=12659620

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Country Link
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10125424B2 (en) 2012-08-29 2018-11-13 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US10400337B2 (en) 2012-08-29 2019-09-03 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing lithium, associated methods for treating metal substrates, and related coated metal substrates
US10920324B2 (en) 2012-08-29 2021-02-16 Ppg Industries Ohio, Inc. Zirconium pretreatment compositions containing molybdenum, associated methods for treating metal substrates, and related coated metal substrates
US11518960B2 (en) 2016-08-24 2022-12-06 Ppg Industries Ohio, Inc. Alkaline molybdenum cation and phosphonate-containing cleaning composition

Also Published As

Publication number Publication date
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