JPH07316475A - Coating composition - Google Patents
Coating compositionInfo
- Publication number
- JPH07316475A JPH07316475A JP6131245A JP13124594A JPH07316475A JP H07316475 A JPH07316475 A JP H07316475A JP 6131245 A JP6131245 A JP 6131245A JP 13124594 A JP13124594 A JP 13124594A JP H07316475 A JPH07316475 A JP H07316475A
- Authority
- JP
- Japan
- Prior art keywords
- color
- coating composition
- titanium dioxide
- flop
- particle diameter
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT 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
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
- C09C1/3607—Titanium dioxide
- C09C1/3653—Treatment with inorganic compounds
- C09C1/3661—Coating
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、赤味色相変化を伴うフ
リップ・フロップ効果を示すいわゆる特異な色彩のダウ
ンフロップ性を呈する、意匠性に優れたメタリック塗料
のような塗料組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition such as a metallic paint which exhibits a so-called peculiar color down-flop property showing a flip-flop effect accompanied by a reddish hue change and which is excellent in design.
【０００２】[0002]
【従来の技術】近年、超微粒子二酸化チタンを含有する
メタリック塗色は、その塗膜の垂直の角度から観察（フ
ェイス）すると黄色（金色）様の色彩を呈し、斜めから
観察（フロップ）すると青色系の色彩を呈する特殊な光
学的特性（フリップ・フロップ効果）を有するという既
存の色材では得られない特殊な色彩を呈するため、自動
車のメタリック塗料等において注目されている。2. Description of the Related Art In recent years, metallic coating colors containing ultrafine titanium dioxide have a yellow (gold) -like color when observed (face) from a vertical angle of the coating film, and blue when observed obliquely (flop). Since it has a special optical characteristic (flip-flop effect) that exhibits a system color and cannot be obtained with existing color materials, it has been attracting attention in metallic paints for automobiles.
【０００３】従来、このようなフリップ・フロップ効果
を呈する塗料組成物としては、粒子径が０．００５〜
０．２μｍの超微粒子二酸化チタンをアルミフレークの
ような金属フレーク顔料或いは雲母チタンのような金属
光沢顔料と共に樹脂媒体に配合して、優れたフリップ・
フロップ効果を呈する意匠性に優れた塗料組成物とする
ことが提案されている。（例えば、特開昭63-183965,特
開昭64-11170, 特開昭64-43577, 特開平1-161072）Conventionally, a coating composition exhibiting such a flip-flop effect has a particle diameter of 0.005 to 0.005.
An ultra-fine titanium dioxide of 0.2 μm is mixed with a metallic flake pigment such as aluminum flake or a metallic luster pigment such as titanium mica in a resin medium to obtain an excellent flip.
It has been proposed to provide a coating composition having a flop effect and excellent in designability. (For example, JP-A 63-183965, JP-A 64-11170, JP-A 64-43577, JP-A 1-161072)
【０００４】[0004]
【発明が解決しようとする課題】ところで従来、自動車
やその他高級塗装仕上げ用のメタリック塗料において
は、メタリック塗装のメタリック性を損なわないよう
に、平均一次粒子径が通常０．００５〜０．０４μｍま
での透明性の高い超微粒子二酸化チタンが使用されてい
る。このものを使用したメタリック塗装仕上げ塗膜は、
前記したようにフロップカラーは青白く、フェイスカラ
ーは黄色（金色）を呈するフリップ・フロップ効果を奏
するものであるが、近時、自動車や高級塗装仕上げ調度
品などにおける彩色意匠性の多様化、高級化の要望は一
層強まってきており、さらに個別化に豊んだ優れた彩色
意匠性のフリップ・フロップ効果を呈するメタリック塗
装が強く希求されている。Conventionally, in metallic paints for automobiles and other high-grade paint finishes, the average primary particle diameter is usually 0.005 to 0.04 μm so as not to impair the metallic properties of the metallic paint. Highly transparent ultrafine titanium dioxide is used. The metallic paint finish coating using this one is
As mentioned above, the flop color is pale, and the face color is yellow (gold), which has a flip-flop effect, but recently, the diversification and sophistication of the color design of automobiles and high-quality paint finish furnishings. There is a strong demand for a metallic coating that exhibits a flip-flop effect with an excellent coloring design that is highly individualized.
【０００５】[0005]
【課題を解決するための手段】本発明者達は、前記した
ようなメタリック塗装における彩色意匠性の個別化の課
題を解決すべく種々検討を進めた結果、特定の粒子径を
有する微粒子二酸化チタンをリン片状金属顔料と１対
０．１〜１０の重量比で含有する塗料組成物が、塗膜に
した場合にメタリック感を実質的に損なうことなく、赤
味色相変化を伴うフリップ・フロップ効果を示し、優れ
た彩色意匠性を有し、前記メタリック塗装における課題
を解決し得ることを見出し、本発明を完成した。Means for Solving the Problems As a result of various investigations by the present inventors to solve the above-mentioned problems of individualizing the color design in metallic coating, fine titanium dioxide particles having a specific particle diameter have been obtained. A flip-flop with a reddish hue change without substantially impairing the metallic feel when a coating composition containing a scaly metal pigment in a weight ratio of 1 to 0.1 to 10 is formed. The present invention has been completed by finding out that the effect is exhibited, the coloring property is excellent, and the problems in the metallic coating can be solved.
【０００６】すなわち本発明は、 １．平均単一粒子径が０．０５〜０．１３μｍの微粒子
二酸化チタンとリン片状金属顔料とを１対０．１〜１０
の重量比で含み、塗膜にした場合に赤味色相変化を伴う
フリップ・フロップ効果を示す塗料組成物、 ２．赤味色相変化が、フェイスカラー（正反射光カラ
ー）とフロップカラー（散乱光カラー）のａ値色差の最
大値が３以上となることを特徴とする前記１項記載の塗
料組成物。 ３．赤味色相変化が、フェイスカラー（正反射光カラ
ー）とフロップカラー（散乱光カラー）のａ値色差の最
大値が５以上となることを特徴とする前記１項記載の塗
料組成物。 ４．微粒子二酸化チタンの平均単一粒子径が０．０６〜
０．０９μｍであることを特徴とする前記１、２または
３項記載の塗料組成物、 ５．微粒子二酸化チタンが単一粒子径粒度分布におい
て、累積重量％で８０％以上が０．０５〜０．１μｍで
あることを特徴とする前記１、２、３または４項記載の
塗料組成物、 ６．微粒子二酸化チタンが、その粒子表面にアルミニウ
ム、ケイ素、チタニウム、ジルコニウム及びスズの群か
ら選ばれた少なくとも１種の元素の含水酸化物または酸
化物の被覆を有するものであることを特徴とする前記
１、２、３、４または５項記載の塗料組成物及び、 ７．リン片状金属顔料がアルミ箔であることを特徴とす
る前記１項記載の塗料組成物である。That is, the present invention is as follows: Fine titanium dioxide particles having an average single particle diameter of 0.05 to 0.13 μm and scaly metal pigments in a ratio of 1 to 0.1 to 10.
1. A coating composition containing a weight ratio of 1. and showing a flip-flop effect accompanied by a reddish hue change when formed into a coating film. 2. The coating composition according to claim 1, wherein the change in reddish hue has a maximum a value color difference of 3 or more between the face color (regular reflection light color) and the flop color (scattered light color). 3. 2. The coating composition according to the above item 1, wherein the maximum change in the a-value color difference between the face color (regular reflection light color) and the flop color (scattered light color) is 5 or more. 4. The average single particle diameter of fine particle titanium dioxide is 0.06 to
4. The coating composition according to the above 1, 2, or 3, wherein the coating composition has a thickness of 0.09 μm. 6. The coating composition according to the above 1, 2, 3 or 4, wherein the fine particle titanium dioxide has a cumulative particle diameter distribution of 80% or more in a single particle diameter particle size distribution of 0.05 to 0.1 µm. ． The fine titanium dioxide has a hydrous oxide or a coating of an oxide of at least one element selected from the group consisting of aluminum, silicon, titanium, zirconium and tin on the surface of the fine particles thereof. 6. The coating composition according to item 2, 3, 4 or 5. The coating composition according to the above item 1, wherein the flaky metal pigment is an aluminum foil.
【０００７】本発明の塗料組成物で用いられる微粒子二
酸化チタンは、電子顕微鏡法による平均単一粒子径が
０．０５〜０．１３μｍの微粒子二酸化チタンであっ
て、種々の方法によって製造し得るが、例えば、TiCl4
水溶液をNaOH水溶液のようなアルカリで中和し、焼成す
る方法、この際、TiCl4 水溶液にアルカリを添加して
も、アルカリにTiCl4 水溶液を添加しても、或いは、同
時に並行して添加してもよい。また、硫酸チタニアを加
熱加水分解し、解膠する方法などによって得られるも
の、さらには含水酸化チタンをアルカリで処理し、得ら
れた反応生成物を塩酸で加熱処理して得られた超微粒子
二酸化チタンを焼成する方法などが挙げられる。なお、
上記の微粒子二酸化チタンは、その表面が例えばアルミ
ニウム、ケイ素、チタニウム、ジルコニウム、スズ、セ
リウムなどの金属の酸化物で被覆されたものであっても
よく、耐光性などをより一層好ましいものとすることが
できる。微粒子二酸化チタンの平均単一粒子径が、前記
範囲より小さきに過ぎると所望の色相変化を呈さない明
るさ変化だけの通常のメタリック塗膜となり、また前記
範囲より大きに過ぎるとフリップ・フロップ効果を呈さ
ないソリッド感の塗膜となり易い。The fine particle titanium dioxide used in the coating composition of the present invention is fine particle titanium dioxide having an average single particle diameter of 0.05 to 0.13 μm as determined by electron microscopy and can be produced by various methods. , For example, TiCl 4
The aqueous solution was neutralized with an alkali such as aqueous NaOH solution, and calcining, this time, even with the addition of alkali to the TiCl 4 aqueous solution, it is added TiCl 4 aqueous solution alkaline or by adding in parallel at the same time May be. Further, those obtained by a method such as hydrolyzing and titrating peptization of titania sulfate, and further, hydrous titanium oxide is treated with alkali, and an ultrafine particle dioxide obtained by heat-treating the obtained reaction product with hydrochloric acid. Examples include a method of firing titanium. In addition,
The fine particle titanium dioxide may be one whose surface is coated with an oxide of a metal such as aluminum, silicon, titanium, zirconium, tin or cerium, which makes light resistance and the like more preferable. You can If the average single particle diameter of the fine particle titanium dioxide is smaller than the above range, it becomes a normal metallic coating film with only a change in brightness that does not exhibit the desired hue change, and if it is larger than the above range, a flip-flop effect is produced. It tends to be a solid coating that does not appear.
【０００８】本発明で用いられるリン片状金属顔料とし
ては、アルミ箔、ステンレス箔、ニッケル箔、ブロンズ
箔、スズ箔、銅箔等が挙げられ、中でも顔料ペーストの
形態で市販されているアルミ箔が望ましい。このアルミ
箔に追加して黄銅フレーク、ステンレスフレーク、銀フ
レーク及び他の貴金属フレーク、パール顔料なども使用
することができる。Examples of the flaky metal pigment used in the present invention include aluminum foil, stainless steel foil, nickel foil, bronze foil, tin foil, copper foil and the like, and among them, aluminum foil commercially available in the form of pigment paste. Is desirable. In addition to this aluminum foil, brass flakes, stainless flakes, silver flakes and other noble metal flakes, pearl pigments and the like can also be used.
【０００９】本発明の塗料組成物は、前記微粒子二酸化
チタンと上記リン片状金属顔料とを１対０．１／１０の
重量比で含むものであって、これらを適当な樹脂に分散
させて塗料化したものである。微粒子二酸化チタンが、
前記割合より少なきに過ぎると所望の色相変化を呈さな
い明るさ変化だけの通常のメタリック塗膜となり、また
前記割合より多きに過ぎるとフリップ・フロップ効果を
呈さないソリッド感の塗膜となり易い。ここで用いられ
る樹脂としては、当該分野で普通に用いられるものであ
って、熱可塑性又は熱硬化性樹脂が挙げられ、具体的に
はアクリル樹脂、メラミン樹脂、ウレタン樹脂、ポリエ
ステル樹脂、アルキッド樹脂、アクリルラッカー重合体
などが挙げられる。これらの樹脂は通常、塗料組成物の
10〜50重量％望ましくは20〜40重量％の割合で配合され
る。The coating composition of the present invention comprises the fine particle titanium dioxide and the scaly metal pigment in a weight ratio of 1: 0.1 / 10, and these are dispersed in an appropriate resin. It is a paint. Particulate titanium dioxide
If it is less than the above-mentioned ratio, a normal metallic coating film having only a change in brightness which does not exhibit a desired hue change is obtained, and if it is more than the above-mentioned ratio, a coating film having a solid feeling which does not exhibit a flip-flop effect tends to be obtained. The resin used here is one that is commonly used in the art, and includes a thermoplastic or thermosetting resin, specifically, an acrylic resin, a melamine resin, a urethane resin, a polyester resin, an alkyd resin, Examples thereof include acrylic lacquer polymers. These resins are usually used in coating compositions.
10 to 50% by weight, preferably 20 to 40% by weight.
【００１０】本発明の塗料組成物においては、上記主成
分の他に酢酸ブチル、トルエン、キシレン、ブタノー
ル、エチルセロソルブ、ブチルセロソルブ、メチルエチ
ルケトン、メチルイソブチルケトン、酢酸エチル、水な
どの各種の溶剤と架橋剤を含有する。溶剤は、使用する
熱可塑性又は熱硬化性樹脂の種類に応じて適宜選択する
ことができる。これらの溶剤は、普通、塗料組成物の40
〜80重量％、望ましくは50〜70重量％の割合で配合され
る。また、本発明の塗料組成物においては、前記以外の
着色顔料や紫外線吸収剤などが適当量配合されてもよ
い。着色顔料としては、例えばカーボンブラック、ペリ
レン赤、酸化鉄、フタロシアニンブルー、フタロシアニ
ングリーン、アントラピリミジン黄、キナクリドン赤が
挙げられる。また、紫外線吸収剤としては、例えばサリ
チル酸系、ベンゾフェノン系、ベンゾトリアゾール系、
シアノアクリレート系などがある。In the coating composition of the present invention, in addition to the above main components, various solvents such as butyl acetate, toluene, xylene, butanol, ethyl cellosolve, butyl cellosolve, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate and water, and a crosslinking agent. Contains. The solvent can be appropriately selected according to the type of thermoplastic or thermosetting resin used. These solvents are usually used in 40% of the coating composition.
It is blended in a proportion of -80% by weight, preferably 50-70% by weight. Further, in the coating composition of the present invention, a coloring pigment other than the above, an ultraviolet absorber and the like may be blended in appropriate amounts. Examples of the color pigment include carbon black, perylene red, iron oxide, phthalocyanine blue, phthalocyanine green, anthrapyrimidine yellow, and quinacridone red. Examples of the ultraviolet absorber include salicylic acid-based, benzophenone-based, benzotriazole-based,
There are cyanoacrylate type.
【００１１】本発明の塗料組成物は、金属鋼板、ガラ
ス、セラミックス、アスベスト、木材、プラスチックス
などの基体材料上に塗布することにより、特異な色彩の
フリップ・フロップ効果を呈する、意匠性に優れた塗膜
を得ることができる。従来のように平均粒子径が０．０
０５〜０．０５μｍの超微粒子二酸化チタンを配合した
塗料組成物の場合は、塗膜はそれと垂直の角度から観察
（フェイス）すると黄色（金色）様の色彩を呈し、斜め
から観察（フロップ）すると青色系の色彩を呈するよう
なフリップ・フロップ効果が得られる。一方、本発明の
塗料組成物のように平均粒子径が０．０５〜０．１３μ
ｍ微粒子二酸化チタンを配合した場合は、従来のものと
は異なった赤味の色相変化を示す。このような性質を利
用して、金属の基体上に塗布したり、更には自動車の上
塗りとしても使用することができる。なお、本発明の塗
料組成物を自動車塗装用として用いる場合は、ベースコ
ートとして塗布し、その上に透明なトップコートを塗布
するのが望ましい。ベースコートおよび透明なトップコ
ートは、はけ塗、吹き付け、浸漬、流し塗などのような
通常の方法で基体に塗布することができる。特に、自動
車の仕上げ塗装用としては、普通、耐蝕性プライマーが
塗布された基体に吹き付け塗装することが一般的であ
り、この方法には、圧縮空気吹き付け、静電吹き付け、
ホットスプレー法、エアスプレー法などの種々の形式の
ものがある。The coating composition of the present invention exhibits a unique color flip-flop effect by being applied onto a base material such as a metal steel plate, glass, ceramics, asbestos, wood and plastics, and is excellent in design. A coated film can be obtained. The average particle size is 0.0
In the case of a coating composition containing ultrafine titanium dioxide having a particle size of 05 to 0.05 μm, the coating film has a yellow (golden) color when observed (face) from an angle perpendicular to it, and when observed obliquely (flop). A flip-flop effect that produces a bluish color is obtained. On the other hand, like the coating composition of the present invention, the average particle size is 0.05 to 0.13 μm.
When m fine particle titanium dioxide is added, a reddish hue change different from the conventional one is exhibited. Utilizing these properties, it can be applied on a metal substrate or even used as a top coat for automobiles. When the coating composition of the present invention is used for coating automobiles, it is desirable to apply it as a base coat and then apply a transparent top coat thereon. The basecoat and clear topcoat can be applied to the substrate by conventional methods such as brushing, spraying, dipping, flow coating and the like. Particularly, for finish coating of automobiles, it is generally common to spray-coat a substrate coated with a corrosion-resistant primer, and this method includes compressed air spraying, electrostatic spraying,
There are various types such as a hot spray method and an air spray method.
【００１２】[0012]
実施例１ （微粒子二酸化チタンの製造）TiO2として200g/lの濃度
のTiCl4 水溶液700ml とNa2Oとして100g/lの濃度のNaOH
水溶液を、系のpHを５〜９に維持するように水中に並行
添加した。pH７に調整した後、濾過、洗浄し、得られた
ケーキを電気炉にて780 ℃で２時間焼成し、その後乾式
粉砕、湿式粉砕を行った。得られた粉末を100g/lのスラ
リーに調整し、このスラリー１リットルを70℃に加熱し
た。スラリー固形分に対してSnO2として１重量％の塩化
第一スズ水溶液を添加し、次にZrO2として２重量％の硫
酸ジルコニウム水溶液を添加した後、水酸化ナトリウム
水溶液を添加してpH７に調整した。更に、Al2O3 として
５重量％のアルミン酸ナトリウム水溶液と硫酸とを、系
のpHを７〜１０に維持するように並行添加して、スズ、
ジルコニウム、アルミニウムの含水酸化物を沈殿させ
た。この後、濾過、洗浄し、乾燥した後乾式粉砕仕手電
子顕微鏡法による平均単一粒子径が0.06μｍで、0.05〜
0.1 μｍの粒度のものが80％以上であるルチル型微粒子
二酸化チタンを得た（試料Ａ）。Example 1 (Production of fine particle titanium dioxide) 700 ml of an aqueous TiCl 4 solution having a concentration of 200 g / l as TiO 2 and NaOH having a concentration of 100 g / l as Na 2 O
The aqueous solution was added in parallel to the water to maintain the system pH at 5-9. After the pH was adjusted to 7, it was filtered and washed, and the obtained cake was baked at 780 ° C. for 2 hours in an electric furnace, and then dry crushed and wet crushed. The obtained powder was adjusted to a slurry of 100 g / l, and 1 liter of this slurry was heated to 70 ° C. 1 wt% stannous chloride aqueous solution was added as SnO 2 to the slurry solid content, then 2 wt% zirconium sulfate aqueous solution was added as ZrO 2 , and then sodium hydroxide aqueous solution was added to adjust the pH to 7. did. Further, 5 wt% sodium aluminate aqueous solution as Al 2 O 3 and sulfuric acid were added in parallel so as to maintain the pH of the system at 7 to 10, tin,
Hydrous oxides of zirconium and aluminum were precipitated. After that, it is filtered, washed and dried, and then the dry pulverized finish electron microscope method has an average single particle diameter of 0.06 μm and 0.05 to
A rutile-type fine particle titanium dioxide having a particle size of 0.1 μm was 80% or more was obtained (Sample A).
【００１３】（塗料組成物の製造）前記試料Ａ7.5gを、
アクリル樹脂／ブチル化メラミン樹脂＝８／２（重量
比）の混合ワニス80.6g （不揮発分53％）中へペイント
シェーカーを用いて分散、塗料化した後、アルミペース
トを加え（重量比で試料Ａ／Al＝１／１）、よく混合し
て本発明のメタリック塗料組成物とした。(Production of coating composition) 7.5 g of the above sample A was
Acrylic resin / Butylated melamine resin = 8/2 (weight ratio) 80.6 g (nonvolatile content 53%) of mixed varnish was dispersed using a paint shaker to make a paint, and then aluminum paste was added (weight A of sample A / Al = 1/1), and mixed well to obtain the metallic coating composition of the present invention.
【００１４】（塗料組成物の評価）この塗料組成物を鋼
板上に乾燥膜厚が18μｍになるように塗布し、30分セッ
ティング後アクリル系クリヤーを乾燥膜厚が12μｍにな
るように塗布し、30分セッティング後、130 ℃で30分間
焼付けた。この塗布板を変角測色計GCMS-3型（村上色研
製）を用い、入射角45°、測定角40°（フェイスカラ
ー）、−25°（フロップカラー）で測色し、ａ値色差を
下記式により求めた結果、ａ値色差＝10となった。 ａ値色差＝フェイスカラーａ値（40°）−フロップカラ
ーａ値（−25°）(Evaluation of Coating Composition) This coating composition was applied on a steel sheet so that the dry film thickness was 18 μm, and after setting for 30 minutes, acrylic clear was applied so that the dry film thickness was 12 μm. After setting for 30 minutes, it was baked at 130 ° C for 30 minutes. This coating plate was measured with a gonio-colorimeter GCMS-3 (Murakami Color Research Laboratory) at an incident angle of 45 °, a measuring angle of 40 ° (face color), and a temperature of -25 ° (flop color). As a result of obtaining by the following formula, a value color difference = 10. a value color difference = face color a value (40 °) -flop color a value (-25 °)
【００１５】実施例２ （微粒子二酸化チタンの製造）TiCl4 水溶液の加水分解
により得られた含水酸化チタンを、TiO2換算100g/lの濃
度の水性懸濁液とした。この水性懸濁液２リットルに48
％NaOH水溶液1400g を攪拌しながら添加し、95℃で120
分加熱後、濾過し、十分に洗浄を行った。洗浄ケーキを
水で100g/l×1.5 リットルにレパルプし、フラスコに入
れ、35％塩酸570gを攪拌しながら30分間で添加した後、
95℃まで加熱し、90分間熟成した後、濾過、洗浄した。
得られたケーキを780 ℃で焼成し、以下実施例１と同様
にして、平均単一粒子径が0.08μｍのルチル型微粒子二
酸化チタン（0.05〜0.1 μｍの粒度分布は、全体の80％
以上であった）を得た（試料Ｂ）。Example 2 (Production of Fine Particle Titanium Dioxide) Hydrous titanium oxide obtained by hydrolysis of an aqueous TiCl 4 solution was used as an aqueous suspension having a concentration of 100 g / l in terms of TiO 2 . 48 to 2 liters of this aqueous suspension
% NaOH aqueous solution (1400 g) is added with stirring and the mixture is heated at 95 ° C for 120%.
After heating for a minute, the mixture was filtered and thoroughly washed. The washed cake was repulped to 100 g / l x 1.5 liters with water, placed in a flask, and 570 g of 35% hydrochloric acid was added with stirring for 30 minutes.
After heating to 95 ° C. and aging for 90 minutes, filtration and washing were performed.
The cake thus obtained was calcined at 780 ° C., and rutile type titanium dioxide fine particles having an average single particle diameter of 0.08 μm (particle size distribution of 0.05 to 0.1 μm was 80% of the whole) in the same manner as in Example 1.
The above was obtained) (Sample B).
【００１６】（塗料組成物の製造）、（塗料組成物の評
価） 前記試料Ｂを用い、実施例１と同様に塗料化し、塗布
後、測色を行った結果、ａ値色差は15であった。(Production of coating composition), (Evaluation of coating composition) Using the sample B, a coating material was formed in the same manner as in Example 1, and after coating, color measurement was carried out. As a result, the a-value color difference was 15. It was
【００１７】実施例３〜６ （微粒子二酸化チタンの製造）、（塗料組成物の製
造）、（塗料組成物の評価） 実施例１において、下記表１の条件以外は、実施例１と
同様にして微粒子二酸化チタンを製造し、塗料組成物を
製造し、評価した。Examples 3 to 6 (Production of Fine Particle Titanium Dioxide), (Production of Coating Composition), (Evaluation of Coating Composition) Example 1 was carried out in the same manner as in Example 1 except for the conditions shown in Table 1 below. To produce fine particle titanium dioxide, a coating composition was prepared and evaluated.
【００１８】[0018]
【表１】 [Table 1]
【００１９】比較例１〜５ 実施例１において、下記表２の条件以外は、実施例１と
同様にして塗料組成物を製造し、評価した。Comparative Examples 1 to 5 A coating composition was prepared and evaluated in the same manner as in Example 1 except for the conditions shown in Table 2 below.
【００２０】[0020]
【表２】 [Table 2]
【００２１】前記実施例１〜６及び比較例１〜５の評価
結果を、表３に示す。Table 3 shows the evaluation results of Examples 1 to 6 and Comparative Examples 1 to 5.
【００２２】[0022]
【表３】 [Table 3]
【００２３】[0023]
【発明の効果】以上説明したように、平均単一粒子径が
０．０５〜０．１３μｍの微粒子二酸化チタンを配合し
た本発明の塗料組成物は、従来の青味色相変化とは異な
った赤味色相変化を伴うフリップ・フロップ効果を呈す
る意匠性に優れたものであることが判る。As described above, the coating composition of the present invention containing fine particle titanium dioxide having an average single particle diameter of 0.05 to 0.13 μm has a red color different from the conventional bluish hue change. It can be seen that the design is excellent in that it exhibits a flip-flop effect with a change in taste hue.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 坂井 章人 三重県四日市市石原町１番地 石原産業株 式会社四日市事業所内 (72)発明者 服部 雅一 三重県四日市市石原町１番地 石原産業株 式会社四日市事業所内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Akito Sakai 1 Ishihara-cho, Yokkaichi-shi, Mie Ishihara Industrial Co., Ltd. Yokkaichi Plant (72) Inventor Masakazu Hattori 1-site, Ishihara-cho, Yokkaichi-shi, Mie Ishihara Sangyo Ceremony company Yokkaichi office
Claims (7)
ｍの微粒子二酸化チタンとリン片状金属顔料とを１対
０．１〜１０の重量比で含み、塗膜にした場合に赤味色
相変化を伴うフリップ・フロップ効果を示す塗料組成
物。1. The average single particle diameter is 0.05 to 0.13 μm.
A coating composition comprising the fine particle titanium dioxide of m and the scaly metal pigment in a weight ratio of 1 to 0.1 to 10, and showing a flip-flop effect with a reddish hue change when formed into a coating film.
射光カラー）とフロップカラー（散乱光カラー）のａ値
色差の最大値が３以上となることを特徴とする請求項１
記載の塗料組成物。2. The reddish hue change is such that the maximum value of the a-value color difference between the face color (regular reflection light color) and the flop color (scattered light color) is 3 or more.
The coating composition described.
射光カラー）とフロップカラー（散乱光カラー）のａ値
色差の最大値が５以上となることを特徴とする請求項１
記載の塗料組成物。3. The reddish hue change is such that the maximum value of the a-value color difference between the face color (regular reflection light color) and the flop color (scattered light color) is 5 or more.
The coating composition described.
０．０６〜０．０９μｍであることを特徴とする請求項
１、２または３記載の塗料組成物。4. The coating composition according to claim 1, 2 or 3, wherein the fine titanium dioxide particles have an average single particle diameter of 0.06 to 0.09 μm.
布において、累積重量％で８０％以上が０．０５〜０．
１μｍであることを特徴とする請求項１、２、３または
４記載の塗料組成物。5. In the particle size distribution of a single particle size of fine particle titanium dioxide, 80% or more in cumulative weight% is 0.05 to 0.
It is 1 micrometer, The coating composition of Claim 1, 2, 3 or 4 characterized by the above-mentioned.
アルミニウム、ケイ素、チタニウム、ジルコニウム及び
スズの群から選ばれた少なくとも１種の元素の含水酸化
物または酸化物の被覆を有するものであることを特徴と
する請求項１、２、３、４または５記載の塗料組成物。6. The fine titanium dioxide particles have a surface coated with a hydrous oxide or oxide of at least one element selected from the group consisting of aluminum, silicon, titanium, zirconium and tin. The coating composition according to claim 1, 2, 3, 4 or 5.
を特徴とする請求項１記載の塗料組成物。7. The coating composition according to claim 1, wherein the flaky metal pigment is an aluminum foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13124594A JP3346650B2 (en) | 1994-05-20 | 1994-05-20 | Paint composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13124594A JP3346650B2 (en) | 1994-05-20 | 1994-05-20 | Paint composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07316475A true JPH07316475A (en) | 1995-12-05 |
| JP3346650B2 JP3346650B2 (en) | 2002-11-18 |
Family
ID=15053404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13124594A Expired - Lifetime JP3346650B2 (en) | 1994-05-20 | 1994-05-20 | Paint composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3346650B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999054415A1 (en) * | 1998-04-15 | 1999-10-28 | Nof Corporation | Method for formation of coating film and coating composition |
| JP2006321751A (en) * | 2005-05-19 | 2006-11-30 | Tayca Corp | Nail color having high flip-flop effect |
| JP2011122036A (en) * | 2009-12-10 | 2011-06-23 | Dainichiseika Color & Chem Mfg Co Ltd | Resin composition exerting color flip-flop effect |
| WO2017164234A1 (en) * | 2016-03-22 | 2017-09-28 | 新日鐵住金株式会社 | Precoated metal plate |
-
1994
- 1994-05-20 JP JP13124594A patent/JP3346650B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999054415A1 (en) * | 1998-04-15 | 1999-10-28 | Nof Corporation | Method for formation of coating film and coating composition |
| JP2006321751A (en) * | 2005-05-19 | 2006-11-30 | Tayca Corp | Nail color having high flip-flop effect |
| JP2011122036A (en) * | 2009-12-10 | 2011-06-23 | Dainichiseika Color & Chem Mfg Co Ltd | Resin composition exerting color flip-flop effect |
| WO2017164234A1 (en) * | 2016-03-22 | 2017-09-28 | 新日鐵住金株式会社 | Precoated metal plate |
| JPWO2017164234A1 (en) * | 2016-03-22 | 2018-04-12 | 新日鐵住金株式会社 | Pre-coated metal plate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3346650B2 (en) | 2002-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5137575A (en) | Chromatic pigments comprising a coloring metal oxide coating on transparent titanium oxide core particles of 0.01 to 0.1 micron size | |
| EP0404378B1 (en) | Coating composition | |
| US4494993A (en) | Nacreous pigments, their preparation and use | |
| US5536448A (en) | Dendrite or asteroidal titanium dioxide micro-particles | |
| US3331699A (en) | Nacreous glass flake pigment compositions | |
| DE60017592T2 (en) | PRECIOUS METAL COLOR EFFECT MATERIALS AND THEIR PRODUCTION | |
| JPS6358863B2 (en) | ||
| EP1509575B8 (en) | Rutile titanium dioxide effect pigments and production thereof | |
| US5702518A (en) | Gold pigments | |
| WO2000077099A1 (en) | Methods and compositions related to pearlescent pigments | |
| US5228911A (en) | Oxidized graphite flaky particles and pigments based thereon | |
| JP4153066B2 (en) | Method for producing strongly cohesive titanium oxide | |
| JP3346650B2 (en) | Paint composition | |
| US5753024A (en) | Grey pigments containing tin | |
| KR100227054B1 (en) | Pearlscent pigment and process for producing the same | |
| JPH07751B2 (en) | Fine particle titanium dioxide powder | |
| JP4190174B2 (en) | High iris color titanium oxide and its manufacturing method | |
| JP3183362B2 (en) | Paint composition | |
| JPH0781093B2 (en) | Mica coated with titanium compound | |
| KR100215375B1 (en) | Oxidized graphite flaky particles and pigments based thereon | |
| AU611065B2 (en) | Opacifying agent and its preparation | |
| JP3044949B2 (en) | Decorative pigments | |
| JPH04214779A (en) | Coating composition | |
| JPH07157686A (en) | Bluish brilliant white nacreous pigment | |
| US3450550A (en) | Inorganic blue to green pigments |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080906 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090906 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100906 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100906 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110906 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120906 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120906 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130906 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130906 Year of fee payment: 11 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140906 Year of fee payment: 12 |
|
| EXPY | Cancellation because of completion of term |