JPH07292277A - Titanium dioxide pigment - Google Patents
Titanium dioxide pigmentInfo
- Publication number
- JPH07292277A JPH07292277A JP12669794A JP12669794A JPH07292277A JP H07292277 A JPH07292277 A JP H07292277A JP 12669794 A JP12669794 A JP 12669794A JP 12669794 A JP12669794 A JP 12669794A JP H07292277 A JPH07292277 A JP H07292277A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- compound
- zirconium
- aluminum
- titanium dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は最近の、例えば自動車、
家電機器、工業用機器、建築物等の高級塗装仕上げ指向
を満足する塗料及びプラスチックスに必要な光沢発現
性、また長期屋外暴露時の耐久性いわゆる耐候性に優れ
た白色顔料として好適な二酸化チタンに関する。FIELD OF THE INVENTION The present invention has been recently developed, for example in automobiles,
Titanium dioxide suitable as a white pigment excellent in glossiness required for paints and plastics that satisfy the high-quality paint finish orientation for home appliances, industrial equipment, buildings, etc., and also excellent in weather resistance after long-term outdoor exposure Regarding
【０００２】[0002]
【従来の技術】従来からこの様な要求を満たすために数
多くの提案がなされており、チタニル硫酸溶液を加水分
解して得られた溶液に無機系化合物を添加したり、二酸
化チタン表面を被覆する方法が行われてきた。後者の方
法の１つとして無定形の高密度シリカを被覆し、その上
層に例えばアルミニウムの水和酸化物の被覆を施す方法
があるが、耐候性には有効である半面、顔料として要求
される分散性及び光沢が充分得られない。最近では二酸
化チタン表面に錫及びジルコニウムの水和酸化物を被覆
し、その外部にアルミニウムの水和酸化物を被覆する方
法（特願昭５５−１６２３７３）や、二酸化チタン表面
に最内層として錫及びジルコニウムの水和酸化物、中間
層としてチタンの水和酸化物、最外層としてアルミニウ
ムの水和酸化物をそれぞれ被覆する方法（特願昭６０−
１２２０１８）等が挙げられる。しかし要求性能が次第
に高度になり、これらの要請を完全に満足することが難
しくなってきた。2. Description of the Related Art Many proposals have hitherto been made in order to meet such requirements, and an inorganic compound is added to a solution obtained by hydrolyzing a titanyl sulfuric acid solution or a titanium dioxide surface is coated. The method has been done. As one of the latter methods, there is a method in which amorphous high-density silica is coated and an upper layer thereof is coated with, for example, a hydrated oxide of aluminum, but it is effective for weather resistance, but it is required as a pigment. Sufficient dispersibility and gloss cannot be obtained. Recently, a method of coating hydrated oxides of tin and zirconium on the surface of titanium dioxide and coating the hydrated oxide of aluminum on the outside (Japanese Patent Application No. 55-162373), or tin and zirconium as the innermost layer on the surface of titanium dioxide. A method of coating a hydrated oxide of zirconium, a hydrated oxide of titanium as an intermediate layer, and a hydrated oxide of aluminum as an outermost layer (Japanese Patent Application No. 60-
122018) and the like. However, the required performance has become more sophisticated, and it has become difficult to completely satisfy these requirements.
【０００３】[0003]
【発明が解決しようとする課題】本発明は前記問題点を
解決せんとするものであって、二酸化チタン粒子表面に
重層で複数の無機系化合物が被覆されていても、粘膜の
光沢発現性を損なうことなく耐候性に優れた性能をもつ
被覆二酸化チタン顔料が得られることの知見を得、特に
高度の耐候性、塗膜光沢が要求される自動車等の高級塗
装仕上げ用塗料に好適な二酸化チタン顔料を提供するこ
とを目的とする。DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned problems. Even if the surface of titanium dioxide particles is coated with a plurality of inorganic compounds in a multi-layer structure, the mucosal gloss developability is improved. We obtained the finding that a coated titanium dioxide pigment with excellent weather resistance can be obtained without damaging it, and titanium dioxide suitable for high-grade paint finishes for automobiles, etc., where particularly high weather resistance and coating gloss are required. The purpose is to provide a pigment.
【０００４】[0004]
【課題を解決するための手段】本発明はアルミニウム化
合物をＡｌ２Ｏ３として０．１〜２重量％あるいはアル
ミニウム化合物とジルコニウム化合物をＡｌ２Ｏ３，Ｚ
ｒＯ２として含量で０．１〜５重量％存在させたものを
含有するルチル型二酸化チタン（以下基体という）の表
面に酸化珪素、酸化錫、酸化ジルコニウム及び酸化アル
ミニウムをＳｉＯ２，ＳｎＯ２，ＺｒＯ２，Ａｌ２Ｏ３
としてそれぞれ１〜６重量％、０．１〜３重量％、０．
１〜５重量％、１〜５重量％存在させた二酸化チタン顔
料（基体が８１〜９７．８重量％）である。According to the present invention, 0.1 to 2 % by weight of aluminum compound is Al 2 O 3 or aluminum compound and zirconium compound are Al 2 O 3 , Z.
silicon oxide on the surface of the rutile titanium dioxide containing what was content in the presence of 0.1 to 5 wt% as r O 2 (hereinafter referred to as substrate), tin oxide, zirconium oxide and aluminum oxide S i O 2, S n O 2, Z r O 2 , Al 2 O 3
1 to 6% by weight, 0.1 to 3% by weight, and 0.
1 to 5% by weight, and 1 to 5% by weight of titanium dioxide pigment (base: 81 to 97.8% by weight).
【０００５】ここで基体はチタニル硫酸溶液あるいは四
塩化チタンを加水分解して得られる水酸化チタン（メタ
チタン酸等）に所定量のアルミニウム、ジルコニウム化
合物を混合し、９００〜１，０００℃で焼成したもので
ある。使用するアルミニウム、ジルコニウム化合物とし
ては硫酸アルミニウム、水酸化アルミニウム、硫酸ジル
コニウム、炭酸ジルコニウム等が挙げられる。Here, the substrate is a titanyl sulfuric acid solution or titanium hydroxide (meta-titanic acid, etc.) obtained by hydrolyzing titanium tetrachloride with a predetermined amount of an aluminum or zirconium compound and baked at 900 to 1,000 ° C. It is a thing. Examples of the aluminum and zirconium compounds used include aluminum sulfate, aluminum hydroxide, zirconium sulfate, zirconium carbonate and the like.
【０００６】アルミニウム酸化物の存在量はＡｌ２Ｏ３
として０．１〜２重量％であり、アルミニウム酸化物と
ジルコニウム酸化物の合量の存在量はＡｌ２Ｏ３，Ｚｒ
Ｏ２の合計として０．１〜５重量％であり、０．１重量
％以下では耐候性に関して満足な結果が得られず、２重
量％（合量の場合は５重量％）以上では白色度、分散性
等の顔料特性、また塗膜性能に劣る。The abundance of aluminum oxide is Al 2 O 3
As a 0.1-2 wt%, the abundance of the total amount of aluminum oxide and zirconium oxide is Al 2 O 3, Z r
The total amount of O 2 is 0.1 to 5% by weight, and when 0.1% by weight or less, satisfactory results are not obtained with respect to weather resistance, and when 2% by weight (5% by weight in the case of total amount) or more, whiteness is obtained. , Inferior in pigment properties such as dispersibility and coating film performance.
【０００７】該基体に珪素の酸化物、錫の酸化物、ジル
コニウムの酸化物、アルミニウムの酸化物を存在させる
には該基体１００〜５００ｇ／ｌの水性スラリーを５０
〜１００℃に保ち、所定量の珪素化合物を一定のｐＨを
保ちながら徐々に添加、あるいは添加した後徐々に中和
して酸化物又は水和酸化物として基体の表面に沈着さ
せ、３０〜９０分間熟成反応を行った後、錫化合物、ジ
ルコニウム化合物の水溶液を同時、あるいは順番に添加
し徐々に中和して酸化物又は水和酸化物として基体の表
面に沈着させ、３０〜９０分間熟成反応を行い、さらに
アルミニウム化合物の水溶液を一定のｐＨを保ちながら
徐々に添加して酸化物又は水和酸化物として基体の表面
に沈着させ、３０〜９０分間熟成反応を行った後、水洗
濾過し乾燥後粉砕処理を施して二酸化チタン顔料製品と
する。In order to allow silicon oxide, tin oxide, zirconium oxide, and aluminum oxide to be present in the substrate, 50 to 100 g / l of the aqueous slurry of the substrate is used.
Maintained at -100 ° C and a predetermined amount of a silicon compound is gradually added while maintaining a constant pH, or after being added, the mixture is gradually neutralized to be deposited as an oxide or hydrated oxide on the surface of the substrate. After aging for 30 minutes, an aqueous solution of a tin compound and a zirconium compound are added simultaneously or in sequence and gradually neutralized to deposit as oxides or hydrated oxides on the surface of the substrate, and aging reaction for 30 to 90 minutes Then, an aqueous solution of an aluminum compound is gradually added while keeping a constant pH to deposit it on the surface of the substrate as an oxide or a hydrated oxide. After aging reaction for 30 to 90 minutes, washing with water, filtration and drying are performed. Post-grinding is performed to obtain a titanium dioxide pigment product.
【０００８】使用する水溶性の珪素化合物、水溶性の錫
化合物、水溶性のジルコニウム化合物、水溶性のアルミ
ニウム化合物はケイ酸ナトリウム、ケイ酸カリウム、塩
化スズ、硫酸ジルコニウム、塩化ジルコニウム、硝酸ジ
ルコニウム、硫酸アルミニウム、アルミン酸ナトリウ
ム、硝酸ナトリウム等が挙げられる。The water-soluble silicon compound, water-soluble tin compound, water-soluble zirconium compound and water-soluble aluminum compound used are sodium silicate, potassium silicate, tin chloride, zirconium sulfate, zirconium chloride, zirconium nitrate and sulfuric acid. Aluminum, sodium aluminate, sodium nitrate, etc. may be mentioned.
【０００９】珪素化合物、錫化合物、ジルコニウム化合
物、アルミニウム化合物はＳｉＯ２として１〜６重量
％、ＳｎＯ２として０．１〜３重量％，ＺｒＯ２として
０．１〜５重量％、Ａｌ２Ｏ３として１〜５重量％であ
る。[0009] Silicon compounds, tin compounds, zirconium compounds, aluminum compounds 1-6 wt% as S i O 2, 0.1 to 3 wt% as S n O 2, 0.1 to 5 weight as Z r O 2 %, And Al 2 O 3 is 1 to 5% by weight.
【００１０】珪素化合物がＳｉＯ２として１重量％以下
では耐候性に対する効果が小さく、６重量％以上では光
沢が低くなる。錫化合物がＳｎＯ２として０．１以下で
は耐候性に対する効果が小さく、３重量％以上では分散
性、光沢が低下するなど顔料特性、塗膜性能が損なわれ
る。ジルコニウム化合物がＺｒＯ２として０．１重量％
以下では耐候性に対する効果が小さく、５重量％以上で
は隠蔽力が落ちる。アルミニウム化合物がＡｌ２Ｏ３と
して１重量％以下では耐候性に対する効果が小さく、５
重量％以上では隠蔽力が落ちる。If the silicon compound is 1 wt% or less as S i O 2 , the effect on the weather resistance is small, and if it is 6 wt% or more, the gloss becomes low. Tin compounds is less effect on the weather resistance is 0.1 or less as S n O 2, pigment properties like dispersibility, gloss decreases, film performance is impaired at 3 wt% or more. Zirconium compound as Z r O 2 0.1 wt%
If it is less than 5% by weight, the hiding power will be poor. When the amount of the aluminum compound as Al 2 O 3 is 1% by weight or less, the effect on the weather resistance is small and 5
If it is more than 10% by weight, the hiding power will decrease.
【００１１】[0011]
【実施例】以下に実施例により具体的に説明する。[Examples] Specific examples will be described below.
【実施例１】チタニル硫酸溶液を加水分解し、水洗濾過
することによって得られるメタチタン酸に、重量基準で
Ａｌ２Ｏ３として０．５％の硫酸アルミニウム水溶液を
添加し十分に混練した後焙焼して得られた二酸化チタン
基体の水性スラリー（ＴｉＯ２濃度３８０ｇ／ｌ）を６
０℃に加熱後ケイ酸ナトリウム溶液を該基体の重量基準
でＳｉＯ２として５％添加してこのスラリー温度を８０
℃とした。次いで硫酸を６０分間かけて添加し、スラリ
ーのｐＨを４に調整して二酸化チタンの表面に珪素の水
和酸化物を沈殿させ、その後６０分間熟成させた。引続
きスラリー温度を７０℃としｐＨを水酸化ナトリウム水
溶液で８．５に維持しながら５０分間かけて塩化第一錫
溶液を該基体の重量基準でＳｎＯ２として０．５％添加
して錫の水和酸化物を沈殿させ、その後２０分間熟成さ
せた。さらに水酸化ナトリウム水溶液でｐＨを８．５に
維持しながら５０分間かけて硫酸ジルコニウム溶液を該
基体の重量基準でＺｒＯ２として１．２％添加してジル
コニウムの水和酸化物を沈殿させ、その後２０分間熟成
させた。引続き硫酸溶液でｐＨを８．５に維持しながら
９０分間かけてアルミン酸ナトリウム溶液を該基体の重
量基準でＡｌ２Ｏ３として３．５％添加してアルミニウ
ムの水和酸化物を沈殿させ、その後２０分間熟成させ
た。次いで硫酸溶液を添加してスラリーのｐＨを７と
し、６０分間熟成した後水洗濾過し、１３０℃で５時間
乾燥し、粉砕して珪素、錫、ジルコニウム及びアルミニ
ウムの水和酸化物で被覆された本発明の二酸化チタン顔
料を得た。（顔料Ａ）Example 1 A metatitanic acid obtained by hydrolyzing a titanyl sulfuric acid solution, washing with water, and filtering was added with a 0.5% aqueous solution of aluminum sulfate as Al 2 O 3 on a weight basis, sufficiently kneaded, and then roasted. The titanium dioxide-based aqueous slurry (T i O 2 concentration 380 g / l) obtained by
0 ℃ after heating sodium silicate solution based on the weight of said substrate to be added 5% as S i O 2 The slurry temperature 80
℃ was made. Then, sulfuric acid was added over 60 minutes, the pH of the slurry was adjusted to 4, and a hydrated oxide of silicon was precipitated on the surface of titanium dioxide, followed by aging for 60 minutes. Tin was subsequently added 0.5% stannous chloride solution over 50 minutes while maintaining the slurry temperature to 8.5 pH with aqueous sodium hydroxide and 70 ° C. as S n O 2 by weight of the base body The hydrated oxide of 1. was precipitated and then aged for 20 minutes. PH to precipitate the Z r O 2 as an additive to the hydrated oxide of zirconium 1.2% in over 50 minutes while maintaining the 8.5 weight of said substrate a zirconium sulfate solution further sodium hydroxide solution Then, it was aged for 20 minutes. Subsequently, while maintaining the pH at 8.5 with a sulfuric acid solution, sodium aluminate solution was added 3.5% as Al 2 O 3 based on the weight of the substrate over 90 minutes to precipitate a hydrated oxide of aluminum, Then, it was aged for 20 minutes. Next, a sulfuric acid solution was added to adjust the pH of the slurry to 7, the mixture was aged for 60 minutes, washed with water, filtered, dried at 130 ° C. for 5 hours, pulverized, and coated with a hydrated oxide of silicon, tin, zirconium, and aluminum. A titanium dioxide pigment of the present invention was obtained. (Pigment A)
【００１２】[0012]
【実施例２】二酸化チタン基体の製法で、重量基準でＡ
ｌ２Ｏ３として０．５％の硫酸アルミニウム水溶液及び
重量基準でＺｒＯ２として１．０％の炭酸ジルコニウム
水溶液をメタチタン酸に添加し、焙焼することで得られ
るアルミニウム及びジルコニウムを含有する二酸化チタ
ン基体の水性スラリーを使用すること以外は実施例１と
同様に被覆処理して本発明の酸化チタン顔料を得た。
（顔料Ｂ）[Example 2] A method of manufacturing a titanium dioxide substrate, in which A was used on a weight basis.
It contains aluminum and zirconium which are obtained by adding 0.5% aluminum sulfate aqueous solution as l 2 O 3 and 1.0% zirconium carbonate aqueous solution as Z r O 2 to metatitanic acid on a weight basis and roasting. The titanium oxide pigment of the present invention was obtained by the same coating treatment as in Example 1 except that an aqueous slurry of titanium dioxide base was used.
(Pigment B)
【００１３】[0013]
【比較例】実施例１，２の本発明顔料と比較するため、
次の様にして顔料Ｃ〜Ｆを製造した。 Ｃ：硫酸アルミニウム水溶液、炭酸ジルコニウム水溶液
の何れも添加しない二酸化チタンの水性スラリーを使用
すること以外は実施例１と同様に被覆処理した。 Ｄ：錫の水和酸化物を被覆処理しないこと以外は実施例
１と同様に処理した。 Ｅ：錫及びジルコニウムの水和酸化物を被覆処理しない
こと以外は実施例１と同様に処理した。 Ｆ：珪素の水和酸化物を被覆処理しないこと以外は実施
例１と同様に処理した。Comparative Example To compare with the pigments of the present invention of Examples 1 and 2,
Pigments C to F were manufactured as follows. C: The coating treatment was performed in the same manner as in Example 1 except that an aqueous slurry of titanium dioxide to which neither an aqueous solution of aluminum sulfate nor an aqueous solution of zirconium carbonate was added was used. D: Treated in the same manner as in Example 1 except that the hydrated oxide of tin was not coated. E: The same treatment as in Example 1 was performed except that the hydrated oxide of tin and zirconium was not coated. F: The same treatment as in Example 1 was performed except that the hydrated oxide of silicon was not coated.
【試験例】前記実施例及び比較例の二酸化チタン顔料Ａ
〜Ｆについてその性能を試験し表１の結果を得た。[Test Example] Titanium dioxide pigment A of the above Examples and Comparative Examples
The performance was tested for ~ F and the results shown in Table 1 were obtained.
【００１４】[0014]
【表１】 [Table 1]
【００１５】表１の性能評価は次の様にして行った。The performance evaluation in Table 1 was performed as follows.
試験片の作成 Ａ〜Ｆの二酸化チタン顔料をオイルフリーアルキド樹脂
／メラミン樹脂（４／１重量比）ワニス中へ混和し、ペ
イントシェーカー（レッドデビル社製＃５１１０）で分
散塗料化した後、化成被膜処理軟鋼板に約４５μ厚（焼
付け後塗膜として）塗布し、１４０℃で３０分間焼付け
てこれを試験片とした。 鏡面光沢の測定 試験板の初期光沢（６０゜−６０゜鏡面光沢）及び暴露
後光沢の測定にはグロスメーター（村上色彩技術研究所
製、ＧＭ−２６）を用いて行った。 促進耐候性評価 促進耐候性評価はカーボンアーク型サンシャインウエザ
ーメーター装置（スガ試験機ＫＫ製、ＷＥ−ＳＵＮ−Ｄ
Ｃ型）内で試験片を促進暴露し、一定時間毎に上記「鏡
面光沢の測定」に従って評価した。また白亜化度は日本
塗料検査協会の塗膜評価基準に従って測定した９６０時
間暴露後の塗膜表面の白亜化発生程度で評価した。ここ
で白亜化発生程度は１０を白亜化が発生していないこと
とし、１０〜０までの評価で数値が小さくなるに従って
白亜化発生程度が大きいことを示す。Preparation of test pieces The titanium dioxide pigments A to F were mixed in an oil-free alkyd resin / melamine resin (4/1 weight ratio) varnish, and dispersed into a paint with a paint shaker (Red Devil Co. # 5110), followed by chemical conversion. The coated mild steel sheet was applied with a thickness of about 45 μm (as a coating film after baking) and baked at 140 ° C. for 30 minutes to prepare a test piece. Measurement of specular gloss The initial gloss (60 ° -60 ° specular gloss) of the test plate and the gloss after exposure were measured using a gloss meter (GM-26 manufactured by Murakami Color Research Laboratory). Accelerated weathering resistance evaluation Accelerated weathering resistance evaluation was carried out using a carbon arc type sunshine weather meter device (made by Suga Testing Machine KK, WE-SUN-D
The test piece was subjected to accelerated exposure in (C type) and evaluated at regular intervals according to the above "Measurement of specular gloss". The degree of chalking was evaluated by the degree of chalking on the surface of the coating film after exposure for 960 hours, which was measured according to the coating film evaluation criteria of the Japan Paint Inspection Association. Here, the degree of chalking occurrence is 10 when the chalking does not occur, and indicates that the degree of chalking occurrence increases as the numerical value decreases in the evaluation of 10 to 0.
【００１６】[0016]
【発明の効果】本発明により、高級塗装仕上げ塗料に使
用されるに耐え得る高光沢を、長期にわたって維持でき
る二酸化チタン顔料を提供することができるようになっ
た。Industrial Applicability According to the present invention, it is possible to provide a titanium dioxide pigment capable of maintaining a high gloss for a long period of time, which can be used in a high-grade paint finish.
Claims (1)
０．１〜２重量％あるいはアルミニウム化合物とジルコ
ニウム化合物をＡｌ２Ｏ３，ＺｒＯ２として含量で０．
１〜５重量％含有するルチル型二酸化チタン（以下基体
という）の表面に酸化珪素、酸化錫、酸化ジルコニウム
及び酸化アルミニウムをＳｉＯ２，ＳｎＯ２，Ｚ
ｒＯ２，Ａｌ２Ｏ３としてそれぞれ１〜６重量％、０．
１〜３重量％、０．１〜５重量％、１〜５重量％存在さ
せた二酸化チタン顔料（基体が８１〜９７．８重量
％）。1. A 0 at a content of 0.1 to 2% by weight of aluminum compound as Al 2 O 3 or an aluminum compound and a zirconium compound as Al 2 O 3, Z r O 2.
Silicon oxide on the surface of 1 to 5% by weight content to rutile titanium dioxide (referred to hereinafter base), tin oxide, zirconium oxide and aluminum oxide S i O 2, S n O 2, Z
r O 2, Al 2 O 3, respectively 6% by weight, 0.
1-3 wt%, 0.1-5 wt%, 1-5 wt% titanium dioxide pigment present (81-97.8 wt% substrate).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12669794A JPH07292277A (en) | 1994-04-28 | 1994-04-28 | Titanium dioxide pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12669794A JPH07292277A (en) | 1994-04-28 | 1994-04-28 | Titanium dioxide pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07292277A true JPH07292277A (en) | 1995-11-07 |
Family
ID=14941616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12669794A Pending JPH07292277A (en) | 1994-04-28 | 1994-04-28 | Titanium dioxide pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07292277A (en) |
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| EP2267088A2 (en) | 2009-06-26 | 2010-12-29 | Sakai Chemical Industry Co., Ltd. | Surface-modified titanium dioxide particle and method for producing the same |
| JP2015093901A (en) * | 2013-11-11 | 2015-05-18 | アイカ工業株式会社 | Aqueous coating material composition |
| EP2160082A4 (en) * | 2007-05-18 | 2016-08-24 | Denka Company Ltd | Metal base circuit board |
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-
1994
- 1994-04-28 JP JP12669794A patent/JPH07292277A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4838798B2 (en) * | 2004-07-31 | 2011-12-14 | クローノス インターナショナル インコーポレイテッド | Post-treatment method of titanium dioxide pigment |
| WO2006012969A1 (en) * | 2004-07-31 | 2006-02-09 | Kronos International, Inc. | Method for post-treating titanium dioxide pigments |
| AU2005268984B2 (en) * | 2004-07-31 | 2010-07-29 | Kronos International, Inc. | Method for post-treating titanium dioxide pigments |
| JP2009004718A (en) * | 2007-05-18 | 2009-01-08 | Denki Kagaku Kogyo Kk | Metal base circuit board |
| EP2160082A4 (en) * | 2007-05-18 | 2016-08-24 | Denka Company Ltd | Metal base circuit board |
| JP2010150087A (en) * | 2008-12-25 | 2010-07-08 | Sakai Chem Ind Co Ltd | Titanium dioxide pigment and production method thereof |
| EP2202278A1 (en) | 2008-12-25 | 2010-06-30 | Sakai Chemical Industry Co., Ltd. | Titanium dioxide pigment and method for producing the same |
| JP2010280852A (en) * | 2009-06-05 | 2010-12-16 | Kaneka Corp | Resin composition for aqueous paint, and paint obtained by compounding resin composition for aqueous paint |
| EP2267088A2 (en) | 2009-06-26 | 2010-12-29 | Sakai Chemical Industry Co., Ltd. | Surface-modified titanium dioxide particle and method for producing the same |
| JP2011006292A (en) * | 2009-06-26 | 2011-01-13 | Sakai Chem Ind Co Ltd | Titanium dioxide particles and method for producing the same |
| US8070874B2 (en) | 2009-06-26 | 2011-12-06 | Sakai Chemical Industry, Co., Ltd. | Surface-modified titanium dioxide particle and method for producing the same |
| JP2015093901A (en) * | 2013-11-11 | 2015-05-18 | アイカ工業株式会社 | Aqueous coating material composition |
| WO2018123928A1 (en) | 2016-12-28 | 2018-07-05 | 中国塗料株式会社 | Anti-fouling paint composition, anti-fouling paint film, base material having anti-fouling paint film attached thereto and method for producing same, and fouling prevention method |
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