JP4668583B2 - Titanium dioxide pigment - Google Patents
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Description
本発明は、水性塗料用の二酸化チタン顔料に関する。 The present invention relates to a titanium dioxide pigment for aqueous paint.
水溶解型、コロイダルディスパージョン型、エマルジョン型等の水性塗料は、環境負荷が小さく、作業環境の安全・衛生性が高く、また、省資源の点でも優れており、近年、需要が高まっている。中でも、水溶解型やコロイダルディスパージョン型塗料は自動車、建材、家電品等の高級工業用塗料の分野で、有機溶剤型塗料からの代替が期待されている。このため、塗料の主要構成成分である二酸化チタン顔料にも、水性塗料への対応が求められており、例えば、二酸化チタン顔料に有機リン酸エステル化合物を被覆したり（特許文献１参照）、あるいは二酸化チタン顔料に高密度（緻密）シリカの第一被覆層及び多孔質シリカの第二被覆層を被覆したり（特許文献２参照）する技術が提案されている。 Water-soluble paints such as water-soluble, colloidal dispersion, and emulsion paints have a low environmental impact, high work environment safety and hygiene, and are excellent in terms of resource conservation. . Of these, water-soluble and colloidal dispersion-type paints are expected to replace organic solvent-type paints in the field of high-grade industrial paints such as automobiles, building materials, and home appliances. For this reason, the titanium dioxide pigment, which is a main component of the paint, is also required to be compatible with water-based paints. A technique for coating a titanium dioxide pigment with a first coating layer of high-density (dense) silica and a second coating layer of porous silica has been proposed (see Patent Document 2).
しかし、一般的に、水性塗料は、有機溶剤系塗料と比較して、保管安定性が十分ではなく、特許文献１記載の二酸化チタン顔料でも保管安定性の問題は十分に解決されているとはいい難い。このため、これを配合した水性塗料を長期間保管すると、二酸化チタン顔料が強く凝集してしまい、再分散を行っても初期の分散状態に戻すことは困難である。また、特許文献２に記載の二酸化チタン顔料は、概して保管安定性には優れているものの、光沢等の塗膜外観に優れたものを得るのは困難であった。 However, in general, water-based paints are not sufficiently stable when compared with organic solvent-based paints, and the problem of storage stability is sufficiently solved even with the titanium dioxide pigment described in Patent Document 1. It ’s not good. For this reason, when the water-based paint blended with this is stored for a long period of time, the titanium dioxide pigments strongly aggregate and it is difficult to return to the initial dispersed state even if redispersion is performed. Moreover, although the titanium dioxide pigment described in Patent Document 2 is generally excellent in storage stability, it has been difficult to obtain a pigment having excellent coating appearance such as gloss.
本発明は、水性塗料に配合した時に、塗膜外観のみならず、優れた保管安定性をも付与できる二酸化チタン顔料を提供するものである。 The present invention provides a titanium dioxide pigment capable of imparting not only the appearance of a coating film but also excellent storage stability when blended in an aqueous paint.
本発明者らは、これらの問題を解決すべく鋭意研究を重ねた結果、第一被覆層として緻密シリカを、第二被覆層として多孔質シリカを被覆した二酸化チタン顔料に、更に、特定の有機リン酸エステル化合物を被覆すると、これを用いた水性塗料の塗膜外観のみならず、保管安定性をも向上することを見出し、本発明を完成させた。 As a result of intensive studies to solve these problems, the inventors of the present invention have added a specific organic material to a titanium dioxide pigment coated with dense silica as the first coating layer and porous silica as the second coating layer. It has been found that when a phosphoric ester compound is coated, not only the coating film appearance of the aqueous paint using the same but also the storage stability is improved, and the present invention has been completed.
すなわち、本発明は、二酸化チタン粒子の表面に緻密シリカからなる第一の被覆層、多孔質シリカからなる第二の被覆層、有機化合物からなる第三の被覆層を有し、第三の被覆層に少なくとも下記式１及び式２で表される有機リン酸エステル化合物の混合物（式１及び式２中のｎが６、混合比が重量比で０．７：１〜１．５：１の範囲）が含まれることを特徴とする水性塗料用二酸化チタン顔料である。 That is, the present invention has a first coating layer made of dense silica, a second coating layer made of porous silica, and a third coating layer made of an organic compound on the surface of the titanium dioxide particles, A mixture of at least organophosphate compounds represented by the following formula 1 and formula 2 in the layer (n in formula 1 and formula 2 is 6 and the mixing ratio is 0.7: 1 to 1.5: 1 by weight) A titanium dioxide pigment for water-based paints.
本発明の二酸化チタン顔料は、水性塗料に優れた保管安定性と塗膜外観を付与できる。 The titanium dioxide pigment of the present invention can impart excellent storage stability and coating film appearance to water-based paints.
本発明は、水性塗料用二酸化チタン顔料であって、二酸化チタン粒子の表面に緻密シリカからなる第一の被覆層、多孔質シリカからなる第二の被覆層、有機化合物からなる第三の被覆層を有し、第三の被覆層に少なくとも下記式１及び式２で表される有機リン酸エステル化合物の混合物（式１及び式２中のｎが６、混合比が重量比で０．７：１〜１．５：１の範囲）が含まれることを特徴とする。本発明は、それぞれの被覆層が、実質的に中間層を介することなく被覆されたものであり、本発明の二酸化チタン顔料を用いた水性塗料は光沢、隠ペイ性等の塗膜外観が優れ、長期間保管しても顔料の凝集がほとんど生じない。本発明では、第一及び第二の被覆により、保管安定性が改良、また、前記有機リン酸エステル化合物は、水性塗料中でこのような二酸化チタン顔料を高度に分散させるのに、最も適したものであると推測される。従って、第一及び二の被覆層を有する二酸化チタン顔料に、前記以外の有機リン酸エステル化合物を用いても、所望の塗膜外観は得られない。 The present invention relates to a titanium dioxide pigment for water-based paints, the first coating layer comprising dense silica on the surface of the titanium dioxide particles, the second coating layer comprising porous silica, and the third coating layer comprising an organic compound. And a mixture of organophosphate compounds represented by the following formulas 1 and 2 in the third coating layer (n in the formulas 1 and 2 is 6, the mixing ratio is 0.7: 1 to 1.5: 1) . In the present invention, each coating layer is coated substantially without an intermediate layer, and the aqueous paint using the titanium dioxide pigment of the present invention is excellent in coating film appearance such as gloss and hiding property. Even when stored for a long time, the pigments hardly aggregate. In the present invention, the first and second coatings improve storage stability, and the organophosphate compound is most suitable for highly dispersing such titanium dioxide pigments in aqueous paints. Presumed to be. Therefore, even if an organic phosphate ester compound other than the above is used for the titanium dioxide pigment having the first and second coating layers, the desired coating appearance cannot be obtained.
本発明における緻密シリカ、多孔質シリカを構成するシリカは、無水酸化ケイ素、含水酸化ケイ素、水和酸化ケイ素、水酸化ケイ素を包含する化合物である。それぞれの被覆量は、二酸化チタン粒子に対し、ＳｉＯ２換算で０．５〜１０重量％の範囲にあるのが好ましく、より好ましい範囲は、０．５〜５重量％である。第三の被覆層には、前記有機リン酸エステル化合物が、二酸化チタン粒子に対し０．１〜５重量％の範囲で含まれているのが好ましく、０．３〜２重量％の範囲がより好ましい。式１と式２の化合物の混合比は、重量比で０．０５：１〜２０：１の範囲にあるのが好ましく、０．１：１〜１５：１の範囲がより好ましい。 The silica constituting the dense silica and porous silica in the present invention is a compound including anhydrous silicon oxide, hydrous silicon oxide, hydrated silicon oxide, and silicon hydroxide. Each coating amount is preferably in the range of 0.5 to 10% by weight in terms of SiO 2 with respect to the titanium dioxide particles, and more preferably in the range of 0.5 to 5% by weight. The third coating layer preferably contains the organophosphate compound in a range of 0.1 to 5% by weight with respect to the titanium dioxide particles, more preferably in a range of 0.3 to 2% by weight. preferable. The mixing ratio of the compounds of formula 1 and formula 2 is preferably in the range of 0.05: 1 to 20: 1 by weight, more preferably in the range of 0.1: 1 to 15: 1.
第三の被覆層には、前記有機リン酸エステル化合物以外にも、本発明の効果を阻害しない範囲で、工業的に不純物として混入する下記式３で表される有機リン酸エステル化合物や、乾式粉砕助剤、分散助剤等として各種の有機化合物が含まれていてもよい。有機リン酸エステル化合物以外に用いることができる有機化合物としては、トリメチロールプロパン、トリメチロールエタン、ペンタエリスリトール等のポリオール類、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン類またはそれらの有機酸塩等の誘導体等が挙げられる。これらの有機化合物は、前記リン酸エステル化合物と混合した状態で第三の被覆層を形成していても、前記リン酸エステル化合物の被覆層の下面、上面または両面に、その他の有機化合物の被覆層が積層された状態で第三の被覆層を形成していてもよく、特に制限は無い。その被覆量は、二酸化チタン粒子に対し０．０１〜３重量％の範囲が好ましく、０．０５〜２重量％の範囲が更に好ましい。 In the third coating layer, in addition to the organic phosphate compound, an organic phosphate compound represented by the following formula 3 that is industrially mixed as an impurity as long as the effects of the present invention are not impaired, Various organic compounds may be included as a grinding aid, a dispersion aid, and the like. Organic compounds that can be used in addition to the organic phosphate compound include polyols such as trimethylolpropane, trimethylolethane, and pentaerythritol, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, or organic acids thereof. Examples thereof include derivatives such as salts. Even if these organic compounds form a third coating layer in a state of being mixed with the phosphoric ester compound, other organic compounds are coated on the lower surface, upper surface or both surfaces of the phosphoric ester compound coating layer. The 3rd coating layer may be formed in the state where the layer was laminated, and there is no restriction in particular. The coating amount is preferably in the range of 0.01 to 3% by weight and more preferably in the range of 0.05 to 2% by weight with respect to the titanium dioxide particles.
二酸化チタン粒子は、例えば、硫酸チタン溶液を加水分解し、得られた含水酸化チタンを焼成するいわゆる硫酸法や、ハロゲン化チタンを気相酸化するいわゆる塩素法で製造されたものを用いることができる。その平均粒子径（電子顕微鏡写真法による５０％累積径）は、０．１〜１．０μｍの範囲が好ましく、０．１〜０．４μｍの範囲が更に好ましい。結晶形は、アナタース型、ルチル型の１種又はそれらの混合物のいずれでもよいが、高級工業用塗料には耐候性が優れたルチル型を主体とする二酸化チタン粒子を用いるのが好ましい。 As the titanium dioxide particles, for example, those produced by a so-called sulfuric acid method in which a titanium sulfate solution is hydrolyzed and the resulting hydrous titanium oxide is fired, or in a so-called chlorine method in which titanium halide is vapor-phase oxidized can be used. . The average particle diameter (50% cumulative diameter by electron micrograph) is preferably in the range of 0.1 to 1.0 μm, and more preferably in the range of 0.1 to 0.4 μm. The crystal form may be either one of anatase type, rutile type or a mixture thereof, but it is preferable to use titanium dioxide particles mainly composed of rutile type having excellent weather resistance for high-grade industrial paints.
二酸化チタン粒子への緻密シリカからなる第一の被覆層の被覆は、公知の方法、例えば、特開昭５３−３３２２８号公報等に記載の方法により行うことができる。特開昭５３−３３２２８号公報に記載の方法は、二酸化チタン粒子のスラリーを８０〜１００℃の範囲の温度に維持しながら、好ましくはスラリーのｐＨを９〜１０．５の範囲に調整し、ケイ酸ナトリウムを急速に添加した後、９〜１０．５の範囲のｐＨで中和し、その後、８０〜１００℃の範囲の温度を５０〜６０分間保持するものである。本発明においては、更に、二酸化チタン粒子の水性スラリーを、８０℃以上の温度でｐＨを９以上に調整し、ケイ酸塩を添加して、酸性化合物で徐々にｐＨが４〜６の範囲で中和する方法によっても、第一の被覆層を得ることができる。 The titanium dioxide particles can be coated with the first coating layer made of dense silica by a known method, for example, a method described in JP-A No. 53-33228. The method described in JP-A-53-33228 preferably adjusts the pH of the slurry to a range of 9 to 10.5 while maintaining the slurry of titanium dioxide particles at a temperature in the range of 80 to 100 ° C. After the rapid addition of sodium silicate, it is neutralized at a pH in the range of 9 to 10.5 and then maintained at a temperature in the range of 80 to 100 ° C. for 50 to 60 minutes. In the present invention, the aqueous slurry of titanium dioxide particles is further adjusted to a pH of 9 or higher at a temperature of 80 ° C. or higher, silicate is added, and the pH is gradually in the range of 4 to 6 with an acidic compound. The first coating layer can also be obtained by the neutralization method.
多孔質シリカからなる第二の被覆層は、第一の被覆層を被覆した後、引き続き、水性スラリーのｐＨを１〜４の範囲に調整し、ｐＨをこの範囲に維持しながらケイ酸塩と酸性化合物を同時に添加しｐＨが６〜８の範囲で中和することで得られる。 After coating the first coating layer, the second coating layer made of porous silica is continuously adjusted to the pH of the aqueous slurry in the range of 1 to 4, and the silicate and the pH are maintained in this range. It is obtained by adding an acidic compound at the same time and neutralizing the pH in the range of 6-8.
二酸化チタン粒子の水性スラリーは、製造設備、製造能力等に応じてその濃度を設定するが、工業的には１００〜６００ｇ／リットルの範囲が好ましく、２００〜４００ｇ／リットルの範囲が更に好ましい。二酸化チタン粒子の凝集程度に応じて、縦型サンドミル、横型サンドミル、ボールミル等の湿式粉砕機を用いて、適宜分散させてもよい。また、必要に応じて分散剤を用いてもよい。分散剤としては、例えば、ヘキサメタリン酸ナトリウム、ピロリン酸ナトリウム等のリン酸化合物、ケイ酸ナトリウム、ケイ酸カリウム等のケイ酸化合物が挙げられる。分散剤の使用量は、リン酸化合物であれば、二酸化チタン粒子に対しリン換算で０．０１〜３重量％の範囲が好ましい。ケイ酸塩には、ケイ酸ナトリウム、ケイ酸カリウム等を用いることができ、ｐＨ調整、中和等に用いる酸性化合物としては、硫酸、塩酸等の無機酸や、酢酸、ギ酸等の有機酸等が、塩基性化合物としては、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等のアルカリ金属またはアルカリ土類金属の水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属またはアルカリ土類金属の炭酸塩、アンモニア、炭酸アンモニウム、硝酸アンモニウム等のアンモニウム化合物等が挙げられる。 The concentration of the aqueous slurry of titanium dioxide particles is set according to production equipment, production capacity, etc., but is preferably in the range of 100 to 600 g / liter, more preferably in the range of 200 to 400 g / liter. Depending on the degree of aggregation of the titanium dioxide particles, they may be appropriately dispersed using a wet pulverizer such as a vertical sand mill, horizontal sand mill, or ball mill. Moreover, you may use a dispersing agent as needed. Examples of the dispersant include phosphoric acid compounds such as sodium hexametaphosphate and sodium pyrophosphate, and silicate compounds such as sodium silicate and potassium silicate. If the usage-amount of a dispersing agent is a phosphoric acid compound, the range of 0.01-3 weight% in conversion of phosphorus with respect to titanium dioxide particle is preferable. As the silicate, sodium silicate, potassium silicate, etc. can be used. Acidic compounds used for pH adjustment, neutralization, etc. include inorganic acids such as sulfuric acid and hydrochloric acid, organic acids such as acetic acid and formic acid, etc. However, basic compounds include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and alkali metal or alkaline earth metal carbonates such as sodium carbonate and potassium carbonate. And ammonium compounds such as ammonia, ammonium carbonate, and ammonium nitrate.
第三の被覆層は、第一及び第二の被覆層を形成した二酸化チタン粒子をスラリーから固液分離し、必要に応じて洗浄を行い、次いで乾燥した後、（１）乾式粉砕機中に前記有機リン酸エステル化合物をそれぞれを単独で添加するか、予め混合物として添加し、二酸化チタン粒子を粉砕しながら被覆する方法、または、（２）乾式粉砕後、ヘンシェルミキサー、スーパーミキサー等の高速撹拌機を用い、二酸化チタン粒子を撹拌しながら前記の化合物をそれぞれを単独で、または混合物で添加して、二酸化チタン粒子と混合して被覆する方法等により行うことができる。（１）の方法は、連続的に生産できるので、工業的に好ましい方法である。固液分離には、フィルタープレス、ロールプレス等の通常工業的に用いられる濾過器を用いることができる。乾燥にはバンド式ヒーター、バッチ式ヒーター等が、乾式粉砕にはハンマーミル、ピンミル等の衝撃粉砕機、ローラーミル、パラペライザー、解砕機等の摩砕粉砕機、ジェットミル、スネイルミル等の気流粉砕機、噴霧乾燥機等を用いることができる。 The third coating layer is obtained by solid-liquid separation of the titanium dioxide particles forming the first and second coating layers from the slurry, washing as necessary, then drying, and (1) in a dry pulverizer. A method of adding each of the organic phosphate compounds individually or in advance as a mixture and coating the titanium dioxide particles while pulverizing, or (2) high-speed stirring such as Henschel mixer and super mixer after dry pulverization Using a machine, the above compounds can be added individually or in a mixture while stirring the titanium dioxide particles, and mixed with the titanium dioxide particles to coat the titanium dioxide particles. The method (1) is an industrially preferable method because it can be produced continuously. For solid-liquid separation, a filter that is usually used industrially, such as a filter press or a roll press, can be used. Band type heater, batch type heater, etc. are used for drying. A machine, a spray dryer or the like can be used.
以下に本発明の実施例を示すが、本発明はこれらに制限されるものではない。 Examples of the present invention are shown below, but the present invention is not limited thereto.
実施例１
塩素法で得られた二酸化チタン粒子を、水酸化ナトリウムでｐＨを１０．５とした水に分散させ水性スラリーとし、サンドミルを用いて湿式粉砕し分級した後、ＴｉＯ２濃度を３００ｇ／リットルに調整した。このスラリー４リットルを撹拌しながら、７５℃に昇温し、温度を保持しながらケイ酸ナトリウム水溶液を添加し、３０分間撹拌し混合した後、液温を９０℃に昇温し、１規定の硫酸水溶液を約３ミリリットル／分の速度で４０分間添加して、pHが５となるまで中和した。その後、液温を７０℃に調整し、液温を保持しながら撹拌して６０分間熟成し、緻密シリカ（二酸化チタン粒子に対しＳｉＯ２として５重量％）からなる第一の被覆層を形成した。引き続き、硫酸を添加してｐＨを２に調整し、撹拌しながら、前記ケイ酸ナトリウム水溶液を、ｐＨを２に保持するように硫酸と共に添加した。次いで、２規定の硫酸水溶液を約１ミリリットル／分の速度で６０分間添加して、pHが８となるまで中和した。その後、液温を７０℃に、ｐＨを７に調整し、液温とｐＨを保持しながら撹拌して６０分間熟成し、多孔質シリカ（二酸化チタン粒子に対しＳｉＯ２として２重量％）からなる第二の被覆層を形成した。次いで、濾過・水洗、乾燥した後、ジェットミルで二酸化チタン粒子を粉砕しながら、二酸化チタン粒子に対して０．５重量％の式１及び２で表される化合物の混合物（式１及び式２中のｎが６、混合比が重量比で０．７：１〜１．５：１の範囲）をジェットミルに添加して、第三の被覆層を形成し、本発明の二酸化チタン顔料（試料Ａ）を得た。
Example 1
Titanium dioxide particles obtained by the chlorine method are dispersed in water having a pH of 10.5 with sodium hydroxide to form an aqueous slurry, wet pulverized using a sand mill and classified, and then the TiO 2 concentration is adjusted to 300 g / liter. did. While stirring 4 liters of this slurry, the temperature was raised to 75 ° C., an aqueous sodium silicate solution was added while maintaining the temperature, and after stirring and mixing for 30 minutes, the temperature of the solution was raised to 90 ° C. An aqueous sulfuric acid solution was added at a rate of about 3 ml / min for 40 minutes to neutralize the pH to 5. Thereafter, the liquid temperature was adjusted to 70 ° C., and the mixture was stirred and aged for 60 minutes while maintaining the liquid temperature to form a first coating layer made of dense silica (5% by weight as SiO 2 with respect to titanium dioxide particles). . Subsequently, sulfuric acid was added to adjust the pH to 2, and while stirring, the sodium silicate aqueous solution was added together with sulfuric acid so as to maintain the pH at 2. Next, a 2N aqueous sulfuric acid solution was added at a rate of about 1 ml / min for 60 minutes to neutralize the pH to 8. Thereafter, the liquid temperature is adjusted to 70 ° C., the pH is adjusted to 7, and the liquid is stirred and aged for 60 minutes while maintaining the liquid temperature and pH, and is composed of porous silica (2% by weight as SiO 2 with respect to titanium dioxide particles). A second coating layer was formed. Next, after filtering, washing with water and drying, the titanium dioxide particles are pulverized with a jet mill, and 0.5% by weight of the mixture of the compounds represented by the formulas 1 and 2 with respect to the titanium dioxide particles (formulas 1 and 2). N is 6 and the mixing ratio is in the range of 0.7: 1 to 1.5: 1 by weight) to the jet mill to form the third coating layer. Sample A) was obtained.
比較例１
実施例１で用いた有機リン酸エステル化合物に替えて、式４及び式５で表される有機リン酸エステル化合物の混合物（混合比が重量比で０．７：１〜１．５：１の範囲）を用いた以外は、実施例１と同様にして二酸化チタン顔料（試料B）を得た。
Comparative Example 1
Instead of the organic phosphate compound used in Example 1, a mixture of the organic phosphate compounds represented by Formula 4 and Formula 5 (mixing ratio is 0.7: 1 to 1.5: 1 by weight). A titanium dioxide pigment (sample B) was obtained in the same manner as in Example 1 except that the range) was used.
比較例２
実施例１で用いた有機リン酸エステル化合物に替えて、式６及び式７で表される有機リン酸エステル化合物の混合物（混合比が重量比で０．７：１〜１．５：１の範囲）を用いた以外は、実施例１と同様にして二酸化チタン顔料（試料Ｃ）を得た。
Comparative Example 2
Instead of the organic phosphate compound used in Example 1, a mixture of organic phosphate compounds represented by Formula 6 and Formula 7 (mixing ratio is 0.7: 1 to 1.5: 1 by weight). A titanium dioxide pigment (sample C) was obtained in the same manner as in Example 1 except that the range) was used.
比較例３
有機リン酸エステル化合物を被覆しなかったこと以外は実施例１と同様にして、二酸化チタン顔料（試料Ｄ）を得た。
Comparative Example 3
A titanium dioxide pigment (sample D) was obtained in the same manner as in Example 1 except that the organic phosphate compound was not coated.
比較例４
市販の二酸化チタン顔料ＣＲ−９０（石原産業（株）製：緻密シリカ、アルミナ被覆）に、実施例１と同様にして有機リン酸エステル化合物を被覆して二酸化チタン顔料（試料Ｅ）を得た。
Comparative Example 4
Commercially available titanium dioxide pigment CR-90 (Ishihara Sangyo Co., Ltd .: dense silica, alumina-coated) was coated with an organophosphate compound in the same manner as in Example 1 to obtain a titanium dioxide pigment (sample E). .
評価１：保管安定性の評価
実施例１、比較例１〜４の二酸化チタン顔料（試料Ａ〜Ｅ）を、表１に示す処方１にて容量５００ｃｃの縦型サンドミルに仕込み、３０００回転で２０分間分散して分散ペーストを調整した後、表２に示す処方２にて、樹脂成分１重量部に対し二酸化チタン顔料１重量部、固形分体積濃度５４％の水性塗料を得た。この水性塗料を、Ｎｏ．４フォードカップで塗料粘度が３０秒になるように純水で希釈した。希釈後の塗料を三週間静置し、目視により二酸化チタン顔料の凝集・沈降状態を判定した。結果を、表３に示す。
Evaluation 1: Evaluation of Storage Stability Titanium dioxide pigments (Samples A to E) of Example 1 and Comparative Examples 1 to 4 were charged into a vertical sand mill having a capacity of 500 cc with the formulation 1 shown in Table 1, and 20 rotations at 3000 rpm. After dispersing for a minute to prepare a dispersion paste, an aqueous coating material having a titanium dioxide pigment content of 1 part by weight and a solid content volume concentration of 54% with respect to 1 part by weight of the resin component was obtained according to the formulation 2 shown in Table 2. This water-based paint was designated as “No. It was diluted with pure water so that the viscosity of the paint was 30 seconds in a 4 Ford cup. The diluted paint was allowed to stand for 3 weeks, and the aggregation / sedimentation state of the titanium dioxide pigment was visually determined. The results are shown in Table 3.
評価２：光沢度の評価
評価１で用いた希釈塗料を、６ミルアプリケーターでガラス板に塗布し、３０分間静置してから、１４５℃の温度で３０分間焼き付け塗膜化した。得られた塗膜の６０°光沢度をグロスメーター（ＧＭ−２６Ｄ型／村上色材研究所製）を用いて計測した。結果を、表３に示す。
Evaluation 2: dilution paints used in Evaluation Evaluation 1 of glossiness, was applied to a glass plate by a 6 mil applicator, after standing for 30 minutes, was baked film coating for 30 minutes at a temperature of 145 ° C.. The 60 ° glossiness of the obtained coating film was measured using a gloss meter (GM-26D type / manufactured by Murakami Color Research Laboratory). The results are shown in Table 3.
表３より、二酸化チタン顔料として緻密シリカからなる第一の被覆層、多孔質シリカからなる第二の被覆層、さらには式１及び式２で表される特定の有機リン酸エステル化合物の混合物（式１及び式２中のｎが６、混合比が重量比で０．７：１〜１．５：１の範囲）からなる第三の被覆層を有するものを水性塗料に配合した場合にのみ、水性塗料の保管安定性と塗膜の光沢度が共に優れていることが判る。
From Table 3, as a titanium dioxide pigment, a first coating layer composed of dense silica, a second coating layer composed of porous silica, and a mixture of specific organophosphate compounds represented by Formulas 1 and 2 ( Only when an aqueous coating material is blended with a third coating layer in which n in Formula 1 and Formula 2 is 6, and the mixing ratio is in the range of 0.7: 1 to 1.5: 1 by weight. It can be seen that both the storage stability of the water-based paint and the glossiness of the coating film are excellent.
本発明は、水性塗料に、特に、自動車、建材、家電品等の高級工業用の水性塗料に有用である。
The present invention is useful for water-based paints, and particularly for water-based paints for high-grade industries such as automobiles, building materials, and home appliances.
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