JP2004083904A - Titanium dioxide pigment, its preparation and resin composition using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an anatase type titanium dioxide pigment excellent in opacifying property, and to provide a method for producing the same and to provide a resin composition using the same. <P>SOLUTION: The anatase type titanium dioxide pigment contains 98-100% of the anatase type crystal and has 0.2-0.4 μm of average particle diameter and 95-97 of linseed oil color L values. The titanium dioxide pigment of the invention has characteristics peculiar to anatase type, for example optical properties such as bluish hue or the like, physical properties such as low hardness or the like and has high opacifying performance never obtained in conventional anatase type titanium dioxide pigment. <P>COPYRIGHT: (C)2004,JPO

Description

　本発明は、隠ペイ性に優れたアナターゼ型二酸化チタン顔料及びその製造方法並びにそれを用いた樹脂組成物に関する。 The present invention relates to an anatase-type titanium dioxide pigment excellent in covert payability, a method for producing the same, and a resin composition using the same.

　二酸化チタンは白色顔料として塗料、インキ、プラスチックス、紙等の広い分野で使用されており、現在、市販されているものは、結晶形によりアナターゼ型とルチル型とに大きく分類される。アナターゼ型はルチル型と比較して、短波長の光の反射率が高い（青味の色調を呈する）、紫外部の光の吸収が小さい、硬度が低い、誘電率が低い、比重が小さい等の特徴を有するが、一方でルチル型より可視光の屈折率が小さく、隠ペイ性が低いという顔料の基本的な性質で劣るので、アナターゼ型の特徴が十分に利用されていない。ところで、高隠ペイ性が求められる樹脂組成物で用いられる顔料濃度は、例えば、塗料、インキ等であれば、通常、二酸化チタン顔料が樹脂成分１重量部に対し０．５重量部以上、プラスチックス等であれば、通常、０．０５重量部以上である。市販のアナターゼ型二酸化チタン顔料は平均粒子径が０．１〜０．１８μｍの範囲にあり、アナターゼ型二酸化チタン顔料の隠ペイ性が低い原因は、前述のように可視光の屈折率が低いというアナターゼ型の基本特性にもよるが、理論上、最も優れた隠ペイ性が得られる最適粒子径に対し、粒子径が小さ過ぎるという点にもある。 チ タ ン Titanium dioxide is used as a white pigment in a wide range of fields such as paints, inks, plastics, and paper. Currently, commercially available titanium dioxide is roughly classified into anatase type and rutile type depending on the crystal form. The anatase type has a higher reflectance of short-wavelength light (has a bluish color tone), a lower absorption of ultraviolet light, a lower hardness, a lower dielectric constant, a lower specific gravity, etc., as compared with the rutile type. On the other hand, since the pigments are inferior to the rutile type in terms of the basic properties of the pigment, such as having a lower refractive index of visible light and lower concealment property, the characteristics of the anatase type are not fully utilized. By the way, the pigment concentration used in a resin composition for which a high hiding power is required is, for example, usually 0.5 parts by weight or more of titanium dioxide pigment per 1 part by weight of a resin component in the case of paints and inks. In general, the amount is 0.05 parts by weight or more. Commercially available anatase-type titanium dioxide pigments have an average particle diameter in the range of 0.1 to 0.18 μm, and the cause of the low hidden payability of the anatase-type titanium dioxide pigment is that the refractive index of visible light is low as described above. Although it depends on the basic characteristics of the anatase type, the particle size is too small in theory, relative to the optimum particle size at which the best hidden payability can be obtained.

　平均粒子径が０．２μｍ以上のアナターゼ型二酸化チタン顔料の製造方法として、例えば、含水酸化チタン中のＴｉＯ_２に対し、Ｋ_２Ｏ換算で０．２〜０．６重量％の範囲に相当するカリウム酸化物と、Ｐ_２Ｏ_５換算で０．１５〜０．５５重量％の範囲に相当するリン酸化物とを焼成処理剤として含水酸化チタンに加え、好ましくは更にＡｌ_２Ｏ_３換算で０．２重量％以上のアルミニウム化合物を加えて、４６０℃から１０２０℃にまで一定の時間を掛け徐々に温度を上げながら加熱焼成する方法が知られている（特許文献1参照）。また、含水酸化チタン中のＴｉＯ_２に対し、Ａｌ_２Ｏ_３換算で０．１〜０．５重量％の範囲に相当するアルミニウム化合物、Ｋ_２Ｏ換算で０．1〜０．7重量％の範囲に相当するカリウム化合物、及び、Ｐ_２Ｏ_５換算で０．２〜１重量％の範囲に相当するリン化合物を焼成処理剤として含水酸化チタンに加え、少なくとも１０００℃以上の温度で加熱焼成する方法も知られている（特許文献２参照）。 As a method for producing an anatase type titanium dioxide pigment having an average particle diameter of 0.2 μm or more, for example, it corresponds to a range of 0.2 to 0.6% by weight in terms of K ₂ O with respect to TiO _{2 in} hydrous titanium oxide. Potassium oxide and phosphorus oxide corresponding to the range of 0.15 to 0.55% by weight in terms of P ₂ O ₅ are added to the hydrated titanium oxide as a calcination agent, and preferably 0 to 0 in terms of Al ₂ O _3. There is known a method of adding 0.2% by weight or more of an aluminum compound and heating and baking while gradually increasing the temperature from 460 ° C. to 1020 ° C. over a certain period of time (see Patent Document 1). Further, based on TiO ₂ in the hydrous titanium oxide, an aluminum compound corresponding to the range of 0.1 to 0.5% by weight in terms of Al ₂ O ₃ , and 0.1 to 0.7% by weight in terms of K ₂ O. A potassium compound corresponding to the above range and a phosphorus compound corresponding to a range of 0.2 to 1% by weight in terms of P ₂ O ₅ are added to the hydrated titanium oxide as a sintering agent, and sintering is performed at a temperature of at least 1000 ° C. A method is also known (see Patent Document 2).

特開平８−２２５３２４号公報（第１頁）JP-A-8-225324 (page 1) 特開平９−１８８５１８号公報（第１頁）JP-A-9-188518 (page 1)

　しかしながら、前記特許文献1記載の方法では、白色顔料としては十分な白色度が得られず、前記特許文献２記載の方法では、加熱焼成温度が高く、加熱焼成中にアナターゼ型結晶の一部がルチル型に転位するので、得られた顔料には２〜８重量％程度のルチル型二酸化チタンが含まれ、アナターゼ型の特徴が得られ難く、また粒子間の焼結も生じ易く、分散性の優れた二酸化チタン顔料が得られ難い。本発明は、以上に述べた従来技術の問題点を克服し、隠ペイ性の優れたアナターゼ型二酸化チタン顔料及びその製造方法並びにそれを用いた樹脂組成物を提供するものである。 However, in the method described in Patent Document 1, sufficient whiteness cannot be obtained as a white pigment, and in the method described in Patent Document 2, the heating and firing temperature is high, and a part of the anatase crystal is Since the pigment is rearranged into a rutile type, the obtained pigment contains about 2 to 8% by weight of rutile type titanium dioxide, it is difficult to obtain an anatase type feature, and sintering between particles easily occurs, and dispersibility is high. It is difficult to obtain an excellent titanium dioxide pigment. An object of the present invention is to provide an anatase-type titanium dioxide pigment excellent in covert payability, a method for producing the same, and a resin composition using the same, which overcomes the above-mentioned problems of the prior art.

　本発明者らは、これらの問題点を解決すべく鋭意研究を重ねた結果、焼成処理剤としてアルミニウム化合物、カリウム化合物、リン化合物を用い、これらの添加量及びカリウム化合物とリン化合物の添加比率を特定範囲にすると、１０００℃未満の焼成温度で、粒子径が大きく白色度が優れたアナターゼ型の二酸化チタン顔料が得られることを見出た。また、得られた二酸化チタン顔料は樹脂組成物に用いると、優れた隠ペイ性を示し、しかもルチル型にはないアナターゼ型の特性を有することを見出し、本発明を完成した。 The present inventors have conducted intensive studies to solve these problems, and as a result, using an aluminum compound, a potassium compound, and a phosphorus compound as a sintering treatment agent, the addition amount of these compounds and the addition ratio of the potassium compound and the phosphorus compound were determined. It was found that, when the specific range is set, an anatase-type titanium dioxide pigment having a large particle size and excellent whiteness can be obtained at a firing temperature of less than 1000 ° C. Further, they have found that when the obtained titanium dioxide pigment is used in a resin composition, it exhibits excellent hidden payability and has anatase-type properties which are not found in the rutile type, and thus completed the present invention.

　すなわち、本発明は、（１）アナターゼ型結晶を９８〜１００％の範囲で含み、０．２〜０．４μｍの範囲の平均粒子径を有し、白色度がアマニ油カラーのＬ値で９５〜９７の範囲にあることを特徴とする二酸化チタン顔料、（２）含水酸化チタンを加熱焼成するアナターゼ型二酸化チタン顔料の製造方法において、焼成処理剤として含水酸化チタン中のＴｉＯ_２に対しＡｌ_２Ｏ_３換算で０．０２〜０．２重量％の範囲に相当するアルミニウム化合物、Ｋ_２Ｏ換算で０．２〜１重量％、Ｐ_２Ｏ_５換算で０．０２〜０．５重量％の範囲に相当し、且つＫ_２Ｏ／Ｐ_２Ｏ_５が１．５／１〜１０／１の範囲にあるカリウム化合物及びリン酸化合物を用い、８００℃以上１０００℃未満の温度で加熱焼成することを特徴とする二酸化チタン顔料の製造方法、（３）前記二酸化チタン顔料を用いた樹脂組成物である。 That is, the present invention provides (1) an anatase type crystal in a range of 98 to 100%, an average particle diameter in a range of 0.2 to 0.4 μm, and a whiteness of 95% in linseed oil color L value. (2) a method for producing an anatase-type titanium dioxide pigment by heating and calcining hydrated titanium oxide, wherein the calcination agent is Al ₂ with respect to TiO ₂ in the hydrated titanium oxide. Aluminum compound corresponding to the range of 0.02 to 0.2% by weight in terms of O ₃ , 0.2 to 1% by weight in terms of K ₂ O, and 0.02 to 0.5% by weight in terms of P ₂ O ₅ Using a potassium compound and a phosphoric acid compound corresponding to the range and having K ₂ O / P ₂ O _{5 in} the range of 1.5 / 1 to 10/1, and heating and firing at a temperature of 800 ° C. or more and less than 1000 ° C. Titanium dioxide pigment characterized by the following And (3) a resin composition using the titanium dioxide pigment.

　本発明の二酸化チタン顔料はアナターゼ型特有の特性、例えば青味色調等の光学的特性、低い硬度等の物理的特性を有し、しかも、従来のアナターゼ型酸化チタン顔料には無い高隠ペイ性を有するので各種の樹脂組成物に、中でも塗料用樹脂、インキ用樹脂、プラスチックス用樹脂を配合した樹脂組成物に有用である。 The titanium dioxide pigment of the present invention has properties specific to anatase type, for example, optical properties such as blue tint, physical properties such as low hardness, and high opacity which is not present in conventional anatase type titanium oxide pigments. Therefore, it is useful for various resin compositions, especially for resin compositions in which a resin for paint, a resin for ink, and a resin for plastics are blended.

　本発明は二酸化チタン顔料であって、アナターゼ型結晶を９８〜１００％の範囲で含み、０．２〜０．４μｍの範囲の平均粒子径を有し、白色度がアマニ油カラーのＬ値で９５〜９７の範囲にあることを特徴とする。本発明では平均粒子径を高隠ペイ性が求められる樹脂組成物に用いられる顔料濃度（例えば、塗料、インキであれば、樹脂成分１重量部に対し二酸化チタン顔料が０．５重量部以上、プラスチックスであれば、樹脂成分１重量部に対し二酸化チタン顔料が０．０５重量部以上）に最も適した前記範囲にすることで、本来、屈折率の低いアナターゼ型二酸化チタンに、優れた隠ペイ性を付与している。本発明の二酸化チタン顔料においては、アマニ油カラーによるＬ値で表して、９５〜９７の範囲の白色度を有している。また、加工時に剪断力が働き難いプラスチックスのような分野では、塗料やインキと比較して、高顔料濃度になる程、二酸化チタン顔料を分散させ難いが、本発明の二酸化チタン顔料は粒子径が大きく、表面エネルギーが小さいので、分散性に優れている。 The present invention relates to a titanium dioxide pigment which contains anatase type crystals in the range of 98 to 100%, has an average particle size in the range of 0.2 to 0.4 μm, and has whiteness as L value of linseed oil color. It is in the range of 95 to 97. In the present invention, the average particle size is determined by the pigment concentration used in the resin composition required to have high concealment payability (for example, in the case of paints and inks, the titanium dioxide pigment is 0.5 parts by weight or more per 1 part by weight of the resin component, In the case of plastics, the titanium dioxide pigment is 0.05 parts by weight or more with respect to 1 part by weight of the resin component). It gives payability. The titanium dioxide pigment of the present invention has a whiteness in the range of 95 to 97 as represented by L value based on linseed oil color. In addition, in fields such as plastics where shearing force does not easily work during processing, as compared with paints and inks, the higher the pigment concentration, the more difficult it is to disperse the titanium dioxide pigment. And the surface energy is small, so that the dispersibility is excellent.

　アナターゼ型結晶の含有量が前記範囲より低いと、アナターゼ型二酸化チタンが有する青味の色調、紫外部吸収能、硬度等の特徴が発現し難くなる。平均粒子径が前記範囲より小さいと所望の効果が得られないばかりでなく、表面エネルギーが大きくなり、分散性も低下する。前記範囲より平均粒子径を大きくしても、更なる隠ペイ性の向上は認められず、むしろ、アナターゼ型の特徴の一つである短波長の光の反射率が低下し、黄味色調を呈するようになる。より好ましい平均粒子径の範囲は、０．２〜０．３μｍである。中でも、粒度分布の幅が狭ければ、所望の効果が得られ易く、本発明では、０．２〜０．４μｍの範囲の粒子径を有する粒子を、重量基準で５０〜１００％、好ましくは６０〜１００％の範囲で含むものが特に好ましい。尚、本発明では、Ｘ線回折によりルチル型結晶の含有量（Ｒ（％））を求め、１００−Ｒ（％）をアナターゼ型の含有量とする。また、平均粒子径は電子顕微鏡法により測定した、一次粒子の累積５０％粒子径であり、一次粒子とは、通常の工業的に用いられる機械的方法では、ほとんど崩壊することのない最小単位の粒子を言う。 と If the content of the anatase type crystal is lower than the above range, characteristics such as bluish color tone, ultraviolet absorption ability, and hardness of anatase type titanium dioxide are difficult to be exhibited. If the average particle size is smaller than the above range, not only the desired effect cannot be obtained, but also the surface energy increases and the dispersibility decreases. Even if the average particle size is larger than the above range, further improvement in hidden payability is not recognized, but rather, the reflectance of short-wavelength light, which is one of the features of the anatase type, is reduced, and the yellow tint is reduced. Will be presented. A more preferable range of the average particle diameter is 0.2 to 0.3 μm. Above all, if the width of the particle size distribution is narrow, a desired effect is easily obtained, and in the present invention, particles having a particle size in the range of 0.2 to 0.4 μm are 50 to 100% by weight, preferably 50 to 100%. Those containing in the range of 60 to 100% are particularly preferred. In the present invention, the content (R (%)) of the rutile type crystal is determined by X-ray diffraction, and 100-R (%) is defined as the content of the anatase type. The average particle size is a cumulative 50% particle size of primary particles measured by electron microscopy, and primary particles are the smallest unit that hardly disintegrates in a general industrial mechanical method. Say particles.

　本発明の二酸化チタン顔料は、表面が被覆されていなくても良いが、アナターゼ型二酸化チタンは光触媒活性が高く、耐光性や耐候性が低いので、少なくとも何らかの無機化合物で被覆されているのが好ましい。また、二酸化チタン顔料は親水性を有するので、樹脂成分との高度な親和性を付与するためには、更に有機化合物で被覆するのが好ましい。 The titanium dioxide pigment of the present invention may not be coated on the surface, but the anatase type titanium dioxide has high photocatalytic activity and low light resistance and weather resistance, so it is preferably coated with at least some inorganic compound. . In addition, since the titanium dioxide pigment has hydrophilicity, it is preferable that the titanium dioxide pigment is further coated with an organic compound in order to impart a high affinity to the resin component.

　本発明の二酸化チタン顔料の表面被覆に用いることのできる無機化合物としては、アルミニウム化合物、ケイ素化合物、ジルコニウム化合物、スズ化合物、チタニウム化合物、アンチモン化合物等が挙げられ、これらを１種被覆することも、２種以上の被覆を積層したり、２種以上の無機化合物を混合して被覆する等して、組み合せて用いることもできる。これらの無機化合物が酸化物、水酸化物、水和酸化物、リン酸塩から選ばれる少なくとも1種であれば、更に好ましい。無機化合物の被覆層は、被覆処理工程におけるｐＨ、温度等の処理条件を制御することにより、被覆層を多孔質にしたり、緻密なものにできることが知られており、本発明では、このような被覆層の性状も、特に制限されない。それぞれの無機化合物の被覆量は、用いる樹脂組成物の用途や、無機化合物の種類にもよるが、概ね０．０５〜１５重量％の範囲である。より好ましい範囲は、塗料組成物やインキ組成物に用いる二酸化チタン顔料の場合は０．１〜１５重量％、プラスチックス組成物の場合は０．０５〜５重量％の範囲である。尚、前記の被覆量は、酸化物、水酸化物、水和酸化物の場合は、酸化物基準（例えば、アルミニウムの水和酸化物はＡｌ_２Ｏ_３として）で、リン酸塩の場合はリン酸塩基準（例えば、リン酸アルミニウムはＡｌＰＯ_４として）で表している。 Examples of the inorganic compound that can be used for the surface coating of the titanium dioxide pigment of the present invention include aluminum compounds, silicon compounds, zirconium compounds, tin compounds, titanium compounds, antimony compounds, and the like. Two or more kinds of coatings may be laminated, or two or more kinds of inorganic compounds may be mixed and coated, and used in combination. It is more preferable that these inorganic compounds are at least one selected from oxides, hydroxides, hydrated oxides, and phosphates. It is known that a coating layer of an inorganic compound can make the coating layer porous or dense by controlling treatment conditions such as pH and temperature in the coating treatment step. The properties of the coating layer are not particularly limited. The coating amount of each inorganic compound is generally in the range of 0.05 to 15% by weight, depending on the use of the resin composition to be used and the kind of the inorganic compound. A more preferred range is 0.1 to 15% by weight for a titanium dioxide pigment used in a coating composition or an ink composition, and 0.05 to 5% by weight for a plastics composition. The coating amount of the, if the oxides, hydroxides, hydrated oxides, an oxide basis (e.g., as a hydrated oxide of aluminum Al ₂ O _3), when the phosphate Expressed on a phosphate basis (eg, aluminum phosphate as AlPO ₄ ).

　表面被覆に用いる好ましい無機化合物は、ケイ素、ジルコニウム、スズ、アンチモンの化合物、望ましくはそれらの水和酸化物である。ケイ素の水和酸化物は耐候性の観点では、緻密な状態で被覆するのが好ましい。アルミニウム、チタニウムの水和酸化物は、樹脂成分との親和性を向上させたり、製造工程における脱水、乾燥、粉砕等の操作性を改良する効果が知られており、少なくとも二酸化チタン顔料の最外殻には、アルミニウムの水和酸化物を被覆するのが好ましい。 好 ま し い Preferred inorganic compounds used for the surface coating are silicon, zirconium, tin and antimony compounds, preferably hydrated oxides thereof. The hydrated oxide of silicon is preferably coated in a dense state from the viewpoint of weather resistance. Aluminum and titanium hydrated oxides are known to have an effect of improving the affinity with the resin component and improving the operability such as dehydration, drying, and pulverization in the production process. The shell is preferably coated with a hydrated oxide of aluminum.

　本発明の二酸化チタン顔料の表面被覆に用いることのできる有機化合物としては、多価アルコール、アルカノールアミンまたはその誘導体、有機ケイ素化合物、高級脂肪酸またはその金属塩等が挙げられる。具体的には、例えば、多価アルコールとしてはトリメチロールエタン、トリプロパノールエタン、ペンタエリスリトール等が、アルカノールアミンとしてはトリエチルアミン等が、有機ケイ素化合物としてはジメチルポリシロキサン、メチルハイドロジェンポリシロキサン等のポリシロキサン類や、ヘキシルトリメトキシシラン等のアルキルシラン類、及び、アミノシラン、ビニルシラン、フェニルシラン等のシランカップリング剤等のオルガノシラン類等が、高級脂肪酸としてはステアリン酸等が、高級脂肪酸の金属塩としてはステアリン酸マグネシウム、ステアリン酸亜鉛等が挙げられる。これらは１種被覆することも、２種以上を組合せて被覆することもできる。これら有機化合物の種類、その組合せ、被覆順序等も、目的に応じて選択できる。有機化合物の総被覆量は、好ましくは０．０１〜５重量％の範囲であり、更に好ましい範囲は０．０５〜２重量％である。 有機 Examples of the organic compound that can be used for the surface coating of the titanium dioxide pigment of the present invention include a polyhydric alcohol, an alkanolamine or a derivative thereof, an organosilicon compound, a higher fatty acid or a metal salt thereof, and the like. Specifically, for example, polyhydric alcohols include trimethylolethane, tripropanolethane, pentaerythritol, and the like, alkanolamines include triethylamine, and the like, and organosilicon compounds include dimethylpolysiloxane and methylhydrogenpolysiloxane. Siloxanes, alkylsilanes such as hexyltrimethoxysilane, and organosilanes such as silane coupling agents such as aminosilane, vinylsilane, and phenylsilane; stearic acid and the like as higher fatty acids; and metal salts of higher fatty acids. Examples thereof include magnesium stearate and zinc stearate. These can be coated alone or in combination of two or more. The kind of these organic compounds, the combination thereof, the coating order and the like can be selected according to the purpose. The total coating amount of the organic compound is preferably in the range of 0.01 to 5% by weight, and more preferably 0.05 to 2% by weight.

　表面被覆組成の具体的な一例として、Ａｌ_２Ｏ_３換算で１〜５重量％、好ましくは１〜４重量％の範囲のアルミニウムの水和酸化物が被覆されたものが挙げられる。このものは、分散性が優れているので、高光沢を求められる塗料に適している。アナターゼ型は光触媒活性が高いので、耐候性を求められる塗料には、前記のアルミニウムの水和酸化物の被覆層を第二層（外層）とし、その内部の第一層（二酸化チタン顔料の表面）として、ＳｉＯ_２換算で１〜１０重量％、好ましくは１〜５重量％の範囲のケイ素の水和酸化物の緻密層を、被覆したものが適している。あるいは、ケイ素の水和酸化物に替えて、ＺｒＯ_２換算で０．０５〜５重量％、好ましく０．０５〜２重量％の範囲のジルコニウムの水和酸化物を被覆しても良く、更にＳｎＯ_２換算で０．０５〜５重量％、好ましく０．０５〜２重量％の範囲のスズの水和酸化物を、前記のジルコニウムの水和酸化物の被覆層と積層させても良い。前記の無機化合物を被覆した二酸化チタン顔料に、０．１〜２重量％、好ましくは０．１〜１重量％の範囲の多価アルコール、好ましくはトリメチロールエタンまたはトリメチロールプロパンを被覆すると、更に塗料用樹脂成分との親和性が高くなり、好ましい。 As a specific example of the surface coating composition, one coated with a hydrated oxide of aluminum in the range of 1 to 5% by weight, preferably 1 to 4% by weight in terms of Al ₂ O ₃ is mentioned. Since this is excellent in dispersibility, it is suitable for a paint requiring high gloss. Since the anatase type has a high photocatalytic activity, the coating layer of aluminum hydrated oxide is used as the second layer (outer layer) and the first layer inside (the surface of the titanium dioxide pigment) As), those coated with a dense layer of hydrated silicon oxide in the range of 1 to 10% by weight, preferably 1 to 5% by weight in terms of SiO ₂ are suitable. Alternatively, the hydrated oxide of zirconium may be coated in the range of 0.05 to 5% by weight, preferably 0.05 to ₂ % by weight in terms of ZrO ₂ , instead of the hydrated oxide of silicon. Tin hydrated oxide in the range of 0.05 to 5% by weight, preferably 0.05 to ₂ % by weight in terms of ₂ may be laminated with the above-mentioned hydrated oxide coating layer of zirconium. When the titanium dioxide pigment coated with the inorganic compound is coated with 0.1 to 2% by weight, preferably 0.1 to 1% by weight of a polyhydric alcohol, preferably trimethylolethane or trimethylolpropane, Affinity with the resin component for paint is increased, which is preferable.

　別の一例として、ＳｉＯ_２換算で２〜１０重量％、好ましくは２〜６重量％の範囲のケイ素の水和酸化物が、第一層（内層）として被覆され、Ａｌ_２Ｏ_３換算で１〜１０重量％、好ましくは１〜５重量％の範囲のアルミニウムの水和酸化物が、第二層（外層）として被覆されたものが挙げられる。このものは、インキ用二酸化チタン顔料として、特に裏刷りグラビアインキ用やフレキソインキ用として隠ペイ性が高く、印刷適性にも優れている。ケイ素の水和酸化物の被覆は緻密な被覆層とするか、多孔質の被覆層とするか、あるいは緻密層と多孔質層を積層するかは、前記の被覆量の範囲内で選択できる。フレキソインキ用としては、ケイ素及びアルミニウムの水和酸化物が前記範囲で被覆されているものの中で、総被覆量を５〜１５重量％の範囲にするのが特に好ましい。あるいは、ケイ素の水和酸化物を被覆せず、アルミニウムの水和酸化物のみをＡｌ_２Ｏ_３換算で５〜１５重量％、好ましくは５〜１０重量％の範囲の被覆したものも、フレキソインキに用いることができる。ケイ素化合物に替えて、ＴｉＯ_２換算で０．１〜５重量％、好ましく０．１〜２重量％の範囲のチタニウムの水和酸化物が、第一層（内層）として被覆されると、光沢が高くなり、表刷りグラビアインキに適したものとなる。前記の被覆を行った二酸化チタン顔料に、０．１〜２重量％、好ましくは０．１〜１重量％の範囲の多価アルコール、好ましくはトリメチロールエタンまたはトリメチロールプロパンを被覆すると、インキ樹脂成分との親和性が高くなり、更に好ましい。 As another example, a hydrated oxide of silicon in a range of 2 to 10% by weight, preferably 2 to 6% by weight in terms of SiO ₂ is coated as the first layer (inner layer), and 1% in terms of Al ₂ O _3. The second layer (outer layer) is coated with a hydrated oxide of aluminum in the range of 10 to 10% by weight, preferably 1 to 5% by weight. This is a titanium dioxide pigment for inks, especially for gravure inks for back printing and for flexo inks, and has high hidden payability and excellent printability. Whether the coating of the silicon hydrated oxide is a dense coating layer, a porous coating layer, or a stack of the dense layer and the porous layer can be selected within the above-described range of the coating amount. For flexo inks, it is particularly preferable that the total coating amount is in the range of 5 to 15% by weight among the hydrated oxides of silicon and aluminum coated in the above range. Alternatively, a flexo ink which is not coated with a hydrated oxide of silicon but is coated with only a hydrated oxide of aluminum in a range of 5 to 15% by weight, preferably 5 to 10% by weight in terms of Al ₂ O ₃ is also used. Can be used. When a hydrated titanium oxide in the range of 0.1 to 5% by weight, preferably 0.1 to ₂ % by weight in terms of TiO2 is coated as the first layer (inner layer) instead of the silicon compound, the gloss becomes And becomes suitable for front-print gravure ink. When the coated titanium dioxide pigment is coated with 0.1 to 2% by weight, preferably 0.1 to 1% by weight of a polyhydric alcohol, preferably trimethylolethane or trimethylolpropane, an ink resin is obtained. The affinity with the component is increased, which is more preferable.

　更に別の一例として、Ａｌ_２Ｏ_３換算で０．０５〜３重量％、好ましくは０．１〜２重量％の範囲のアルミニウムの水和酸化物が被覆されたものが挙げられる。このものをプラスチックス用二酸化チタン顔料として用いると、光触媒活性がある程度抑制され、また、アルミニウムの水和酸化物に由来する水分の保有量も少ないので、高温度での加工に適している。あるいは、アルミニウム化合物に替えて、リン酸アルミニウム水和物をＡｌＰＯ_４換算で０．１〜５重量％、好ましくは０．５〜３重量％の範囲で被覆すると、更に耐光性が向上する。このような無機化合物を被覆した二酸化チタン顔料に、さらに０．１〜２重量％、好ましくは０．１〜１重量％の範囲の有機化合物を被覆すると、樹脂成分との親和性が高くなるので、より好ましい。好ましい有機化合物としてはトリメチロールエタン、トリメチロールプロパン等の多価アルコール、ポリシロキサン類、アルキルシラン類、アミノシラン等の有機ケイ素化合物、ステアリン酸等の高級脂肪酸が挙げられる。有機ケイ素化合物、高級脂肪酸は、二酸化チタンの表面を疎水性にするので、樹脂成分との高度な親和性が得られるばかりでなく、吸湿水分量が著しく抑制される。更には、プラスチックスに配合されるＢＨＴ等のフェノール系酸化防止剤の変色を防止する効果も有する。 As yet another example, 0.05-3% by weight in terms _{of Al} 2 _{O 3} preferably include those hydrated oxide of aluminum in the range of 0.1 to 2% by weight was coated. When this is used as a titanium dioxide pigment for plastics, the photocatalytic activity is suppressed to some extent and the amount of water derived from hydrated aluminum oxide is small, so that it is suitable for processing at high temperatures. Alternatively, instead of the aluminum compound, 0.1 to 5% by weight of aluminum phosphate hydrate in AlPO ₄ terms, preferably when coated with 0.5 to 3 wt%, further improvement in light resistance. If the titanium dioxide pigment coated with such an inorganic compound is further coated with an organic compound in the range of 0.1 to 2% by weight, preferably 0.1 to 1% by weight, the affinity with the resin component increases. Is more preferable. Preferred organic compounds include polyhydric alcohols such as trimethylolethane and trimethylolpropane; organosilicon compounds such as polysiloxanes, alkylsilanes and aminosilane; and higher fatty acids such as stearic acid. Organic silicon compounds and higher fatty acids make the surface of titanium dioxide hydrophobic, so that not only high affinity with the resin component can be obtained, but also the amount of moisture absorbed is significantly suppressed. Further, it has an effect of preventing discoloration of a phenolic antioxidant such as BHT blended in plastics.

　次いで、本発明は焼成処理剤の存在下、含水酸化チタンを加熱焼成するアナターゼ型二酸化チタン顔料の製造方法であって、焼成処理剤として含水酸化チタン中のＴｉＯ_２に対しＡｌ_２Ｏ_３換算で０．０２〜０．２重量％未満の範囲に相当するアルミニウム化合物、Ｋ_２Ｏ換算で０．２〜１重量％、Ｐ_２Ｏ_５換算で０．０２〜０．５重量％未満の範囲に相当し、且つＫ_２Ｏ／Ｐ_２Ｏ_５が１．５／１〜１０／１の範囲にあるカリウム化合物及びリン酸化合物を用い、８００℃以上１０００℃未満の温度で加熱焼成することを特徴とする。カリウム化合物とリン酸化合物には相乗的に作用して生成する粒子の形状を整える効果があり、アルミニウム化合物には加熱焼成時に二酸化チタンが還元されて白色度が低下する現象を抑制する働きをすると考えられる。このため、高温度下で焼き込んで粒子径を大きくするには、前記範囲の量のカリウム化合物、リン酸化合物、アルミニウム化合物を必要とする。一方、リン酸化合物は添加量が多くなり過ぎると、粒子成長を阻害すると推測され、大粒子を得るためにはより高温度での加熱焼成が必要になるが、アナターゼ型結晶は高温度でルチル型に転位し易い性質を有するので、ルチル型の生成を抑えられない。しかし、本発明ではカリウム化合物とリン酸化合物との添加比率を前記範囲とすることで、１０００℃未満の温度でも粒子成長させることができ、実質的にアナターゼ型結晶を有し、粒子径が大きく、白色度が優れた所望の二酸化チタン顔料が得られると考えられる。 Then, the present invention is the presence of a firing treatment agent, a process for producing anatase titanium dioxide pigment that firing hydrous titanium oxide, in terms of Al ₂ O ₃ with respect to TiO ₂ in the hydrous oxide in the titanium as the firing treatment agent aluminum compound corresponding to the range of less than 0.02 to 0.2 wt%, 0.2 to _1% by weight _{K 2} O in _terms, in the range of less than 0.02 wt% in terms _of P 2 _{O 5} It is characterized by using a potassium compound and a phosphoric acid compound, which have a K ₂ O / P ₂ O _{5 in} the range of 1.5 / 1 to 10/1, and are heated and fired at a temperature of 800 ° C. or more and less than 1000 ° C. And The potassium compound and the phosphoric acid compound act synergistically to adjust the shape of the generated particles, and the aluminum compound acts to suppress the phenomenon that titanium dioxide is reduced during heating and firing to reduce the whiteness. Conceivable. Therefore, in order to increase the particle diameter by baking at a high temperature, potassium compounds, phosphoric acid compounds, and aluminum compounds in the above ranges are required. On the other hand, if the added amount of the phosphate compound is too large, it is presumed that the particle growth is inhibited, and heating and baking at a higher temperature are required to obtain large particles. Since it has the property of easily dislocating to the mold, the formation of the rutile form cannot be suppressed. However, in the present invention, by setting the addition ratio of the potassium compound and the phosphoric acid compound to the above range, particles can be grown even at a temperature of less than 1000 ° C., having substantially anatase crystal and having a large particle diameter. It is considered that a desired titanium dioxide pigment having excellent whiteness is obtained.

　アルミニウム化合物、カリウム化合物、リン酸化合物の好ましい範囲は、それぞれ０．０５〜０．２重量％未満、０．２〜０．５重量％、０．０２〜０．２重量％であり、カリウム化合物とリン酸化合物の好ましい比率の範囲は２／１〜１０／１である。本発明ではアルミニウム化合物としては酸化アルミニウム、塩化アルミニウム等を、カリウム化合物としては水酸化カリウム、塩化カリウム等を、リン酸化合物としてはオルトリン酸、メタリン酸、ピロリン酸及びそれらの塩等を用いることができる。これら焼成処理剤の添加方法は、例えば、含水酸化チタンを水等の分散媒に分散させ、前記焼成処理剤を添加、混合する等特に制限は無い。 The preferred ranges of the aluminum compound, the potassium compound, and the phosphoric acid compound are 0.05 to less than 0.2% by weight, 0.2 to 0.5% by weight, and 0.02 to 0.2% by weight, respectively. The preferred range of the ratio between the and the phosphoric acid compound is 2/1 to 10/1. In the present invention, aluminum oxide and aluminum chloride are used as the aluminum compound, potassium hydroxide and potassium chloride are used as the potassium compound, and orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid and salts thereof are used as the phosphoric acid compound. it can. There is no particular limitation on the method of adding the calcination agent, for example, by dispersing hydrated titanium oxide in a dispersion medium such as water and adding and mixing the calcination agent.

　上記焼成処理剤の存在下で含水酸化チタンを加熱焼成して平均粒子径が０．２〜０．４μｍのアナターゼ型二酸化チタン顔料を得る。本発明で用いる含水酸化チタンはアナターゼ型構造を有し、所謂硫酸法と呼ばれる二酸化チタン顔料の製造方法によって得ることができる。例えば、イルミナイト鉱、チタンスラグ等のチタン含有鉱石を必要に応じて粉砕し、硫酸で溶解させながらチタン成分と硫酸とを反応させて、硫酸チタニル（ＴｉＯＳＯ₄）を生成させ、静置分級、濾過した後、硫酸チタニルを加熱加水分解すると所望の含水酸化チタンが得られる。あるいは、予め調整した核晶の存在下で、前記硫酸チタニルを加熱加水分解させる方法も適用できる。核晶は、例えば、含水酸化チタンを熟成させることで得られる。用いる含水酸化チタンの粒子径は０．００１〜０．０１μｍが好ましい。また、含水酸化チタンに含まれる硫酸根はＳＯ_４換算で多くとも０．１重量％であることが望ましい。硫酸根が０．１重量％より多く含まれると、加熱焼成により得られるアナターゼ型二酸化チタンの白色度が低下してしまい、顔料としては使用に適さなくなる。加熱焼成の温度は、８００〜９８０℃の範囲が更に好ましい。加熱焼成には、ロータリーキルン、トンネルキルン等公知の機器を用いることができる。 The hydrous titanium oxide is heated and calcined in the presence of the calcining agent to obtain an anatase type titanium dioxide pigment having an average particle diameter of 0.2 to 0.4 μm. The hydrous titanium oxide used in the present invention has an anatase structure and can be obtained by a so-called sulfuric acid method, which is a method for producing a titanium dioxide pigment. For example, a titanium-containing ore such as illuminite ore or titanium slag is pulverized as necessary, and a titanium component is reacted with sulfuric acid while dissolving with sulfuric acid to produce titanyl sulfate (TiOSO ₄ ). After filtration, titanyl sulfate is heated and hydrolyzed to obtain the desired hydrous titanium oxide. Alternatively, a method of heating and hydrolyzing the titanyl sulfate in the presence of a previously prepared nucleus crystal can also be applied. The nucleus crystal is obtained, for example, by aging hydrous titanium oxide. The particle diameter of the hydrous titanium oxide used is preferably 0.001 to 0.01 μm. Further, it is desirable that the sulfate group contained in the hydrous titanium oxide is at most 0.1% by weight in terms of SO ₄ . If the sulfate group is contained in an amount of more than 0.1% by weight, the whiteness of anatase-type titanium dioxide obtained by heating and sintering is reduced, and the pigment is not suitable for use. The heating and firing temperature is more preferably in the range of 800 to 980 ° C. Known equipment such as a rotary kiln and a tunnel kiln can be used for the heating and firing.

　所望の粒子径の二酸化チタン粒子が得られた後は、公知の方法により、湿式粉砕、脱水・洗浄、乾燥、乾式粉砕してもよい。また、それぞれの工程の間で無機化合物、有機化合物の被覆処理を適宜行ってもよい。湿式粉砕には縦型サンドミル、横型サンドミル等が、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、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、噴霧乾燥機等の機器を用いることができる。 After the titanium dioxide particles having the desired particle size are obtained, wet grinding, dehydration / washing, drying, and dry grinding may be performed by a known method. In addition, a coating treatment with an inorganic compound or an organic compound may be appropriately performed between the respective steps. Vertical sand mill, horizontal sand mill, etc. for wet pulverization, band type heater, batch type heater, etc. for drying, impact pulverizer such as hammer mill, pin mill, pulverizer etc. for dry pulverization, jet An apparatus such as an airflow pulverizer such as a mill and a snail mill, and a spray dryer can be used.

　無機化合物の被覆は、二酸化チタン粒子を水等の媒液に分散させスラリーにした後、好ましくは更に湿式粉砕した後、目的とする無機化合物の塩の溶液を添加し、酸性化合物または塩基性化合物を添加したり、無機化合物の塩と酸性化合物または塩基性化合物とを同時に添加する等して中和反応させて無機化合物を二酸化チタン粒子の表面に沈着させることにより行える。本発明で用いることのできる無機化合物の塩としては、例えば、アルミニウム化合物の塩であればアルミン酸ナトリウム、硫酸アルミニウム、硝酸アルミニウム等が、ケイ素化合物の塩であればケイ酸ナトリウム、ケイ酸カリウム等が、ジルコニウム化合物の塩であれば塩化ジルコニウム等が、スズ化合物の塩であれば塩化スズ等が、チタニウム化合物の塩であれば塩化チタン、硫酸チタン等が挙げられる。また、酸性化合物としては、例えば、硫酸、塩酸等の無機酸、酢酸等の有機酸が、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、炭酸ナトリ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あるいは炭酸化物、アンモニア等のアンモニウム化合物、アミン類等を用いることができる。 The coating of the inorganic compound is performed by dispersing the titanium dioxide particles in a medium such as water to form a slurry, preferably after further wet grinding, and then adding a salt solution of the target inorganic compound to the acidic compound or the basic compound. Or by simultaneously adding a salt of an inorganic compound and an acidic compound or a basic compound to cause a neutralization reaction, thereby depositing the inorganic compound on the surface of the titanium dioxide particles. Examples of the salt of the inorganic compound that can be used in the present invention include, for example, sodium aluminate, aluminum sulfate, and aluminum nitrate for an aluminum compound salt, and sodium silicate and potassium silicate for a silicon compound salt. Examples thereof include zirconium chloride and the like for a salt of a zirconium compound, tin chloride and the like for a salt of a tin compound, and titanium chloride and titanium sulfate for a salt of a titanium compound. Examples of the acidic compound include inorganic acids such as sulfuric acid and hydrochloric acid and organic acids such as acetic acid. Examples of the basic compound include sodium hydroxide, potassium hydroxide and alkali metal such as sodium carbonate. Hydroxides or carbonates, ammonium compounds such as ammonia, amines and the like can be used.

　多価アルコール、アルカノールアミンまたはその誘導体、ポリシロキサン類、高級脂肪酸またはその金属塩等のように、二酸化チタン粒子の表面と結合しないか、結合力の弱い有機化合物を被覆する場合は、二酸化チタン粒子を乾式粉砕後にヘンシェルミキサー、スーパーミキサー等の高速攪拌機を用いて二酸化チタン粒子と有機化合物とを混合して被覆したり、あるいは、乾式粉砕機中に二酸化チタン粒子と有機化合物を添加して、粉砕と混合・被覆処理を同時に行う、所謂乾式処理を適用するのが好ましい。気流粉砕機を用いて粉砕と被覆処理を同時に行う方法は、均一に被覆され易く、処理能力も高いので、工業的に好ましい。オルガノシラン類のように、二酸化チタン粒子の表面と反応し強く結合する有機化合物を被覆する場合は、湿式粉砕後あるいは無機化合物の被覆処理後の二酸化チタンスラリーに有機化合物を添加し被覆する、所謂湿式処理を適用することもできる。また、ステアリン酸ソーダ等の高級脂肪酸塩を、二酸化チタンスラリー中で中和反応させ、高級脂肪酸の被覆層を形成させる方法も用いることができる。 In the case of coating with an organic compound that does not bind to the surface of titanium dioxide particles or has a weak binding force, such as polyhydric alcohol, alkanolamine or a derivative thereof, polysiloxanes, higher fatty acids or metal salts thereof, titanium dioxide particles After dry milling, the titanium dioxide particles and the organic compound are mixed and coated using a high-speed stirrer such as a Henschel mixer or a super mixer, or the titanium dioxide particles and the organic compound are added to the dry mill to grind. It is preferable to apply a so-called dry process in which the mixing and coating processes are simultaneously performed. The method of simultaneously performing the pulverization and the coating treatment using an airflow pulverizer is industrially preferable because it is easy to coat uniformly and has a high processing ability. When coating with an organic compound that reacts strongly with the surface of the titanium dioxide particles, such as organosilanes, the organic compound is added to the titanium dioxide slurry after wet pulverization or after the coating treatment with an inorganic compound, so-called coating. Wet processing can also be applied. In addition, a method in which a higher fatty acid salt such as sodium stearate is subjected to a neutralization reaction in a titanium dioxide slurry to form a higher fatty acid coating layer can also be used.

　更に、本発明は前記二酸化チタン顔料と樹脂成分とを含む樹脂組成物である。本発明の樹脂組成物は、前記二酸化チタン顔料を含むことで、従来のアナターゼ型酸化チタンが有する光学的特性、物理的特性に加えて高隠ペイ性も付与される。また、本発明は、前記二酸化チタン顔料を高濃度で配合することができ、樹脂成分の種類を選択することにより、塗料、紙、繊維等の各種用途に有用な樹脂組成物とすることができる。中でも塗料用樹脂組成物、インキ用樹脂組成物、プラスチックス用樹脂組成物として有用である。具体的な顔料濃度は用途によって異なるが、例えば、塗料用樹脂組成物やインキ用樹脂組成物であれば、樹脂成分１重量部に対し二酸化チタン顔料０．５〜１０重量部が、プラスチックス用樹脂組成物であれば、樹脂成分１重量部に対し二酸化チタン顔料０．０５〜２重量部が、好ましい。本発明には、前記二酸化チタン顔料及び樹脂成分以外に、溶剤、添加剤、充填剤等が含まれていてもよい。 Further, the present invention is a resin composition containing the titanium dioxide pigment and a resin component. When the resin composition of the present invention contains the above-mentioned titanium dioxide pigment, in addition to the optical properties and physical properties of the conventional anatase-type titanium oxide, high concealment payability is also provided. In addition, the present invention can mix the titanium dioxide pigment at a high concentration, and by selecting the type of the resin component, can provide a resin composition useful for various uses such as paint, paper, and fiber. . Among them, it is useful as a resin composition for paints, a resin composition for inks, and a resin composition for plastics. The specific pigment concentration varies depending on the application. For example, in the case of a resin composition for a paint or a resin composition for an ink, 0.5 to 10 parts by weight of a titanium dioxide pigment for 1 part by weight of a resin component is used for plastics. In the case of a resin composition, 0.05 to 2 parts by weight of a titanium dioxide pigment is preferable per 1 part by weight of the resin component. In the present invention, a solvent, an additive, a filler, and the like may be contained in addition to the titanium dioxide pigment and the resin component.

　塗料用樹脂を含む本発明の樹脂組成物は、隠ペイ性が高いばかりでなく、青味色調を求められる分野では、短波長の光の反射率が高いというアナターゼ型の特性により、有色顔料・染料、蛍光増白剤等で調色する必要が無いので、鮮やかな色調の白色が得られる。塗料用樹脂として紫外線硬化型樹脂を用いると、アナターゼ型二酸化チタンは、可視部に近接した波長の紫外線を吸収し難いので、ルチル型のような硬化阻害が生じ難くなる。塗料用樹脂を含む本発明の樹脂組成物は、金属、木材、プラスチックス、コンクリート等広範囲の基材の塗装に用いることができるが、特に屋内用の部材の塗装に適している。塗装方法はハケ塗り、ローラー塗装、スプレー塗装、ディップ塗装、静電塗装等公知の方法を適用でき、特に制限を受けない。 The resin composition of the present invention containing a coating resin is not only high in hidden payability, but also in the field where a bluish hue is required, the color pigment / Since it is not necessary to perform toning with a dye, a fluorescent whitening agent, or the like, a bright white color can be obtained. When an ultraviolet-curable resin is used as the resin for the coating, the anatase-type titanium dioxide hardly absorbs ultraviolet rays having a wavelength close to the visible region, so that hardening inhibition such as a rutile type hardly occurs. The resin composition of the present invention containing a coating resin can be used for coating a wide range of base materials such as metal, wood, plastics and concrete, but is particularly suitable for coating indoor members. Known coating methods such as brush coating, roller coating, spray coating, dip coating, and electrostatic coating can be applied, and there is no particular limitation.

　樹脂成分が塗料用樹脂である本発明の樹脂組成物に含まれる二酸化チタン顔料として、Ａｌ_２Ｏ_３換算で１〜５重量％、好ましくは１〜４重量％の範囲のアルミニウムの水和酸化物が被覆されている二酸化チタン顔料を用いると、光沢の優れた塗膜の得られる樹脂組成物となる。また、前記のアルミニウムの水和酸化物の被覆層を第二層（外層）とし、その内部の第一層（二酸化チタン顔料の表面）として、ＳｉＯ_２換算で１〜１０重量％、好ましくは１〜５重量％の範囲のケイ素の水和酸化物の緻密層が被覆されていると、耐候性に優れた塗膜の得られる樹脂組成物になる。あるいは、ケイ素の水和酸化物に替えて、ＺｒＯ_２換算で０．０５〜５重量％、好ましく０．０５〜２重量％の範囲のジルコニウムの水和酸化物を被覆しても良く、更にＳｎＯ_２換算で０．０５〜５重量％、好ましく０．０５〜２重量％の範囲のスズの水和酸化物を、前記のジルコニウムの水和酸化物の被覆層と積層させても良い。更に、０．１〜２重量％、好ましくは０．１〜１重量％の範囲の多価アルコール、好ましくはトリメチロールエタンまたはトリメチロールプロパンで被覆されていると、樹脂成分との親和性が高くなり、塗料の生産性が向上するばかりでなく、より光沢の優れた塗膜を提供できる。 As the titanium dioxide pigment contained in the resin composition of the present invention in which the resin component is a coating resin, a hydrated oxide of aluminum in the range of 1 to 5% by weight, preferably 1 to 4% by weight in terms of Al ₂ O ₃ When a titanium dioxide pigment coated with is used, a resin composition having a glossy coating film can be obtained. The aluminum hydrated oxide coating layer is a second layer (outer layer), and the inner first layer (the surface of the titanium dioxide pigment) is 1 to 10% by weight in terms of SiO ₂ , preferably 1 to 10% by weight. When the dense layer of the hydrated silicon oxide in the range of 5 to 5% by weight is coated, the resulting resin composition can provide a coating film having excellent weather resistance. Alternatively, the hydrated oxide of zirconium may be coated in the range of 0.05 to 5% by weight, preferably 0.05 to ₂ % by weight in terms of ZrO ₂ , instead of the hydrated oxide of silicon. Tin hydrated oxide in the range of 0.05 to 5% by weight, preferably 0.05 to ₂ % by weight in terms of ₂ may be laminated with the above-mentioned hydrated oxide coating layer of zirconium. Further, when coated with a polyhydric alcohol in the range of 0.1 to 2% by weight, preferably 0.1 to 1% by weight, preferably trimethylolethane or trimethylolpropane, the affinity with the resin component is high. As a result, not only the productivity of the paint is improved, but also a coating film with more excellent gloss can be provided.

　塗料用樹脂成分は、例えば、アルキド系樹脂、アクリル系樹脂、ポリエステル系樹脂、エポキシ系樹脂、アミノ系樹脂、フッ素系樹脂、変成シリコーン系樹脂、ウレタン系樹脂、ビニル系樹脂等が挙げられ、適宜選択できる。これらの塗料用樹脂成分は、有機溶剤溶解型、水溶型、エマルジョン型等特に制限は無く、硬化方式も加熱硬化型、常温硬化型、紫外線硬化型、電子線硬化型等制限は受けない。本発明の塗料用樹脂を含む樹脂組成物には、アルコール類、エステル類、エーテル類、ケトン類、芳香族炭化水素類、脂肪族炭化水素類等の有機溶剤、水またはそれらの混合溶剤が、溶媒として含まれていても良く、溶媒は樹脂成分との適性に応じて選択する。その他にも、目的に応じて有機顔料、無機顔料、染料等の着色剤、増量剤、界面活性剤、可塑剤、硬化助剤、ドライヤー、消泡剤、増粘剤、乳化剤、フロー調整剤、皮張り防止剤、色分れ防止剤、紫外線吸収剤、防カビ剤等の各種添加剤、充填剤等が含まれていても良い。あるいは、硬化剤、硬化助剤、硬化性樹脂成分を別に硬化液とし、塗装時に塗料に混合して用いる二液性塗料とすることもできる。紫外線硬化型樹脂を含む樹脂組成物には、更に光重合開始剤、光増感剤等を添加するのが好ましい。 The coating resin component includes, for example, an alkyd resin, an acrylic resin, a polyester resin, an epoxy resin, an amino resin, a fluorine resin, a modified silicone resin, a urethane resin, and a vinyl resin. You can choose. These resin components for coating materials are not particularly limited, such as an organic solvent-soluble type, a water-soluble type, and an emulsion type, and the curing method is not limited, such as a heat curable type, a room temperature curable type, an ultraviolet curable type, and an electron beam curable type. The resin composition containing the coating resin of the present invention, alcohols, esters, ethers, ketones, aromatic hydrocarbons, organic solvents such as aliphatic hydrocarbons, water or a mixed solvent thereof, It may be contained as a solvent, and the solvent is selected according to suitability with the resin component. In addition, depending on the purpose, organic pigments, inorganic pigments, coloring agents such as dyes, extenders, surfactants, plasticizers, curing aids, dryers, defoamers, thickeners, emulsifiers, flow regulators, Various additives such as an anti-skinning agent, an anti-separation agent, an ultraviolet absorber, a fungicide, and a filler may be contained. Alternatively, it is also possible to prepare a two-part paint used as a curing liquid separately from a curing agent, a curing assistant, and a curable resin component, and mixed with the paint at the time of coating. It is preferable to further add a photopolymerization initiator, a photosensitizer and the like to the resin composition containing the ultraviolet curable resin.

　本発明の樹脂組成物は、樹脂成分として塗料用樹脂を用いる場合には、前記二酸化チタン顔料と塗料用樹脂成分とに、必要に応じて各種溶媒を添加し、サンドミル、ディスパー、ボールミル、ペイントシェイカー、２本ロールミル、３本ロールミル等の分散機を用いて分散させることにより得られる。前記の各種添加剤、充填剤は分散時に加えることも、分散後の塗料に加えることもできる。 When the resin composition of the present invention uses a paint resin as a resin component, various solvents are added as necessary to the titanium dioxide pigment and the paint resin component, and a sand mill, a disper, a ball mill, a paint shaker It is obtained by dispersing using a dispersing machine such as a two-roll mill or a three-roll mill. The above-mentioned various additives and fillers can be added at the time of dispersion or can be added to the paint after dispersion.

　インキ用樹脂を含む本発明の樹脂組成物を、特に、裏刷り、表刷り等のグラビア印刷用インキに用いると、硬度が低いというアナターゼ型二酸化チタンの特性により、ドクターブレードの磨耗が抑制され、版カブリ、ドクター筋等の印刷欠陥が生じ難く、且つ、隠ペイ性が優れたものとなる。また、近年、印刷の高速化や、環境負荷の低い水溶性インキ、ノントルエン型インキ、紫外線硬化型インキへの移行が求められており、これらの技術では乾燥速度を速くすることがポイントになっている。現在、一つの解決方法として、塗膜の膜厚を薄くする方向で検討が進められているが、薄膜にすると従来と同等の隠ペイ性が得られず、隠ペイ性を上げるために顔料濃度を高くするとドクターブレードが摩耗し易くなる。本発明は前記のようにドクターブレードの磨耗が抑制されるので、高顔料濃度化が容易となる。更に、フレキソ印刷でもドクターブレードを用いる印刷方法が普及しており、この分野でも磨耗したドクターブレードの交換による生産性の低下が問題になっているが、本発明を用いるとドクターブレードの交換間隔を長くできる。インキ用樹脂を含む本発明の樹脂組成物は、前記のグラビア印刷、フレキソ印刷以外の凹版印刷、凸版印刷、平版印刷、孔版印刷に用いる各種印刷インキにも有用であり、印刷する基材は、プラスチックス・フィルム、紙、金属箔等特に制限を受けない。更に、本発明は最終的な印刷インキとしてばかりでなく、調色用インキ、カラーチップ等の中間品にも適用される。 The resin composition of the present invention containing an ink resin, especially, when used for gravure printing ink such as back printing, front printing, etc., due to the properties of anatase type titanium dioxide having low hardness, wear of the doctor blade is suppressed, Printing defects such as plate fog and doctor streaks are less likely to occur, and the hidden payability is excellent. In recent years, there has been a demand for faster printing and a shift to water-soluble inks, non-toluene-type inks, and UV-curable inks, which have a low environmental impact. ing. Currently, as one solution, studies are being conducted in the direction of reducing the thickness of the coating film.However, if the film thickness is reduced, the same hidden payability as before can not be obtained. When the height is increased, the doctor blade is easily worn. In the present invention, since the wear of the doctor blade is suppressed as described above, it is easy to increase the pigment concentration. Furthermore, a printing method using a doctor blade has become widespread even in flexographic printing, and in this field, the problem of productivity reduction due to replacement of a worn doctor blade is a problem. Can be long. The resin composition of the present invention containing an ink resin is also useful for various printing inks used for gravure printing, intaglio printing other than flexographic printing, letterpress printing, lithographic printing, stencil printing, and a printing substrate, There are no particular restrictions on plastics film, paper, metal foil, etc. Further, the present invention is applied not only to final printing inks but also to intermediate products such as toning inks and color chips.

　樹脂成分がインキ用樹脂である本発明の樹脂組成物に含まれる二酸化チタン顔料として、第一層（内層）にＳｉＯ_２換算で２〜１０重量％、好ましくは２〜５重量％の範囲のケイ素の水和酸化物の被覆層を有し、更に第二層（外層）にＡｌ_２Ｏ_３換算で１〜１０重量％、好ましくは１〜６重量％の範囲のアルミニウムの水和酸化物の被覆層を有する二酸化チタン顔料を用いると、隠ペイ性が高く、印刷適性にも優れ、裏刷りグラビア印刷やフレキソ印刷に適した樹脂組成物となる。ケイ素の水和酸化物の被覆層は、緻密層、多孔質層、緻密層と多孔質層との積層等、適宜選択できる。フレキソインキには、ケイ素及びアルミニウムの水和酸化物が、総被覆量として５〜１５重量％の範囲で被覆した二酸化チタン顔料を用いるのが特に好ましい。あるいは、ケイ素の水和酸化物を被覆せず、アルミニウムの水和酸化物のみをＡｌ_２Ｏ_３換算で５〜１５重量％、好ましくは５〜１０重量％の範囲の被覆した二酸化チタン顔料も、フレキソインキに用いることができる。ケイ素化合物に替えて、ＴｉＯ_２換算で０．１〜５重量％、好ましく０．１〜２重量％の範囲のチタニウムの水和酸化物が、第一層（内層）として被覆された二酸化チタン顔料を用いると、光沢が高く、表刷りグラビア印刷に適したものとなる。０．１〜２重量％、好ましくは０．１〜１重量％の範囲の多価アルコール、好ましくはトリメチロールエタンまたはトリメチロールプロパンで被覆された二酸化チタン顔料を用いると、顔料と樹脂成分との親和性が高くなり、表面平滑性や光沢に優れたインキ塗膜を形成できる樹脂組成物となる。 As the titanium dioxide pigment contained in the resin composition of the present invention in which the resin component is a resin for ink, the first layer (inner layer) contains silicon in an amount of 2 to 10% by weight, preferably 2 to 5% by weight in terms of SiO _2. has a coating layer of hydrated oxide, further second layer 1-10 wt% in terms of Al ₂ O ₃ in (outer layer), preferably the coating of hydrated oxide of aluminum in the range of 1-6 wt% When a titanium dioxide pigment having a layer is used, a resin composition having high covert payability and excellent printability and suitable for back printing gravure printing and flexographic printing can be obtained. The coating layer of the silicon hydrated oxide can be appropriately selected from a dense layer, a porous layer, and a laminate of the dense layer and the porous layer. For the flexographic ink, it is particularly preferable to use a titanium dioxide pigment coated with a hydrated oxide of silicon and aluminum in a total coating amount of 5 to 15% by weight. Alternatively, a titanium dioxide pigment coated with only aluminum hydrated oxide in the range of 5 to 15% by weight, preferably 5 to 10% by weight in terms of Al ₂ O ₃ without coating with silicon hydrated oxide, It can be used for flexographic inks. A titanium dioxide pigment coated as a first layer (inner layer) with a hydrated titanium oxide in an amount of 0.1 to 5% by weight, preferably 0.1 to ₂ % by weight in terms of TiO2, in place of the silicon compound Is high in glossiness and suitable for front-print gravure printing. When using a titanium dioxide pigment coated with a polyhydric alcohol in the range of 0.1 to 2% by weight, preferably 0.1 to 1% by weight, preferably trimethylolethane or trimethylolpropane, the pigment and resin component The resin composition has an increased affinity and can form an ink coating film having excellent surface smoothness and gloss.

　用いるインキ用樹脂成分は、印刷方法、印刷する基材の種類等によって適宜選択でき、例えば、ウレタン系樹脂、塩酢ビ系樹脂、塩素化ポリプロピレン系樹脂、ポリアミド系樹脂、アクリル系樹脂、マレイン酸系樹脂、環化ゴム系樹脂、硝化綿、ロジン等を用いることができる。これらのインキ用樹脂成分は、有機溶剤溶解型、水溶型、エマルジョン型等特に制限は無く、硬化方式も常温硬化型、加熱硬化型、紫外線硬化型、電子線硬化型等制限は受けない。本発明のインキ用樹脂を含む樹脂組成物には、アルコール類、エステル類、エーテル類、ケトン類、芳香族炭化水素類、脂肪族炭化水素類等の有機溶剤、水またはそれらの混合溶剤が、溶媒として含まれていても良く、溶媒は樹脂成分との適性に応じて選択できる。その他にも、使用場面に応じて有機顔料、無機顔料、染料等の着色剤、増量剤、界面活性剤、帯電防止剤、可塑剤、硬化助剤、消泡剤、滑剤、酸化防止剤、紫外線吸収剤、キレート剤等の各種添加剤、充填剤等が含まれていても良い。 The ink resin component to be used can be appropriately selected depending on the printing method, the type of the substrate to be printed, and the like. For example, urethane resin, vinyl chloride resin, chlorinated polypropylene resin, polyamide resin, acrylic resin, and maleic acid Resin, cyclized rubber resin, nitrified cotton, rosin and the like can be used. These ink resin components are not particularly limited, such as an organic solvent-soluble type, a water-soluble type, and an emulsion type, and the curing method is not limited, such as a room temperature curing type, a heat curing type, an ultraviolet curing type, and an electron beam curing type. In the resin composition containing the ink resin of the present invention, alcohols, esters, ethers, ketones, aromatic hydrocarbons, organic solvents such as aliphatic hydrocarbons, water or a mixed solvent thereof, It may be contained as a solvent, and the solvent can be selected according to suitability for the resin component. In addition, colorants such as organic pigments, inorganic pigments, dyes, etc., extenders, surfactants, antistatic agents, plasticizers, curing aids, defoamers, lubricants, antioxidants, and ultraviolet rays depending on the use scene Various additives such as an absorbent and a chelating agent, a filler and the like may be contained.

　本発明の樹脂組成物は、樹脂成分としてインキ用樹脂を用いる場合には、前記二酸化チタン顔料とインキ用樹脂成分とに、必要に応じて各種溶媒を添加し、サンドミル、アトライター、ディスパー、ボールミル、ペイントシェイカー、２本ロールミル、３本ロールミル等の分散機を用いて分散させることにより得られる。あるいは、前記顔料と樹脂成分とを練肉し、チップ化することもできる。前記の各種添加剤、充填剤は分散時に加えることも、分散後のインキに加えることもできる。 When the resin composition of the present invention uses an ink resin as a resin component, various solvents are added as necessary to the titanium dioxide pigment and the ink resin component, and a sand mill, an attritor, a disper, and a ball mill are added. , A paint shaker, a two-roll mill, a three-roll mill, or the like. Alternatively, the pigment and the resin component may be cut into chips to form chips. The various additives and fillers described above can be added at the time of dispersion or can be added to the ink after dispersion.

　プラスチック用樹脂を含む本発明の樹脂組成物を、特に、耐水紙等のラミネート加工品に用いると、短波長の光の反射率が高いというアナターゼ型二酸化チタンの特性により、独特の青味色調を付与することができ、しかも、隠ペイ性が優れたものとなる。このため、顔料濃度を低くすることができ、レーシング、ピンホールのような表面欠陥がほとんどない組成物が得られる。また、プラスチック用樹脂を含む本発明の樹脂組成物は射出成形品、押出成形品、インフレーション加工品、カレンダー加工品等の用途にも有用であり、ラミネート加工品に限定されるものではない。更に、本発明は最終的な成形品としてばかりでなく、カラーペレット、マスターバッチ（カラーコンセントレーション）等の中間品にも適用される。 When the resin composition of the present invention containing a resin for plastics is used in a laminated product such as water-resistant paper, a unique blue tint is produced due to the characteristic of anatase type titanium dioxide that the reflectance of short-wavelength light is high. Can be provided, and the hidden payability is excellent. Therefore, the pigment concentration can be reduced, and a composition having almost no surface defects such as racing and pinholes can be obtained. In addition, the resin composition of the present invention containing a resin for plastics is also useful for applications such as injection molded products, extruded products, inflation processed products, calendered products, and is not limited to laminated products. Further, the present invention is applied not only to final molded products, but also to intermediate products such as color pellets and master batches (color concentration).

　樹脂成分がプラスチックス用樹脂である本発明の樹脂組成物に含まれる二酸化チタン顔料として、Ａｌ_２Ｏ_３換算で０．０５〜２重量％、好ましくは０．１〜１．５重量％の範囲のアルミニウムの水和酸化物で被覆されている二酸化チタン顔料を用いると、耐光性が優れ、また、無機化合物に由来する水分の保有量も少ないので、高温度での加工に適したものとなる。アルミニウム化合物に替えて、リン酸アルミニウム水和物をＡｌＰＯ_４換算で０．１〜２重量％、好ましくは０．５〜２重量％の範囲で被覆した二酸化チタン顔料を用いると、耐光性がより優れた組成物となる。更に、０．１〜２重量％、好ましくは０．１〜１重量％の範囲の多価アルコール、好ましくはトリメチロールエタンまたはトリメチロールプロパン、有機ケイ素化合物、好ましくはポリシロキサン類またはオルガノシラン類、高級脂肪酸、好ましくはステアリン酸から選ばれる少なくとも１種で被覆されている二酸化チタン顔料を用いると、樹脂成分との親和性が高くなり、二酸化チタン顔料の分散不良粒子がほとんど生じない表面外観の優れた組成物が得られる。少なくとも有機ケイ素化合物または高級脂肪酸で被覆されている二酸化チタン顔料を用いると、二酸化チタンの表面が疎水性になるので、吸湿水分量が著しく抑制され、プラスチックスに配合されるＢＨＴ等のフェノール系酸化防止剤の変色も抑制されるので、より好ましい組成物が得られる。 As the titanium dioxide pigment contained in the resin composition of the present invention in which the resin component is a resin for plastics, a range of 0.05 to ₂ % by weight, preferably 0.1 to 1.5% by weight in terms of Al ₂ O _3. The use of titanium dioxide pigment coated with a hydrated oxide of aluminum has excellent light resistance and also has a small amount of water derived from inorganic compounds, making it suitable for processing at high temperatures. . Instead of the aluminum compound, 0.1 to 2% by weight of aluminum phosphate hydrate in AlPO ₄ terms, and preferably using a titanium dioxide pigment coated with a range of 0.5 to 2 wt%, more light fastness It becomes an excellent composition. Furthermore, polyhydric alcohols in the range of 0.1 to 2% by weight, preferably 0.1 to 1% by weight, preferably trimethylolethane or trimethylolpropane, organosilicon compounds, preferably polysiloxanes or organosilanes, When a titanium dioxide pigment coated with at least one selected from higher fatty acids, preferably stearic acid, is used, the affinity for the resin component is increased, and the titanium dioxide pigment has an excellent surface appearance with few poorly dispersed particles. The resulting composition is obtained. When a titanium dioxide pigment coated with at least an organosilicon compound or a higher fatty acid is used, the surface of the titanium dioxide becomes hydrophobic, so that the amount of water absorbed by moisture is remarkably suppressed, and phenol-based oxidation such as BHT blended in plastics is performed. Since discoloration of the inhibitor is also suppressed, a more preferable composition is obtained.

　プラスチックス用樹脂成分は、加工方法等によって適宜選択でき、例えば、ポリオレフィン樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、ポリスチレン樹脂、ＡＢＳ樹脂、ポリエステル樹脂、芳香族系樹脂、ナイロン樹脂、ポリカーボネート樹脂、セルロース樹脂、ポリ乳酸樹脂等の熱硬化型樹脂や、フェノール樹脂、ウレタン樹脂、不飽和ポリエステル樹脂等の熱可塑型樹脂を用いることができ、特に制限は無い。本発明のプラスチックス樹脂を含む樹脂組成物には、前記二酸化チタン顔料とプラスチックス用樹脂成分の他にも、目的に応じて有機顔料、無機顔料、染料等の着色剤、増量剤、界面活性剤、可塑剤、滑剤・安定剤、帯電防止剤、酸化防止剤、紫外線吸収剤、光安定化剤、難燃剤、増白剤、殺菌剤、補強材等の各種添加剤、充填剤等が含まれていても良い。 The resin component for plastics can be appropriately selected depending on the processing method and the like. For example, polyolefin resin, vinyl chloride resin, vinyl acetate resin, polystyrene resin, ABS resin, polyester resin, aromatic resin, nylon resin, polycarbonate resin, cellulose resin Thermosetting resins such as polylactic acid resins, and thermoplastic resins such as phenol resins, urethane resins, and unsaturated polyester resins can be used without any particular limitation. In the resin composition containing the plastics resin of the present invention, in addition to the titanium dioxide pigment and the plastics resin component, depending on the purpose, an organic pigment, an inorganic pigment, a coloring agent such as a dye, a bulking agent, a surfactant, Includes additives, plasticizers, lubricants / stabilizers, antistatic agents, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, brighteners, bactericides, reinforcing materials, and other additives, fillers, etc. It may be.

　本発明の樹脂組成物は、樹脂成分としてプラスチック用樹脂を用いる場合には前記二酸化チタン顔料とプラスチックス用樹脂成分とに、必要に応じて上記の添加剤、充填剤を添加し、一軸または二軸エクストルーダー等の押出成形機、カレンダーロール等のロール成形機、バンバリーミキサー等の加圧ミキサー等を用いた公知の方法で分散させることで得られる。あるいは、押出成形機や加圧ミキサーを用いてペレット化した後、射出成形機または上記の各種成形機により成形しても良い。 When a resin for plastics is used as the resin component, the resin composition of the present invention may contain the above-mentioned additives and fillers, if necessary, to the titanium dioxide pigment and the resin component for plastics, to form a uniaxial or biaxial resin. It can be obtained by a known method using an extruder such as a shaft extruder, a roll forming machine such as a calender roll, a pressure mixer such as a Banbury mixer, or the like. Alternatively, after pelletizing using an extruder or a pressurized mixer, molding may be performed using an injection molding machine or the above-described various molding machines.

　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。 実 施 Examples of the present invention are shown below, but the present invention is not limited to these.

１．二酸化チタン顔料及びその製造方法に係わる実施例
実施例１
（１）二酸化チタン粒子の調製
　含水酸化チタン中のＴｉＯ_２に対し、Ａｌ_２Ｏ_３換算で０．１重量％に相当する硫酸アルミニウム、Ｋ_２Ｏ換算で０．３重量％に相当する水酸化カリウム及びＰ_２Ｏ_５換算で０．１５重量％に相当するオルトリン酸を焼成処理剤として含水酸化チタン（粒子径０．００５μｍ）に添加し、電気炉を用いて９６０℃の温度で１時間加熱焼成して、アナターゼ型二酸化チタン粒子を得た。得られた二酸化チタン粒子をＴｉＯ_２濃度が３００ｇ／リットルの水性スラリーとし、水酸化ナトリウム水溶液を添加してｐＨを１０．５として分散させた後、サンドミルで粉砕し、静置分級を行った。 1. Examples relating to titanium dioxide pigment and method for producing the same Example 1
(1) Preparation of Titanium Dioxide Particles Aluminum sulfate equivalent to 0.1% by weight in terms of Al ₂ O ₃ and hydroxylation equivalent to 0.3% by weight in terms of K ₂ O based on TiO _{2 in} hydrous titanium oxide. Orthophosphoric acid equivalent to 0.15% by weight in terms of potassium and P ₂ O ₅ is added to hydrated titanium oxide (particle diameter 0.005 μm) as a calcining agent, and heated at 960 ° C. for 1 hour using an electric furnace. By calcining, anatase type titanium dioxide particles were obtained. The obtained titanium dioxide particles were made into an aqueous slurry having a TiO ₂ concentration of 300 g / liter, and an aqueous solution of sodium hydroxide was added to disperse the particles to a pH of 10.5. Then, the particles were pulverized with a sand mill and subjected to static classification.

（２）表面処理
　分級後のスラリーを１０００ミリリットル分取し、温度を６０℃に保持しながら、攪拌下で、硫酸を添加してｐＨを９に調整した後、アルミン酸ナトリウム水溶液（Ａｌ_２Ｏ_３として１５０ｇ／リットル）４０ミリリットルと硫酸とを、ｐＨを８〜９に維持するよう２０分間かけて添加した。次いで、硫酸でｐＨを７に調整した後３０分間熟成した。熟成後、吸引濾過器で濾過、水洗し、１２０℃で２０時間乾燥した後、ジェットミルで粉砕して、平均粒子径が０．２５μｍで、酸化アルミニウム水和物をＡｌ_２Ｏ_３換算で２重量％被覆した本発明の二酸化チタン顔料（試料Ａ）を得た。試料Ａに含まれる硫酸根はＳＯ_４換算で０．０３重量％であった。 (2) Surface treatment 1000 ml of the classified slurry was taken, and while maintaining the temperature at 60 ° C., the pH was adjusted to 9 by adding sulfuric acid under stirring, and then a sodium aluminate aqueous solution (Al ₂ O) 40 milliliters (150 g / l as ₃ ) and sulfuric acid were added over 20 minutes to maintain the pH at 8-9. Next, the pH was adjusted to 7 with sulfuric acid, and the mixture was aged for 30 minutes. After aging, the mixture was filtered with a suction filter, washed with water, dried at 120 ° C. for 20 hours, and then pulverized with a jet mill to obtain an aluminum oxide hydrate having an average particle size of 0.25 μm and an aluminum oxide hydrate of ₂ % in terms of Al ₂ O _3. A titanium dioxide pigment of the present invention (sample A) coated by weight% was obtained. The sulfate group contained in Sample A was 0.03% by weight in terms of SO ₄ .

実施例２
　酸化アルミニウム水和物の被覆量をＡｌ_２Ｏ_３換算で０．５重量％とした以外は実施例１と同様にして本発明の二酸化チタン顔料（試料Ｂ）を得た。 Example 2
A titanium dioxide pigment (sample B) of the present invention was obtained in the same manner as in Example 1, except that the coating amount of aluminum oxide hydrate was changed to 0.5% by weight in terms of Al ₂ O ₃ .

実施例３
　含水酸化チタン中のＴｉＯ_２に対し、水酸化カリウムの添加量を、Ｋ_２Ｏ換算で０．３２重量％に、オルトリン酸の添加量を、Ｐ_２Ｏ_５換算で０．０８重量％にし、９３０℃で１時間加熱焼成したこと以外は実施例１と同様にして、平均粒子径が０．３μｍの本発明の二酸化チタン顔料（試料Ｃ）を得た。 Example 3
With respect to TiO ₂ in the hydrous titanium oxide, the amount of potassium hydroxide added was 0.32% by weight in terms of K ₂ O, and the amount of orthophosphoric acid was 0.08% by weight in terms of P ₂ O ₅ , A titanium dioxide pigment of the present invention (Sample C) having an average particle diameter of 0.3 μm was obtained in the same manner as in Example 1 except that the composition was heated and calcined at 930 ° C. for 1 hour.

実施例４
　含水酸化チタン中のＴｉＯ_２に対し、水酸化カリウムの添加量をＫ_２Ｏ換算で０．３６重量％に、オルトリン酸の添加量をＰ_２Ｏ_５換算で０．０４重量％にし、９２０℃で１時間加熱焼成したこと以外は実施例１と同様にして、平均粒子径が０．３μｍの本発明の二酸化チタン顔料（試料Ｄ）を得た。 Example 4
The amount of potassium hydroxide added was 0.36% by weight in terms of K ₂ O and the amount of orthophosphoric acid was 0.04% by weight in terms of P ₂ O _{5 based on} TiO _{2 in} hydrous titanium oxide. In the same manner as in Example 1 except that the mixture was heated and baked for 1 hour, a titanium dioxide pigment of the present invention (Sample D) having an average particle diameter of 0.3 μm was obtained.

実施例５
　実施例１で得た分級後スラリーを１０００ミリリットル分取し、温度を８０℃に保持しながら、撹拌下で、ケイ酸ナトリウム水溶液（ＳｉＯ_２として１５０ｇ／リットル）１２０ミリリットルを６０分間かけて添加し、硫酸で１２０分間かけてｐＨを５に調整した後、６０分間熟成した。次に、水酸化ナトリウム水溶液でｐＨを９に調整した後、アルミン酸ナトリウム水溶液（Ａｌ_２Ｏ_３として１５０ｇ／リットル）６０ミリリットルと硫酸とを、ｐＨを８〜９に維持するよう３０分間かけて添加し、硫酸でｐＨを７に調整した後、６０分間熟成した。熟成後、実施例１と同様に水洗、乾燥、粉砕して、平均粒子径が０．２５μｍで、第一層に酸化ケイ素水和物をＳｉＯ_２換算で６重量％被覆し、最外層に酸化アルミニウム水和物をＡｌ_２Ｏ_３換算で３重量％被覆した本発明の二酸化チタン顔料（試料Ｅ）を得た。 Example 5
After classification, the slurry obtained in Example 1 was collected in an amount of 1,000 ml, and while maintaining the temperature at 80 ° C., 120 ml of an aqueous sodium silicate solution (150 g / l as SiO ₂ ) was added over 60 minutes with stirring. After adjusting the pH to 5 over 120 minutes with sulfuric acid, the mixture was aged for 60 minutes. Next, after adjusting the pH to 9 with an aqueous solution of sodium hydroxide, 60 ml of an aqueous solution of sodium aluminate (150 g / liter as Al ₂ O ₃ ) and sulfuric acid were added over 30 minutes to maintain the pH at 8 to 9. After the addition, the pH was adjusted to 7 with sulfuric acid, and the mixture was aged for 60 minutes. After aging, washing, drying and pulverization were carried out in the same manner as in Example 1, the average particle diameter was 0.25 μm, the first layer was coated with 6% by weight of silicon oxide hydrate in terms of SiO ₂ , and the outermost layer was oxidized. A titanium dioxide pigment (Sample E) of the present invention in which aluminum hydrate was coated at 3% by weight in terms of Al ₂ O ₃ was obtained.

実施例６
　実施例１で得た分級後スラリーを１０００ミリリットル分取し、温度を７０℃に保持しながら、撹拌下で、硫酸を添加してｐＨを３に調整した後、ケイ酸ナトリウム水溶液（ＳｉＯ_２として１５０ｇ／リットル）６０ミリリットルを２０分間かけて添加し、硫酸で１０分間かけてｐＨを５に調整した後、３０分間熟成した。次に、水酸化ナトリウム水溶液でｐＨを９に調整した後、アルミン酸ナトリウム水溶液（Ａｌ_２Ｏ_３として１５０ｇ／リットル）６０ミリリットルと硫酸とを、ｐＨを８〜９に維持するよう３０分間かけて添加し、硫酸でｐＨを７に調整した後、３０分間熟成した。熟成後、実施例１と同様に水洗、乾燥、粉砕して、平均粒子径が０．２５μｍで、第一層に酸化ケイ素水和物をＳｉＯ_２換算で３重量％被覆し、最外層に酸化アルミニウム水和物をＡｌ_２Ｏ_３換算で３重量％被覆した本発明の二酸化チタン顔料（試料Ｆ）を得た。 Example 6
After classification, the slurry obtained in Example 1 was collected in an amount of 1000 ml, and while maintaining the temperature at 70 ° C., the pH was adjusted to 3 by adding sulfuric acid under stirring, and then an aqueous solution of sodium silicate (as SiO ₂₎ was added. (150 g / l) 60 ml was added over 20 minutes, the pH was adjusted to 5 over 10 minutes with sulfuric acid, and then ripened for 30 minutes. Next, after adjusting the pH to 9 with an aqueous solution of sodium hydroxide, 60 ml of an aqueous solution of sodium aluminate (150 g / liter as Al ₂ O ₃ ) and sulfuric acid were added over 30 minutes to maintain the pH at 8 to 9. The mixture was added, the pH was adjusted to 7 with sulfuric acid, and the mixture was aged for 30 minutes. After aging, washing, drying and pulverization were carried out in the same manner as in Example 1, the average particle diameter was 0.25 μm, the first layer was coated with silicon oxide hydrate at 3% by weight in terms of SiO ₂ , and the outermost layer was oxidized. A titanium dioxide pigment (Sample F) of the present invention in which aluminum hydrate was coated at 3% by weight in terms of Al ₂ O ₃ was obtained.

実施例７
　実施例１で得た分級後スラリーを１０００ミリリットル分取し、温度を６０℃に保持しながら、撹拌下で、ケイ酸ナトリウム水溶液（ＳｉＯ_２として１５０ｇ／リットル）８０ミリリットルを６０分間かけて添加し、３０分間熟成した。次に、アルミン酸ナトリウム水溶液（Ａｌ_２Ｏ_３として１５０ｇ／リットル）８０ミリリットルを４０分間かけて添加し、硫酸で３０分間かけてｐＨを７に調整した後、６０分間熟成した。熟成後、実施例１と同様に水洗、乾燥、粉砕して、平均粒子径が０．２５μｍで、酸化ケイ素水和物をＳｉＯ_２換算で４重量％、酸化アルミニウム水和物をＡｌ_２Ｏ_３換算で４重量％混合被覆した本発明の二酸化チタン顔料（試料Ｇ）を得た。 Example 7
After the classification obtained in Example 1, 1000 ml of the slurry was collected, and 80 ml of an aqueous solution of sodium silicate (150 g / l as SiO ₂ ) was added thereto over 60 minutes while stirring at a temperature of 60 ° C. And aged for 30 minutes. Next, 80 ml of an aqueous solution of sodium aluminate (150 g / l as Al ₂ O ₃ ) was added over 40 minutes, and the pH was adjusted to 7 over 30 minutes with sulfuric acid, followed by aging for 60 minutes. After aging, the powder was washed with water, dried and pulverized in the same manner as in Example 1 to have an average particle diameter of 0.25 μm, silicon oxide hydrate of 4% by weight in terms of SiO ₂ , and aluminum oxide hydrate of Al ₂ O _3. The titanium dioxide pigment of the present invention (sample G) coated in a mixed amount of 4% by weight was obtained.

比較例１
　含水酸化チタン中のＴｉＯ_２に対し、硫酸アルミニウムの添加量を０．０５重量％、水酸化カリウムの添加量を０．４重量％、オルトリン酸の添加量を０．４重量％とし、９２０℃で１時間加熱焼成したこと以外は実施例１と同様にして比較試料の二酸化チタン顔料（試料Ｈ）を得た。この二酸化チタン顔料の平均粒子径は０．１６μｍであった。 Comparative Example 1
The addition amount of aluminum sulfate was 0.05% by weight, the addition amount of potassium hydroxide was 0.4% by weight, and the addition amount of orthophosphoric acid was 0.4% by weight based on TiO ₂ in the hydrated titanium oxide. A titanium dioxide pigment (sample H) as a comparative sample was obtained in the same manner as in Example 1 except that the mixture was heated and calcined for 1 hour. The average particle size of this titanium dioxide pigment was 0.16 μm.

比較例２
　９８０℃で１時間加熱焼成したこと以外は比較例１と同様にして比較試料の二酸化チタン顔料（試料Ｉ）を得た。この二酸化チタン顔料の平均粒子径は０．２５μｍであった。 Comparative Example 2
A titanium dioxide pigment (sample I) as a comparative sample was obtained in the same manner as in comparative example 1 except that heating and firing were performed at 980 ° C. for 1 hour. The average particle size of this titanium dioxide pigment was 0.25 μm.

比較例３
　含水酸化チタン中のＴｉＯ_２に対し、硫酸アルミニウムの添加量を０．１重量％、水酸化カリウムの添加量を０．４重量％、オルトリン酸の添加量を０．８重量％とし、１０１０℃で１時間加熱焼成したこと以外は実施例１と同様にして比較試料の二酸化チタン顔料（試料Ｊ）を得た。この二酸化チタン顔料の平均粒子径は０．２５μｍであった。 Comparative Example 3
The amount of aluminum sulfate added was 0.1% by weight, the amount of potassium hydroxide added was 0.4% by weight, and the amount of orthophosphoric acid was 0.8% by weight based on TiO ₂ in the hydrous titanium oxide. A titanium dioxide pigment (sample J) as a comparative sample was obtained in the same manner as in Example 1 except that the mixture was heated and calcined for 1 hour. The average particle size of this titanium dioxide pigment was 0.25 μm.

比較例４
　含水酸化チタン中のＴｉＯ_２に対し、硫酸アルミニウムの添加量を０．１重量％、水酸化カリウムの添加量を０．３重量％、オルトリン酸の添加量を０．４５重量％とし、１０４０℃で１時間加熱焼成したこと以外は実施例１と同様にして比較試料の二酸化チタン顔料（試料Ｋ）を得た。この二酸化チタン顔料の平均粒子径は０．３μｍであった。 Comparative Example 4
1040 ° C., with the addition amount of aluminum sulfate being 0.1% by weight, the addition amount of potassium hydroxide being 0.3% by weight, and the addition amount of orthophosphoric acid being 0.45% by weight based on TiO _{2 in} hydrated titanium oxide. A titanium dioxide pigment (sample K) as a comparative sample was obtained in the same manner as in Example 1 except that the mixture was heated and calcined for 1 hour. The average particle size of this titanium dioxide pigment was 0.3 μm.

比較例５
　酸化アルミニウム水和物の被覆量をＡｌ_２Ｏ_３換算で０．５重量％とした以外は比較例１と同様にして比較試料の二酸化チタン顔料（試料Ｌ）を得た。 Comparative Example 5
A titanium dioxide pigment of a comparative sample (sample L) was obtained in the same manner as in comparative example 1 except that the coating amount of aluminum oxide hydrate was changed to 0.5% by weight in terms of Al ₂ O ₃ .

比較例６
　比較例１で得た平均粒子径０．１６μｍのアナターゼ型二酸化チタン粒子を用い、実施例５と同様に表面処理して比較試料の二酸化チタン顔料（試料Ｍ）を得た。 Comparative Example 6
Using the anatase type titanium dioxide particles having an average particle diameter of 0.16 μm obtained in Comparative Example 1, surface treatment was performed in the same manner as in Example 5 to obtain a titanium dioxide pigment (Sample M) as a comparative sample.

比較例７
　平均粒子径が０．２５μｍのルチル型二酸化チタン粒子を用い、実施例１と同様に表面処理して比較試料の二酸化チタン顔料（試料Ｎ）を得た。 Comparative Example 7
Using rutile-type titanium dioxide particles having an average particle diameter of 0.25 μm, surface treatment was carried out in the same manner as in Example 1 to obtain a titanium dioxide pigment (sample N) as a comparative sample.

比較例８
　比較例７で用いたルチル型二酸化チタン粒子を用い、実施例６と同様に表面処理して比較試料の二酸化チタン顔料（試料Ｏ）を得た。 Comparative Example 8
Using the rutile-type titanium dioxide particles used in Comparative Example 7, the same surface treatment as in Example 6 was performed to obtain a comparative titanium dioxide pigment (Sample O).

評価１：白色度（アマニ油カラー）の評価
　実施例１〜７及び比較例１〜８で得られた試料（Ａ〜Ｏ）の白色度を、ＪＩＳＫ５１１６に準じた方法により評価を行った。先ず、試料２．０ｇとアマニ油１．２５ミリリットルを、ガラス板上でへらで軽く混合した後、ハンドマラーで５０回転練り合わせ、ペーストを調製する。前記ペーストを１０ミルのフィルムアプリケーターを用い、ガラス板上に塗布する。塗布したペーストのハンター表色系によるＬ値を色差計（Ｚ−１００１ＤＰ型：日本電色工業製）を用いて測定した。結果を表１に示す。Ｌ値の高い試料が、白色度が優れている。 Evaluation 1: Evaluation of whiteness (linseed oil color) The whiteness of the samples (A to O) obtained in Examples 1 to 7 and Comparative Examples 1 to 8 was evaluated by a method according to JISK5116. First, 2.0 g of a sample and 1.25 ml of linseed oil are lightly mixed with a spatula on a glass plate, and then kneaded 50 times with a hand muller to prepare a paste. The paste is applied on a glass plate using a 10 mil film applicator. The L value of the applied paste in a Hunter color system was measured using a color difference meter (Z-1001DP type: manufactured by Nippon Denshoku Industries). Table 1 shows the results. A sample having a high L value has excellent whiteness.

評価２：アナターゼ含有量の測定
　実施例１〜７及び比較例１〜８で得られた試料（Ａ〜Ｏ）を、アルミセルに表面が平滑になるように充填した後、Ｘ線回折装置（ＲＡＤ−２ＶＣ型：リガク製）を用いて、ルチル型結晶の含有量（Ｒ（％））を求めた。１００−Ｒ（％）をアナターゼ型（Ａ型）の含有量とした。結果を表１に示す。 Evaluation 2: Measurement of Anatase Content After the samples (A to O) obtained in Examples 1 to 7 and Comparative Examples 1 to 8 were filled into an aluminum cell so that the surface became smooth, an X-ray diffractometer (RAD) was used. -2VC type: manufactured by Rigaku Corporation), and the content (R (%)) of the rutile type crystal was determined. 100-R (%) was defined as the content of the anatase type (A type). Table 1 shows the results.

評価３：粒度分布の評価
　実施例１〜７及び比較例１〜８で得られた試料（Ａ〜Ｏ）について、電子顕微鏡写真よりパーティクルアナライザー（ＴＧＺ３型：カール・ツァイス社製）を用いて、粒子径が０．２〜０．４μｍの粒子の粒度分布を測定した。粒度分布は重量基準に基づく。結果を表１に示す。 Evaluation 3: Evaluation of particle size distribution For the samples (A to O) obtained in Examples 1 to 7 and Comparative Examples 1 to 8, using a particle analyzer (TGZ3: manufactured by Carl Zeiss) from an electron micrograph, The particle size distribution of particles having a particle diameter of 0.2 to 0.4 μm was measured. Particle size distribution is based on weight. Table 1 shows the results.

２．塗料用樹脂を含む樹脂組成物に係わる実施例
実施例８〜１１、比較例９〜１４
　実施例１〜４及び比較例１〜５、７で得られた試料（Ａ〜Ｄ、Ｈ〜Ｌ、Ｎ）を用い、処方１にて容量１３０ｃｃのガラス製容器に仕込み、ペイントコンディショナー（レッドデビル社製）を用いて２０分間分散して分散液を調整した後、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４６％の樹脂組成物（塗料）を得た。それぞれを実施例８〜１１、比較例９〜１４（試料ａ〜ｊ）とする。 2. Examples relating to a resin composition containing a resin for paint, Examples 8 to 11 and Comparative Examples 9 to 14
Using the samples (A to D, H to L, and N) obtained in Examples 1 to 4 and Comparative Examples 1 to 5 and 7 and charging them in a glass container having a capacity of 130 cc according to Formulation 1, paint conditioner (Red Devil) After dispersing the dispersion for 20 minutes using the above method, a resin composition (paint) having a composition of 1 part by weight of the titanium dioxide pigment and 1 part by weight of the solid component and a solid content of 46% by volume was prepared according to Formulation 2. Got. These are Examples 8 to 11 and Comparative Examples 9 to 14 (samples a to j), respectively.

評価４：隠ペイ性、白色度、色調の評価
　実施例８〜１１及び比較例９〜１４の樹脂組成物（塗料）（試料ａ〜ｊ）を、＃３０バーコーターを用いて白黒チャート紙上に塗布し、また、＃６０バーコーターにて白チャート紙上に塗布し、いずれも１１０℃で４０分間焼きつけ、塗膜化した。白黒チャート紙上に塗布した塗膜黒地上の反射率（Ｙ_Ｂ値）、白地上の反射率（Ｙ_Ｗ値）、及び、白チャート紙上に塗布した塗膜のハンター表色系によるＬ値、ｂ値を、カラーコンピューター（ＳＭ−７型：スガ試験機製）を用いて計測した。隠蔽率（Ｃ_Ｒ値）は、下式１に従って算出した。結果を表４に示す。Ｃ_Ｒ値の高いものが隠ペイ性に優れ、Ｌ値の高いものが白色度が高く、ｂ値の小さいものが青味の色調である。本発明の二酸化チタン顔料は、従来のルチル型二酸化チタン顔料とほぼ同等の隠ペイ性、白色度を有し、しかもアナターゼ型特有の青味の色調を有している。
式１：隠蔽率（Ｃ_Ｒ）＝（Ｙ_Ｂ／Ｙ_Ｗ）×１００　（％） Evaluation 4: Evaluation of Hidden Payability, Whiteness, and Color Tone The resin compositions (paints) (samples a to j) of Examples 8 to 11 and Comparative Examples 9 to 14 were printed on black and white chart paper using a # 30 bar coater. It was coated on white chart paper with a # 60 bar coater, and baked at 110 ° C. for 40 minutes to form a coating. Reflectivity on coating black coated black and white chart paper (Y _B value), the reflectance on the white background (Y _W value), and, L value according to the Hunter color system of the coating film coated on a white chart paper, b The value was measured using a color computer (SM-7: manufactured by Suga Test Instruments). The concealment ratio ( _CR value) was calculated according to the following equation 1. Table 4 shows the results. Excellent high is hiding resistant C _R value, having a high L value high whiteness, having a small b value is color bluish. The titanium dioxide pigment of the present invention has almost the same hiding power and whiteness as the conventional rutile-type titanium dioxide pigment, and has a bluish tone unique to the anatase type.
Formula 1: Concealment ratio (C _R ) = (Y _B / Y _W ) × 100 (%)

３‐1．インキ用樹脂を含む樹脂組成物（溶剤系グラビアインキ）に係わる実施例
実施例１２〜１５、比較例１５〜１８
　実施例１、５〜７の二酸化チタン顔料（試料Ａ、Ｅ〜G）を、処方３にて容量１３０ｃｃのガラス製容器に仕込み、ペイントコンディショナー（レッドデビル社製）を用いて３０分間分散して分散液を調整した後、処方４にて、樹脂成分１重量部に対し二酸化チタン顔料４重量部、固形分体積濃度３７．５％の、本発明の樹脂組成物（グラビアインキ組成物）を得た。これを実施例１２〜１５（試料ｋ〜ｎ）とする。また、比較例１、６〜８の二酸化チタン顔料（試料Ｈ、Ｍ〜Ｏ）についても同様にして、グラビアインキ組成物とした。それぞれを比較例１５〜１８（試料ｏ〜ｒ）とする。 3-1. Examples relating to a resin composition (solvent-based gravure ink) containing an ink resin Examples 12 to 15 and Comparative Examples 15 to 18
The titanium dioxide pigments of Examples 1 and 5 to 7 (Samples A and E to G) were charged into a glass container having a capacity of 130 cc according to Formulation 3 and dispersed using a paint conditioner (manufactured by Red Devil Co.) for 30 minutes. After preparing the dispersion liquid, the resin composition (gravure ink composition) of the present invention having a prescription of 4 parts by weight of titanium dioxide pigment per 1 part by weight of the resin component and a solid content volume concentration of 37.5% was obtained. Was. These are designated as Examples 12 to 15 (samples k to n). Gravure ink compositions were similarly prepared for the titanium dioxide pigments of Comparative Examples 1 and 6 to 8 (samples H and MO). These are referred to as Comparative Examples 15 to 18 (samples r).

３‐２．インキ用樹脂を含む樹脂組成物（水性フレキソインキ）に係わる実施例
実施例１６〜１９、比較例１９〜２２
　実施例１、５〜７の二酸化チタン顔料（試料Ａ、Ｅ〜G）を、処方５にて容量１３０ｃｃのガラス製容器に仕込み、ペイントコンディショナー（レッドデビル社製）を用いて３０分間分散して分散液を調整した後、処方６にて、樹脂成分１重量部に対し二酸化チタン顔料６．３重量部、固形分体積濃度５４．５％の、本発明の樹脂組成物（水性フレキソインキ組成物）を得た。これを実施例１６〜１９（試料ｓ〜ｖ）とする。また、比較例１、６〜８の二酸化チタン顔料（試料Ｈ、Ｍ〜Ｏ）についても同様にして、水性フレキソインキ組成物とした。それぞれを比較例１９〜２２（試料ｗ〜ｚ）とする。 3-2. Examples relating to a resin composition (aqueous flexographic ink) containing a resin for inks Examples 16 to 19 and Comparative Examples 19 to 22
The titanium dioxide pigments of Examples 1 and 5 to 7 (Samples A and E to G) were charged into a glass container having a capacity of 130 cc according to Formulation 5 and dispersed using a paint conditioner (manufactured by Red Devil Co.) for 30 minutes. After preparing the dispersion, the resin composition of the present invention (water-based flexographic ink composition) was prepared according to Formula 6 in which 6.3 parts by weight of a titanium dioxide pigment and 54.5% solids volume concentration were added to 1 part by weight of the resin component. ) Got. These are designated as Examples 16 to 19 (samples s to v). In addition, the aqueous flexographic ink compositions were similarly prepared for the titanium dioxide pigments of Comparative Examples 1 and 6 to 8 (samples H and MO). These are referred to as Comparative Examples 19 to 22 (samples w to z).

評価５：隠ペイ性評価
　実施例１２〜１５（試料ｋ〜ｎ）、比較例１５〜１８（試料ｏ〜ｒ）のグラビアインキ組成物を、実用系の印刷粘度になるように、トルエン／イソプロピルアルコール／メチルエチルケトン＝３／２／５の混合溶剤にて、＃３ザーンカップ粘度１５〜１６秒に希釈、調整した。この希釈インキを、＃１６バーコーターを用いてＰＥＴフィルム上に塗布し、３０分間自然乾燥させて塗膜化した。フィルム背面（塗膜の無い面）に黒チャート紙を合わせ、塗膜の反射率（Ｙ値）及びハンター表色系によるｂ値をカラーコンピューター（ＳＭ−７型：スガ試験機製）を用いて測定した。また、実施例１６〜１９（試料ｓ〜ｖ）、比較例１９〜２２（試料ｗ〜ｚ）の水性フレキソインキ組成物を、実用系の印刷粘度になるように、純水にて、＃４ザーンカップ粘度７〜８秒に希釈、調整した。この希釈インキを、＃１６バーコーターを用いて段ボール紙上に塗布し、１時間自然乾燥させて塗膜化した。フィルム背面に黒チャート紙を合わせ、塗膜の反射率（Ｙ値）及びハンター表色系によるｂ値をカラーコンピューター（ＳＭ−７型：スガ試験機製）を用いて測定した。その結果を表９に示す。反射率が高いものが隠ペイ性が高く、ｂ値の小さいものが青味色調である。 Evaluation 5: Evaluation of Hidden Pay Property The gravure ink compositions of Examples 12 to 15 (samples k to n) and Comparative Examples 15 to 18 (samples o to r) were mixed with toluene / isopropyl so as to have a practical printing viscosity. The mixture was diluted and adjusted to a # 3 Zahn cup viscosity of 15 to 16 seconds with a mixed solvent of alcohol / methyl ethyl ketone = 3/2/5. This diluted ink was applied on a PET film using a # 16 bar coater and dried naturally for 30 minutes to form a coating film. A black chart paper is placed on the back surface of the film (the surface without the coating film), and the reflectance (Y value) of the coating film and the b value according to the Hunter color system are measured using a color computer (SM-7: manufactured by Suga Test Instruments). did. The aqueous flexographic ink compositions of Examples 16 to 19 (samples s to v) and Comparative Examples 19 to 22 (samples w to z) were subjected to # 4 with pure water so as to have a printing viscosity of a practical system. The Zahn cup was diluted and adjusted to a viscosity of 7 to 8 seconds. This diluted ink was applied on corrugated paper using a # 16 bar coater, and was naturally dried for 1 hour to form a coating film. The black chart paper was attached to the back of the film, and the reflectance (Y value) of the coating film and the b value according to the Hunter color system were measured using a color computer (SM-7: manufactured by Suga Test Instruments). Table 9 shows the results. Those with high reflectance have high hidden payability, and those with small b-value have blue tint.

評価６：ラミネート後の隠ペイ性評価
　実施例１２〜１５（試料ｋ〜ｎ）、比較例１５〜１８（試料ｏ〜ｒ）のグラビアインキ組成物を、実用系の印刷粘度になるように、トルエン／イソプロピルアルコール／メチルエチルケトン＝３／２／５の混合溶剤にて、＃３ザーンカップ粘度１５〜１６秒に希釈、調整した。この希釈インキを、＃４バーコーターを用いてＰＥＴフィルム上に塗布し、３０分間自然乾燥させた後、その塗膜上にウレタン樹脂（ＩＢ−４２２、三洋化成製、固形分３０重量％）を＃１６バーコーターで塗布して、その上からＯＰＰフィルムを塗膜に貼り合わせた。得られたフィルムを蛍光灯に透かして、その透過度合いを目視判定し、ラミネート後の隠ペイ性の評価とした。評価基準は以下の通である。
（優）判定○：フィルムの透過度が低い〜判定×：フィルムの透過度が高い（劣） Evaluation 6: Evaluation of hidden payability after lamination The gravure ink compositions of Examples 12 to 15 (samples k to n) and Comparative Examples 15 to 18 (samples o to r) were prepared so as to have a practical printing viscosity. It was diluted and adjusted with a mixed solvent of toluene / isopropyl alcohol / methyl ethyl ketone = 3/2/5 to a # 3 Zahn cup viscosity of 15 to 16 seconds. The diluted ink is applied on a PET film using a # 4 bar coater, and naturally dried for 30 minutes. Then, a urethane resin (IB-422, manufactured by Sanyo Chemical Industries, solid content 30% by weight) is applied on the coated film. It was applied with a # 16 bar coater, and the OPP film was adhered to the coating from above. The obtained film was put through a fluorescent lamp, the degree of transmission was visually determined, and the hidden payability after lamination was evaluated. The evaluation criteria are as follows.
(Excellent) Judgment ：: Film transmittance is low to Judgment X: Film transmittance is high (Poor)

評価７：金属磨耗性の評価
　評価５で用いた希釈インキ５００ｇを、アブレージョンテスター（ＡＴII型：カール・シュレッダー社製）を用い、５０万回転により試験を行った。試験前後の試験板の重量を測定し、減量を金属摩耗性の評価とした。結果を表９に示す。本発明のインキ樹脂組成物は、従来のルチル型二酸化チタン顔料を用いたものとほぼ同等の隠ペイ性を示し、しかもアナターゼ型特有の金属磨耗性に優れている。 Evaluation 7: Evaluation of Metal Abrasion A 500 g dilution ink used in Evaluation 5 was tested at 500,000 revolutions using an abrasion tester (ATII type, manufactured by Carl Shredder). The weight of the test plate before and after the test was measured, and the weight loss was evaluated as the metal wear property. Table 9 shows the results. The ink resin composition of the present invention exhibits almost the same hidden payability as that obtained by using the conventional rutile-type titanium dioxide pigment, and is excellent in the metal abrasion characteristic peculiar to the anatase type.

４．プラスチックス用樹脂を含む樹脂組成物に係わる実施例
実施例２０、比較例２３
　実施例２の二酸化チタン顔料（試料Ｂ）を処方７の混合物とした。この混合物を、二軸押出機（ラボプラストミル：東洋精機製作所製、Ｌ／Ｄ＝２５、Ｄ＝２０ｍｍφ）を用いて、樹脂温度が２８０℃になるように加熱溶融し、１時間かけて混練して、Ｔダイにより厚さ５０μｍのフィルムに成形することで、樹脂成分１重量部に対し二酸化チタン顔料を１重量部含む、本発明の樹脂組成物（プラスチックス樹脂組成物）を得た。これを実施例２０（試料ａ'）とする。尚、二軸押出機の押出口には、１４５０メッシュのスクリーンを装着した。比較例５の二酸化チタン顔料（試料Ｌ）についても同様にして、プラスチックス樹脂組成物とした。これを、比較例２３（試料ｂ'）とする。 4. Examples relating to a resin composition containing a resin for plastics Example 20 and Comparative Example 23
The titanium dioxide pigment of Example 2 (Sample B) was used as a mixture of Formulation 7. This mixture was heated and melted using a twin-screw extruder (Laboplast Mill: manufactured by Toyo Seiki Seisakusho, L / D = 25, D = 20 mmφ) so that the resin temperature became 280 ° C., and kneaded for 1 hour Then, it was formed into a film having a thickness of 50 μm by a T-die to obtain a resin composition (plastics resin composition) of the present invention containing 1 part by weight of a titanium dioxide pigment per 1 part by weight of a resin component. This is designated as Example 20 (sample a ′). In addition, a 1450 mesh screen was attached to the extrusion port of the twin-screw extruder. Similarly, the titanium dioxide pigment of Comparative Example 5 (Sample L) was used as a plastics resin composition. This is designated as Comparative Example 23 (sample b ′).

評価８：隠ペイ性の評価
　実施例２０及び比較例２３（試料ａ'、ｂ'）のポリエチレンフィルムを分光光度計（ＵＶ−２２００Ａ：島津製作所製）を用いて、波長が４４０ｎｍ、５４０ｎｍ、６４０ｎｍの可視光の透過率（Ｔ値）をそれぞれ測定した。結果を表１１に示す。Ｔ値が小さいものが、隠ぺい性に優れている。 Evaluation 8: Evaluation of Hidden Payability The polyethylene films of Example 20 and Comparative Example 23 (samples a ′ and b ′) were measured with a spectrophotometer (UV-2200A: manufactured by Shimadzu Corporation) at wavelengths of 440 nm, 540 nm, and 640 nm. Were measured for visible light transmittance (T value). Table 11 shows the results. Those having a small T value are excellent in hiding.

評価９：分散性の評価
　実施例２０及び比較例２３（試料ａ'、ｂ'）をポリエチレンフィルムに成形した際に、混練前後の押出機の押出口における樹脂圧を測定した。結果を表１１に示す。その差（ΔＰ）が小さいものが、分散性に優れている。本発明のプラスチックス樹脂組成物は、従来のアナターゼ型二酸化チタン顔料を用いたものより隠ペイ性に優れているばかりでなく、分散性にも優れている。 Evaluation 9: Evaluation of Dispersibility When Example 20 and Comparative Example 23 (samples a ′ and b ′) were formed into a polyethylene film, the resin pressure at the extrusion port of the extruder before and after kneading was measured. Table 11 shows the results. Those having a small difference (ΔP) have excellent dispersibility. The plastics resin composition of the present invention is more excellent in dispersibility as well as in hidden payability than those using the conventional anatase type titanium dioxide pigment.

　本発明の二酸化チタン顔料はアナターゼ型特有の特性、例えば青味色調等の光学的特性、低い硬度等の物理的特性を有し、しかも、従来のアナターゼ型酸化チタン顔料には無い高隠ペイ性を有するので各種の樹脂組成物に、中でも塗料用樹脂、インキ用樹脂、プラスチックス用樹脂を配合した樹脂組成物に有用である。
The titanium dioxide pigment of the present invention has properties specific to anatase type, for example, optical properties such as blue tint, physical properties such as low hardness, and high opacity which is not present in conventional anatase type titanium oxide pigments. Therefore, it is useful for various resin compositions, especially for resin compositions in which a resin for paint, a resin for ink, and a resin for plastics are blended.

Claims (17)

アナターゼ型結晶を９８〜１００％の範囲で含み、０．２〜０．４μｍの範囲の平均粒子径を有し、白色度がアマニ油カラーのＬ値で９５〜９７の範囲にあることを特徴とする二酸化チタン顔料。 It contains anatase type crystals in the range of 98 to 100%, has an average particle size in the range of 0.2 to 0.4 μm, and has whiteness in the range of 95 to 97 in L value of linseed oil color. Titanium dioxide pigment. ０．２〜０．４μｍの範囲の粒子径を有する粒子を重量基準で５０〜１００％の範囲で含むことを特徴とする請求項１記載の二酸化チタン顔料。 2. A titanium dioxide pigment according to claim 1, wherein the pigment has a particle size in the range of 0.2 to 0.4 [mu] m in a range of 50 to 100% by weight. 硫酸根の含有量がＳＯ_４換算で多くとも０．１重量％であることを特徴とする請求項１記載の二酸化チタン顔料。 Titanium dioxide pigment according to claim 1, wherein the content of the sulfate is 0.1 wt% at most in terms _of SO _4. 無機化合物、有機化合物から選ばれる少なくとも１種で表面を被覆されることを特徴とする請求項１記載の二酸化チタン顔料。 The titanium dioxide pigment according to claim 1, wherein the surface is coated with at least one selected from an inorganic compound and an organic compound. 無機化合物がアルミニウム化合物、ケイ素化合物、ジルコニウム化合物、スズ化合物、チタニウム化合物、アンチモン化合物から選ばれる少なくとも１種であることを特徴とする請求項４記載の二酸化チタン顔料。 The titanium dioxide pigment according to claim 4, wherein the inorganic compound is at least one selected from an aluminum compound, a silicon compound, a zirconium compound, a tin compound, a titanium compound, and an antimony compound. 無機化合物が酸化物、水和酸化物、水酸化物、リン酸塩から選ばれる少なくとも１種であることを特徴とする請求項５記載の二酸化チタン顔料。 The titanium dioxide pigment according to claim 5, wherein the inorganic compound is at least one selected from oxides, hydrated oxides, hydroxides, and phosphates. それぞれの無機化合物の被覆量が０．０５〜１５重量％の範囲にあることを特徴とする請求項６記載の二酸化チタン顔料。 7. The titanium dioxide pigment according to claim 6, wherein the coating amount of each inorganic compound is in the range of 0.05 to 15% by weight. 有機化合物が多価アルコール、アルカノールアミンまたはその誘導体、有機ケイ素化合物、高級脂肪酸またはその金属塩から選ばれる少なくとも１種であることを特徴とする請求項４記載の二酸化チタン顔料。 The titanium dioxide pigment according to claim 4, wherein the organic compound is at least one selected from polyhydric alcohols, alkanolamines or derivatives thereof, organosilicon compounds, higher fatty acids and metal salts thereof. 有機化合物の総被覆量が０．０１〜５重量％の範囲にあることを特徴とする請求項８記載の二酸化チタン顔料。 9. The titanium dioxide pigment according to claim 8, wherein the total coating amount of the organic compound is in the range of 0.01 to 5% by weight. 焼成処理剤の存在下、含水酸化チタンを加熱焼成するアナターゼ型二酸化チタン顔料の製造方法において、焼成処理剤として含水酸化チタン中のＴｉＯ_２に対しＡｌ_２Ｏ_３換算で０．０２〜０．２重量％の範囲に相当するアルミニウム化合物、Ｋ_２Ｏ換算で０．２〜１重量％、Ｐ_２Ｏ_５換算で０．０２〜０．５重量％の範囲に相当し、且つＫ_２Ｏ／Ｐ_２Ｏ_５が１．５／１〜１０／１の範囲にあるカリウム化合物及びリン酸化合物を用い、８００℃以上１０００℃未満の温度で加熱焼成することを特徴とする二酸化チタン顔料の製造方法。 In a method for producing an anatase-type titanium dioxide pigment, in which hydrated titanium oxide is heated and calcined in the presence of a calcination agent, the calcination agent is 0.02 to 0.2 in terms of Al ₂ O ₃ relative to TiO _{2 in} hydrated titanium oxide. Aluminum compound corresponding to the range of 0.2 to 1% by weight in terms of K ₂ O, 0.02 to 0.5% by weight in terms of P ₂ O ₅ , and K ₂ O / P _A method for producing a titanium dioxide pigment, characterized in that a potassium compound and a phosphoric acid compound in which ₂ O ₅ is in the range of 1.5 / 1 to 10/1 are heated and calcined at a temperature of 800 ° C. or more and less than 1000 ° C. 粒子径が０．００１〜０．０１μｍである含水酸化チタンを用いることを特徴とする請求項１０に記載の二酸化チタン顔料の製造方法。 The method for producing a titanium dioxide pigment according to claim 10, wherein a hydrous titanium oxide having a particle diameter of 0.001 to 0.01 µm is used. 二酸化チタン顔料と樹脂成分とを含む樹脂組成物であって、二酸化チタン顔料がアナターゼ型結晶を９８〜１００％の範囲で含み、０．２〜０．４μｍの範囲の平均粒子径を有し、白色度がアマニ油カラーのＬ値で９５〜９７の範囲にあることを特徴とする樹脂組成物。 A resin composition comprising a titanium dioxide pigment and a resin component, wherein the titanium dioxide pigment contains anatase-type crystals in a range of 98 to 100% and has an average particle size in a range of 0.2 to 0.4 μm, A resin composition having a whiteness in the range of 95 to 97 in L value of linseed oil color. 二酸化チタン顔料が０．２〜０．４μｍの範囲の粒子径を有する粒子を重量基準で５０〜１００％の範囲で含むことを特徴とする請求項１２記載の樹脂組成物。 13. The resin composition according to claim 12, wherein the titanium dioxide pigment contains particles having a particle diameter in the range of 0.2 to 0.4 [mu] m in a range of 50 to 100% by weight. 樹脂成分が塗料用樹脂、インキ用樹脂またはプラスチックス用樹脂であることを特徴とする請求項１２記載の樹脂組成物。 The resin composition according to claim 12, wherein the resin component is a resin for paint, a resin for ink, or a resin for plastics. 二酸化チタン顔料を塗料用樹脂成分１重量部に対し０．５〜１０重量部含むことを特徴とする請求項１２記載の樹脂組成物。 13. The resin composition according to claim 12, comprising 0.5 to 10 parts by weight of the titanium dioxide pigment per 1 part by weight of the resin component for coating. 二酸化チタン顔料をインキ用樹脂成分１重量部に対し０．５〜１０重量部含むことを特徴とする請求項１２記載の樹脂組成物。 13. The resin composition according to claim 12, comprising 0.5 to 10 parts by weight of the titanium dioxide pigment per 1 part by weight of the resin component for ink. 二酸化チタン顔料をプラスチックス用樹脂成分１重量部に対し０．０５〜２重量部含むことを特徴とする請求項１２記載の樹脂組成物。
13. The resin composition according to claim 12, comprising 0.05 to 2 parts by weight of the titanium dioxide pigment per 1 part by weight of the resin component for plastics.