JPH0693204A - Production of highly masking white pigment - Google Patents
Production of highly masking white pigmentInfo
- Publication number
- JPH0693204A JPH0693204A JP24230392A JP24230392A JPH0693204A JP H0693204 A JPH0693204 A JP H0693204A JP 24230392 A JP24230392 A JP 24230392A JP 24230392 A JP24230392 A JP 24230392A JP H0693204 A JPH0693204 A JP H0693204A
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- titanium oxide
- weight
- parts
- pigment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、我国で唯一国内で全量
を供給できる鉱物資源であって、量的、品位的にも優れ
た石灰石を原料とする白色度の高い炭酸カルシウムを主
材とし、酸化チタンとの複合系で顔料に必要不可欠な分
散性及び親和性の極めて良好な高隠蔽性の白色顔料を比
較的安価に製造し得る方法に関するものである。BACKGROUND OF THE INVENTION The present invention is the only mineral resource in Japan that can supply the entire amount in Japan, and is mainly composed of high-whiteness calcium carbonate made from limestone which is excellent in quantity and quality. The present invention relates to a method for relatively inexpensively producing a white pigment having a high hiding property, which has a very good dispersibility and affinity which are indispensable for a pigment in a complex system with titanium oxide.
【０００２】プラスチック、塗料、インキ、シーラン
ト、化粧品あるいは製紙等の業界では、酸化チタンを主
体とした隠蔽力の高い白色顔料のニーズが高く、さらに
そのマトリックスあるいはビヒクルへの分散性、親和性
が優れ、高い機能性を発揮する白色顔料が要求されてい
る。In the fields of plastics, paints, inks, sealants, cosmetics, paper making, etc., there is a great need for white pigments mainly composed of titanium oxide and having high hiding power, and further, their dispersibility in a matrix or vehicle and their affinity are excellent. However, white pigments exhibiting high functionality are required.
【０００３】[0003]
【従来の技術】このような顔料に隠蔽性を付与するため
の条件として、次の２項目をあげることができる。2. Description of the Related Art The following two items can be mentioned as conditions for imparting hiding power to such pigments.
【０００４】１．屈折率が２．５の白色顔料である酸化
チタンの如き、高い屈折率を有すること、ちなみに炭酸
カルシウムは屈折率が１．５で体質顔料の域を出ない ２．光学的に見て粒子径が０．２〜０．４μｍで、個々
の粒子がよく分散されていること。1. 1. It has a high refractive index such as titanium oxide which is a white pigment with a refractive index of 2.5. By the way, calcium carbonate has a refractive index of 1.5 and does not exceed the range of an extender pigment. Optically, the particle size is 0.2 to 0.4 μm, and the individual particles are well dispersed.
【０００５】これらの条件を満たすために上記第１項に
関連して、特公昭５５−４１６６２号公報では、炭酸カ
ルシウムに水酸化チタンゾルを反応せしめて表面をチタ
ン酸カルシウムで改質させる方法、特開平１−２２４２
２０号公報では、水酸化チタンに過酸化水素水を加えて
得られたチタン酸水溶液を加熱することにより、無機基
材表面に酸化チタンを析出させる方法、特開平２−５１
４１９号公報では、酸化チタン等の高屈折率の微粒子を
核として炭酸カルシウムを成長させる方法が提案されて
いる。同様に、上記第２項の粒子径制御についても種々
の試みがなされてきた。In order to satisfy these conditions, in relation to the above-mentioned item 1, Japanese Patent Publication No. 55-41662 discloses a method of reacting calcium carbonate with titanium hydroxide sol to modify the surface with calcium titanate, Kaihei 1-2242
JP-A-2-51 discloses a method of precipitating titanium oxide on the surface of an inorganic substrate by heating an aqueous solution of titanic acid obtained by adding hydrogen peroxide solution to titanium hydroxide.
Japanese Patent No. 419 proposes a method of growing calcium carbonate using fine particles having a high refractive index such as titanium oxide as nuclei. Similarly, various attempts have been made to control the particle size in the above item 2.
【０００６】一方、炭酸カルシウムの表面処理法は、湿
式法と乾式法に大別されるが、乾式法と称する手法の１
例として、プラスチック等に混練しても余り悪影響を及
ぼさない耐酸性の粘土鉱物であるＳｉＯ2・Ａｌ2Ｏ3に
有機酸を吸着させた後、炭酸カルシウムと混合する方法
が特開昭５６−５５４５９号公報において試みられてい
る。しかしこの場合、炭酸カルシウムとプラスチックと
の親和性は向上するものの、隠蔽性においては低下する
傾向さえ認められ、高隠蔽性なる機能は全く期待できな
いものであった。On the other hand, the surface treatment method of calcium carbonate is roughly classified into a wet method and a dry method.
As an example, there is a method of adsorbing an organic acid to SiO 2 .Al 2 O 3, which is an acid-resistant clay mineral that does not have a bad influence even if it is kneaded with plastics, and then mixing with calcium carbonate. It is attempted in Japanese Patent No. 55459. However, in this case, although the affinity between calcium carbonate and the plastic was improved, the hiding property tended to be lowered, and the function of high hiding property could not be expected at all.
【０００７】[0007]
【発明が解決しようとする課題】本発明者らは、上記第
１項を重点に、炭酸カルシウムの隠蔽性向上を計るた
め、粒子の表面が高隠蔽性の顔料で被覆されていれば、
中心部は隠蔽性の低い体質顔料でもよく、極端に云え
ば、中心部は空洞でバルーン状であっても、その効果は
表面の顔料特性に依存するものであるとの見解の基に、
炭酸カルシウムの表面に酸化チタンを被覆させる方法に
つき、鋭意研究を行なった。DISCLOSURE OF THE INVENTION In order to improve the hiding power of calcium carbonate, the present inventors have focused on the above-mentioned item 1, so that if the surface of the particles is coated with a highly hiding pigment,
The central portion may be an extender pigment having a low hiding property, and in an extreme case, even if the central portion is hollow and has a balloon shape, based on the view that the effect depends on the pigment characteristics of the surface,
An intensive study was conducted on a method for coating the surface of calcium carbonate with titanium oxide.
【０００８】また生成した高隠蔽性の白色顔料をプラス
チック、例えばポリプロピレン、ポリエチレン中に混練
した場合に、個々の粒子がこれらのポリマー中で極めて
高度に分散すること、及び粒子とポリマーとの界面にボ
イトが存在せず非常に親和性が良好で耐衝撃強度等の物
性面で優れた機能性の発揮し得ることも強く要望されて
いる。Further, when the produced highly hiding white pigment is kneaded in a plastic such as polypropylene or polyethylene, the individual particles are extremely highly dispersed in these polymers, and at the interface between the particles and the polymer. It is also strongly demanded that there is no voit, the affinity is very good, and the excellent functionality in terms of physical properties such as impact strength can be exhibited.
【０００９】それ故、炭酸カルシウム粒子個々の凝集を
防止して分散性をより良くし、炭酸カルシウムと酸化チ
タンとの結合を強くすると共にさらに炭酸カルシウム-
酸化チタン複合体のプラスチック中での分散性と親和性
を向上させることを主要命題に、炭酸カルシウム粒子表
面にアクリル酸をバインダーとして酸化チタンを均一に
結合させて、炭酸カルシウム系の高隠蔽性白色顔料を得
ることを課題としている。Therefore, the calcium carbonate particles are prevented from agglomerating to improve the dispersibility, strengthen the bond between calcium carbonate and titanium oxide, and further increase the calcium carbonate-
The main proposition is to improve the dispersibility and affinity of the titanium oxide composite in plastics. By uniformly binding the titanium oxide using acrylic acid as a binder to the surface of the calcium carbonate particles, a calcium carbonate-based high concealing white The challenge is to obtain a pigment.
【００１０】[0010]
【課題を解決するための手段】上記主要命題に対する対
応策は、次の２項目より成る。[Means for Solving the Problems] Countermeasures against the above-mentioned main proposition consist of the following two items.
【００１１】１．粒子個々の凝集を防止し、分散性をよ
り良くするため、分散剤としてポリアクリル酸のアルカ
リ金属塩を利用する。1. An alkali metal salt of polyacrylic acid is used as a dispersant in order to prevent aggregation of individual particles and improve dispersibility.
【００１２】２．炭酸カルシウム-酸化チタン複合体を
形成させると共に、プラスチック中での親和性の向上と
結合を強くするために、アクリル酸モノマーを利用す
る。2. Acrylic acid monomer is used to form calcium carbonate-titanium oxide complex and to improve affinity and strengthen binding in plastics.
【００１３】したがって本発明は、炭酸カルシウムにポ
リアクリル酸のアルカリ金属塩を処理した後、予めアク
リル酸モノマーを吸着せしめた酸化チタンで粉末同士の
混合撹拌をすることにより、上記課題を解決する。Therefore, the present invention solves the above-mentioned problems by treating calcium carbonate with an alkali metal salt of polyacrylic acid and then mixing and stirring the powders with titanium oxide having an acrylic acid monomer adsorbed in advance.
【００１４】[0014]
【作用】顔料としての炭酸カルシウムには、単に石灰石
を粉砕分級した重質炭酸カルシウムと石灰石を焼成分解
して得たＣａＯを水で消化したＣａ(ＯＨ)2に炭酸ガス
を導入して作る合成炭酸カルシウムとがある。[Function] For calcium carbonate as a pigment, a synthesis is made by introducing carbon dioxide gas into Ca (OH) 2 digested with water to obtain heavy calcium carbonate obtained by simply crushing and classifying limestone and CaO obtained by firing and decomposing limestone. There is calcium carbonate.
【００１５】本発明に係る方法では、いずれの炭酸カル
シウムを使用しても所期の目的は達成し得るが、操業性
及びコストの面よりＢＥＴ比表面積が８〜１２ｍ2／ｇ
の重質炭酸カルシウムが最も適当である。In the method according to the present invention, the intended purpose can be achieved by using any calcium carbonate, but in view of operability and cost, the BET specific surface area is 8 to 12 m 2 / g.
Most suitable is heavy calcium carbonate.
【００１６】この重質炭酸カルシウムをヘンシェルミキ
サーに入れ、撹拌しながら３０〜４０％濃度で分子量が
３，０００〜１０，０００のポリアクリル酸のアルカリ
金属塩を純分換算で１〜５重量部／ＣａＣＯ3（以下、
単に「重量部」という）噴霧添加し、摩擦熱も含めた間
接加熱により１００〜１１０℃に上昇せしめる。This heavy calcium carbonate is put into a Henschel mixer, and 1 to 5 parts by weight in terms of pure content of an alkali metal salt of polyacrylic acid having a concentration of 30 to 40% and a molecular weight of 3,000 to 10,000 with stirring. / CaCO 3 (hereinafter,
Spray addition (simply referred to as "parts by weight") and increase to 100 to 110 ° C by indirect heating including frictional heat.
【００１７】一方、別系で０．１〜５重量部のアクリル
酸モノマーを湿潤させた１〜５０重量部の酸化チタン
を、前記ヘンシェルミキサーに添加し、撹拌を続行する
ことにより、このアクリル酸は、炭酸カルシウムと酸化
チタンとのバインダーとして働く以外に、徐々に炭酸カ
ルシウム表面に移行して反応し、粒子表面の角がとれ、
凹部のボイドを失くしながら、プラスチック中での分散
性を良くし、親和性の優れた高隠蔽性の白色顔料を製造
し得たものである。On the other hand, 1 to 50 parts by weight of titanium oxide obtained by wetting 0.1 to 5 parts by weight of acrylic acid monomer in a separate system was added to the Henschel mixer, and stirring was continued to obtain this acrylic acid. In addition to acting as a binder between calcium carbonate and titanium oxide, is gradually transferred to the calcium carbonate surface and reacts, and the corners of the particle surface are removed,
It is possible to produce a white pigment having a high hiding property, which has good affinity with plasticity while improving the dispersibility in plastic while eliminating voids in the recesses.
【００１８】この生成品は、単にアクリル酸のみで表面
処理した炭酸カルシウムに比較し、遥かに隠蔽性におい
てすぐれていると共に、炭酸カルシウムと酸化チタンと
を同じ比率で単に混合したものとの比較では、物性面で
の優劣が明らかに相異していた。This product is far superior in hiding power to calcium carbonate surface-treated only with acrylic acid, and compared with a mixture of calcium carbonate and titanium oxide in the same ratio. The physical properties were obviously different.
【００１９】なおプラスチックの種類、使用目的により
炭酸カルシウムは、重質炭酸カルシウム以外に、０．０
２〜０．１μｍの膠質炭酸カルシウムや０．１〜５．０
μｍの軽質炭酸カルシウム等の合成品を使用することも
勿論可能である。In addition to heavy calcium carbonate, calcium carbonate may be 0.0
2-0.1 μm colloidal calcium carbonate or 0.1-5.0
Of course, it is also possible to use a synthetic product such as light calcium carbonate of μm.
【００２０】添加量としては、炭酸カルシウム１００部
に対し、酸化チタンでは１〜５０重量部、ポリアクリル
酸のアルカリ金属塩では１〜５重量部、アクリル酸モノ
マーでは０．１〜５重量部が有効である。As an addition amount, 1 to 50 parts by weight of titanium oxide, 1 to 5 parts by weight of an alkali metal salt of polyacrylic acid, and 0.1 to 5 parts by weight of an acrylic acid monomer are added to 100 parts of calcium carbonate. It is valid.
【００２１】[0021]
【発明の効果】炭酸カルシウムを本体とし、その分散剤
としてポリアクリル酸ソーダを、また同質のアクリル酸
モノマーをバインダーとして酸化チタンを炭酸カルシウ
ムの表面に均一に結合させることにより、高い隠蔽性を
有し物性強度的にも優れた機能性をもつプラスチック用
の安価な白色顔料を製造し、各種業界に大きく貢献し得
る。EFFECT OF THE INVENTION By using calcium carbonate as a main body, sodium polyacrylate as a dispersant for the main body, and titanium oxide uniformly bound on the surface of calcium carbonate by using the same quality acrylic acid monomer as a binder, a high hiding property can be obtained. It is possible to manufacture inexpensive white pigments for plastics that have excellent physical properties and strength, and make a great contribution to various industries.
【００２２】[0022]
【実施例】本発明の実施例および比較例をあげてさらに
具体的に説明する。なお本発明はこれらの実施例により
制限されるものではない。EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. The present invention is not limited to these examples.
【００２３】実施例１ 容量２０リットルのヘンシェルミキサーにＢＥＴ比表面
積１２ｍ2／ｇの重質炭酸カルシウム４ｋｇを投入後、
撹拌しながらポリアクリル酸ソーダを純分換算で２重量
部噴霧添加し、１０５℃でそのまま１０分間撹拌を続け
た。この中へあらかじめ別の容器で十分撹拌混合したア
ナターゼ型酸化チタン（石原産業Ａ−２２０）２．５重
量部とアクリル酸モノマー１重量部を徐々に添加し、さ
らに１５分間撹拌を継続することにより高隠蔽性の白色
顔料を得た。 Example 1 After adding 4 kg of heavy calcium carbonate having a BET specific surface area of 12 m 2 / g to a Henschel mixer having a capacity of 20 liters,
While stirring, 2 parts by weight of sodium polyacrylate in terms of pure content was spray-added, and stirring was continued for 10 minutes at 105 ° C. 2.5 parts by weight of anatase-type titanium oxide (Ishihara Sangyo A-220) and 1 part by weight of acrylic acid monomer, which had been sufficiently stirred and mixed in another container, were gradually added to this, and stirring was continued for another 15 minutes. A white pigment with high hiding power was obtained.
【００２４】実施例２ 酸化チタンの量を５重量部、アクリル酸モノマーを２重
量部としたほかは、実施例１と同様にして、顔料を得
た。 Example 2 A pigment was obtained in the same manner as in Example 1 except that the amount of titanium oxide was 5 parts by weight and the acrylic acid monomer was 2 parts by weight.
【００２５】実施例３ 酸化チタンの量を１０重量部としたほかは、実施例２と
同様にして、顔料を得た。 Example 3 A pigment was obtained in the same manner as in Example 2 except that the amount of titanium oxide was 10 parts by weight.
【００２６】実施例４ 酸化チタンの量を２０重量部としたほかは、実施例２と
同様にして、顔料を得た。 Example 4 A pigment was obtained in the same manner as in Example 2 except that the amount of titanium oxide was 20 parts by weight.
【００２７】実施例５ 酸化チタンの量を３０重量部としたほかは、実施例２と
同様にして、顔料を得た。 Example 5 A pigment was obtained in the same manner as in Example 2 except that the amount of titanium oxide was 30 parts by weight.
【００２８】実施例６ 酸化チタンの量を５０重量部としたほかは、実施例２と
同様にして、顔料を得た。 Example 6 A pigment was obtained in the same manner as in Example 2 except that the amount of titanium oxide was 50 parts by weight.
【００２９】比較例１ 容量２０リットルのヘンシェルミキサーにＢＥＴ比表面
積１２ｍ2／ｇの重質炭酸カルシウム４ｋｇを投入後、
撹拌しながらポリアクリル酸ソーダを１重量部噴霧添加
し、そのまま１５分間撹拌を続けて比較試料とした。 Comparative Example 1 4 kg of heavy calcium carbonate having a BET specific surface area of 12 m 2 / g was charged into a Henschel mixer having a capacity of 20 liters,
While stirring, 1 part by weight of sodium polyacrylate was added by spraying, and stirring was continued for 15 minutes to obtain a comparative sample.
【００３０】比較例２ 容量２０リットルのヘンシェルミキサーにＢＥＴ比表面
積１２ｍ2／ｇの重質炭酸カルシウム４ｋｇを投入し
た。この中へあらかじめ別の容器で十分撹拌混合したア
ナターゼ型酸化チタン（石原産業Ａ−２２０）２．５重
量部とアクリル酸モノマー１重量部を徐々に添加し、さ
らに１５分間撹拌を継続して比較試料とした。 Comparative Example 2 4 kg of heavy calcium carbonate having a BET specific surface area of 12 m 2 / g was charged into a Henschel mixer having a capacity of 20 liters. 2.5 parts by weight of anatase-type titanium oxide (Ishihara Sangyo A-220) and 1 part by weight of acrylic acid monomer, which had been sufficiently stirred and mixed in another container, were gradually added to this, and the mixture was further stirred for 15 minutes for comparison. It was used as a sample.
【００３１】比較例３ 酸化チタンの量を５重量部、アクリル酸モノマーを２重
量部としたほかは、比較例２と同様にして、試料を得
た。 Comparative Example 3 A sample was obtained in the same manner as Comparative Example 2 except that the amount of titanium oxide was 5 parts by weight and the acrylic acid monomer was 2 parts by weight.
【００３２】比較例４ 酸化チタンの量を１０重量部としたほかは、比較例３と
同様にして、試料を得た。 Comparative Example 4 A sample was obtained in the same manner as Comparative Example 3 except that the amount of titanium oxide was 10 parts by weight.
【００３３】比較例５ 酸化チタンの量を３０重量部としたほかは、比較例３と
同様にして、試料を得た。 Comparative Example 5 A sample was obtained in the same manner as in Comparative Example 3 except that the amount of titanium oxide was 30 parts by weight.
【００３４】比較例６ 酸化チタンの量を５０重量部としたほかは、比較例３と
同様にして、試料を得た。 Comparative Example 6 A sample was obtained in the same manner as Comparative Example 3 except that the amount of titanium oxide was 50 parts by weight.
【００３５】比較例７ 比較例１のアクリル酸モノマーで処理した重質炭酸カル
シウムに酸化チタンを１０重量部加え、ヘンシェルミキ
サーで１５分間撹拌混合して比較試料とした。 Comparative Example 7 Ten parts by weight of titanium oxide was added to the heavy calcium carbonate treated with the acrylic acid monomer of Comparative Example 1 and stirred and mixed for 15 minutes with a Henschel mixer to prepare a comparative sample.
【００３６】比較例８ 酸化チタンの量を３０重量部としたほかは、比較例７と
同様にして、試料を得た。 Comparative Example 8 A sample was obtained in the same manner as in Comparative Example 7 except that the amount of titanium oxide was 30 parts by weight.
【００３７】比較例９ 酸化チタンの量を５０重量部としたほかは、比較例７と
同様にして、試料を得た。 Comparative Example 9 A sample was obtained in the same manner as in Comparative Example 7 except that the amount of titanium oxide was 50 parts by weight.
【００３８】比較例１０ ＢＥＴ比表面積１２ｍ2／ｇの重質炭酸カルシウムを比
較試料とした。 Comparative Example 10 Heavy calcium carbonate having a BET specific surface area of 12 m 2 / g was used as a comparative sample.
【００３９】比較例１１ ＢＥＴ比表面積１２ｍ2／ｇの重質炭酸カルシウムに酸
化チタンを１０重量部加え、ヘンシェルミキサーで１５
分間撹拌混合して比較試料とした。 Comparative Example 11 10 parts by weight of titanium oxide was added to heavy calcium carbonate having a BET specific surface area of 12 m 2 / g, and 15 parts were added using a Henschel mixer.
The mixture was stirred and mixed for a minute to give a comparative sample.
【００４０】比較例１２ 酸化チタンの量を３０重量部としたほかは、比較例１１
と同様にして試料を得た。 Comparative Example 12 Comparative Example 11 except that the amount of titanium oxide was 30 parts by weight.
A sample was obtained in the same manner as in.
【００４１】以上の実施例、比較例で得られた顔料につ
いての隠蔽力の測定結果とプラスチックに充填剤として
使用した場合の応用物性を表１に示す。なお、隠蔽力の
測定方法、応用物性試験の処方は以下の通りである。Table 1 shows the results of measuring the hiding power of the pigments obtained in the above Examples and Comparative Examples and the applied physical properties when they were used as fillers in plastics. The method for measuring the hiding power and the prescription for the applied physical property test are as follows.
【００４２】隠蔽力の測定方法 試料とフタル酸ジオクチル（ＤＯＰ）を適量混合し、フ
ーバーマーラーでペースト状にしたものをクリプトメー
ター（ＪＩＳ Ｋ５１０１、５４００）を使用して隠蔽
力を測定した。 Method for measuring hiding power The hiding power was measured using a cryptometer (JIS K5101, 5400) prepared by mixing a sample and dioctyl phthalate (DOP) in an appropriate amount and forming a paste with Hoover Mahler.
【００４３】応用物性試験処方 住友ノーブレンＷ１０１ＳなるＰＰを１００重量部と、
各試料を５０重量部とを予備混合後、先ず、２００℃で
１０分間ロール混練し、シート状に取出しペレタイザー
でペレット化して、しかる後、射出成型機により樹脂温
度２３０℃でＡＳＴＭ規格試験片を作成し、下記方法に
従い、白色度、衝撃強さ、伸びを測定したものである。 Applied physical property test formulation 100 parts by weight of PP, Sumitomo Noblen W101S,
After premixing each sample with 50 parts by weight, first, roll kneading at 200 ° C. for 10 minutes, take out into a sheet form and pelletize with a pelletizer, and then, according to an injection molding machine, a resin temperature of 230 ° C. The whiteness, impact strength and elongation were measured according to the following methods.
【００４４】 ・白色度…ＪＩＳ Ｐ８１２３（４５°−０°） ・衝撃強さ…ＡＳＴＭ Ｄ２５６ ・伸び…ＡＳＴＭ Ｄ６３８Whiteness ... JIS P8123 (45 ° -0 °) Impact strength ... ASTM D256 Elongation ... ASTM D638
【００４５】[0045]
【表１】 [Table 1]
【００４６】以上、本発明の優れた効果は明白である。As described above, the excellent effect of the present invention is clear.
Claims (1)
カリ金属塩を処理した後、予めアクリル酸モノマーを吸
着せしめた酸化チタンで粉末同士の混合撹拌をする、炭
酸カルシウム系高隠蔽性白色顔料の製造方法。1. A method for producing a calcium carbonate-based high concealing white pigment, which comprises treating calcium carbonate with an alkali metal salt of polyacrylic acid, and then mixing and stirring the powders with titanium oxide having an acrylic acid monomer adsorbed in advance. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24230392A JPH0693204A (en) | 1992-09-10 | 1992-09-10 | Production of highly masking white pigment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24230392A JPH0693204A (en) | 1992-09-10 | 1992-09-10 | Production of highly masking white pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0693204A true JPH0693204A (en) | 1994-04-05 |
Family
ID=17087223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24230392A Pending JPH0693204A (en) | 1992-09-10 | 1992-09-10 | Production of highly masking white pigment |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0693204A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1415960A2 (en) | 2002-10-30 | 2004-05-06 | Murata Manufacturing Co., Ltd. | Method for making raw dielectric ceramic powder, dielectric ceramic and monolithic ceramic capacitor |
| JP2010280763A (en) * | 2009-06-02 | 2010-12-16 | Okutama Kogyo Co Ltd | Pigment composition for coating |
| JP2012121752A (en) * | 2010-12-07 | 2012-06-28 | Daio Paper Corp | Composite particle, composite particle internally added paper, and coated paper |
-
1992
- 1992-09-10 JP JP24230392A patent/JPH0693204A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1415960A2 (en) | 2002-10-30 | 2004-05-06 | Murata Manufacturing Co., Ltd. | Method for making raw dielectric ceramic powder, dielectric ceramic and monolithic ceramic capacitor |
| EP1415960A3 (en) * | 2002-10-30 | 2006-05-10 | Murata Manufacturing Co., Ltd. | Method for making raw dielectric ceramic powder, dielectric ceramic and monolithic ceramic capacitor |
| JP2010280763A (en) * | 2009-06-02 | 2010-12-16 | Okutama Kogyo Co Ltd | Pigment composition for coating |
| JP2012121752A (en) * | 2010-12-07 | 2012-06-28 | Daio Paper Corp | Composite particle, composite particle internally added paper, and coated paper |
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