JP2004244461A - Colored pigment - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、着色顔料に関し、更に詳しくは、少なくとも表面が多孔質リン酸カルシウム系化合物からなる粒子を母粒子とし、その表面に顔料を担持させた複合体からなり、低シェアで分散させることができ、例えば、インキ用途においては、顔料がパルプとの隙間に埋没するのを防ぐことにより発色性を向上し、樹脂成形品、シーラント、塗料等の用途においても、高い分散性を有するので発色性が向上し、色むらを防止できる着色顔料に関する。
【０００２】
【従来の技術】
例えばインクにおいては、紙に印字した場合、パルプの隙間に顔料が埋没し、発色性の低下の原因となる問題があり、樹脂成形品においても顔料の分散不良による発色性の低下や色むらの問題がある。また、着色顔料を分散させる場合、例えばインクの場合、ボールミル、サンドミルなどの、高シャアの分散機を使用するので、その工程が煩雑になる問題がある。また、層構造型乳化重合体を染料で着色してなる着色樹脂の水性分散体が提案されているが、微細な樹脂粒子にする必要があるため、工程が煩雑になり、また経済的にも問題の残るものである（例えば、特許文献１参照）。
【０００３】
【特許文献１】
特開平５−２５５５６７号公報
【０００４】
【課題を解決するための手段】
本発明者等は、上記問題を解決するために鋭意検討した結果、少なくとも粒子表面が多孔質リン酸カルシウム系化合物からなる粒子を母粒子とし、その表面に顔料を担持させることにより、低シェアで分散し、優れた発色性を有する着色顔料が得られることを見いだし、本発明を完成した。
【０００５】
即ち、本発明の請求項１に係る発明は、少なくとも表面が多孔質リン酸カルシウム系化合物からなる粒子を母粒子とし、その表面に有機顔料、無機顔料から選ばれた少なくとも１種の顔料を母粒子に対して０．１〜８０重量％担持させた複合体からなる着色顔料を内容とする。
【０００６】
本発明の請求項２に係る発明は、顔料の担持量が１〜５０重量％である請求項１記載の着色顔料を内容とする。
【０００７】
本発明の請求項３に係る発明は、顔料の担持量が１０〜３０重量％である請求項１又は２記載の着色顔料を内容とする。
【０００８】
本発明の請求項４に係る発明は、多孔質リン酸カルシウム系化合物の原子比Ｃａ／Ｐが５．５６以下である請求項１〜３のいずれか１項に記載の着色顔料を内容とする。
【０００９】
本発明の請求項５に係る発明は、多孔質リン酸カルシウム系化合物の原子比Ｃａ／Ｐが３．３３以下である請求項１〜４のいずれか１項に記載の着色顔料を内容とする。
【００１０】
本発明の請求項６に係る発明は、多孔質リン酸カルシウム系化合物が化学式Ｃａ１０（ＰＯ４ ）６ ・（ＯＨ）２ のヒドロキシアパタイトである請求項１〜５のいずれか１項に記載の着色顔料を内容とする。
【００１１】
本発明の請求項７に係る発明は、母粒子が下記の式（ａ）〜（ｃ）を満足する粒子からなる請求項１〜６のいずれか１項に記載の着色顔料を内容とする。
（ａ）０．１≦ｄｘ≦２０
（ｂ）２≦Ｖ≦３０
（ｃ）５≦Ｓｗ≦２００
但し、
ｄｘ：電子顕微鏡写真により測定した平均粒子径（μｍ）
Ｖ ：ＪＩＳＫ５１０１−９１ ２０．１ 顔料試験方法の静置法による見掛け比容（ｍｌ／ｇ）
Ｓｗ：窒素吸着法によるＢＥＴ比表面積（ｍ２ ／ｇ）
【００１２】
本発明の請求項８に係る発明は、母粒子が下記の式（ｄ）〜（ｆ）を満足する粒子からなる請求項１〜７のいずれか１項に記載の着色顔料を内容とする。
（ｄ）０．１≦ｄｘ≦１０
（ｅ）５≦Ｖ≦２０
（ｆ）５≦Ｓｗ≦１５０
但し、ｄｘ、Ｖ、Ｓｗは請求項７に記載のものと同じ。
【００１３】
本発明の請求項９に係る発明は、母粒子が下記の式（ｇ）及び（ｈ）を満足する粒子からなる請求項１〜８いずれか１項に記載の着色顔料を内容とする。
（ｇ）１≦α≦３ 但し、α＝ｄ５０／ｄｘ
（ｈ）０≦β≦３ 但し、β＝（ｄ９０−ｄ１０）／ｄ５０
ｄｘ ：電子顕微鏡写真により測定した平均粒子径（μｍ）
α ：分散係数
ｄ５０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子の５０％平均粒子径（μｍ）。
β ：シャープネス。
ｄ９０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子のふるい通過側累計９０％粒子径（μｍ）。
ｄ１０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子のふるい通過側累計１０％粒子径（μｍ）。
【００１４】
本発明の請求項１０に係る発明は、母粒子が下記の式（ｉ）及び（ｊ）を満足する請求項１〜９いずれか１項に記載の着色顔料を内容とする。
（ｉ）１≦α≦２
（ｊ）０≦β≦２
但し、α、βは請求項９に記載のものと同じ。
【００１５】
本発明の請求項１１に係る発明は、母粒子が脂肪酸、脂肪酸の金属塩、脂肪酸のアンモニウム塩、脂肪酸エステルから選ばれた少なくとも１種の界面活性剤を表面コーティングした粒子からなる請求項１〜１０のいずれか１項に記載の着色顔料を内容とする。
【００１６】
本発明の請求項１２に係る発明は、界面活性剤の表面コーティング量が、粒子に対して０．１〜４０重量％である請求項１１のいずれか１項に記載の着色顔料を内容とする。
【００１７】
本発明の請求項１３に係る発明は、界面活性剤の表面コーティング量が、粒子に対し５〜３０重量％である請求項１１又は１２記載の着色顔料を内容とする。
【００１８】
【発明の実施の形態】
本発明の着色顔料は、少なくとも表面が多孔質リン酸カルシウム系化合物からなる粒子を母粒子とし、その表面に顔料を母粒子に対して０．１〜８０重量％担持させた複合体からなることを特徴とする。
【００１９】
本発明の着色顔料の最も重要な特徴は、少なくとも表面が多孔質リン酸カルシウム系化合物からなる粒子を母粒子とすることであり、これにより多孔質部分に所定量の顔料を確実に担持させることができる。また、多孔質構造を有することから、粒子の見掛け比容が高いため、少量の使用で有機顔料及び無機顔料が担持される表面積が充分に確保できる。
【００２０】
本発明における母粒子を構成する粒子の表面は、多孔質リン酸カルシウム系化合物であり、粒子径の調整が容易で、優れた分散性、均一性を有し、粒子の安定性等から、化学式Ｃａ１０（ＰＯ４ ）６ ・（ＯＨ）２ のヒドロキシアパタイトであることが好ましい。リン酸カルシウム系化合物のＣａ／Ｐの原子比は、多孔質構造による見掛け比容、比表面積の高さという観点から、５．５６以下が好ましく、３．３３以下がさらに好ましい。
【００２１】
本発明の着色顔料の母粒子を構成する粒子の平均粒子径ｄｘ（μｍ）は、特に制限はないが、０．１≦ｄｘ≦２０が好ましく、０．１≦ｄｘ≦１０がさらに好ましい。０．１μｍ未満の場合、凝集の原因となり、インクの場合、パルプの隙間に着色顔料が埋没してしまい発色性の低下や色むらになる傾向にある。また、２０μｍを越える場合、着色顔料が沈降、凝固してしまい静置安定性が低下するだけでなく、粒子が大きすぎるため、色むらや、樹脂成形品の表面荒れを起こす傾向にある。尚、平均粒子径ｄｘは、走査型電子顕微鏡を用いて、異なった視野から約１００個の単粒子と認めることが出来る粒子のみを計測した。測定粒子径は定方向径について測定し、このようにして得られた粒子径から求めた個数平均径である。但し、一次粒子が針状・柱状ないし不定形の場合は、一つの一次粒子の最長径と最短径の積の平方根をｄｘとする。
【００２２】
本発明の母粒子を構成する粒子の見掛け比容Ｖ（ｍｌ／ｇ）は、特に制限はないが、２≦Ｖ≦３０が好ましく、５≦Ｖ≦２０がさらに好ましい。３０ｍｌ／ｇを越える場合、樹脂等と混合がしずらく、分散性の低下の原因となり、粉塵等のハンドリング面での問題が起こる傾向にある。また、２ｍｌ／ｇ未満の場合は、粒子個数が少なくなり、少量添加では充分な効果が得られない傾向にある。
【００２３】
本発明の母粒子を構成する粒子のＢＥＴ比表面積Ｓｗ（ｍ２ ／ｇ）は、特に制限はないが、５≦Ｓｗ≦２００が好ましく、５≦Ｓｗ≦１５０がさらに好ましい。５ｍ２ ／ｇ未満の場合、顔料が十分に担持できない傾向にあり、２００ｍｇ／ｇを越える場合、顔料を担持しても母粒子の表面が露出してしまう傾向にある。
【００２４】
本発明の母粒子を構成する粒子の分散係数αは、特に限定はないが、１≦α≦３が好ましく、１≦α≦２がさらに好ましい。αが３を越える場合、また、αが１未満の場合、粒子の凝集が起こり、粒子径が不均一になるので、発色性の低下、色むらになる傾向にある。
【００２５】
本発明の母粒子を構成する粒子のシャープネスβは、特に限定はないが、０≦β≦３が好ましく、０≦β≦２がさらに好ましい。βが２を越える場合、粒度分布がブロードになり、微小粒子及び粗大粒子の含有率が多くなるため、分散性が低下する傾向にある。
【００２６】
本発明の母粒子を構成する粒子は、分散性の向上等の目的で表面処理剤により表面コーティングすることができる。表面処理剤は特に限定されないが、脂肪酸、その金属塩、そのアンモニウム塩、脂肪酸エステルから選ばれた少なくとも１種の界面活性剤を表面コーティングしたものが好ましい。
脂肪酸としては、例えば、Ｃ＝８以上のラウリン酸（Ｃ＝１２）、ミリスチン酸（Ｃ＝１４）、パルミチン酸（Ｃ＝１６）、ステアリン酸（Ｃ＝１８）等が挙げられる。それら脂肪酸の金属塩としては、例えば、Ｎａ、Ｋ、Ｌｉ等のアルカリ金属が好ましく、その他、Ａｌ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ等の金属塩も使用できる。脂肪酸エステルとしては、例えば、ステアリン酸ステアレート、ステアリン酸ラウレート、パルミチン酸ステアレート、パルミチン酸ラウレート、また一価のアルコールから生成されるエステルのみならず、グリセリン等の多価アルコールから生成する脂肪酸エステルも挙げられる。これらは１種又は２種以上組み合わせて用いられる。
多孔質構造を有するものや、比表面積が高い粒子を少量添加で均一にコーティングする場合、例えば脂肪酸では、ラウリン酸等低分子量のものが好ましい場合がある。
またその表面コーティング量は、特に限定はないが、粒子表面を均一にコーティングするという観点から、粒子に対して０．１〜４０重量％が好ましく、５〜３０重量％がさらに好ましい。
【００２７】
また、粒子の分散性、安定性等をさらに高めるために、シランカップリング剤やチタネートカップリング剤等のカッリング剤、有機酸、例えば、樹脂酸、アクリル酸等のα、βモノエチレン性不飽和カルボン酸及び、そのエステル類、シュウ酸、クエン酸、酒石酸等の有機酸、フッ酸等の無機酸、それらの重合物及び共重合物、それらの塩、又はヘキサメタリン酸ソーダ、ピロリン酸、ピロリン酸ソーダ、トリポリリン酸、トリポリリン酸ソーダ、トリメタリン酸、ハイポリリン酸等の縮合リン酸及びその塩等を、常法に従い添加又は表面コーティングしてもさしつかえない。添加量又は表面コーティング量は、０．０１〜５０重量％が好ましい。０．０１未満では効果が充分でなく、一方、５０重量％を超えると、凝集の原因となり、機械的物性が低下する傾向にある。
【００２８】
上記の如き本発明の母粒子を構成する粒子は、例えば、表１に記載の混合条件により得られるが、平均粒子径ｄｘ、見掛け比容Ｖ、ＢＥＴ比表面積Ｗ、分散係数α、シャープネスβをコントロールする際に、特に大きく影響する混合条件としては、混合、熟成時の撹拌羽根周速、Ｃａ／Ｐの原子比である。撹拌羽根周速が低すぎた場合、混合、熟成時に凝集が起こり、平均粒子径ｄｘが大きくなりすぎたり、分散係数α、シャープネスβにも悪影響を及ぼし、撹拌羽根周速が高すぎる場合、撹拌力によって水懸濁液温度が急激に上昇してしまい、反応系の温度コントロールが困難になるだけでなく、製造コストにも大きく影響する。また、Ｃａ／Ｐの原子比が高すぎた場合、粒子に占める多孔質構造を有するリン酸カルシウム系化合物の割合が小さくなるため、見掛け比容Ｖ及びがＢＥＴ比表面積Ｗ低下してしまい、Ｃａ／Ｐの原子比が低すぎた場合、多孔質リン酸カルシウム系化合物粒子自体が形成できなくなる傾向にある。
【００２９】
本発明の着色顔料に使用される顔料は、有機顔料、無機顔料から選ばれる。これらの顔料には、特に限定はないが、例えば、アゾレーキ、不溶性アゾ顔料、縮合アゾ顔料、キレートアゾ顔料などのアゾ顔料、フタロシアニン顔料、ペリレン顔料、チオインジゴ顔料、イソインドリノン顔料、キノフタロン顔料などの多環式顔料類、染料キレートなどの各種有機顔料や、ベンガラ、酸化クロム、鉄黒などの酸化物、カドミウムイエロー、クロムバーミリオン、紺青、群青、黄色酸化鉄などの各種無機顔料や、カーボンブラックなどがあげられ、これらは単独でまたは２種以上を混合して用いることができる。
【００３０】
顔料の母粒子への把持量は母粒子に対して０．１〜８０重量％であり、より好ましくは、１〜５０重量％、更に好ましくは、１０〜３０重量％である。０．１重量％未満の場合、母粒子を多量に使用しないと着色効果が発揮されないため、インク、塗料の粘度上昇、樹脂成形品の強度低下、表面の荒れ等の物性面に悪影響を及ぼすので好ましくない。８０重量％を越えた場合、母粒子が顔料を完全に担持しきれないので発色性の低下、インクや塗料中での沈降、凝集の原因となるので好ましくない。
また、顔料の母粒子への担持方法は特に限定はないが、例えばヘンシェルミキサーやタンブラーミキサー等の混合機に、まず所定量の母粒子を添加し、撹拌しながら所定量の顔料を添加し１０〜３０分程度撹拌すればよい。
【００３１】
【実施例】
以下に本発明を実施例を挙げてさらに詳しく説明するが、本発明は、その要旨を越えない限り、かかる実施例に制限されるものではない。
【００３２】
（本発明の着色顔料の母粒子の調製）
炭酸カルシウムの水懸濁液分散体ａ：
比重１．０５５で温度が８℃の石灰乳（水酸化カルシウムの水懸濁液）７０００リッターに、炭酸ガス濃度２７重量％の炉ガスを２４ｍ３ の流速で導通しｐＨ９まで炭酸化反応を行い、その後４０〜５０℃で５時間撹拌熟成を行うことにより粒子間のアルカリを溶出させｐＨ１０．８として分散させ、電子顕微鏡写真より測定した平均粒子径０．０５μｍで粒度分布測定器（（株）島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径が０．４８μｍ である炭酸カルシウムの水懸濁液分散体を調製した。
【００３３】
炭酸カルシウムの水懸濁液分散体ｂ：
丸尾カルシウム（株）製重質炭酸カルシウム「スーパーＳＳＳ」（１．２ｍ２／ｇ ）に水を添加混合後、ＴＫホモミキサー（５０００ｒｐｍ、１５分間）にて撹拌分散させて固形分濃度２５％の電子顕微鏡写真より測定した平均粒子径３μｍで粒度分布測定器（（株）島津製作所製ＳＡ−ＣＰ３）により測定した平均粒子径が３．４μｍ である炭酸カルシウムの水懸濁液分散体ｂを調製した。
【００３４】
上記の炭酸カルシウムの水懸濁液とリン酸の希釈水溶液を表１に記載の混合条件で混合反応させた後、常法で表面処理、脱水、乾燥後、解砕を行った。得られた粒子Ｄ１〜Ｄ５、及び、市販の珪酸カルシウム（商品名：フローライト、トクヤマ製）Ｄ６、市販のヒドロキシアパタイト（商品名：リン酸三カルシウム、太平化学産業製）Ｄ７、市販の炭酸カルシウム（商品名：重質炭酸カルシウム、丸尾カルシウム製）Ｄ８の粉体物性を表２に示す。
また、粒子表面を比較するために、粒子Ｄ１と市販のヒドロキシアパタイト粒子Ｄ７の粒子構造を示す電子顕微鏡写真をそれぞれ図１、図２に示す。図１、図２より、粒子Ｄ１は多孔質構造を有しているのに対し、市販のヒドロキシアパタイト粒子Ｄ７は微細な粒子の凝集物であり、多孔質構造を有するものではないことが確認される。
【００３５】
【表１】
【表２】
実施例１〜１２
母粒子として、粒子Ｄ１〜Ｄ５を、ヘンシェルミキサー（カワタ製：スーパーミキサーＳＭＧ−２００）に３ｋｇ投入し、４００ｒｐｍで撹拌しながら、黄色顔料（ピグメントイエロー１４（Ｃ．Ｉ．２１０９５））を６００ｇ投入した後、９００ｒｐｍで２０分間撹拌し着色顔料Ｃ１〜Ｃ１２を得た。
【００３８】
比較例１〜１０
母粒子として、粒子Ｄ１を用いて、上記黄色顔料を３ｇ及び２５００ｇにする以外は実施例と同様に混合撹拌し、着色顔料Ｃ１３、Ｃ１４を得た。
また母粒子として、粒子Ｄ１、Ｄ５〜Ｄ８を使用する以外は実施例と同様に混合撹拌し、着色顔料Ｃ１５〜Ｃ２２を得た。
【００３９】
【表３】
応用例１〜１２、応用比較例１〜１０
実施例１〜１２の着色顔料Ｃ１〜Ｃ１２、比較例１〜１０の着色顔料Ｃ１３〜Ｃ２２を２０重量部、スチレン−アクリル酸共重合体（酸価：１００、アンモニア水中和、固形分：２５重量％）２０重量部、エチレングリコール５重量部、イオン交換水５５重量部をディゾルバー３４００ｒｐｍで１時間撹拌し顔料分散液を得た。これら顔料分散液に３０重量％水溶性カルボンイミド５部を添加し９０℃で５時間撹拌した後、モノエタノールアミンでｐＨ８．５、固形分濃度２０重量％となるように調整し、黄色顔料分散液を得た。これら黄色顔料分散液１５重量部、ジエチレングリコール１５重量部、２−ピロリドン１０重量部、グリセリン５重量部、ベンズイソチアゾリン０．１重量部、イオン交換水５４重量部を３０分間撹拌しインクを得た。
これらのインクについて、印字の発色性について試験を行った。即ち、普通紙のＰＰＣ用紙（コクヨ製）に得られたインクを用いて印刷した印字の発色状態を目視にて観察し、下記の基準で評価した。なお、印字は、市販のインクジェットプリンター（キャノン製、ＢＪ−２００）を用いて行った。評価結果を表４に示す。
◎：極めて良好
○：良好
△：やや不良
×不良
【００４１】
【表４】
応用例１３〜２４、応用比較例１１〜２０
実施例１〜１２の着色顔料Ｃ１〜Ｃ１２、比較例１〜１０の着色顔料Ｃ１３〜Ｃ２２を２０ｇとポリプロピレン樹脂ペレット１０ｋｇをブレンドしたものを混練押し出し機で混練し、該徐放体を配合したポリプロピレン樹脂ペレットを得た。このペレットを射出成形法にて、ポリプロピレン成形品を得た。
これら成形品の外観（発色性、色むら、分散性）を目視にて観察し、下記の基準で評価した。評価結果を表５に示す。
◎：極めて良好
○：良好
△：やや不良
×不良
【００４３】
【表５】
【発明の効果】
叙上のとおり、本発明の着色顔料は、少なくとも粒子表面が多孔質リン酸カルシウム系化合物からなる粒子を母粒子とし、その表面に顔料を担持させることにより、低シェアで分散し、優れた発色性を有する。
【図面の簡単な説明】
【図１】粒子Ｄ１の電子顕微鏡写真（１０，０００倍）である。
【図２】市販のヒドロキシアパタイト粒子Ｄ７の電子顕微鏡写真（１０，０００倍）である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a coloring pigment, and more specifically, at least a surface of which is composed of a porous calcium phosphate-based compound as a base particle, is composed of a composite having a pigment supported on the surface thereof, and can be dispersed at a low share. For example, in ink applications, color development is improved by preventing pigments from being buried in gaps with pulp, and in applications such as resin moldings, sealants, and paints, high dispersibility improves color development. And a colored pigment capable of preventing color unevenness.
[0002]
[Prior art]
For example, in the case of ink, when printing on paper, there is a problem that the pigment is buried in the gaps of the pulp and causes a decrease in the color developing property. There's a problem. In the case of dispersing the coloring pigment, for example, in the case of ink, a high-sharing dispersing machine such as a ball mill or a sand mill is used, so that there is a problem that the process becomes complicated. Further, an aqueous dispersion of a colored resin obtained by coloring the layer structure type emulsion polymer with a dye has been proposed, but since it is necessary to make fine resin particles, the process becomes complicated and also economically. The problem remains (for example, see Patent Document 1).
[0003]
[Patent Document 1]
JP-A-5-255567
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above problems, and as a result, at least a particle surface is made of a porous calcium phosphate-based compound as a base particle, and by supporting a pigment on the surface, the particles are dispersed at a low share. It has been found that a color pigment having excellent coloring properties can be obtained, and the present invention has been completed.
[0005]
That is, the invention according to claim 1 of the present invention is characterized in that at least one surface is made of particles made of a porous calcium phosphate-based compound, and at least one pigment selected from organic pigments and inorganic pigments is made into mother particles. On the other hand, the content is a coloring pigment composed of a composite loaded with 0.1 to 80% by weight.
[0006]
The invention according to claim 2 of the present invention includes the colored pigment according to claim 1, wherein the amount of the pigment carried is 1 to 50% by weight.
[0007]
The invention according to claim 3 of the present invention includes the colored pigment according to claim 1 or 2, wherein the amount of the pigment carried is 10 to 30% by weight.
[0008]
The invention according to claim 4 of the present invention includes the coloring pigment according to any one of claims 1 to 3, wherein the atomic ratio Ca / P of the porous calcium phosphate compound is 5.56 or less.
[0009]
The invention according to claim 5 of the present invention includes the coloring pigment according to any one of claims 1 to 4, wherein the atomic ratio Ca / P of the porous calcium phosphate compound is 3.33 or less.
[0010]
The invention according to claim 6 of the present invention is the coloring pigment according to any one of claims 1 to 5, wherein the porous calcium phosphate-based compound is hydroxyapatite having a chemical formula of Ca 10 (PO 4 ) 6. (OH) 2. The contents.
[0011]
The invention according to claim 7 of the present invention includes the coloring pigment according to any one of claims 1 to 6, wherein the base particles are particles satisfying the following formulas (a) to (c).
(A) 0.1 ≦ dx ≦ 20
(B) 2 ≦ V ≦ 30
(C) 5 ≦ Sw ≦ 200
However,
dx: average particle diameter (μm) measured by electron micrograph
V: JIS K5101-91 20.1 Apparent specific volume (ml / g) by static test of pigment test method
Sw: BET specific surface area by nitrogen adsorption method (m 2 / g)
[0012]
The invention according to claim 8 of the present invention includes the coloring pigment according to any one of claims 1 to 7, wherein the base particles are particles satisfying the following formulas (d) to (f).
(D) 0.1 ≦ dx ≦ 10
(E) 5 ≦ V ≦ 20
(F) 5 ≦ Sw ≦ 150
However, dx, V, and Sw are the same as those described in claim 7.
[0013]
The invention according to claim 9 of the present invention includes the color pigment according to any one of claims 1 to 8, wherein the base particles are particles satisfying the following formulas (g) and (h).
(G) 1 ≦ α ≦ 3, where α = d50 / dx
(H) 0 ≦ β ≦ 3 where β = (d90−d10) / d50
dx: average particle diameter (μm) measured by electron micrograph
α: Dispersion coefficient d50: 50% average particle diameter (μm) of particles measured by a Microtrac FRA laser type particle size distribution meter.
β: sharpness.
d90: 90% total particle diameter (μm) of particles passing through the sieve measured by a Microtrac FRA laser type particle size distribution analyzer.
d10: Total 10% particle diameter (μm) of particles passing through the sieve measured by a Microtrac FRA laser type particle size distribution meter.
[0014]
The invention according to claim 10 of the present invention includes the coloring pigment according to any one of claims 1 to 9 in which the base particles satisfy the following formulas (i) and (j).
(I) 1 ≦ α ≦ 2
(J) 0 ≦ β ≦ 2
However, α and β are the same as those described in claim 9.
[0015]
In the invention according to claim 11 of the present invention, the mother particles are particles coated with at least one surfactant selected from fatty acids, metal salts of fatty acids, ammonium salts of fatty acids, and fatty acid esters. 10. The coloring pigment according to any one of items 10 to 10.
[0016]
The invention according to claim 12 of the present invention includes the color pigment according to any one of claims 11 to 11, wherein the surface coating amount of the surfactant is 0.1 to 40% by weight based on the particles. .
[0017]
The invention according to claim 13 of the present invention includes the color pigment according to claim 11 or 12, wherein the surface coating amount of the surfactant is 5 to 30% by weight based on the particles.
[0018]
BEST MODE FOR CARRYING OUT THE INVENTION
The coloring pigment of the present invention is characterized in that at least the surface is composed of a composite in which particles composed of a porous calcium phosphate compound are used as base particles, and the pigment is supported on the surface in an amount of 0.1 to 80% by weight based on the base particles. And
[0019]
The most important feature of the coloring pigment of the present invention is that at least the surface is made of particles composed of a porous calcium phosphate-based compound as mother particles, whereby a predetermined amount of the pigment can be surely carried on the porous portion. . Further, since the particles have a porous structure, the apparent specific volume of the particles is high, so that a small amount of use can sufficiently secure the surface area on which the organic pigment and the inorganic pigment are supported.
[0020]
The surface of the particles constituting the base particles in the present invention is a porous calcium phosphate-based compound, the particle diameter of which is easily adjusted, has excellent dispersibility and uniformity, and has the chemical formula Ca 10 (PO 4 ) 6. (OH) 2 is preferably hydroxyapatite. The atomic ratio of Ca / P of the calcium phosphate compound is preferably 5.56 or less, more preferably 3.33 or less, from the viewpoint of apparent specific volume due to the porous structure and the height of the specific surface area.
[0021]
The average particle diameter dx (μm) of the particles constituting the base particles of the color pigment of the present invention is not particularly limited, but is preferably 0.1 ≦ dx ≦ 20, and more preferably 0.1 ≦ dx ≦ 10. When the thickness is less than 0.1 μm, it causes agglomeration, and in the case of ink, the coloring pigment is buried in the gaps of the pulp, which tends to cause a decrease in color development and uneven color. On the other hand, if it exceeds 20 μm, the color pigments settle and solidify, and not only the stability during standing is reduced, but also because the particles are too large, color unevenness and surface roughness of the resin molded article tend to occur. The average particle diameter dx was measured using a scanning electron microscope for only particles that could be recognized as about 100 single particles from different visual fields. The measurement particle diameter is a number average diameter measured from the diameter in a fixed direction and determined from the particle diameter thus obtained. However, when the primary particles are acicular, columnar or irregular, the square root of the product of the longest diameter and the shortest diameter of one primary particle is dx.
[0022]
The apparent specific volume V (ml / g) of the particles constituting the base particles of the present invention is not particularly limited, but is preferably 2 ≦ V ≦ 30, more preferably 5 ≦ V ≦ 20. If it exceeds 30 ml / g, it is difficult to mix with a resin or the like, which causes a reduction in dispersibility, and there is a tendency that problems in handling such as dusts occur. If it is less than 2 ml / g, the number of particles tends to be small, and a small amount tends to fail to provide a sufficient effect.
[0023]
The BET specific surface area Sw (m 2 / g) of the particles constituting the base particles of the present invention is not particularly limited, but is preferably 5 ≦ Sw ≦ 200, more preferably 5 ≦ Sw ≦ 150. When it is less than 5 m 2 / g, the pigment tends not to be sufficiently supported, and when it exceeds 200 mg / g, the surface of the base particles tends to be exposed even when the pigment is supported.
[0024]
The dispersion coefficient α of the particles constituting the base particles of the present invention is not particularly limited, but is preferably 1 ≦ α ≦ 3, and more preferably 1 ≦ α ≦ 2. If α exceeds 3, or if α is less than 1, particles will aggregate and the particle diameter will be non-uniform, which tends to cause a decrease in color development and uneven color.
[0025]
The sharpness β of the particles constituting the base particles of the present invention is not particularly limited, but is preferably 0 ≦ β ≦ 3, and more preferably 0 ≦ β ≦ 2. If β exceeds 2, the particle size distribution becomes broad and the content of fine particles and coarse particles increases, so that the dispersibility tends to decrease.
[0026]
The particles constituting the base particles of the present invention can be surface-coated with a surface treating agent for the purpose of improving dispersibility and the like. The surface treatment agent is not particularly limited, but is preferably a surface-coated surface of at least one surfactant selected from fatty acids, metal salts thereof, ammonium salts thereof, and fatty acid esters.
Examples of the fatty acid include lauric acid having C = 8 or more (C = 12), myristic acid (C = 14), palmitic acid (C = 16), and stearic acid (C = 18). As metal salts of these fatty acids, for example, alkali metals such as Na, K, and Li are preferable, and metal salts such as Al, Mn, Fe, Co, Ni, Cu, and Zn can also be used. Examples of the fatty acid ester include stearic acid stearate, stearic acid laurate, palmitic acid stearate, palmitic acid laurate, and esters formed from monohydric alcohols, as well as fatty acid esters formed from polyhydric alcohols such as glycerin. Are also mentioned. These are used alone or in combination of two or more.
In the case of uniformly coating a substance having a porous structure or particles having a high specific surface area by adding a small amount, for example, a fatty acid having a low molecular weight such as lauric acid may be preferable.
The surface coating amount is not particularly limited, but is preferably from 0.1 to 40% by weight, more preferably from 5 to 30% by weight based on the particles, from the viewpoint of uniformly coating the particle surface.
[0027]
Further, in order to further enhance the dispersibility, stability, etc. of the particles, a coupling agent such as a silane coupling agent or a titanate coupling agent, an organic acid, for example, a resin acid, α, β monoethylenically unsaturated such as acrylic acid, etc. Carboxylic acids and esters thereof, organic acids such as oxalic acid, citric acid, tartaric acid, inorganic acids such as hydrofluoric acid, their polymers and copolymers, their salts, or sodium hexametaphosphate, pyrophosphoric acid, and pyrophosphoric acid Condensed phosphoric acid such as soda, tripolyphosphoric acid, sodium tripolyphosphate, trimetaphosphoric acid, and high polyphosphoric acid, and salts thereof may be added or surface-coated according to a conventional method. The addition amount or the surface coating amount is preferably 0.01 to 50% by weight. If it is less than 0.01, the effect is not sufficient. On the other hand, if it exceeds 50% by weight, it causes agglomeration and the mechanical properties tend to decrease.
[0028]
The particles constituting the base particles of the present invention as described above can be obtained, for example, under the mixing conditions shown in Table 1. However, the average particle diameter dx, apparent specific volume V, BET specific surface area W, dispersion coefficient α, and sharpness β The mixing conditions that greatly affect the control are the peripheral speed of the stirring blade during mixing and aging, and the atomic ratio of Ca / P. If the stirring blade peripheral speed is too low, agglomeration occurs during mixing and maturation, the average particle diameter dx becomes too large, and the dispersion coefficient α and the sharpness β are also adversely affected.If the stirring blade peripheral speed is too high, stirring occurs. The force causes the water suspension temperature to rise rapidly, which not only makes it difficult to control the temperature of the reaction system, but also greatly affects the production cost. If the atomic ratio of Ca / P is too high, the ratio of the calcium phosphate-based compound having a porous structure to the particles becomes small, so that the apparent specific volume V and the BET specific surface area W decrease, and Ca / P If the atomic ratio is too low, the porous calcium phosphate compound particles tend to be unable to form.
[0029]
The pigment used for the coloring pigment of the present invention is selected from organic pigments and inorganic pigments. Although there is no particular limitation on these pigments, for example, azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, chelate azo pigments, phthalocyanine pigments, perylene pigments, thioindigo pigments, isoindolinone pigments, quinophthalone pigments, etc. Various organic pigments such as cyclic pigments and dye chelates, oxides such as red iron oxide, chromium oxide and iron black, various inorganic pigments such as cadmium yellow, chrome vermilion, navy blue, ultramarine blue, yellow iron oxide, and carbon black These can be used alone or in combination of two or more.
[0030]
The amount of the pigment to be gripped by the base particles is from 0.1 to 80% by weight, preferably from 1 to 50% by weight, and more preferably from 10 to 30% by weight, based on the base particles. If the content is less than 0.1% by weight, the coloring effect is not exhibited unless a large amount of the base particles are used, so that the physical properties such as an increase in the viscosity of the ink and the paint, a decrease in the strength of the resin molded product, and a rough surface are adversely affected. Not preferred. If the amount exceeds 80% by weight, the base particles cannot completely support the pigment, which causes a decrease in color development, sedimentation in ink or paint, and aggregation, which is not preferable.
The method of supporting the pigment on the base particles is not particularly limited. For example, a predetermined amount of the base particles is first added to a mixer such as a Henschel mixer or a tumbler mixer, and a predetermined amount of the pigment is added while stirring. It may be stirred for about 30 minutes.
[0031]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to such Examples unless it exceeds the gist.
[0032]
(Preparation of mother particles of coloring pigment of the present invention)
Aqueous suspension dispersion of calcium carbonate a:
A furnace gas having a carbon dioxide gas concentration of 27% by weight was passed through 7000 liters of lime milk (aqueous suspension of calcium hydroxide) at a specific gravity of 1.055 and a temperature of 8 ° C. at a flow rate of 24 m 3 to carry out a carbonation reaction to pH 9. Then, the mixture is stirred and aged at 40 to 50 ° C. for 5 hours to elute the alkali between the particles, disperse the mixture to a pH of 10.8, and measure the particle size distribution with an average particle size of 0.05 μm measured from an electron micrograph (trade name). An aqueous suspension dispersion of calcium carbonate having an average particle diameter of 0.48 μm measured by Shimadzu SA-CP3) was prepared.
[0033]
Aqueous suspension dispersion of calcium carbonate b:
After adding and mixing water to heavy calcium carbonate “Super SSS” (1.2 m 2 / g) manufactured by Maruo Calcium Co., Ltd., the mixture was stirred and dispersed with a TK homomixer (5000 rpm, 15 minutes) to obtain a solid content of 25%. An aqueous suspension dispersion b of calcium carbonate having an average particle diameter of 3 μm measured from an electron micrograph and an average particle diameter of 3.4 μm measured by a particle size distribution analyzer (SA-CP3 manufactured by Shimadzu Corporation) is prepared. did.
[0034]
After the above-mentioned aqueous suspension of calcium carbonate and the diluted aqueous solution of phosphoric acid were mixed and reacted under the mixing conditions shown in Table 1, surface treatment, dehydration, drying and crushing were carried out in a conventional manner. Obtained particles D1 to D5, commercially available calcium silicate (trade name: Florite, manufactured by Tokuyama) D6, commercially available hydroxyapatite (trade name: tricalcium phosphate, manufactured by Taihei Chemical Industry) D7, commercially available calcium carbonate (Product name: heavy calcium carbonate, manufactured by Maruo Calcium) Table 2 shows the powder properties of D8.
In addition, in order to compare the particle surfaces, electron micrographs showing the particle structures of the particles D1 and the commercially available hydroxyapatite particles D7 are shown in FIGS. 1 and 2, respectively. From FIG. 1 and FIG. 2, it is confirmed that the particle D1 has a porous structure, whereas the commercially available hydroxyapatite particles D7 are aggregates of fine particles and do not have a porous structure. You.
[0035]
[Table 1]
[Table 2]
Examples 1 to 12
3 kg of the particles D1 to D5 as a base particle are put into a Henschel mixer (manufactured by Kawata: Super Mixer SMG-200), and 600 g of a yellow pigment (Pigment Yellow 14 (CI. 21095)) is charged while stirring at 400 rpm. After that, the mixture was stirred at 900 rpm for 20 minutes to obtain coloring pigments C1 to C12.
[0038]
Comparative Examples 1 to 10
Using the particles D1 as the base particles, mixing and stirring were performed in the same manner as in the example except that the amount of the yellow pigment was changed to 3 g and 2500 g, thereby obtaining coloring pigments C13 and C14.
In addition, mixing and stirring were performed in the same manner as in the example except that particles D1 and D5 to D8 were used as mother particles, to obtain coloring pigments C15 to C22.
[0039]
[Table 3]
Application Examples 1 to 12, Application Comparative Examples 1 to 10
20 parts by weight of the color pigments C1 to C12 of Examples 1 to 12 and C13 to C22 of Comparative Examples 1 to 10, a styrene-acrylic acid copolymer (acid value: 100, neutralized with ammonia water, solid content: 25% by weight) %) 20 parts by weight of ethylene glycol, 5 parts by weight of ethylene glycol, and 55 parts by weight of ion-exchanged water were stirred with a dissolver 3400 rpm for 1 hour to obtain a pigment dispersion. 5 parts of a 30% by weight water-soluble carboxylic imide was added to these pigment dispersions, and the mixture was stirred at 90 ° C. for 5 hours, and then adjusted with monoethanolamine to pH 8.5 and a solid content concentration of 20% by weight. A liquid was obtained. 15 parts by weight of the yellow pigment dispersion, 15 parts by weight of diethylene glycol, 10 parts by weight of 2-pyrrolidone, 5 parts by weight of glycerin, 0.1 parts by weight of benzisothiazoline and 54 parts by weight of ion-exchanged water were stirred for 30 minutes to obtain an ink.
These inks were tested for print color development. That is, the state of color development of prints printed using ink obtained on plain PPC paper (manufactured by KOKUYO) was visually observed, and evaluated according to the following criteria. In addition, printing was performed using a commercially available inkjet printer (manufactured by Canon, BJ-200). Table 4 shows the evaluation results.
：: extremely good ：: good や: slightly bad x bad
[Table 4]
Application Examples 13 to 24, Application Comparative Examples 11 to 20
A blend of 20 g of the color pigments C1 to C12 of Examples 1 to 12 and the color pigments C13 to C22 of Comparative Examples 1 to 10 and 10 kg of polypropylene resin pellets is kneaded by a kneading extruder, and the polypropylene is blended with the sustained-release body. A resin pellet was obtained. The pellet was obtained by injection molding to obtain a polypropylene molded product.
The appearance (coloring properties, uneven coloring, dispersibility) of these molded articles was visually observed and evaluated according to the following criteria. Table 5 shows the evaluation results.
：: extremely good ○: good や: slightly bad x bad
[Table 5]
【The invention's effect】
As described above, the coloring pigment of the present invention has a particle having at least a particle surface made of a porous calcium phosphate compound as a base particle, and the pigment is supported on the surface, thereby dispersing at a low share, and exhibiting excellent coloring properties. Have.
[Brief description of the drawings]
FIG. 1 is an electron micrograph (× 10,000) of a particle D1.
FIG. 2 is an electron micrograph (× 10,000) of commercially available hydroxyapatite particles D7.
Claims (13)
（ａ）０．１≦ｄｘ≦２０
（ｂ）２≦Ｖ≦３０
（ｃ）５≦Ｓｗ≦２００
但し、
ｄｘ：電子顕微鏡写真により測定した平均粒子径（μｍ）
Ｖ ：ＪＩＳＫ５１０１−９１ ２０．１ 顔料試験方法の静置法による見掛け比容（ｍｌ／ｇ）
Ｓｗ：窒素吸着法によるＢＥＴ比表面積（ｍ２ ／ｇ）The coloring pigment according to any one of claims 1 to 6, wherein the base particles are particles satisfying the following formulas (a) to (c).
(A) 0.1 ≦ dx ≦ 20
(B) 2 ≦ V ≦ 30
(C) 5 ≦ Sw ≦ 200
However,
dx: average particle diameter (μm) measured by electron micrograph
V: JIS K5101-91 20.1 Apparent specific volume (ml / g) by static test of pigment test method
Sw: BET specific surface area by nitrogen adsorption method (m 2 / g)
（ｄ）０．１≦ｄｘ≦１０
（ｅ）５≦Ｖ≦２０
（ｆ）５≦Ｓｗ≦１５０
但し、ｄｘ、Ｖ、Ｓｗは請求項７に記載のものと同じ。The coloring pigment according to any one of claims 1 to 7, wherein the base particles are particles satisfying the following formulas (d) to (f).
(D) 0.1 ≦ dx ≦ 10
(E) 5 ≦ V ≦ 20
(F) 5 ≦ Sw ≦ 150
However, dx, V, and Sw are the same as those described in claim 7.
（ｇ）１≦α≦３ 但し、α＝ｄ５０／ｄｘ
（ｈ）０≦β≦３ 但し、β＝（ｄ９０−ｄ１０）／ｄ５０
ｄｘ ：電子顕微鏡写真により測定した平均粒子径（μｍ）
α ：分散係数
ｄ５０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子の５０％平均粒子径（μｍ）。
β ：シャープネス。
ｄ９０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子のふるい通過側累計９０％粒子径（μｍ）。
ｄ１０：マイクロトラックＦＲＡレーザー式粒度分布計により測定した粒子のふるい通過側累計１０％粒子径（μｍ）。The coloring pigment according to any one of claims 1 to 8, wherein the base particles are particles satisfying the following formulas (g) and (h).
(G) 1 ≦ α ≦ 3, where α = d50 / dx
(H) 0 ≦ β ≦ 3 where β = (d90−d10) / d50
dx: average particle diameter (μm) measured by electron micrograph
α: Dispersion coefficient d50: 50% average particle diameter (μm) of particles measured by a Microtrac FRA laser type particle size distribution meter.
β: sharpness.
d90: 90% total particle diameter (μm) of particles passing through the sieve measured by a Microtrac FRA laser type particle size distribution analyzer.
d10: Total 10% particle diameter (μm) of particles passing through the sieve measured by a Microtrac FRA laser type particle size distribution meter.
（ｉ）１≦α≦２
（ｊ）０≦β≦２
但し、α、βは請求項９に記載のものと同じ。The color pigment according to any one of claims 1 to 9, wherein the base particles satisfy the following formulas (i) and (j).
(I) 1 ≦ α ≦ 2
(J) 0 ≦ β ≦ 2
However, α and β are the same as those described in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003033620A JP2004244461A (en) | 2003-02-12 | 2003-02-12 | Colored pigment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003033620A JP2004244461A (en) | 2003-02-12 | 2003-02-12 | Colored pigment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004244461A true JP2004244461A (en) | 2004-09-02 |
Family
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003033620A Pending JP2004244461A (en) | 2003-02-12 | 2003-02-12 | Colored pigment |
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| Country | Link |
|---|---|
| JP (1) | JP2004244461A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010001965A1 (en) * | 2008-07-04 | 2010-01-07 | 株式会社トクヤマ | Coating composition |
| US20120232190A1 (en) * | 2007-12-12 | 2012-09-13 | Gane Patrick A C | Composites of inorganic microparticles having a phosphated surface and alkaline earth carbonate nanoparticles |
| JP2013501077A (en) * | 2009-08-04 | 2013-01-10 | ロレアル | Composite pigment and preparation method thereof |
| JP2013533336A (en) * | 2010-06-07 | 2013-08-22 | オムヤ・デイベロツプメント・アー・ゲー | Use of 2-aminoethanol as an additive in aqueous suspensions of calcium carbonate containing materials |
| JP2014221910A (en) * | 2007-05-07 | 2014-11-27 | ユーエス コスメティクス コーポレイション | Thoroughly extended color bulk powder, bulk dispersion and application method thereof |
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2003
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2014221910A (en) * | 2007-05-07 | 2014-11-27 | ユーエス コスメティクス コーポレイション | Thoroughly extended color bulk powder, bulk dispersion and application method thereof |
| US20120232190A1 (en) * | 2007-12-12 | 2012-09-13 | Gane Patrick A C | Composites of inorganic microparticles having a phosphated surface and alkaline earth carbonate nanoparticles |
| US20120252933A1 (en) * | 2007-12-12 | 2012-10-04 | Gane Patrick A C | Composites of inorganic microparticles having a phosphated surface and alkaline earth carbonate nanoparticles |
| US8541494B2 (en) | 2007-12-12 | 2013-09-24 | Omya International Ag | Composites of inorganic microparticles having a phosphated surface and alkaline earth carbonate nanoparticles |
| US8808855B2 (en) * | 2007-12-12 | 2014-08-19 | Omya International Ag | Composites of inorganic microparticles having a phosphated surface and alkaline earth carbonate nanoparticles |
| US8808849B2 (en) * | 2007-12-12 | 2014-08-19 | Omya International Ag | Composites of inorganic microparticles having a phosphated surface and alkaline earth carbonate nanoparticles |
| TWI457405B (en) * | 2007-12-12 | 2014-10-21 | Omya Int Ag | Composites of inorganic microparticles having a phosphated surface and alkaline earth carbonate nanoparticles |
| WO2010001965A1 (en) * | 2008-07-04 | 2010-01-07 | 株式会社トクヤマ | Coating composition |
| JP2013501077A (en) * | 2009-08-04 | 2013-01-10 | ロレアル | Composite pigment and preparation method thereof |
| JP2013533336A (en) * | 2010-06-07 | 2013-08-22 | オムヤ・デイベロツプメント・アー・ゲー | Use of 2-aminoethanol as an additive in aqueous suspensions of calcium carbonate containing materials |
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