JP4522948B2 - Pigment dispersion, composition for color filter, and color filter - Google Patents

Description

  The present invention relates to a pigment dispersion used in a color liquid crystal display device, a color filter composition, a cured product formed using the same, and a color filter, and more specifically, a pigment dispersion suitable for blue pixel formation. The present invention relates to a body, a composition for a color filter and a cured product thereof.

Color filters are widely used for the purpose of colorization of liquid crystal display devices and the like, and generally, red, green, and blue pixels are arranged in a mosaic pattern. As a method for producing this color filter, a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method and the like are known. In particular, a pigment dispersion method in which fine pixels are formed by photolithography using a color filter composition (hereinafter also referred to as a color resist ink) in which a pigment is dispersed together with a photosensitive resin and / or a monomer, Since it is used, it is excellent in light resistance, heat resistance and solvent resistance.
In principle, many known pigments can be used in the pigment dispersion method. For example, JP-A-5-281414 discloses several tens of red, green, blue, yellow and purple pigments as color resist ink colorants. It is disclosed across species. In addition, the pigment of each pixel is generally selected so that the transmission characteristics of the pixel match the light emission characteristics of the backlight. For example, in addition to the red pigment, a yellow pigment and an orange pigment are used for red pixels, and a green color is used for green pixels. A desired transmission characteristic is imparted by mixing a yellow pigment in addition to the pigment and a blue pixel with a violet pigment in a certain ratio in addition to the blue pigment.
However, recent demands for high definition, high brightness, and high color reproducibility for liquid crystal display devices are high, and there is a demand for further increase in brightness and saturation of color filters. Only a limited number of devices exhibit high levels of lightness and saturation. For example, a violet pigment is often used together with pigment blue 15: 6, which is a copper phthalocyanine-based blue pigment, as a color resist ink for forming a blue pixel. As disclosed in US Pat. No. 5, the pigment violet 23, which is a violet pigment made of carbazole dioxazine, is almost the only one that can be used successfully.
The pigment violet 23 is often mixed for the purpose of enhancing the blue purity of the copper phthalocyanine blue pigment that slightly transmits green light because the blue transmission region is on the short wavelength side of the copper phthalocyanine blue pigment. However, in the method of mixing two pigments having different transmission ranges, there is a trade-off between high brightness and high saturation, and the pigment violet 23 is greatly different in transmission range from the copper phthalocyanine blue pigment and has a low transmittance. This method used has a problem that a high level of lightness and saturation cannot be satisfied at the same time.
As described above, in the preparation of a color filter used in a liquid crystal display device or the like, it is essential to adjust the color material having transmission characteristics suitable for the purpose and purpose of the color resist ink used, and carbazole dioxazine purple pigment. There has been a demand for highly brightened color resist inks using pigments instead of.
On the other hand, a subphthalocyanine compound is known as one of the pigments. Japanese Patent Application Laid-Open No. 11-24255 and Japanese Patent Application Laid-Open No. 2001-318462 disclose a photopolymerizable composition using the subphthalocyanine compound. However, these photopolymerizable compositions pay attention to the photosensitizing action of the subphthalocyanine compound in the visible light region, dissolve the subphthalocyanine compound in the photosensitive resin composition, and perform argon laser (514 nm) or YAG ( Second harmonic) It is used as a photosensitizer for visible light such as long-wavelength laser light such as laser (532 nm), and is used as a color filter composition by dispersing a subphthalocyanine compound as a coloring material. There is no suggestion.

（但し、Ｘ_１〜Ｘ_１２のうち、少なくとも６個がハロゲン原子であり、残りは水素原子を示す。Ｙはハロゲン原子又はヒドロキシル基を示す。）
更に、本発明は、着色材（以下、成分（Ａ）ともいう）、分散剤（以下、成分（Ｂ）ともいう）、溶剤（以下、成分（Ｃ）ともいう）、感光性樹脂及び／又は単量体（以下、成分（Ｄ）ともいう）及び光重合開始剤（以下、成分（Ｅ）ともいう）を含有してなるカラーフィルター用組成物において、成分（Ａ）の着色材成分として前記一般式（１）で示されるサブフタロシアニン化合物からなる顔料を全着色材中０．５重量％以上含有し、成分（Ｅ）の光重合開始剤を成分（Ｄ）の感光性樹脂及び／又は単量体に対して０．１〜２０重量％含有し、前記組成物中の着色材（Ａ）と樹脂固形分（Ｒ）との各成分の合計重量比で表される（Ａ）／（Ｒ）が０．０５〜１．５の範囲であることを特徴とする。
更に、本発明は、前記のカラーフィルター用組成物を硬化して得られる硬化物である。また、本発明は、青色画素を形成する硬化膜が前記の硬化物からなるカラーフィルターである。
以下、本発明の顔料分散体について説明する。
本発明の顔料分散体は、着色材（成分（Ａ））、分散剤（成分（Ｂ））及び溶剤（成分（Ｃ））を必須成分として含有し、所定の顔料粒度としたものであることが好ましい。また、本発明の顔料分散体は、カラーフィルター用組成物として有用である。本発明の顔料分散体をカラーフィルター用組成物として使用する場合は、更に、感光性樹脂及び／又は単量体（成分（Ｄ））及び（Ｅ）光重合開始剤（成分（Ｅ））を必須成分として含有することが好ましい。また、必要により他の樹脂類及びその他の表面調整剤、消泡剤等の各種添加剤を配合することができる。
成分（Ａ）の着色材には、前記一般式（１）で示されるサブフタロシアニン化合物からなる顔料を全着色材中０．５重量％以上含有することを必要とする。一般式（１）において、Ｘ_１〜Ｘ_１２のうち、少なくとも６個はハロゲン原子であり残りは水素原子である。ハロゲン原子としては、フッ素、塩素、臭素、ヨウ素等のいずれでもよいが、色相の点から塩素又は臭素が好ましい。更に好ましくは、一般式（１）中のＸ_１〜Ｘ_１２の全てが塩素又は臭素であるものが用いられる。なお、１つの分子内に複数種のハロゲン原子が結合していてもよい。一般式（１）中のＹはハロゲン原子又はヒドロキシル基であるが、取り扱いに優れる点から塩素又は臭素が好ましい。
成分（Ａ）は、上記サブフタロシアニン系顔料を全着色材中０．５重量％以上、好ましくは５重量％以上、より更に好ましくは４０重量％以上、更に好ましくは７０重量％以上含有するものであればよく、他の顔料や染料を併用して用いることもできる。好ましくは、上記サブフタロシアニン系顔料を４０〜１００重量％、他の顔料を０〜６０重量％の範囲で使用することである。青色のカラーレジストインキを調製するために適した他の着色材としては、色相の点から青色、紫色の顔料が好ましく、例えばピグメント・ブルー１５、同１５：１、同１５：２、同１５：３、同１５：４、同１５：６、同１６、同６０、同８０、ピグメント・バイオレット１９、同２３、同３７等を挙げることができるが、併用可能な顔料はこれらに限定されるものではない。
本発明において、着色材としてサブフタロシアニン系顔料を用いる理由は、顔料の有する特異な分光特性に起因する。つまり、液晶表示装置等のバックライトには、赤、緑及び青の三原色に対応する波長（一般的に６１０ｎｍ、５４５ｎｍ及び４３５ｎｍ）に鋭い発光を有する高演色性の三波長型蛍光ランプが広く用いられており、この三波長の発光をそれぞれ効果的に透過し他の二波長の発光を遮光することが高水準の赤、緑及び青の明彩度性を示すために必要である。本発明のサブフタロシアニンよりなる顔料を主たる着色材として含むカラーフィルター用組成物を用いて製作されるカラーフィルターは、３７０〜５１０ｎｍ付近及び６３０ｎｍより長波長域に透過を、５２０〜６２０ｎｍ付近に吸収を持つ優れた分光特性を示すために、三波長型蛍光ランプの青の発光を効果的に透過し、緑及び赤の発光を効果的に遮光することができる。そのために、本発明のカラーフィルターは高水準の明彩度性を有し、これを用いる液晶表示装置等に高水準の明彩度性を与えることができる。
サブフタロシアニン系顔料の製造は、一般的にはサブフタロシアニン化合物を合成しそれを顔料化することで成される。サブフタロシアニン化合物の合成方法は公知であり、その例としては、Ａ．Ｍｅｌｌｅｒ ａｎｄ Ａ．Ｏｓｓｋｏ，Ｍｏｎａｔｓｈｅｆｔｅ ｆｕｒ Ｃｈｅｍｉｅ １０３，１５０−１５５（１９７２）などが挙げられる。具体的には、三ハロゲン化硼素１モルと必要に応じてベンゼン環の水素原子がハロゲン置換されたフタロニトリル３モルを反応させることで合成できる。こうして得られたサブフタロシアニン化合物には副反応等によって生ずる不純物が含まれていることが多いが、例えば濾過洗浄やソックスレー抽出を行うことにより不純物を取り除くことができる。ここで、不純物としては、原料の三ハロゲン化硼素の加水分解生成物、未反応のフタロニトリル等を挙げることができる。濾過洗浄やソックスレー抽出で用いる溶媒については、特に制約はない。例えばメタノール、エタノール等のアルコール系溶剤、アセトン、メチルエチルケトン等のケトン系溶剤、トルエン、キシレン等の芳香族系溶剤等を用いることができる。また、必要に応じて、フタロニトリル又はハロゲン以外の置換フタロニトリルを出発原料として、無置換又は置換サブフタロシアニンを合成した後、公知の方法によりハロゲン化を行なってもよい。しかし、合成法及び精製法は上記の方法に限定されるものではない。
顔料化する方法としては公知の方法が利用でき、例えばサブフタロシアニン化合物を濃硫酸等の強酸に溶解した後、大量の水中に投入して微細顔料を生成させるアシッドペースティング法、同様に強酸に分散してこれを大量の水中に注いで微細顔料を生成させるアシッドスラリー法等を挙げることができる。また、高水準の明彩度性を有するカラーフィルターを得るには、着色材として更に微粒化した顔料を用いることが好ましいが、微粒化する方法も公知の方法が利用でき、例えば塩の存在下でミル破砕するソルトミリング法、ソルベントソルトミリング法等を挙げることができる。本発明においては、顔料化及び微粒化の方法も上記の方法に限定されるものではない。本発明で使用される顔料は、一次粒子の平均粒子径が１０〜５００ｎｍの範囲であることが好ましく、３０〜３００ｎｍの範囲であることがより好ましく、更には５０〜２００ｎｍの範囲であることが最も好ましい。
成分（Ｂ）の分散剤としては、その種類は特に限定されるものではないが、分散安定性に優れる点から、（ａ）ポリ（低級アルキレンイミン）及び（ｂ）ポリアリルアミンから選ばれる１種又は２種以上の含窒素化合物に、遊離のカルボキシル基を有する（ｉ）ポリエステル、（ｉｉ）ポリアミド及び（ｉｉｉ）ポリエステルアミドから選ばれる１種又は２種以上のカルボキシル基含有化合物を反応させてアミド又は塩を形成させてなるグラフトポリマーを用いることが好ましい。
（ａ）ポリ（低級アルキレンイミン）は、一級（−ＮＨ_２）、二級（−ＮＨ−）及び三級（−Ｎ＜）のアミノ基を低級アルキレン鎖（−Ｒ−、例えば−ＣＨ_２ＣＨ_２−）で結合した分枝構造を有するポリマーであり。（ｂ）ポリアリルアミンは、［−ＣＨ_２−ＣＨ（ＣＨ_２ＮＨ_２）−］_ｎなる構造を有するポリマーである。また、（ｉ）、（ｉｉ）及び（ｉｉｉ）のカルボキシル基含有化合物は、末端又は側鎖等に少なくとも１つのカルボキシル基を有し、これが（ａ）又は（ｂ）のアミノ基等の少なくとも一部と反応して−ＮＨＣＯ−又はＮＨ_３ ^＋・⁻ＯＣＯ−等を形成してグラフトポリマーを形成する。
上記グラフトポリマーは、顔料に吸着してアンカーの役割を果たす塩基性部分（ａ）又は（ｂ）と、立体反発効果により分散性を付与する高分子鎖部分（ｉ）、（ｉｉ）又は（ｉｉｉ）の両方を有する分散剤である。このようなグラフトポリマーの製造方法は公知であり、例えば特公昭６３−３００５７号公報及び特開平９−１６９８２１号公報に開示されている。
また、グラフトポリマーの塩基性部分のサブフタロシアニン系顔料への吸着性をより高めるために、顔料骨格に酸性の官能基を導入した顔料誘導体型の分散助剤を分散剤と併用することもできる。上記の分散助剤は、色相の点から青色又は紫色のものが好ましく、例えば銅フタロシアニンのスルホン酸誘導体、サブフタロシアニンのスルホン酸誘導体、キナクリドンのスルホン酸誘導体、カルバゾールジオキサジンのスルホン酸誘導体等を挙げることができる。
なお、成分（Ｂ）の分散剤は、上記のようなグラフトポリマーに限定されず、分散能を有するものであればよく、分散剤、分散促進剤等として市販されているもの又はその同等品を含む。樹脂類の中には、顔料の表面に吸着して顔料を分散させる働きを有するものがある。このような樹脂類は分散能を有するので分散剤に含まれる。したがって、成分（Ｄ）の感光性樹脂及び／又は単量体が分散能を有する場合は、これを分散剤として用いてもよい。ただし、高粘度物質である樹脂類は一般に分散を安定させる作用（分散安定能）は有するが分散能を有さず、このように分散能を有さないものは分散剤とは扱わない。本発明において、分散剤は樹脂成分の一成分となり得る。
成分（Ｃ）の溶剤としては、顔料の分散性と分散剤を配合した場合にはその溶解性に優れる点から、エステル類、ケトン類、グリコールエーテル類、含窒素系溶剤等を好ましく用いることができる。例えば、エステル類では酢酸エチル、酢酸ブチル、乳酸エチル、γ−ブチロラクトン等、ケトン類ではメチルイソブチルケトン、シクロヘキサノン等、グリコールエーテル類ではエチルセロソルブ、エチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールジメチルエーテル等、含窒素系溶剤ではジメチルホルムアミド、ジメチルアセトアミド等をそれぞれ挙げることができる。これらの溶剤は、配合される樹脂類及びその他の添加物の構成、顔料の耐溶剤性、塗布性に応じて適宜選択すれば良く、単独で用いても良いし２種以上を併用しても良い。
ここで、顔料分散体は、必須成分として前記成分（Ａ）の着色材、成分（Ｂ）の分散剤及び成分（Ｃ）の溶剤を含有するが、全固形分は１〜４０重量％であることが好ましく、５〜３５重量％であることがより好ましい。成分（Ａ）の配合率は、顔料分散体中１〜２５重量％であることが好ましく、５〜２０重量％であることがより好ましい。また、成分（Ｂ）の配合率は、顔料に対して１０〜６０重量％であることが好ましく、２０〜５０重量％であることがより好ましい。成分（Ｂ）の含有割合が顔料に対して１０重量％未満では、顔料分散体の分散安定性が不十分となり、反対に６０重量％を超えると、フォトリソグラフィー工程において有効な画素形成能が発揮できなくなる恐れがある。但し、成分（Ｄ）が分散能を有する場合には、６０重量％を超えて含有されても差し支えない。なお、全固形分とは乾燥、硬化又は重合後に残存する成分をいう。通常は、溶剤等の揮発分以外の成分を除いたものが全固形分となる。また、成分（Ｂ）の含有割合の基準となる顔料の量は、着色材中の顔料の合計を意味する。
顔料分散体は顔料を分散剤と共に溶剤に分散させることで得られる。成分（Ｄ）及び成分（Ｅ）を含有させる場合は、これらを同時に加えて分散させて得ることもできるし、あらかじめ、成分（Ｄ）及び成分（Ｅ）を含有させずに第一の顔料分散体を作り、次に成分（Ｄ）及び成分（Ｅ）を配合して第二の顔料分散体を作り、これをカラーフィルター用組成物とすることができる。その製作方法は、特に制限されるものではなく、公知の方法が利用できる。例えばペイントシェーカー、サンドミル、ビーズミル等による分散処理を挙げることができる。本発明で使用される顔料分散体又は組成物中の顔料は、その一次粒子径まで分散されていることが望ましい。すなわち、顔料分散体又は組成物中の顔料の平均粒子径は、１０〜５００ｎｍの範囲であることが好ましく、３０〜３００ｎｍの範囲であることがより好ましく、５０〜２００ｎｍの範囲であることが最も好ましい。顔料の平均粒子径が５００ｎｍを超えると、光の透過率が低下し、また偏光を生じ易くなるため、明度に劣りコントラストの低いカラーフィルターとなり、反対に１０ｎｍ未満では、顔料分散体の分散安定性が不十分となる。
カラーフィルター用組成物中の着色材の割合は、着色濃度等に応じて適宜選定されるが、組成物中の成分（Ａ）の着色材と樹脂固形分（Ｒ）との（Ａ）／（Ｒ）の重量比が０．０５〜１．５の範囲であることが必要であり、好ましくは、０．１〜１の範囲である。この比が０．０５に満たないと着色性能が十分発揮できず良好なカラーフィルターを形成できなくなり、また、１．５を超えるとフォトリソグラフィー工程において有効な画素形成能が発揮できなくなる。なお、樹脂固形分（Ｒ）は、前記成分（Ｄ）及び成分（Ｄ）以外の樹脂成分（モノマーを含む）の合計からなる。
成分（Ｄ）の感光性樹脂及び／又は単量体は、光重合性樹脂、光重合性モノマー及び光重合性オリゴマーの少なくとも１種以上から選ばれ、エチレン性不飽和結合を有するものである。カラーフィルター用組成物には硬化した状態で樹脂となるものを含めば良く、未硬化の状態では樹脂化していない成分のみが含まれる場合を含む。本発明における樹脂固形分には、樹脂化する前のモノマーやオリゴマーも固形分として扱うものとする。成分（Ｄ）は、カラーフィルターの製造プロセスを考慮して適宜選択すればよい。
光重合性樹脂、光重合性モノマー及び光重合性オリゴマーとしては、例えば２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−エチルヘキシル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ペンタエリスリトールジ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ビスフェノールＡ型エポキシジ（メタ）アクリレート、ビスフェノールＦ型エポキシジ（メタ）アクリレート、ビスフェノールフルオレン型エポキシジ（メタ）アクリレート等の（メタ）アクリル酸エステル類等が挙げられる。また、アクリル酸（共）重合体、（メタ）アクリル酸（共）重合体、マレイン酸（共）重合体等のビニル樹脂や、ポリエチレンオキサイド、ポリビニルピロリドン、ポリアミド、ポリウレタン、ポリエーテル、ポリエステル等の側鎖にエチレン性二重結合を有する樹脂類も挙げることができる。これらは単独で用いても良いし、２種以上を併用しても良い。また、これらの樹脂は、現像性を高める目的で、側鎖にカルボキシル基、フェノール性水酸基等のアルカリ溶解性置換基を有していることが望ましい。
成分（Ｄ）の感光性樹脂及び／又は単量体の配合率は、本発明のカラーフィルター用組成物中の全固形分中４０〜９５重量％であることが好ましく、５０〜９０重量％であることがより好ましい。組成物中には、必要に応じて他の樹脂類等を配合することができるが、この場合には、他の樹脂類を合わせた合計量が上記範囲に入ることが望ましい。なお、全固形分とは乾燥、硬化後に固形分として残る成分をいい、溶剤を含まず、単量体を含む。
成分（Ｅ）の光重合開始剤としては、例えばアセトフェノン、ｐ−ｔｅｒｔ−ブチルアセトフェノン等のアセトフェノン類、ベンゾフェノン、ｐ，ｐ′−ビス（Ｎ，Ｎ−ジメチルアミノ）ベンゾフェノン等のベンゾフェノン類、ベンゾインエチルエーテル、ベンゾイン−ｔｅｒｔ−ブチルエーテル等のベンゾインエーテル類、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、２−ベンジル−２−（Ｎ，Ｎ−ジメチルアミノ）−１−（４−モルフォリノフェニル）ブタン−１−オン等のα−アミノアルキルフェノン類、２，４，６−トリス（トリクロロメチル）−１，３，５−トリアジン、２−（４−メトキシフェニル）−４，６−ビス（トリクロロメチル）−１，３，５−トリアジン等のトリアジン類、過酸化ベンゾイル、３，３′，４，４′−テトラ（ｔｅｒｔ−ブチルペルオキシカルボニル）ベンゾフェノン等の有機過酸化物類、チオキサントン、２，４−ジエチルチオキサントン等の硫黄化合物類等を挙げることができる。これらは単独で用いても良いし、２種以上を併用しても良い。
光重合開始剤の配合率は、露光感度等に応じて適宜選択されるが、（Ｄ）成分に対して０．１〜２０重量％であることが好ましく、更には０．５〜１５重量％であることが好ましい。含有割合が０．１重量％未満では、感光性が不十分となり、反対に２０重量％を超えると、レジストインキとしての保存安定性に欠ける。
本発明のカラーフィルター用組成物は、上記必須成分を含有する限りその製法は限定されないが、顔料、分散剤及び溶剤を主成分とする顔料分散体を予め製作し、その後、成分（Ｄ）及び（Ｅ）、必要により加えられる樹脂類及びその他の成分と混合することが有利である。
本発明のカラーフィルター用組成物は、上記成分以外に現像性や塗膜形成能を向上させる目的で、バインダー樹脂成分として、アルカリ溶解性を有する樹脂を加えても良い。例えば、ポリエチレンオキサイド、ポリビニルピロリドン、ポリアミド、ポリウレタン、ポリエステル、ポリエーテル等が挙げられるが、主鎖又は側鎖にカルボキシル基を含有しアルカリ現像性に優れるものが好ましい。このようなものには、例えばアクリル酸（共）重合体、（メタ）アクリル酸（共）重合体、マレイン酸（共）重合体等のビニル樹脂類が挙げられる。この他に、水酸基を有する樹脂に酸無水物を付加させたものなども有用である。これらは単独で用いても良いし、２種以上を併用しても良い。
なお、本発明のカラーフィルター用組成物は、必須成分として前記の成分（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）及び（Ｅ）を含有するが、全固形分は１〜４０重量％であることが好ましく、５〜３０重量％であることがより好ましい。
カラーフィルター用組成物を製作する方法としては、予め前記サブフタロシアニン顔料を単独で又は他の顔料と共に分散剤を用いて溶剤に分散させた顔料分散体を製作し、これと樹脂成分、光重合開始剤等を配合する方法や、サブフタロシアニン系顔料を樹脂組成物中に直接分散させる方法等を挙げることができるが、カラーフィルター用組成物の安定性の点から前者の方法が好ましい。また、サブフタロシアニン系顔料を溶解できる高溶解性溶剤を用いてサブフタロシアニン化合物と感光性樹脂を含む組成物中に溶解させてカラーレジストインキとする方法もあるが、耐光性、耐熱性及び耐溶剤性の点で難があるために、顔料化しこれを分散する方法が最も好ましい。
本発明のカラーフィルター用組成物を硬化して得られる硬化物は、当該組成物を基板等に塗布し、光照射、加熱等で硬化させることによって得られる。組成物を塗布する方法としては公知の方法が利用でき、例えばスピンコーター、バーコーター、ダイコーター等の塗布装置による塗布を挙げることができる。塗布後は、ホットプレート、ＩＲオーブン等を用いて乾燥を行なってもよい。
組成物に光照射する方法も公知の方法が利用でき、適用し得る露光光源は特に限定されるものではないが、例えばキセノンランプ、ハロゲンランプ、タングステンランプ、超高圧水銀灯、高圧水銀灯、中圧水銀灯、低圧水銀灯等のランプ光源等が用いられる。ただし、塗布及び光照射の方法は上記の方法に限定されない。
かかる光源にて画像露光を行った後、現像すれば基板上に画像を形成することができる。現像液としては、未露光部分を溶解し露光部分溶解しない現像液であればいかなるものも用いることができる。具体時には、種々の添加物を含んだアルカリ溶液であり、添加物としては、有機溶剤、緩衝剤、界面活性剤等を含有することができる。現像処理方法については特に制限はないが、浸漬現像、スプレー現像、ブラシ現像、超音波現像等の方法が用いられる。
また、塗膜の強度を上げる方法として、熱風オーブンによる加熱硬化を行ってもよい。組成物の硬化条件については特に制約はないが、組成物を硬化して得られる硬化膜の変色、褪色を防ぐために、加熱については２５０℃以下で１時間以内とすることが好ましい。なお、上記のカラーフィルター用組成物の硬化膜を用いてカラーフィルターを製作する方法としては、公知の方法を利用できる。The present invention has been made in view of the drawbacks of the prior art, and is used in liquid crystal display devices and the like, and is a pigment dispersion for forming a (blue) pixel that provides a high level of color saturation, and a composition for a color filter. Another object of the present invention is to provide a cured product and a color filter formed using the same.
That is, according to the present invention, in a pigment dispersion obtained by dispersing a colorant in a solvent together with a dispersant, 0.5% by weight of a pigment composed of a subphthalocyanine compound represented by the following general formula (1) is used as the colorant. It is a pigment dispersion characterized by containing more than%.

(However, among X _{1 to} X ₁₂ , at least 6 are halogen atoms, and the rest represent hydrogen atoms. Y represents a halogen atom or a hydroxyl group.)
Furthermore, the present invention relates to a colorant (hereinafter also referred to as component (A)), a dispersant (hereinafter also referred to as component (B)), a solvent (hereinafter also referred to as component (C)), a photosensitive resin and / or In the composition for a color filter containing a monomer (hereinafter also referred to as component (D)) and a photopolymerization initiator (hereinafter also referred to as component (E)), the colorant component of component (A) The pigment comprising the subphthalocyanine compound represented by the general formula (1) is contained in an amount of 0.5% by weight or more in the total colorant, and the photopolymerization initiator of component (E) is used as the photosensitive resin and / or single component (D). (A) / (R) which is contained in an amount of 0.1 to 20% by weight with respect to the monomer, and is represented by a total weight ratio of each component of the colorant (A) and the resin solid content (R) in the composition. ) Is in the range of 0.05 to 1.5.
Furthermore, this invention is a hardened | cured material obtained by hardening | curing the said composition for color filters. Moreover, this invention is a color filter in which the cured film which forms a blue pixel consists of said hardened | cured material.
Hereinafter, the pigment dispersion of the present invention will be described.
The pigment dispersion of the present invention contains a colorant (component (A)), a dispersant (component (B)) and a solvent (component (C)) as essential components, and has a predetermined pigment particle size. Is preferred. The pigment dispersion of the present invention is useful as a color filter composition. When the pigment dispersion of the present invention is used as a color filter composition, a photosensitive resin and / or monomer (component (D)) and (E) photopolymerization initiator (component (E)) are further added. It is preferable to contain as an essential component. Further, if necessary, various additives such as other resins and other surface conditioners and antifoaming agents can be blended.
The colorant of component (A) needs to contain 0.5% by weight or more of the pigment made of the subphthalocyanine compound represented by the general formula (1) in the total colorant. In the general formula (1), at least 6 of X _{1 to} X ₁₂ are halogen atoms, and the rest are hydrogen atoms. The halogen atom may be any of fluorine, chlorine, bromine, iodine, etc., but chlorine or bromine is preferred from the viewpoint of hue. More preferably, those in which all of X _{1 to} X _{12 in} the general formula (1) are chlorine or bromine are used. A plurality of types of halogen atoms may be bonded in one molecule. Y in the general formula (1) is a halogen atom or a hydroxyl group, and chlorine or bromine is preferred from the viewpoint of excellent handling.
Component (A) contains the above subphthalocyanine pigment in the total colorant in an amount of 0.5% by weight or more, preferably 5% by weight or more, more preferably 40% by weight or more, and further preferably 70% by weight or more. Any other pigments and dyes may be used in combination. Preferably, the subphthalocyanine pigment is used in the range of 40 to 100% by weight, and other pigments in the range of 0 to 60% by weight. Other colorants suitable for preparing a blue color resist ink are preferably blue and purple pigments from the viewpoint of hue. For example, Pigment Blue 15, 15: 1, 15: 2, and 15: 3, 15: 4, 15: 6, 16, 60, 80, Pigment Violet 19, 23, 37, etc. The pigments that can be used in combination are limited to these. is not.
In the present invention, the reason for using the subphthalocyanine pigment as the colorant is due to the unique spectral characteristics of the pigment. In other words, high-color-rendering three-wavelength fluorescent lamps having sharp emission at wavelengths corresponding to the three primary colors of red, green, and blue (generally 610 nm, 545 nm, and 435 nm) are widely used for backlights of liquid crystal display devices and the like. Therefore, it is necessary to effectively transmit the light of the three wavelengths and shield the light of the other two wavelengths in order to exhibit a high level of red, green, and blue color saturation. A color filter manufactured using a composition for a color filter containing a pigment comprising the subphthalocyanine of the present invention as a main colorant transmits light in the vicinity of 370 to 510 nm and longer wavelength than 630 nm, and absorbs in the vicinity of 520 to 620 nm. In order to exhibit the excellent spectral characteristics, it is possible to effectively transmit the blue light emission of the three-wavelength fluorescent lamp and effectively block the green and red light emission. Therefore, the color filter of the present invention has a high level of color saturation, and can provide a high level of color saturation to a liquid crystal display device using the color filter.
The production of a subphthalocyanine pigment is generally performed by synthesizing a subphthalocyanine compound and converting it into a pigment. Methods for synthesizing subphthalocyanine compounds are known. Meller and A.M. Ossko, Monatshefte fur Chemie 103, 150-155 (1972). Specifically, it can be synthesized by reacting 1 mol of boron trihalide with 3 mol of phthalonitrile in which the hydrogen atom of the benzene ring is substituted with a halogen as necessary. The subphthalocyanine compound thus obtained often contains impurities caused by side reactions or the like, but the impurities can be removed by, for example, filtration washing or Soxhlet extraction. Here, examples of the impurity include a hydrolysis product of raw material boron trihalide, unreacted phthalonitrile, and the like. There are no particular restrictions on the solvent used in filtration washing or Soxhlet extraction. For example, alcohol solvents such as methanol and ethanol, ketone solvents such as acetone and methyl ethyl ketone, and aromatic solvents such as toluene and xylene can be used. Further, if necessary, after synthesizing an unsubstituted or substituted subphthalocyanine using a substituted phthalonitrile other than phthalonitrile or halogen as a starting material, halogenation may be performed by a known method. However, the synthesis method and the purification method are not limited to the above methods.
As a method for pigmentation, a known method can be used, for example, an acid pasting method in which a subphthalocyanine compound is dissolved in a strong acid such as concentrated sulfuric acid and then poured into a large amount of water to form a fine pigment, and similarly dispersed in a strong acid. Then, an acid slurry method or the like in which a fine pigment is produced by pouring it into a large amount of water can be used. In order to obtain a color filter having a high level of color saturation, it is preferable to use a further atomized pigment as the colorant. However, a known method can be used for the atomization, for example, in the presence of salt. Examples thereof include a salt milling method and a solvent salt milling method in which the mill is crushed. In the present invention, the pigmentation and atomization methods are not limited to the above methods. The pigment used in the present invention preferably has an average primary particle diameter in the range of 10 to 500 nm, more preferably in the range of 30 to 300 nm, and further in the range of 50 to 200 nm. Most preferred.
The type of the dispersant for component (B) is not particularly limited, but one type selected from (a) poly (lower alkyleneimine) and (b) polyallylamine from the viewpoint of excellent dispersion stability. Alternatively, two or more nitrogen-containing compounds may be reacted with one or two or more carboxyl group-containing compounds selected from (i) polyester having a free carboxyl group, (ii) polyamide, and (iii) polyester amide. Alternatively, it is preferable to use a graft polymer formed by forming a salt.
(A) A poly (lower alkyleneimine) is composed of a primary (—NH ₂ ), secondary (—NH—) and tertiary (—N <) amino group represented by a lower alkylene chain (—R—, for example —CH ₂ CH _2- ) a polymer having a branched structure bonded to each other. (B) Polyallylamine is a polymer having a structure of [—CH ₂ —CH (CH ₂ NH ₂ ) —] _n . In addition, the carboxyl group-containing compound (i), (ii) and (iii) has at least one carboxyl group at the terminal or side chain, which is at least one of the amino group of (a) or (b). parts reacting with a -NHCO- or _NH ³ + ^· - OCO- like form to a form a graft polymer.
The graft polymer is composed of a basic part (a) or (b) that acts as an anchor by adsorbing to a pigment, and a polymer chain part (i), (ii), or (iii) that imparts dispersibility by a steric repulsion effect. ). A method for producing such a graft polymer is known, and disclosed in, for example, Japanese Patent Publication No. 63-30057 and Japanese Patent Application Laid-Open No. 9-169821.
In order to further enhance the adsorptivity of the basic portion of the graft polymer to the subphthalocyanine pigment, a pigment derivative type dispersion aid in which an acidic functional group is introduced into the pigment skeleton may be used in combination with the dispersant. The dispersion aid is preferably blue or purple from the viewpoint of hue. Examples thereof include sulfonic acid derivatives of copper phthalocyanine, sulfonic acid derivatives of subphthalocyanine, sulfonic acid derivatives of quinacridone, and sulfonic acid derivatives of carbazole dioxazine. be able to.
The dispersant of component (B) is not limited to the graft polymer as described above, and any dispersant having a dispersibility may be used, such as those commercially available as dispersants, dispersion accelerators, or the like. Including. Some resins have a function of adsorbing on the surface of the pigment and dispersing the pigment. Such resins are included in the dispersant because they have dispersibility. Therefore, when the photosensitive resin and / or monomer of component (D) has dispersibility, this may be used as a dispersant. However, resins that are high viscosity substances generally have an action of stabilizing dispersion (dispersion stability), but do not have dispersion ability, and those having no dispersion ability are not treated as dispersants. In the present invention, the dispersant can be a component of the resin component.
As the solvent of component (C), it is preferable to use esters, ketones, glycol ethers, nitrogen-containing solvents, etc. from the viewpoint of excellent dispersibility when pigment dispersion and a dispersant are blended. it can. For example, esters include ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, ketones include methyl isobutyl ketone and cyclohexanone, glycol ethers include ethyl cellosolve, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, and the like. Examples of nitrogen-containing solvents include dimethylformamide and dimethylacetamide. These solvents may be appropriately selected according to the composition of the resins to be blended and other additives, the solvent resistance of the pigment, and the coating property, and may be used alone or in combination of two or more. good.
Here, the pigment dispersion contains the colorant of component (A), the dispersant of component (B) and the solvent of component (C) as essential components, but the total solid content is 1 to 40% by weight. It is preferably 5 to 35% by weight. The blending ratio of component (A) is preferably 1 to 25% by weight in the pigment dispersion, and more preferably 5 to 20% by weight. Moreover, it is preferable that it is 10-60 weight% with respect to a pigment, and, as for the compounding ratio of a component (B), it is more preferable that it is 20-50 weight%. When the content ratio of component (B) is less than 10% by weight with respect to the pigment, the dispersion stability of the pigment dispersion becomes insufficient. Conversely, when the content exceeds 60% by weight, effective pixel forming ability is exhibited in the photolithography process. There is a risk that it will not be possible. However, when the component (D) has dispersibility, it may be contained in an amount exceeding 60% by weight. The total solid content means a component remaining after drying, curing or polymerization. Usually, the total solid content is obtained by removing components other than volatile components such as a solvent. Further, the amount of the pigment serving as a reference for the content ratio of the component (B) means the sum of the pigments in the coloring material.
The pigment dispersion can be obtained by dispersing a pigment in a solvent together with a dispersant. When the component (D) and the component (E) are contained, they can be obtained by simultaneously adding and dispersing them, or the first pigment dispersion without containing the component (D) and the component (E) in advance. A body is made, and then component (D) and component (E) are blended to form a second pigment dispersion, which can be used as a color filter composition. The manufacturing method is not particularly limited, and a known method can be used. For example, a dispersion treatment using a paint shaker, a sand mill, a bead mill, or the like can be given. The pigment in the pigment dispersion or composition used in the present invention is desirably dispersed to its primary particle size. That is, the average particle diameter of the pigment in the pigment dispersion or composition is preferably in the range of 10 to 500 nm, more preferably in the range of 30 to 300 nm, and most preferably in the range of 50 to 200 nm. preferable. When the average particle diameter of the pigment exceeds 500 nm, the light transmittance decreases and polarization easily occurs, so that the color filter has poor brightness and low contrast. Conversely, when the average particle diameter is less than 10 nm, the dispersion stability of the pigment dispersion is low. Is insufficient.
The ratio of the colorant in the color filter composition is appropriately selected according to the color concentration and the like, but the (A) / () of the colorant of the component (A) in the composition and the resin solid content (R). The weight ratio of R) needs to be in the range of 0.05 to 1.5, preferably in the range of 0.1 to 1. If this ratio is less than 0.05, the coloring performance cannot be sufficiently exhibited and a good color filter cannot be formed, and if it exceeds 1.5, effective pixel forming ability cannot be exhibited in the photolithography process. In addition, resin solid content (R) consists of the sum total of resin components (a monomer is included) other than the said component (D) and component (D).
The photosensitive resin and / or monomer of component (D) is selected from at least one of a photopolymerizable resin, a photopolymerizable monomer, and a photopolymerizable oligomer, and has an ethylenically unsaturated bond. What is necessary is just to include what becomes resin in the state which hardened | cured in the composition for color filters, and includes the case where only the component which is not resinified is contained in the uncured state. In the resin solid content in the present invention, monomers and oligomers before resinification are handled as solid content. The component (D) may be appropriately selected in consideration of the color filter manufacturing process.
Examples of the photopolymerizable resin, photopolymerizable monomer, and photopolymerizable oligomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and ethylene glycol di (meth). Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) Acrylate, bisphenol A type epoxy di (meth) acrylate, bisphenol F type epoxy di (meth) acrylate, bisphenol fluorene type epoxy di (meth) acrylate Chromatography (meth) acrylic acid esters such as bets and the like. Also, vinyl resins such as acrylic acid (co) polymer, (meth) acrylic acid (co) polymer, maleic acid (co) polymer, polyethylene oxide, polyvinylpyrrolidone, polyamide, polyurethane, polyether, polyester, etc. Resins having an ethylenic double bond in the side chain can also be mentioned. These may be used alone or in combination of two or more. In addition, these resins desirably have an alkali-soluble substituent such as a carboxyl group or a phenolic hydroxyl group in the side chain for the purpose of improving developability.
The blending ratio of the photosensitive resin and / or monomer of component (D) is preferably 40 to 95% by weight, and 50 to 90% by weight, based on the total solid content in the color filter composition of the present invention. More preferably. In the composition, other resins and the like can be blended as necessary. In this case, it is desirable that the total amount of the other resins falls within the above range. The total solid content means a component that remains as a solid content after drying and curing, does not include a solvent, and includes a monomer.
Examples of the photopolymerization initiator of component (E) include acetophenones such as acetophenone and p-tert-butylacetophenone, benzophenones, benzophenones such as p, p'-bis (N, N-dimethylamino) benzophenone, and benzoin ethyl. Ether, benzoin ethers such as benzoin-tert-butyl ether, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2- (N, N-dimethyl) Α-aminoalkylphenones such as amino) -1- (4-morpholinophenyl) butan-1-one, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2- (4 Trimethoxy such as -methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine Organic peroxides such as benzoyl peroxide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, sulfur compounds such as thioxanthone and 2,4-diethylthioxanthone Can do. These may be used alone or in combination of two or more.
The blending ratio of the photopolymerization initiator is appropriately selected according to the exposure sensitivity and the like, but is preferably 0.1 to 20% by weight, more preferably 0.5 to 15% by weight with respect to the component (D). It is preferable that When the content ratio is less than 0.1% by weight, the photosensitivity becomes insufficient. On the other hand, when the content ratio exceeds 20% by weight, the storage stability as a resist ink is insufficient.
The color filter composition of the present invention is not limited in its production method as long as it contains the above essential components, but a pigment dispersion mainly composed of a pigment, a dispersant and a solvent is produced in advance, and then the component (D) and (E) It is advantageous to mix with resins and other components added if necessary.
In the composition for a color filter of the present invention, a resin having alkali solubility may be added as a binder resin component for the purpose of improving developability and coating film forming ability in addition to the above components. For example, polyethylene oxide, polyvinyl pyrrolidone, polyamide, polyurethane, polyester, polyether and the like can be mentioned, and those having a carboxyl group in the main chain or side chain and excellent in alkali developability are preferable. Examples of such resins include vinyl resins such as acrylic acid (co) polymer, (meth) acrylic acid (co) polymer, and maleic acid (co) polymer. In addition, a resin having a hydroxyl group added with an acid anhydride is also useful. These may be used alone or in combination of two or more.
In addition, although the composition for color filters of this invention contains said component (A), (B), (C), (D) and (E) as an essential component, the total solid is 1 to 40 weight. %, And more preferably 5 to 30% by weight.
As a method for producing a composition for a color filter, a pigment dispersion in which the above-mentioned subphthalocyanine pigment is dispersed in a solvent using a dispersant alone or together with another pigment in advance is produced, and the resin component, photopolymerization start Examples thereof include a method of blending an agent and the like, a method of directly dispersing a subphthalocyanine pigment in a resin composition, and the like, but the former method is preferred from the viewpoint of the stability of the color filter composition. In addition, there is a method of making a color resist ink by dissolving it in a composition containing a subphthalocyanine compound and a photosensitive resin using a highly soluble solvent capable of dissolving a subphthalocyanine pigment, but it has light resistance, heat resistance and solvent resistance. Since there is difficulty in the point of property, a method of forming a pigment and dispersing it is most preferable.
A cured product obtained by curing the composition for a color filter of the present invention is obtained by applying the composition to a substrate or the like and curing it by light irradiation, heating or the like. As a method of applying the composition, a known method can be used, and examples thereof include application by a coating apparatus such as a spin coater, a bar coater, and a die coater. After application, drying may be performed using a hot plate, IR oven or the like.
A known method can be used for irradiating the composition with light, and applicable exposure light sources are not particularly limited. For example, a xenon lamp, a halogen lamp, a tungsten lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a medium pressure mercury lamp. A lamp light source such as a low-pressure mercury lamp is used. However, the method of application | coating and light irradiation is not limited to said method.
If image development is performed with such a light source and then developed, an image can be formed on the substrate. Any developer can be used as long as it dissolves the unexposed portion and does not dissolve the exposed portion. Specifically, it is an alkaline solution containing various additives, and the additives can contain an organic solvent, a buffering agent, a surfactant and the like. Although there is no restriction | limiting in particular about the image development processing method, Methods, such as immersion development, spray image development, brush image development, and ultrasonic image development, are used.
As a method for increasing the strength of the coating film, heat curing with a hot air oven may be performed. Although there is no restriction | limiting in particular about the curing conditions of a composition, In order to prevent discoloration and discoloration of the cured film obtained by hardening | curing a composition, it is preferable to make it within 1 hour at 250 degrees C or less. In addition, a well-known method can be utilized as a method of manufacturing a color filter using the cured film of said color filter composition.

  1 and 2 are graphs showing the spectral transmittance of the model color filter.

合成例２
テトラクロロフタロニトリル１５０部に１−クロロナフタレン３００部を加え、窒素雰囲気下、室温で３０分攪拌したのち、予め１ｍｏｌ／Ｌに三塩化硼素を溶解させておいたヘプタン溶液４１７部を滴下する。その後、１８０℃までゆっくり加熱し、更に２００〜２４０℃で１０〜６０分加熱撹拌を行なう。放冷後、析出物を濾取して、アセトン、炭酸水素ナトリウム水溶液、水、メタノールの順で洗浄し乾燥して、式（３）で示されるＣｌ−ドデカクロロサブフタロシアニン硼素錯体６４部（収率４０％）を得た。次いで、この化合物を１０倍量の濃硫酸に溶解させ、この溶液を氷水中に注加し析出した固体を濾取、水洗、乾燥して顔料Ｂを得た。

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to a following example. In the following, “part” means part by weight.
Synthesis example 1
After adding 588 parts of o-dichlorobenzene to 150 parts of tetrachlorophthalonitrile and stirring at room temperature for 30 minutes in a nitrogen atmosphere, 71 parts of boron tribromide is added dropwise. Thereafter, the mixture is slowly heated to 100 ° C. When the reaction becomes mild, the mixture is further heated and stirred at 150 to 180 ° C. for 10 to 60 minutes. After allowing to cool, the precipitate was collected by filtration, washed with acetone, an aqueous solution of sodium hydrogen carbonate, water, and methanol in that order, dried, and 68 parts of a Br-dodecachlorosubphthalocyanine boron complex represented by the formula (2) 41%). Next, this compound was dissolved in 10 times the amount of concentrated sulfuric acid, this solution was poured into ice water, and the precipitated solid was collected by filtration, washed with water and dried to obtain pigment A.

Synthesis example 2
After adding 300 parts of 1-chloronaphthalene to 150 parts of tetrachlorophthalonitrile and stirring at room temperature for 30 minutes in a nitrogen atmosphere, 417 parts of a heptane solution in which boron trichloride is dissolved in advance to 1 mol / L is added dropwise. Then, it heats slowly to 180 degreeC, and also heat-stirs at 200-240 degreeC for 10 to 60 minutes. After allowing to cool, the precipitate was collected by filtration, washed with acetone, an aqueous sodium hydrogen carbonate solution, water and methanol in that order, dried, and 64 parts of Cl-dodecachlorosubphthalocyanine boron complex represented by the formula (3) 40%). Next, this compound was dissolved in 10 times the amount of concentrated sulfuric acid, this solution was poured into ice water, and the precipitated solid was collected by filtration, washed with water and dried to obtain pigment B.

  100 parts of pigment A obtained in Synthesis Example 1 is mixed with 40 parts of a dispersant and 860 parts of propylene glycol monomethyl ether acetate, subjected to a dispersion treatment for 6 hours using a paint shaker, filtered to remove beads, and dispersion 1000 The part was produced. Here, a graft polymer obtained by reacting a polyallylamine with a polyester having a free carboxyl group to form an amide was used as the dispersant. The paint shaker media used 0.4 mmφ glass beads at a filling rate of 40% or 0.4 mmφ zirconia beads at a filling rate of 15%. The dispersion A thus obtained had a solid content concentration of 14% by weight, and the ratio of the coloring material in the total solid content was 71.4% by weight, indicating low viscosity and low thixotropy. Moreover, the average particle diameter of the pigment in the dispersion (diluted to a pigment concentration of 1% by weight) measured using a particle size distribution meter (trade name: Particle Size Analyzer FPAR-1000, manufactured by Otsuka Electronics Co., Ltd.) was 98 nm.

  A dispersion was produced in the same manner as in Example 1 except that the pigment was changed to Pigment B obtained in Synthesis Example 2. The dispersion B thus obtained had a solid content concentration of 14% by weight, and the ratio of the colorant in the total solid content was 71.4% by weight, indicating low viscosity and low thixotropy. The average particle size of the pigment in the dispersion was 102 nm.

130 parts of a 54.2% by weight propylene glycol monomethyl ether acetate solution (trade name: V-259ME, manufactured by Nippon Steel Chemical Co., Ltd.) of an epoxy acrylate resin having a bisphenolfluorene skeleton, 47 parts of dipentaerythritol hexaacrylate, an epoxy having a biphenyl skeleton 17 parts of resin (trade name: Epicoat YX4000HK, manufactured by Japan Epoxy Resin Co., Ltd.), 7 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, p, p′-bis ( N, N-diethylamino) benzophenone 1 part, diethylene glycol dimethyl ether 196 parts, propylene glycol monomethyl ether acetate 75 parts, surfactant 1 part and silane coupling agent 1 part are mixed and stirred sufficiently to form a weak alkaline solution. It was manufactured composition 475 parts containing soluble photosensitive resin.
To 475 parts of the composition containing the photosensitive resin, 525 parts of Dispersion A obtained in Example 1 was blended, and sufficiently stirred until a uniform solution was obtained, thereby producing 1000 parts of a color filter composition. The composition thus obtained had a solid content concentration of 21.6% by weight and a pigment content in the total solid content of 24.3% by weight, indicating low viscosity and low thixotropy.
The color filter composition thus obtained was applied on a blue plate glass substrate having a 5 inch square and a thickness of 1 mm using a spin coater. At this time, the test piece was manufactured by changing the rotation speed of the spin coater. After this test piece was dried, it was covered with a photomask and subjected to UV exposure of 200 mJ / cm ² to cure the color resist ink in the exposed portion. Next, the test piece was alkali-developed with a 0.4% aqueous sodium carbonate solution for 60 seconds to remove the unexposed color resist ink and dried. Finally, the specimen was thermally cured to produce a cured film of color resist ink as a model color filter.
Spectral transmittance, chromaticity (x value, y value) and brightness (Y value) of the produced model color filter were measured using a chromaticity meter (trade name: Color Analyzer TC-1800MK2 manufactured by Tokyo Denshoku Co., Ltd.). However, the light for colorimetry at this time was standard light C. The spectral transmittance of the model color filter obtained in this example is shown in FIG. 1, and the chromaticity and brightness are shown in Table 1.

A color filter composition was prepared in the same manner as in Example 3 except that the pigment dispersion was changed to Dispersion B obtained in Example 2. The composition had a solid content concentration of 21.6% by weight and a pigment content ratio of 24.3% by weight, indicating a low viscosity and low thixotropy. In addition, the spectral transmittance, chromaticity, and brightness of the model color filter were measured for this composition in the same manner as in Example 3. The results are shown in FIG.
Reference example 1
100 parts of Pigment Blue 15: 6 is mixed with 40 parts of a dispersant and 860 parts of propylene glycol monomethyl ether acetate, dispersed for 6 hours using a paint shaker, filtered to remove beads, and dispersion C1000 The part was produced. Here, a graft polymer obtained by reacting a polyallylamine with a polyester having a free carboxyl group to form an amide was used as the dispersant. Further, 0.4 mmφ zirconia beads were used at a filling rate of 15% for the media of the paint shaker. Dispersion C thus obtained had a solid content concentration of 14% by weight and a colorant ratio in the total solid content of 71.4% by weight, indicating low viscosity and low thixotropy. The average particle size of the pigment in the dispersion was 150 nm.

130 parts of a 54.2% by weight propylene glycol monomethyl ether acetate solution (trade name: V-259ME, manufactured by Nippon Steel Chemical Co., Ltd.) of an epoxy acrylate resin having a bisphenolfluorene skeleton, 47 parts of dipentaerythritol hexaacrylate, an epoxy having a biphenyl skeleton 17 parts of resin (trade name: Epicoat YX4000HK, manufactured by Japan Epoxy Resin Co., Ltd.), 7 parts of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, p, p′-bis ( N, N-diethylamino) benzophenone 1 part, diethylene glycol dimethyl ether 196 parts, propylene glycol monomethyl ether acetate 75 parts, surfactant 1 part and silane coupling agent 1 part are mixed and stirred sufficiently to form a weak alkaline solution. It was manufactured composition 475 parts containing soluble photosensitive resin.
475 parts of the composition containing the photosensitive resin is blended with 262.5 parts of the dispersion B obtained in Example 2 and 262.5 parts of the dispersion C obtained in Reference Example 1, and is sufficient until a uniform solution is obtained. And 1,000 parts of a color filter composition were produced. The composition thus obtained had a solid content concentration of 21.6% by weight and a pigment content in the total solid content of 24.3% by weight, indicating low viscosity and low thixotropy. Further, the spectral transmittance of the model color filter was measured for this composition in the same manner as in Example 3. The result is shown in FIG.

比較例３
顔料分散体を参考例１で得られた分散体Ｃに変更した以外は実施例３と同様な方法にて、カラーフィルター用組成物を作製した。この組成物について実施例３と同様な方法にて、モデルカラーフィルターの分光透過率を測定した。その結果を図２に示す。
図１及び図２において、Ｅ３、Ｅ４、Ｅ５及びＥ６はそれぞれ実施例３、実施例４、実施例５及び実施例６を意味し、Ｃ１、Ｃ２及びＣ３はそれぞれ比較例１、比較例２及び比較例３を意味する。図１に示したように、本実施例で得られたモデルカラーフィルターの分光特性は、比較例のモデルカラーフィルターの場合と比較して、三波長型蛍光ランプの青の発光を効果的に透過し、赤及び緑の発光を効果的に遮光することができる高水準の明彩度性を有するものであった。また、その硬化膜は、膜厚均一で凝集析出物等のない塗布性良好なものであった。
本発明のカラーフィルター用組成物からなるモデルカラーフィルターは、表１からも明らかなように、比較例のモデルカラーフィルターの場合と比較して、大幅にＹ値が増大しており、本発明によって高水準の明彩度性を有するカラーフィルターが得られることが判る。

図２に示したように、他の青色顔料と併用する場合においても、本実施例で得られたモデルカラーフィルターの分光特性は、比較例のモデルカラーフィルターの場合と比較して、短波長域（３８０〜４６０ｎｍ付近）の透過率を向上させ、三波長型蛍光ランプの青の発光（４３５ｎｍ付近）を効果的に透過し得る高水準の明彩度性を有するものであった。また、その硬化膜は、膜厚均一で凝集析出物等のない塗布性良好なものであった。A color filter composition was prepared in the same manner as in Example 5 except that the pigment dispersion was changed to 472.5 parts of Dispersion B obtained in Example 2 and 52.5 parts of Dispersion C obtained in Reference Example 1. A product was made. The solid content concentration of the composition was 21.6% by weight, and the ratio of the pigment content in the total solid content was 24.3% by weight, indicating low viscosity and low thixotropy. Further, the spectral transmittance of the model color filter was measured for the composition in the same manner as in Example 3. The result is shown in FIG.
Comparative Example 1
A pigment dispersion was made in the same manner as in Example 1 except that the pigment was changed to Pigment Violet 23, and a color filter composition was prepared in the same manner as in Example 3. With respect to this composition, the spectral transmittance, chromaticity, and brightness of the model color filter were measured in the same manner as in Example 3. The results are shown in FIG.
Comparative Example 2
A pigment dispersion was made in the same manner as in Example 1 except that the pigment was changed to a Cl-subphthalocyanine boron complex pigment represented by the following formula (4). Was made. With respect to this composition, the spectral transmittance, chromaticity, and brightness of the model color filter were measured in the same manner as in Example 3. The results are shown in FIG.

Comparative Example 3
A color filter composition was prepared in the same manner as in Example 3 except that the pigment dispersion was changed to Dispersion C obtained in Reference Example 1. With respect to this composition, the spectral transmittance of the model color filter was measured in the same manner as in Example 3. The result is shown in FIG.
1 and 2, E3, E4, E5 and E6 mean Example 3, Example 4, Example 5 and Example 6, respectively, C1, C2 and C3 mean Comparative Example 1, Comparative Example 2 and This means Comparative Example 3. As shown in FIG. 1, the spectral characteristics of the model color filter obtained in this example are more effectively transmitted through the blue light emission of the three-wavelength fluorescent lamp than the model color filter of the comparative example. However, it has a high level of color saturation that can effectively block red and green light emission. The cured film had a uniform film thickness and good coatability without aggregated precipitates.
As is clear from Table 1, the model color filter comprising the color filter composition of the present invention has a significantly increased Y value compared to the model color filter of the comparative example. It can be seen that a color filter having a high level of color saturation can be obtained.

As shown in FIG. 2, even when used in combination with other blue pigments, the spectral characteristics of the model color filter obtained in this example are shorter than that of the model color filter of the comparative example. The transmissivity (around 380 to 460 nm) was improved, and it had a high level of color saturation that can effectively transmit the blue emission (near 435 nm) of the three-wavelength fluorescent lamp. The cured film had a uniform film thickness and good coatability without aggregated precipitates.

Industrial applicability

  The composition for a color filter of the present invention has a high level of color saturation and is extremely useful in terms of enabling production of a high-quality liquid crystal display or the like.

Claims (5)

In a color filter composition comprising a colorant, a dispersant, a solvent, a photosensitive resin and / or monomer, and a photopolymerization initiator, a subphthalocyanine represented by the following general formula (1) as a colorant component A pigment comprising a compound is contained in an amount of 0.5% by weight or more in the total colorant, a photopolymerization initiator is contained in an amount of 0.1 to 20% by weight based on the photosensitive resin and / or monomer, A composition for a color filter, wherein (A) / (R) represented by a weight ratio of the amount of colorant (A) and the amount of resin solids (R) is in the range of 0.05 to 1.5. .

(However, of X _{1 to} X ₁₂ , at least 6 are halogen atoms, and the rest represent hydrogen atoms. Y represents a halogen atom or a hydroxyl group.) In the pigment comprising the subphthalocyanine compound represented by the general formula (1), X ₁ ~ X ₁₂ The composition for a color filter according to claim 1, wherein all are halogen atoms. At least a part of the dispersant is at least one nitrogen-containing compound selected from the group consisting of (a) poly (ethyleneimine) and (b) polyallylamine, and (i) polyester, (ii) polyamide, and (iii) The color filter composition according to claim 1 or 2, which is a graft polymer obtained by reacting at least one compound having a free carboxyl group selected from the group consisting of polyesteramides. Hardened | cured material obtained by hardening | curing the composition for color filters in any one of Claims 1-3 . The color filter which the hardened film which forms a blue pixel consists of hardened | cured material of Claim 4 .

Images