JP4815895B2 - ε-type copper phthalocyanine pigment composition and method for producing the same - Google Patents
ε-type copper phthalocyanine pigment composition and method for producing the same Download PDFInfo
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- JP4815895B2 JP4815895B2 JP2005189642A JP2005189642A JP4815895B2 JP 4815895 B2 JP4815895 B2 JP 4815895B2 JP 2005189642 A JP2005189642 A JP 2005189642A JP 2005189642 A JP2005189642 A JP 2005189642A JP 4815895 B2 JP4815895 B2 JP 4815895B2
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- Prior art keywords
- copper phthalocyanine
- type copper
- phthalocyanine pigment
- pigment composition
- composition
- Prior art date
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- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 title claims description 174
- 239000000049 pigment Substances 0.000 title claims description 158
- 239000000203 mixture Substances 0.000 title claims description 146
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 40
- 239000000194 fatty acid Substances 0.000 claims description 40
- 229930195729 fatty acid Natural products 0.000 claims description 40
- 150000003839 salts Chemical class 0.000 claims description 40
- 150000004665 fatty acids Chemical class 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 33
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000003801 milling Methods 0.000 claims description 23
- -1 phthalimide alkylated phthalocyanine Chemical class 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000002639 sodium chloride Nutrition 0.000 description 42
- 239000003960 organic solvent Substances 0.000 description 25
- 238000004040 coloring Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- 239000006185 dispersion Substances 0.000 description 18
- 150000001875 compounds Chemical class 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910017053 inorganic salt Inorganic materials 0.000 description 13
- 238000000576 coating method Methods 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- 239000000976 ink Substances 0.000 description 12
- 239000001055 blue pigment Substances 0.000 description 11
- 239000003973 paint Substances 0.000 description 11
- 239000000758 substrate Substances 0.000 description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 238000000227 grinding Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
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- 239000000047 product Substances 0.000 description 8
- 229920005992 thermoplastic resin Polymers 0.000 description 8
- 238000002834 transmittance Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
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- 239000002270 dispersing agent Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
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- 238000010438 heat treatment Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
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- 238000004898 kneading Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002966 varnish Substances 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005642 Oleic acid Substances 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 2
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- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
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- 239000012965 benzophenone Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 2
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
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Description
本発明は、ε型銅フタロシアニン顔料組成物及びその製造方法に関する。 The present invention relates to an ε-type copper phthalocyanine pigment composition and a method for producing the same.
銅フタロシアニン顔料は、α型（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５、同１５：１及び同１５：２）、β型（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：３）及びε型（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：６）の結晶多型を示す。これら結晶型のうちε型は、最も赤味の青色の色相であると共にα型に比べて着色力に優れるという、特異的な特徴を有している。 Copper phthalocyanine pigments are α-type (CI Pigment Blue 15, 15: 1 and 15: 2), β-type (CI Pigment Blue 15: 3) and ε-type (CI Pigment Blue 15). 15: 6). Among these crystal types, the ε-type has a unique characteristic that it is the most reddish blue hue and is excellent in coloring power as compared with the α-type.
この様なε型銅フタロシアニン顔料の製造方法としては、例えば、特許文献１にある様に、ε型銅フタロシアニンを主成分として含有するε型粗製銅フタロシアニン顔料を乾式磨砕してε型銅フタロシアニンとα型銅フタロシアニンとの混合物を製造し、これを大過剰の有機溶剤中で加熱を行うソルベント処理によるε型銅フタロシニン顔料組成物の製造方法が知られている。 As a method for producing such an ε-type copper phthalocyanine pigment, for example, as disclosed in Patent Document 1, an ε-type copper phthalocyanine pigment containing ε-type copper phthalocyanine as a main component is dry-ground and ε-type copper phthalocyanine is used. There is known a method for producing an ε-type copper phthalosinine pigment composition by a solvent treatment in which a mixture of γ-type and copper α-phthalocyanine is produced and heated in a large excess of an organic solvent.
また、α型粗製銅フタロシアニン顔料またはα型銅フタロシアニン顔料を、フタルイミドアルキル化フタロシアニン誘導体と極少量のシードとなるε型銅フタロシアニンと、食塩等の磨砕助剤と共に有機溶剤の存在下で、ニーダー等の混練設備を使い機械的磨砕を行うソルベントソルトミリング処理によるε型銅フタロシニン顔料組成物の製造方法も知られている（特許文献２参照。）。 In addition, an α-type crude copper phthalocyanine pigment or an α-type copper phthalocyanine pigment is mixed with a phthalimide alkylated phthalocyanine derivative, an ε-type copper phthalocyanine serving as a very small amount of seed, and a grinding aid such as salt in the presence of an organic solvent. A method for producing an ε-type copper phthalosinin pigment composition by a solvent salt milling process in which mechanical grinding is performed using a kneading equipment such as the above is also known (see Patent Document 2).
さらに、ε型粗製銅フタロシアニン顔料、α型銅フタロシアニンを含有するε型微細銅フタロシアニン顔料及び窒素吸着法によるＢＥＴ比表面積９０ｍ２／ｇからなる群から選ばれるε型銅フタロシアニンを、食塩等の磨砕助剤と共に有機溶剤の存在下で、ニーダー等の混練設備を使い機械的磨砕を行うソルベントソルトミリング処理によるε型銅フタロシニン顔料の製造方法も知られている（特許文献３参照。） Further, ε-type copper phthalocyanine selected from the group consisting of ε-type crude copper phthalocyanine pigment, ε-type fine copper phthalocyanine pigment containing α-type copper phthalocyanine, and a BET specific surface area of 90 m 2 / g by nitrogen adsorption method, There is also known a method for producing an ε-type copper phthalosinin pigment by a solvent salt milling process in which kneading equipment such as a kneader is used for mechanical grinding in the presence of an organic solvent together with a grinding aid (see Patent Document 3).
前記した各特許文献に記載された製造方法により得られるε型銅フタロシアニン顔料及びその組成物は、いずれも着色力が不充分であるという欠点があった。 Each of the ε-type copper phthalocyanine pigments obtained by the production methods described in each of the above-mentioned patent documents and their compositions have a drawback that their coloring power is insufficient.
本発明が解決しようとする課題は、例えば、印刷インキ、塗料、着色プラスチック成形品、インクジェット記録用インク、カラーフィルタ用レジスト等の調製に青色着色剤として用いた際に、従来のε型銅フタロシアニン顔料より、より優れた着色力を示すε型銅フタロシアニン顔料組成物を提供することにある。 The problems to be solved by the present invention include, for example, conventional ε-type copper phthalocyanine when used as a blue colorant in the preparation of printing inks, paints, colored plastic molded articles, ink jet recording inks, color filter resists, etc. An object of the present invention is to provide an ε-type copper phthalocyanine pigment composition that exhibits better coloring power than a pigment.
本発明者等は、より優れた着色力を示すε型銅フタロシアニン顔料及びその製造方法について鋭意検討したところ、ε型銅フタロシアニン顔料とフタルイミドアルキル化フタロシアニンと高級脂肪酸またはその塩とを含み、高級脂肪酸またはその塩を特定量含有させること、高級脂肪酸またはその塩を任意の段階において含有させ、フタルイミドアルキル化フタロシアニンを含有するα型銅フタロシアニンをソルベントソルトミリング処理することで、前記課題が解決されることを見い出し、本発明を完成するに至った。 The present inventors diligently studied about an ε-type copper phthalocyanine pigment exhibiting superior coloring power and a method for producing the ε-type copper phthalocyanine pigment, including an ε-type copper phthalocyanine pigment, a phthalimidoalkylated phthalocyanine, and a higher fatty acid or a salt thereof. Alternatively, the above-mentioned problem can be solved by containing a specific amount of the salt, adding a higher fatty acid or salt thereof at any stage, and subjecting the α-type copper phthalocyanine containing the phthalimidoalkylated phthalocyanine to a solvent salt milling treatment. As a result, the present invention has been completed.
即ち本発明は、ε型銅フタロシアニン顔料（Ａ）とフタルイミドアルキル化フタロシアニン（Ｂ）と高級脂肪酸またはその塩（Ｃ）とを含有し、質量基準で、前記顔料（Ａ）と前記フタロシアニン（Ｂ）の合計１００部当たり高級脂肪酸またはその塩（Ｃ）１〜１０部であることを特徴とするε型銅フタロシアニン顔料組成物を提供する。 That is, the present invention comprises an ε-type copper phthalocyanine pigment (A), a phthalimidoalkylated phthalocyanine (B), a higher fatty acid or a salt thereof (C), and on a mass basis, the pigment (A) and the phthalocyanine (B). The ε-type copper phthalocyanine pigment composition is characterized in that it is 1 to 10 parts of a higher fatty acid or a salt thereof (C) per 100 parts in total.
また本発明は、α型銅フタロシアニン（Ｘ）と、ε型銅フタロシアニン（Ｙ）と、フタルイミドアルキル化フタロシアニン（Ｂ）とをソルベントソルトミリング処理するε型銅フタロシアニン顔料組成物の製造方法において、高級脂肪酸またはその塩の存在下でソルベントソルトミリング処理することを特徴とする、前記ε型銅フタロシアニン顔料組成物の製造方法を提供する。 Further, the present invention provides a high-level production method of an ε-type copper phthalocyanine pigment composition comprising a solvent salt milling treatment of α-type copper phthalocyanine (X), ε-type copper phthalocyanine (Y), and phthalimidoalkylated phthalocyanine (B). Provided is a process for producing the ε-type copper phthalocyanine pigment composition, characterized by performing a solvent salt milling treatment in the presence of a fatty acid or a salt thereof.
本発明のε型銅フタロシアニン顔料組成物は、高級脂肪酸またはその塩を特定量含有しているので、より着色力に優れる着色物が得られるという格別顕著な効果を奏する。また本発明の製造方法では、前記したε型銅フタロシニン顔料組成物を簡便に製造することが出来るという格別顕著な効果を奏する。 Since the ε-type copper phthalocyanine pigment composition of the present invention contains a specific amount of a higher fatty acid or a salt thereof, there is a particularly remarkable effect that a colored product having more excellent coloring power can be obtained. Moreover, in the manufacturing method of this invention, there exists an especially remarkable effect that the above-mentioned (epsilon) type copper phthalosinine pigment composition can be manufactured simply.
本発明のε型銅フタロシアニン顔料組成物は、青色顔料であるε型銅フタロシアニン顔料（Ａ）と、フタルイミドアルキル化フタロシアニン（Ｂ）と、高級脂肪酸またはその塩（Ｃ）とを含有する。以下、フタルイミドアルキル化フタロシアニン（Ｂ）は誘導体（Ｂ）、高級脂肪酸またはその塩（Ｃ）は、脂肪酸（Ｃ）と略記する。 The ε-type copper phthalocyanine pigment composition of the present invention contains an ε-type copper phthalocyanine pigment (A) that is a blue pigment, a phthalimidoalkylated phthalocyanine (B), and a higher fatty acid or a salt thereof (C). Hereinafter, phthalimidoalkylated phthalocyanine (B) is abbreviated as derivative (B), and higher fatty acid or its salt (C) is abbreviated as fatty acid (C).
ε型銅フタロシアニン顔料（Ａ）は、Ｘ線回折スペクトル（ＣｕＫα線）によるブラッグ角２θ（許容範囲±０．２°）＝９．２°に最も強いピークを有する銅フタロシアニン顔料である。このピークは、α型やβ型とは異なるε型銅フタロシアニン顔料に固有なものである。このε型銅フタロシアニン顔料（Ａ）は、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：６とも呼ばれる。 The ε-type copper phthalocyanine pigment (A) is a copper phthalocyanine pigment having the strongest peak at a Bragg angle 2θ (allowable range ± 0.2 °) = 9.2 ° according to an X-ray diffraction spectrum (CuKα ray). This peak is unique to ε-type copper phthalocyanine pigments different from α-type and β-type. This ε-type copper phthalocyanine pigment (A) is C.I. I. Also called Pigment Blue 15: 6.
誘導体（Ｂ）は、フタルイミドアルキル化フタロシアニンからなる。この誘導体（Ｂ）は、少なくとも一つのフタルイミドアルキル基がフタロシアニン環上の水素原子と置換され結合した、無金属フタロシアニンまたは金属フタロシアニンである。尚、フタルイミドアルキル基として代表的なフタルイミドメチル基は、次の様な基をいう。 The derivative (B) consists of phthalimidoalkylated phthalocyanine. This derivative (B) is a metal-free phthalocyanine or metal phthalocyanine in which at least one phthalimidoalkyl group is substituted and bonded to a hydrogen atom on the phthalocyanine ring. A typical phthalimidomethyl group as a phthalimidoalkyl group refers to the following group.
本発明のε型銅フタロシアニン顔料組成物において、ε型銅フタロシアニン顔料（Ａ）と誘導体（Ｂ）の含有割合は、特に制限されるものではないが、質量基準で、ε型銅フタロシアニン顔料（Ａ）１００部当たり誘導体（Ｂ）１〜２０部とすることが適切な着色力となることから好ましい。 In the ε-type copper phthalocyanine pigment composition of the present invention, the content ratio of the ε-type copper phthalocyanine pigment (A) and the derivative (B) is not particularly limited, but the ε-type copper phthalocyanine pigment (A ) It is preferable that 1 to 20 parts of the derivative (B) per 100 parts is obtained because appropriate coloring power is obtained.
脂肪酸（Ｃ）は、高級脂肪酸またはその塩である。高級脂肪酸は、炭素原子数５〜２４のモノカルボン酸であり、分子内の炭素炭素二重結合の有無により、飽和酸または不飽和酸がある。それは、分枝構造、環状構造、三重結合を分子中に有しても良い。脂肪酸（Ｃ）としては、炭素原子数１０〜２０のモノカルボン酸、好適には、例えば、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、ラウリン酸およびこれらのアルカリ金属塩やアミン塩等を挙げることができる。脂肪酸（Ｃ）は、単一、または二種以上の混合物であっても良い。脂肪酸（Ｃ）は、固体であっても液体であっても良い。ちなみに、飽和酸の多くは固体、不飽和酸の多くは液体である。この脂肪酸（Ｃ）には、ワックスとして用いられている脂肪酸エステルや脂肪酸アミドは、包含されない。本発明における顔料組成物は、これらワックスを含む同様の顔料組成物に比べて優れたものである。 The fatty acid (C) is a higher fatty acid or a salt thereof. Higher fatty acids are monocarboxylic acids having 5 to 24 carbon atoms, and there are saturated acids and unsaturated acids depending on the presence or absence of carbon-carbon double bonds in the molecule. It may have a branched structure, a cyclic structure, or a triple bond in the molecule. Examples of the fatty acid (C) include monocarboxylic acids having 10 to 20 carbon atoms, preferably, for example, palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, lauric acid, and alkali metal salts and amine salts thereof. Etc. The fatty acid (C) may be a single species or a mixture of two or more species. The fatty acid (C) may be solid or liquid. Incidentally, many saturated acids are solids and many unsaturated acids are liquids. This fatty acid (C) does not include fatty acid esters and fatty acid amides used as waxes. The pigment composition in the present invention is superior to similar pigment compositions containing these waxes.
本発明のε型銅フタロシアニン顔料組成物において、脂肪酸（Ｃ）は、ε型銅フタロシアニン顔料（Ａ）と誘導体（Ｂ）の合計１００部当たり１〜１０部である。 In the ε-type copper phthalocyanine pigment composition of the present invention, the fatty acid (C) is 1 to 10 parts per 100 parts in total of the ε-type copper phthalocyanine pigment (A) and the derivative (B).
本発明におけるε型銅フタロシアニン顔料組成物は、そこに含まれる粒子が微細であるほど被着色媒体を着色した際の着色物の着色力を高められる点で、窒素吸着法によるＢＥＴ比表面積７０〜１３０ｍ２／ｇであることが好ましい。窒素吸着法におけるＢＥＴ比表面積は、ＪＩＳ Ｚ ８８３０−１９９０（気体吸着による粉体の比表面積測定方法）に従って測定することが出来る。着色物として、着色力の他に、高い耐光性や耐候性が要求される場合は、このＢＥＴ比表面積は小さい方が好ましい。 In the ε-type copper phthalocyanine pigment composition of the present invention, the finer the particles contained therein, the higher the coloring power of the colored product when coloring the medium to be colored. It is preferably 130 m 2 / g. The BET specific surface area in the nitrogen adsorption method can be measured according to JIS Z 8830-1990 (method for measuring the specific surface area of powder by gas adsorption). In the case where high light resistance and weather resistance are required in addition to coloring power as a colored product, the BET specific surface area is preferably small.
この様なε型銅フタロシアニン顔料組成物は、被着色媒体中への顔料の分散性、分散後の分散安定性が高く、それを液媒体に分散させて得た後記する青色顔料分散液の粘度も低く安定（微細な粒子に分散）であり、この顔料組成物を含有するコーティング剤は、基材に塗布した場合に、均質な塗膜を形成して透明性が高い着色被膜を得ることが出来る。 Such an ε-type copper phthalocyanine pigment composition has high dispersibility of the pigment in the medium to be colored and high dispersion stability after dispersion, and the viscosity of the blue pigment dispersion described below obtained by dispersing it in the liquid medium. It is low and stable (dispersed in fine particles), and the coating agent containing this pigment composition can form a uniform coating film when applied to a substrate to obtain a highly transparent colored coating film. I can do it.
また、この様なε型銅フタロシアニン顔料組成物は、カラーフィルター青色画素部を形成する光硬化性組成物への分散が容易であり、これを硬化する際に多用される３６５ｎｍにおける遮光性が低下することもない（即ち高透過性）。また光硬化感度の低下もなく、現像時の膜へりやパターン流れも起こり難くなるので好ましい。そのため、近年要求されている塗膜の輝度、コントラストおよび光透過率のいずれもが高いカラーフィルター青色画素部をより簡便に得ることが出来る。ここでコントラストとは、２枚の偏光板の偏光方向を平行にして被測定物を挟み込んだ時の透過光強度を２枚の偏光板の偏光方向を垂直にして被測定物を挟み込んだ時の透過光強度で除したものであり、消偏性とも呼ばれるものである。 In addition, such an ε-type copper phthalocyanine pigment composition is easy to disperse in the photocurable composition forming the color filter blue pixel portion, and the light-shielding property at 365 nm often used for curing this is reduced. (Ie high permeability). Further, it is preferable because the photocuring sensitivity is not lowered and the film edge and pattern flow hardly occur during development. Therefore, a color filter blue pixel portion having high brightness, contrast, and light transmittance of a coating film that has been required in recent years can be more easily obtained. Here, the contrast is the transmitted light intensity when the object to be measured is sandwiched with the polarization directions of the two polarizing plates parallel to each other and the object to be measured is sandwiched with the polarization direction of the two polarizers perpendicular to each other. This is divided by the transmitted light intensity and is also called depolarization.
本発明のε型銅フタロシアニン顔料組成物は、例えば、ε型銅フタロシアニン顔料（Ａ）と、誘導体（Ｂ）と、脂肪酸（Ｃ）とを、前記した質量割合となる様に、混合すれば製造することが出来る。ε型銅フタロシアニン顔料組成物は、予め誘導体（Ｂ）と脂肪酸（Ｃ）とを充分に混合した後、それとε型銅フタロシアニン顔料（Ａ）とを混合したり、予めε型銅フタロシアニン顔料（Ａ）と脂肪酸（Ｃ）とを充分に混合した後、それと誘導体（Ｂ）とを混合することで製造することも出来る。必要であれば、ε型銅フタロシアニン顔料（Ａ）、誘導体（Ｂ）及び脂肪酸（Ｃ）を予め混合前に、混合しながら、或いは、混合後に、ボールミリングやアトライター等の公知慣用の手段により摩砕して、前記した好適な比表面積となる様にすることも出来る。 The ε-type copper phthalocyanine pigment composition of the present invention can be produced, for example, by mixing the ε-type copper phthalocyanine pigment (A), the derivative (B), and the fatty acid (C) so that the mass ratio is as described above. I can do it. The ε-type copper phthalocyanine pigment composition is prepared by mixing the derivative (B) and the fatty acid (C) in advance, and then mixing it with the ε-type copper phthalocyanine pigment (A), or by previously mixing the ε-type copper phthalocyanine pigment (A ) And the fatty acid (C) are sufficiently mixed and then mixed with the derivative (B). If necessary, the ε-type copper phthalocyanine pigment (A), the derivative (B) and the fatty acid (C) are mixed in advance before mixing, or after mixing, by known and conventional means such as ball milling or attritor. It can also be ground to achieve the preferred specific surface area described above.
しかしながら、より少量の脂肪酸（Ｃ）でより高い改良効果を発現させ、かつ前記した様な好適な比表面積のε型銅フタロシアニン顔料組成物を簡便に製造する方法がある。それは、α型銅フタロシアニン（Ｘ）と、ε型銅フタロシアニン（Ｙ）と、誘導体（Ｂ）とをソルベントソルトミリング処理するε型銅フタロシアニン顔料組成物の製造方法において、任意の段階において高級脂肪酸またはその塩を含有させることを特徴とする、前記ε型銅フタロシアニン顔料組成物の製造方法である。 However, there is a method for easily producing an ε-type copper phthalocyanine pigment composition that exhibits a higher improvement effect with a smaller amount of fatty acid (C) and has a suitable specific surface area as described above. In the method for producing an ε-type copper phthalocyanine pigment composition in which an α-type copper phthalocyanine (X), an ε-type copper phthalocyanine (Y), and a derivative (B) are subjected to solvent salt milling, The production method of the ε-type copper phthalocyanine pigment composition, characterized by containing the salt.
この製造方法では、ε型銅フタロシアニン（Ｙ）をシードとして、α型銅フタロシアニン（Ｘ）と誘導体（Ｂ）との混合物をソルベントソルトミリング処理する。α型銅フタロシアニン（Ｘ）としては、α型銅フタロシアニン顔料が挙げられる。α型銅フタロシアニン顔料は、Ｃ．Ｉ．ピグメントブルー１５、同１５：１及び同１５：２等の市販品のいずれもを用いることが出来る。Ｘ線回折スペクトルによるブラッグ角２θから、α型銅フタロシアニン（Ｘ）は、シードであるε型銅フタロシアニン（Ｙ）と容易に区別することが出来る。 In this production method, a solvent salt milling treatment is performed on a mixture of α-type copper phthalocyanine (X) and derivative (B) using ε-type copper phthalocyanine (Y) as a seed. Examples of α-type copper phthalocyanine (X) include α-type copper phthalocyanine pigments. The α-type copper phthalocyanine pigment is C.I. I. Any of commercially available products such as CI Pigment Blue 15, 15: 1, and 15: 2 can be used. From the Bragg angle 2θ according to the X-ray diffraction spectrum, α-type copper phthalocyanine (X) can be easily distinguished from ε-type copper phthalocyanine (Y) as a seed.
ε型銅フタロシアニン（Ｙ）はシードであり、それは、α型銅フタロシアニン（Ｘ）の全てを、このソルベントソルトミリング処理により、より簡便にε型銅フタロシアニン顔料に転換させるために用いられる。ソルベントソルトミリングに供する混合物は、質量割合で、α型銅フタロシアニン（Ｘ）＞＞ε型銅フタロシアニン（Ｙ）となる様に調整される。α型銅フタロシアニン（Ｘ）とε型銅フタロシアニン（Ｙ）との質量割合は特に制限されないが、例えば、前者１００部当たり後者０．０５〜８部、中でも０．５〜５部であることが好ましい。 ε-type copper phthalocyanine (Y) is a seed, which is used to more easily convert all α-type copper phthalocyanine (X) into an ε-type copper phthalocyanine pigment by this solvent salt milling treatment. The mixture to be subjected to solvent salt milling is adjusted by mass ratio such that α-type copper phthalocyanine (X) >> ε-type copper phthalocyanine (Y). The mass ratio of α-type copper phthalocyanine (X) and ε-type copper phthalocyanine (Y) is not particularly limited. For example, the latter may be 0.05 to 8 parts per 100 parts, particularly 0.5 to 5 parts. preferable.
また、ε型銅フタロシアニン（Ｙ）としては、前記したε型銅フタロシアニン顔料（Ａ）だけでなく、それより比表面積が小さいε型粗製銅フタロシアニン顔料を用いることも出来る。 As the ε-type copper phthalocyanine (Y), not only the ε-type copper phthalocyanine pigment (A) described above but also an ε-type crude copper phthalocyanine pigment having a smaller specific surface area can be used.
本発明においてソルベントソルトミリング処理とは、α型銅フタロシアニン（Ｘ）とε型銅フタロシアニン（Ｙ）と誘導体（Ｂ）と、無機塩と、有機溶剤とを混練摩砕することを意味する。 In the present invention, solvent salt milling means kneading and grinding α-type copper phthalocyanine (X), ε-type copper phthalocyanine (Y), derivative (B), an inorganic salt, and an organic solvent.
このソルベントソルトミリング処理により、α型銅フタロシアニン（Ｘ）の結晶変換および微細化が同時並行に行われ、またε型フタロシアニン（Ｙ）は、微細化が行われる。この処理により得られたε型銅フタロシアニン顔料組成物からは、被着色媒体への分散性、その中での分散安定性がより向上し、高い着色力の着色物が得られる。 By this solvent salt milling process, crystal conversion and refinement of α-type copper phthalocyanine (X) are performed in parallel, and ε-type phthalocyanine (Y) is refined. From the ε-type copper phthalocyanine pigment composition obtained by this treatment, dispersibility in the medium to be colored and dispersion stability therein are further improved, and a colored product having high coloring power can be obtained.
脂肪酸（Ｃ）は、本発明のε型銅フタロシアニン顔料組成物を製造する任意の段階において、系内に含ませることが出来る。シードや顔料誘導体を含ませることによる効果を最大限発揮させて、α型銅フタロシアニン（Ｘ）をε型銅フタロシニン顔料（Ａ）とするためには、シードであるε型銅フタロシアニン（Ｙ）と誘導体（Ｂ）とがいずれも極力、露出した形で仕込まれることが好ましい。即ち、これらは、いずれも脂肪酸（Ｃ）で被覆されていないことが好ましい。 The fatty acid (C) can be included in the system at any stage for producing the ε-type copper phthalocyanine pigment composition of the present invention. In order to maximize the effects of including seeds and pigment derivatives and to convert α-type copper phthalocyanine (X) into ε-type copper phthalocyanine pigment (A), the seed ε-type copper phthalocyanine (Y) It is preferable that the derivative (B) is charged in an exposed form as much as possible. That is, it is preferable that none of these is coated with the fatty acid (C).
そのため、ソルベントソルトミリング処理は、脂肪酸（Ｃ）を含有したα型銅フタロシアニン（Ｘ）と、脂肪酸（Ｃ）を含まないε型銅フタロシアニン（Ｙ）と、脂肪酸（Ｃ）を含まない誘導体（Ｂ）と、無機塩と、それを溶解しない有機溶剤とを混練摩砕することが好ましい。 Therefore, the solvent salt milling treatment is carried out using α-type copper phthalocyanine (X) containing fatty acid (C), ε-type copper phthalocyanine (Y) not containing fatty acid (C), and derivatives containing no fatty acid (C) (B ), An inorganic salt, and an organic solvent that does not dissolve it are preferably kneaded and ground.
脂肪酸（Ｃ）をα型銅フタロシアニン（Ｘ）に含有させる代表的な方法としては、例えば、α型銅フタロシアニン（Ｘ）の製造前、製造中、製造後に、それを含ませる方法がある。具体的には、例えば、予め得た脂肪酸（Ｃ）を含まないα型銅フタロシアニン（Ｘ）に対して、塩となした脂肪酸（Ｃ）を加えて酸析する方法、脂肪酸（Ｃ）のエマルジョンを加える方法、脂肪酸（Ｃ）をドライブレンドする方法等がある。ソルベントソルトミリング処理において、ε型銅フタロシアニン（Ｙ）と誘導体（Ｂ）とがいずれも露出した形で保たれる様に、フリーの脂肪酸（Ｃ）含有量が極力少ない、脂肪酸（Ｃ）を含有するα型銅フタロシアニン（Ｘ）を用いることが、最も好ましい。 As a typical method of incorporating the fatty acid (C) into the α-type copper phthalocyanine (X), for example, there is a method of including the α-type copper phthalocyanine (X) before, during and after the production. Specifically, for example, a method of adding a salted fatty acid (C) to an α-type copper phthalocyanine (X) that does not contain a fatty acid (C) obtained in advance, and acidifying it, an emulsion of fatty acid (C) And a method of dry blending the fatty acid (C). In the solvent salt milling process, the free fatty acid (C) content is as low as possible and the fatty acid (C) is contained so that both ε-type copper phthalocyanine (Y) and derivative (B) are kept exposed. It is most preferable to use α-type copper phthalocyanine (X).
ソルベントソルトミリング処理は、前記した各原料を混練機に仕込み、その中で混練摩砕することで行うことが出来る。この際の混練手段としては、例えば、ニーダーやミックスマーラー等の混練機が挙げられる。 The solvent salt milling process can be performed by charging each of the above-described raw materials into a kneader and kneading and grinding in the kneader. Examples of the kneading means at this time include kneaders such as a kneader and a mix muller.
前記無機塩としては、水溶性無機塩が好適に使用出来、例えば、塩化ナトリウム、塩化カリウム、硫酸ナトリウム等の無機塩を使用することが好ましい。また、平均粒子径が０．３〜７０μｍの無機塩を使用することがより好ましい。この様な無機塩としては、通常の無機塩を微粉砕することにより容易に得ることが出来る。 As said inorganic salt, water-soluble inorganic salt can be used conveniently, For example, it is preferable to use inorganic salts, such as sodium chloride, potassium chloride, sodium sulfate. It is more preferable to use an inorganic salt having an average particle size of 0.3 to 70 μm. Such an inorganic salt can be easily obtained by pulverizing a normal inorganic salt.
本発明において好適な比表面積のε型銅フタロシアニン顔料組成物を得るに当たっては、無機塩の使用量を、質量換算で、α型銅フタロシアニン（Ｘ）と、ε型銅フタロシアニン（Ｙ）と、誘導体（Ｃ）との合計１部当たり３〜３０部とすることが出来、カラーフィルター画素部を形成するための本顔料組成物を調製する場合には、なかでも７〜３０部とするのが好ましく、特に１５〜３０部とするのが最も好ましい。 In obtaining an ε-type copper phthalocyanine pigment composition having a specific surface area suitable for the present invention, the amount of inorganic salt used is, in terms of mass, α-type copper phthalocyanine (X), ε-type copper phthalocyanine (Y), and derivatives. When the present pigment composition for forming a color filter pixel part is prepared, it is preferably 7 to 30 parts per part in total with (C). In particular, the amount is most preferably 15 to 30 parts.
有機溶剤としては、例えば、ジエチレングリコール、グリセリン、エチレングリコール、プロピレングリコール、液体ポリエチレングルコール、液体ポリプロピレングリコール、２−（メトキシメトキシ）エタノール、２−ブトキシエタノール、２ー（イソペンチルオキシ）エタノール、２−（ヘキシルオキシ）エタノール、ジエチレングリコールモノメチルエーテル、ジエチレングルコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、トリエチレングリコール、トリエチレングリコールモノメチルエーテル、１−メトキシ−２−プロパノール、１−エトキシ−２−プロパノール、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコール等を使用することが出来る。 Examples of the organic solvent include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (Hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol , Dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol It can be used Lumpur and the like.
有機溶剤の使用量は、特に限定されるものではないが、質量換算で、α型銅フタロシアニン（Ｘ）と、ε型銅フタロシアニン（Ｙ）と、誘導体（Ｃ）との合計１部当たり０．０１〜５部が好ましい。 The amount of the organic solvent to be used is not particularly limited, but in terms of mass, the total amount of α-type copper phthalocyanine (X), ε-type copper phthalocyanine (Y), and derivative (C) is 0.00. 01-5 parts are preferred.
本発明においては、色相等を変化させない範囲で必要であれば、金属フタロシアンスルホン酸の様な、フタルイミドアルキル化フタロシアニン以外のフタロシアニン誘導体、モノクロロ銅フタロシアニンやテトラクロロ銅フタロシアニンの様な部分塩素化フタロシアニン化合物を含有させることが出来る。金属フタロシアンスルホン酸や金属フタロシアニン高級脂肪族アミン塩の様な、フタルイミドアルキル化フタロシアニン以外のフタロシアニン誘導体は、ε型銅フタロシアニン顔料組成物を構成する粒子の内部または粒子の表面に存在していることが、粒子を含む被着色媒体の流動性等の改善効果が高くなるので好ましい。 In the present invention, if necessary within the range in which the hue or the like is not changed, phthalocyanine derivatives other than phthalimidoalkylated phthalocyanine, such as metal phthalocyanine sulfonic acid, partially chlorinated phthalocyanine such as monochlorocopper phthalocyanine and tetrachlorocopper phthalocyanine A compound can be contained. Phthalocyanine derivatives other than phthalimidoalkylated phthalocyanine, such as metal phthalocyanine sulfonic acid and metal phthalocyanine higher aliphatic amine salts, must be present inside or on the surface of the particles constituting the ε-type copper phthalocyanine pigment composition. However, it is preferable because the effect of improving the fluidity and the like of the medium to be colored containing particles is increased.
ソルベントソルトミリング処理において、前記した様な無機塩や有機溶剤は、最初の仕込段階で必要量全量を仕込んで以降そのまま、α型銅フタロシアニン（Ｘ）が実質的にε型銅フタロシアニン顔料（Ａ）となるまで、或いは、さらに前記した好適な比表面積の所望の比表面積となるまで摩砕を行っても良いし、必要量の一部だけを仕込んで摩砕を開始し、途中で無機塩および／または有機溶剤の残量を、一括または分割して仕込む様にして摩砕を行う様にしても良い。 In the solvent salt milling process, the inorganic salt and the organic solvent as described above are charged in the initial charging stage with the necessary amount of the whole amount, and then the α-type copper phthalocyanine (X) is substantially the ε-type copper phthalocyanine pigment (A). Or until the desired specific surface area of the above-mentioned suitable specific surface area is reached, grinding may be carried out by charging only a part of the necessary amount, and inorganic salts and Alternatively, the grinding may be performed by charging the remaining amount of the organic solvent in a lump or dividedly.
ソルベントソルトミリング処理時の温度は、３０〜１５０℃が好ましく、なかでも６０〜１２０℃がより好ましい。また、ソルベントソルトミリング処理の時間は、３時間から３６時間が好ましく、なかでも５〜２４時間がより好ましい。 The temperature during the solvent salt milling treatment is preferably 30 to 150 ° C, and more preferably 60 to 120 ° C. The time for the solvent salt milling treatment is preferably 3 hours to 36 hours, and more preferably 5 to 24 hours.
ソルベントソルトミリング中の経時サンプリングから、顔料組成物中のα型からε型への結晶変換の程度や比表面積値等に基づいて、必要とする特性をもった本発明のε型銅フタロシアニン顔料組成物を得るソルベントソルトミリングの条件を選定することが出来る。 Ε-type copper phthalocyanine pigment composition of the present invention having required characteristics based on the degree of crystal conversion from α-type to ε-type in pigment composition, specific surface area value, etc. from sampling over time during solvent salt milling Solvent salt milling conditions for obtaining products can be selected.
本発明のε型銅フタロシアニン顔料組成物は、脂肪酸（Ｃ）を含むε型銅フタロシアニン（Ｙ）を誘導体（Ｂ）の存在下で結晶変換させない様にソルベントソルトミリング処理することで得ることも可能であるが、脂肪酸（Ｃ）を含有するα型銅フタロシアニン（Ｘ）をシードのε型銅フタロシアニン（Ｙ）と誘導体（Ｂ）の存在下で結晶変換と粒子が小さくなる様にソルベントソルトミリング処理する方が、原料の入手、トータルコスト低減化がいずれも容易であると共に、前者の製造方法に比べて製造条件の自由度を大きくとれる点で好ましい。 The ε-type copper phthalocyanine pigment composition of the present invention can be obtained by subjecting the ε-type copper phthalocyanine (Y) containing the fatty acid (C) to a solvent salt milling treatment so as not to cause crystal conversion in the presence of the derivative (B). However, in the presence of ε-type copper phthalocyanine (Y) and derivative (B) as seeds, α-type copper phthalocyanine (X) containing fatty acid (C) is subjected to solvent salt milling so that the crystal transformation and particles become small This is preferable in that it is easy to obtain raw materials and reduce the total cost, and can increase the degree of freedom of manufacturing conditions compared to the former manufacturing method.
こうして、本発明のε型銅フタロシアニン顔料組成物、無機塩、有機溶剤を主成分として含む混合物が得られるが、この混合物から有機溶剤と、無機塩とを除去し、固形物を洗浄、濾過、乾燥、粉砕等を行うことにより、本発明のε型銅フタロシアニン顔料組成物の粉体を得ることが出来る。 Thus, an ε-type copper phthalocyanine pigment composition of the present invention, an inorganic salt, and a mixture containing an organic solvent as main components are obtained. The organic solvent and the inorganic salt are removed from this mixture, and the solid is washed, filtered, By performing drying, pulverization and the like, the powder of the ε-type copper phthalocyanine pigment composition of the present invention can be obtained.
尚、この洗浄方法としては、水洗、湯洗のいずれをも採用することが出来る。水溶性無機塩および有機溶剤を用いた前記混合物の場合は、水洗することで容易に有機溶剤と無機塩を除去することが出来る。比電導度のもとなる物質は、極力除去されていることが好ましい。特に、インクジェット記録用インクやカラーフィルター画素部を調製するための本発明のε型銅フタロシアニン顔料組成物は、比電導度が水あるいは熱水との差において５０μＳ／ｃｍ以下、好ましくは２０μＳ／ｃｍ以下となるまで洗浄を行うのが好ましい。 As this cleaning method, either water washing or hot water washing can be employed. In the case of the mixture using a water-soluble inorganic salt and an organic solvent, the organic solvent and the inorganic salt can be easily removed by washing with water. It is preferable that the material having the specific conductivity is removed as much as possible. In particular, the ε-type copper phthalocyanine pigment composition of the present invention for preparing ink jet recording inks and color filter pixel portions has a specific conductivity of 50 μS / cm or less, preferably 20 μS / cm in terms of the difference from water or hot water. Washing is preferably performed until the following is achieved.
前記した洗浄、濾過後の乾燥方法としては、例えば、乾燥機に設置した加熱源による８０〜１２０℃の加熱等により、液媒体を含んだ本発明のε型銅フタロシアニン顔料組成物の脱水および／または脱溶剤をする回分式あるいは連続式で乾燥する方法等が挙げられる。またその際に使用する乾燥機としては、例えば、箱型乾燥機、バンド乾燥機、スプレードライヤー等が挙げられる。 Examples of the drying method after washing and filtration described above include dehydration and / or dehydration of the ε-type copper phthalocyanine pigment composition of the present invention containing a liquid medium by, for example, heating at 80 to 120 ° C. with a heating source installed in a dryer. Or the method of drying by the batch type or continuous type which removes a solvent, etc. are mentioned. Examples of the dryer used at that time include a box-type dryer, a band dryer, and a spray dryer.
乾燥後の粉砕方法としては、ε型銅フタロシアニン顔料組成物の比表面積を大きくしたり、一次粒子の平均粒子径を小さくするための操作ではなく、箱型乾燥機やバンド乾燥機を使用して乾燥する場合に、ランプ形状等のものとなった顔料組成物を解して粉末化するために行うものであり、例えば、乳鉢、ハンマーミル、ディスクミル、ピンミル、ジェットミル等による粉砕方法が挙げられる。 The pulverization method after drying is not an operation to increase the specific surface area of the ε-type copper phthalocyanine pigment composition or to reduce the average particle size of primary particles, but to use a box-type dryer or a band dryer. When drying, it is performed to dissolve the pigment composition that has become in the shape of a lamp and pulverize, for example, a pulverizing method using a mortar, hammer mill, disk mill, pin mill, jet mill, etc. It is done.
こうして、窒素吸着法によるＢＥＴ比表面積７０〜１３０ｍ２／ｇである本発明のε型銅フタロシアニン顔料組成物の粉末が得られる。また、走査型電子顕微鏡測定による一次粒子径は２０ｎｍ〜８０ｎｍであることが好ましい。比表面積が６０ｍ２／ｇ以下または、一次粒子径が１００ｎｍ以上であると、被着色媒体を着色して得られた着色物の着色力が低下するので好ましくない。 Thus, a powder of the ε-type copper phthalocyanine pigment composition of the present invention having a BET specific surface area of 70 to 130 m 2 / g by a nitrogen adsorption method is obtained. Moreover, it is preferable that the primary particle diameter by a scanning electron microscope measurement is 20 nm-80 nm. If the specific surface area is 60 m 2 / g or less or the primary particle diameter is 100 nm or more, the coloring power of the colored product obtained by coloring the medium to be colored is not preferred.
尚、本発明のε型銅フタロシアニン顔料組成物は、アスペクト比が１に近いほど好ましい。顔料組成物のアスペクト比が大きくなるほど、それの被着色媒体への分散性、その中での分散安定性が低下し、顔料粒子の再凝集が起こりやすくなる。これは、例えば、塗料を調製する際、本発明のε型銅フタロシアニン顔料組成物と従来の青色顔料との混合物を使用して調製された顔料分散液、これを含む光硬化性化合物および／または合成樹脂の組成物の流動性、貯蔵安定性および基材への塗布性の低下、塗膜の透明性等へと繋がる点で好ましくない。 The ε-type copper phthalocyanine pigment composition of the present invention is preferably as the aspect ratio is closer to 1. As the aspect ratio of the pigment composition increases, the dispersibility of the pigment composition in the medium to be colored and the dispersion stability therein decrease, and reaggregation of the pigment particles easily occurs. This is because, for example, when preparing a paint, a pigment dispersion prepared using a mixture of the ε-type copper phthalocyanine pigment composition of the present invention and a conventional blue pigment, a photocurable compound containing the same, and / or The synthetic resin composition is not preferable in terms of fluidity, storage stability, lowering of coating property to a substrate, transparency of a coating film, and the like.
後記するカラーフィルター用の顔料分散液やこれを含む光硬化性化合物および／または合成樹脂の組成物でも、同様のこと言え、カラーフィルター青色画素部を形成するための透明基板への塗布性の低下、同画素部における塗膜の輝度、コントラストおよび光透過率のいずれもが低下する点で好ましくない。 The same applies to pigment dispersions for color filters and compositions of photo-curing compounds and / or synthetic resins containing the pigment dispersions described later, and the applicability to transparent substrates for forming color filter blue pixel portions is reduced. This is not preferable in that all of the brightness, contrast, and light transmittance of the coating film in the pixel portion are lowered.
本発明のε型銅フタロシニアン顔料組成物には、必要であれば、そこに更にその他の青色や紫色の有機顔料を含有させることが出来る。本発明のε型銅フタロシアニン顔料組成物とその他の青色や紫色の有機顔料との混合物に占める本発明のε型銅フタロシアニン顔料組成物の割合が多いほど、前記した様な効果は高くなるが、質量換算で、本発明のε型銅フタロシニアン顔料組成物１００部当たり、その他の青色顔料を１〜２００部を含有させることが出来る。 If necessary, the ε-type copper phthalocyanine pigment composition of the present invention can further contain other blue or purple organic pigments. As the ratio of the ε-type copper phthalocyanine pigment composition of the present invention to the mixture of the ε-type copper phthalocyanine pigment composition of the present invention and other blue or purple organic pigments increases, the above-described effect increases. In terms of mass, 1 to 200 parts of other blue pigments can be contained per 100 parts of the ε-type copper phthalocyanine pigment composition of the present invention.
本発明のε型銅フタロシアニン顔料組成物は、公知慣用の各種用途、例えば、塗料、プラスチック（樹脂成型品）、印刷インキ、ゴム、レザー、カラーフィルター青色画素部、静電荷像現像用トナー、インクジェット記録用インキ、熱転写インキ等の着色にも適用することが出来る。 The ε-type copper phthalocyanine pigment composition of the present invention is used in various known and commonly used applications such as paint, plastic (resin molded product), printing ink, rubber, leather, color filter blue pixel portion, electrostatic charge image developing toner, and ink jet. It can also be applied to coloring recording inks, thermal transfer inks, and the like.
被着色媒体は、常温固体または液体が挙げられ、例えば、ポリオレフィン、ポリ塩化ビニル等の熱可塑性樹脂、レゾール型フェノール樹脂、エポキシ樹脂とエポキシ硬化剤との混合物等の熱硬化性樹脂（組成物）、有機溶剤、光硬化性化合物、光硬化性化合物および分散剤を含有する光硬化性組成物のほか、ワニス、エナメル等が挙げられる。本発明のε型銅フタロシアニン顔料組成物を含有するコーティング剤を塗布することが出来る基材としては、例えば、各種合成樹脂フィルム・シート、ガラス、金属、セラミックス等が挙げられる。 Examples of the medium to be colored include solids at room temperature or liquids. Thermosetting resins (compositions) such as thermoplastic resins such as polyolefin and polyvinyl chloride, resol type phenol resins, and mixtures of epoxy resins and epoxy curing agents. In addition to a photocurable composition containing an organic solvent, a photocurable compound, a photocurable compound and a dispersant, varnish, enamel and the like can be mentioned. Examples of the substrate on which the coating agent containing the ε-type copper phthalocyanine pigment composition of the present invention can be applied include various synthetic resin films / sheets, glass, metal, ceramics and the like.
本発明の好適なε型銅フタロシニアン顔料組成物は、従来公知の方法でカラーフィルター青色画素部、同青色画素部形成用青色顔料の調製に使用することが出来る。本発明のε型銅フタロシニアン顔料組成物を使用してカラーフィルター青色画素部を製造するに当たっては、顔料分散法が好適に採用出来る。 The preferred ε-type copper phthalocyanine pigment composition of the present invention can be used for preparing a color filter blue pixel portion and a blue pigment for forming the blue pixel portion by a conventionally known method. In producing a color filter blue pixel portion using the ε-type copper phthalocyanine pigment composition of the present invention, a pigment dispersion method can be suitably employed.
この方法で代表的な方法は、フォトリソグラフィー法であり、これは、後記する光硬化性組成物を、カラーフィルター用の透明基板のブラックマトリックスを設けた側の面に塗布、加熱乾燥（プリベーク）した後、フォトマスクを介して紫外線を照射することでパターン露光を行って、画素部に対応する箇所の光硬化性化合物を硬化させた後、未露光部分を現像液で現像し、非画素部を除去して画素部を透明基板に固着させる方法である。この方法では、光硬化性組成物の硬化着色皮膜からなる画素部が透明基板上に形成される。 A typical method in this method is a photolithography method, in which a photocurable composition, which will be described later, is applied to a surface of a transparent substrate for a color filter provided with a black matrix, and is dried by heating (prebaking). After that, pattern exposure is performed by irradiating ultraviolet rays through a photomask to cure the photo-curable compound at a location corresponding to the pixel portion, and then developing the unexposed portion with a developer, thereby developing the non-pixel portion. In which the pixel portion is fixed to the transparent substrate. In this method, a pixel portion made of a cured colored film of a photocurable composition is formed on a transparent substrate.
赤色、緑色、青色の各色ごとに、後記する光硬化性組成物を調製して、前記した操作を繰り返すことにより、所定の位置に赤色、緑色、青色の着色画素部を有するカラーフィルターを製造することが出来る。前記した様に、本発明のε型銅フタロシニアン顔料組成物からは、青色画素部、同青色画素部形成用青色顔料が調製される。尚、赤色画素部および緑色画素部を形成するための光硬化性組成物を調製するには、公知慣用の赤色顔料と緑色顔料を使用することが出来る。 A photocurable composition to be described later is prepared for each color of red, green, and blue, and a color filter having red, green, and blue colored pixel portions at predetermined positions is manufactured by repeating the above-described operation. I can do it. As described above, a blue pixel portion and a blue pigment for forming the blue pixel portion are prepared from the ε-type copper phthalocyanine pigment composition of the present invention. In addition, in order to prepare the photocurable composition for forming a red pixel part and a green pixel part, a well-known and usual red pigment and green pigment can be used.
赤色画素部を形成するための顔料としては、例えば、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １７７、同２０９、同２５４等が、緑色画素部を形成するための顔料としては、例えば、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ ７、同１０、同３６、同４７等が挙げられる。これら赤色画素部と緑色画素部の形成には、黄色顔料を併用することも出来る。その後、必要に応じて、未反応の光硬化性化合物を熱硬化させるために、カラーフィルター全体を加熱処理（ポストベーク）することも出来る。 Examples of the pigment for forming the red pixel portion include C.I. I. Pigment Red 177, 209, 254, and the like are pigments for forming a green pixel portion, for example, C.I. I. Pigment Green 7, 10, 10, 36, and the like. A yellow pigment can be used in combination for forming the red pixel portion and the green pixel portion. Thereafter, if necessary, the entire color filter can be heat-treated (post-baked) in order to thermally cure the unreacted photocurable compound.
後記する光硬化性組成物をガラス等の透明基板上に塗布する方法としては、例えば、スピンコート法、ロールコート法、インクジェット法等が挙げられる。 Examples of a method for applying a photocurable composition described later on a transparent substrate such as glass include a spin coat method, a roll coat method, and an ink jet method.
透明基板に塗布した光硬化性組成物の塗膜の乾燥条件は、各成分の種類、配合割合等によっても異なるが、通常、５０〜１５０℃で、１〜１５分間程度である。この加熱処理を一般に「プリベーク」という。また、光硬化性組成物の光硬化に用いる光としては、２００〜５００ｎｍの波長範囲の紫外線、あるいは可視光を使用するのが好ましい。この波長範囲の光を発する各種光源が使用出来る。 Although the drying conditions of the coating film of the photocurable composition apply | coated to the transparent substrate differ also with the kind of each component, a compounding ratio, etc., they are 50-150 degreeC and are about 1 to 15 minutes normally. This heat treatment is generally referred to as “pre-baking”. Moreover, as light used for photocuring of a photocurable composition, it is preferable to use the ultraviolet-ray of a wavelength range of 200-500 nm, or visible light. Various light sources that emit light in this wavelength range can be used.
現像方法としては、例えば、液盛り法、ディッピング法、スプレー法等が挙げられる。光硬化性組成物の露光、現像の後に、必要な色の画素部が形成された透明基板は水洗いし乾燥させる。こうして得られたカラーフィルターは、ホットプレート、オーブン等の加熱装置により、１００〜２８０℃で、所定時間加熱処理（ポストベーク）することによって、着色塗膜中の揮発性成分を除去すると同時に、光硬化性組成物の硬化着色皮膜中に残存する未反応の光硬化性化合物が熱硬化し、カラーフィルターが完成する。 Examples of the developing method include a liquid piling method, a dipping method, and a spray method. After exposure and development of the photocurable composition, the transparent substrate on which the necessary color pixel portion is formed is washed with water and dried. The color filter thus obtained is subjected to heat treatment (post-baking) at 100 to 280 ° C. for a predetermined time by a heating device such as a hot plate or an oven to remove volatile components in the colored coating film, and at the same time, light The unreacted photocurable compound remaining in the cured colored film of the curable composition is thermally cured to complete the color filter.
カラーフィルターの青色画素部を形成するための光硬化性組成物（顔料分散フォトレジストとも呼ばれる。）は、本発明のε型銅フタロシアニン顔料組成物と、分散剤と、光硬化性化合物と、有機溶剤とを必須成分とし、必要に応じて熱可塑性樹脂を用いて、これらを混合することで調製することが出来る。青色画素部を形成する着色樹脂皮膜に、カラーフィルターの実生産で行われるベーキング等に耐え得る強靱性等が要求される場合には、前記光硬化性組成物を調製するに当たって、光硬化性化合物だけでなく、この熱可塑性樹脂を併用することが不可欠である。熱可塑性樹脂を併用する場合には、有機溶剤としては、それを溶解するものを使用するのが好ましい。 A photocurable composition (also called a pigment-dispersed photoresist) for forming a blue pixel portion of a color filter includes an ε-type copper phthalocyanine pigment composition of the present invention, a dispersant, a photocurable compound, and an organic It can be prepared by using a solvent as an essential component and mixing them using a thermoplastic resin as necessary. When the colored resin film that forms the blue pixel portion requires toughness that can withstand baking, etc. performed in the actual production of a color filter, a photocurable compound is used in preparing the photocurable composition. In addition, it is essential to use this thermoplastic resin in combination. When a thermoplastic resin is used in combination, it is preferable to use an organic solvent that dissolves it.
前記光硬化性組成物の製造方法としては、本発明のε型銅フタロシアニン顔料組成物と、有機溶剤と分散剤とを必須成分として使用し、これらを混合し均一となる様に攪拌分散を行って、まずカラーフィルターの青色画素部を形成するための顔料分散液（着色ペーストとも呼ばれる。）を調製してから、そこに、光硬化性化合物と、必要に応じて熱可塑性樹脂や光重合開始剤等を加えて前記光硬化性組成物とする方法が一般的である。 As a method for producing the photocurable composition, the ε-type copper phthalocyanine pigment composition of the present invention, an organic solvent and a dispersant are used as essential components, and these are mixed and stirred and dispersed so as to be uniform. First, prepare a pigment dispersion (also called a colored paste) to form the blue pixel part of the color filter, and then add a photocurable compound and, if necessary, a thermoplastic resin or photopolymerization. The method of adding an agent etc. to make the said photocurable composition is common.
ここで分散剤としては、例えば、ビックケミー社製のディスパービック１３０、ディスパービック１６１、ディスパービック１６２、ディスパービック１６３、ディスパービック１７０、エフカ社製のエフカ４６、エフカ４７等が挙げられる。また、レベリング剤、カップリング剤、カチオン系の界面活性剤等も併せて使用可能である。 Examples of the dispersant include Dispervic 130, Dispersic 161, Dispersic 162, Dispersic 163, Dispersic 170 manufactured by Big Chemie, Fuka 46 and Fuka 47 manufactured by Efka, and the like. Further, a leveling agent, a coupling agent, a cationic surfactant, and the like can be used together.
有機溶剤としては、例えば、トルエンやキシレン、メトキシベンゼン等の芳香族系溶剤、酢酸エチルや酢酸ブチル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート等の酢酸エステル系溶剤、エトキシエチルプロピオネート等のプロピオネート系溶剤、メタノール、エタノール等のアルコール系溶剤、ブチルセロソルブ、プロピレングリコールモノメチルエーテル、ジエチレングリコールエチルエーテル、ジエチレングリコールジメチルエーテル等のエーテル系溶剤、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系溶剤、ヘキサン等の脂肪族炭化水素系溶剤、Ｎ，Ｎ−ジメチルホルムアミド、γ−ブチロラクタム、Ｎ−メチル−２−ピロリドン、アニリン、ピリジン等の窒素化合物系溶剤、γ−ブチロラクトン等のラクトン系溶剤、カルバミン酸メチルとカルバミン酸エチルの４８：５２の混合物の様なカルバミン酸エステル等が挙げられる。有機溶剤としては、特にプロピオネート系、アルコール系、エーテル系、ケトン系、窒素化合物系、ラクトン系等の極性溶媒で水可溶のものが好ましい。水可溶の有機溶剤を使用する場合には、それに水を併用することも出来る。 Examples of the organic solvent include aromatic solvents such as toluene, xylene and methoxybenzene, acetate solvents such as ethyl acetate and butyl acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, and ethoxyethyl propionate. Propionate solvents such as methanol, ethanol solvents such as ethanol, butyl cellosolve, ether solvents such as propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, hexane, etc. Aliphatic hydrocarbon solvents, N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, a Phosphorus, nitrogen compound-based solvent such as pyridine, .gamma.-lactone solvents butyrolactone, carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate acid. As the organic solvent, polar solvents such as propionate-based, alcohol-based, ether-based, ketone-based, nitrogen compound-based, and lactone-based solvents that are water-soluble are particularly preferable. When a water-soluble organic solvent is used, water can be used in combination.
光硬化性組成物の調製に使用する熱可塑性樹脂としては、例えば、ウレタン系樹脂、アクリル系樹脂、ポリアミド酸系樹脂、ポリイミド系樹脂、スチレンマレイン酸系樹脂、スチレン無水マレイン酸系樹脂等が挙げられる。 Examples of the thermoplastic resin used for preparing the photocurable composition include urethane resins, acrylic resins, polyamic acid resins, polyimide resins, styrene maleic acid resins, styrene maleic anhydride resins, and the like. It is done.
光硬化性化合物としては、例えば、１，６−ヘキサンジオールジアクリレート、エチレングリコールジアクリレート、ネオペンチルグリコールジアクリレート、トリエチレングリコールジアクリレート、ビス（アクリロキシエトキシ）ビスフェノールＡ、３−メチルペンタンジオールジアクリレート等のような２官能モノマー、トリメチルロールプロパトントリアクリレート、ペンタエリスリトールトリアクリレート、トリス（２−ヒドロキシエチル）イソシアネート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールペンタアクリレート等の比較的分子量の小さな多官能モノマー、ポリエステルアクリレート、ポリウレタンアクリレート、ポリエーテルアクリレート等の様な比較的分子量の大きな多官能モノマーが挙げられる。 Examples of the photocurable compound include 1,6-hexanediol diacrylate, ethylene glycol diacrylate, neopentyl glycol diacrylate, triethylene glycol diacrylate, bis (acryloxyethoxy) bisphenol A, 3-methylpentanediol di Multifunctional with relatively low molecular weight such as bifunctional monomer such as acrylate, trimethylol propaton triacrylate, pentaerythritol triacrylate, tris (2-hydroxyethyl) isocyanate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate Monofunctional, polyester acrylate, polyurethane acrylate, polyether acrylate, etc. It is.
光重合開始剤としては、例えば、アセトフェノン、ベンゾフェノン、ベンジルジメチルケタノール、ベンゾイルパーオキサイド、２−クロロチオキサントン、１，３−ビス（４’−アジドベンザル）−２−プロパン、１，３−ビス（４’−アジドベンザル）−２−プロパン−２’−スルホン酸、４，４’−ジアジドスチルベン−２，２’−ジスルホン酸等が挙げられる。 Examples of the photopolymerization initiator include acetophenone, benzophenone, benzyldimethylketanol, benzoyl peroxide, 2-chlorothioxanthone, 1,3-bis (4′-azidobenzal) -2-propane, 1,3-bis (4 '-Azidobenzal) -2-propane-2'-sulfonic acid, 4,4'-diazidostilbene-2,2'-disulfonic acid and the like.
前記した様な各材料を使用して、本発明のε型銅フタロシアニン顔料組成物は、質量換算で、その１００部当たり、３００〜１０００部の有機溶剤と、０〜１００部の分散剤とを、均一となる様に攪拌分散して前記顔料分散液を得ることが出来る。次いで該顔料分散液に、本発明のε型銅フタロシアニン顔料組成物１部当たり、熱可塑性樹脂と光硬化性化合物の合計が３〜２０部、光硬化性化合物１部当たり０．０５〜３部の光重合開始剤と、必要に応じてさらに有機溶剤を添加し、均一となる様に攪拌分散してカラーフィルター青色画素部を形成するための光硬化性組成物を得ることが出来る。この様な光硬化性組成物は、通常は、分散粒子の平均粒子径が１００ｎｍ以下となる様に調製される。 Using each material as described above, the ε-type copper phthalocyanine pigment composition of the present invention comprises, in terms of mass, 300 to 1000 parts of an organic solvent and 0 to 100 parts of a dispersant per 100 parts. The pigment dispersion can be obtained by stirring and dispersing so as to be uniform. The pigment dispersion is then combined with 3 to 20 parts of thermoplastic resin and photocurable compound per part of ε-type copper phthalocyanine pigment composition of the present invention, and 0.05 to 3 parts per part of photocurable compound. A photo-curable composition for forming a color filter blue pixel portion can be obtained by adding a photopolymerization initiator and, if necessary, further an organic solvent, and stirring and dispersing so as to be uniform. Such a photocurable composition is usually prepared such that the average particle diameter of the dispersed particles is 100 nm or less.
現像液としては、公知慣用の有機溶剤やアルカリ水溶液を使用することが出来る。特に前記光硬化性組成物に、熱可塑性樹脂または光硬化性化合物が含まれており、これらの少なくとも一方が酸価を有し、アルカリ可溶性を呈する場合には、アルカリ水溶液での洗浄がカラーフィルター青色画素部の形成に効果的である。 As the developer, a publicly known and commonly used organic solvent or alkaline aqueous solution can be used. In particular, when the photocurable composition contains a thermoplastic resin or a photocurable compound, and at least one of them has an acid value and exhibits alkali solubility, the color filter can be washed with an alkaline aqueous solution. This is effective for forming the blue pixel portion.
顔料分散法のうち、フォトリソグラフィー法によるカラーフィルター青色画素部の製造方法について詳記したが、本発明のε型銅フタロシアニン顔料組成物を使用して調製されたカラーフィルター青色画素部は、その他の電着法、転写法、ミセル電解法、ＰＶＥＤ（Ｐｈｏｔｏｖｏｌｔａｉｃ Ｅｌｅｃｔｒｏｄｅｐｏｓｉｔｉｏｎ）法等の方法で青色画素部を形成して、カラーフィルターを製造してもよい。 Among the pigment dispersion methods, the method for producing the color filter blue pixel portion by the photolithography method was described in detail, but the color filter blue pixel portion prepared using the ε-type copper phthalocyanine pigment composition of the present invention was A color filter may be manufactured by forming a blue pixel portion by a method such as an electrodeposition method, a transfer method, a micellar electrolysis method, or a PVED (Photovoltaic Electrodeposition) method.
カラーフィルターは、赤色顔料組成物、緑色顔料組成物、ならびに本発明のε型銅フタロシアニン顔料組成物を使用して得た各色の光硬化性組成物を使用し、平行な一対の透明電極間に液晶材料を封入し、透明電極を不連続な微細区間に分割すると共に、この透明電極上のブラックマトリクスにより格子状に区分けされた微細区間のそれぞれに、赤（Ｒ）、緑（Ｇ）および青（Ｂ）のいずれか１色から選ばれたカラーフィルター着色画素部を交互にパターン状に設ける方法、あるいは基板上にカラーフィルター着色画素部を形成した後、透明電極を設ける様にすることで得ることが出来る。 The color filter is composed of a red pigment composition, a green pigment composition, and a photocurable composition of each color obtained using the ε-type copper phthalocyanine pigment composition of the present invention, and between a pair of parallel transparent electrodes. Liquid crystal material is enclosed, the transparent electrode is divided into discontinuous fine sections, and red (R), green (G) and blue are divided into the fine sections divided into a lattice by the black matrix on the transparent electrode. (B) Obtained by providing a color filter coloring pixel portion selected from any one of the colors alternately in a pattern, or by forming a color filter coloring pixel portion on a substrate and then providing a transparent electrode. I can do it.
以下、製造例、実施例、及び比較例により本発明を詳細に説明する。本発明はこれら実施例に限定されるものではない。尚、特に断りのない限り、「部」及び「％」はいずれも質量基準である。 Hereinafter, the present invention will be described in detail with reference to production examples, examples, and comparative examples. The present invention is not limited to these examples. Unless otherwise specified, both “part” and “%” are based on mass.
質量基準で、α型銅フタロシアニン顔料１００部当たりオレイン酸５部を含有するα型銅フタロシアニン顔料組成物を準備した。
このα型銅フタロシアニン顔料組成物１００部、ベンゼン環に１〜２モルのフタルイミドメチル基が結合したフタルイミドアルキル化銅フタロシアニン５．６部、シードとして市販ε型銅フタロシアニン顔料（Ｃ．Ｉ．ピグメントブルー１５：６）５．６部、塩化ナトリウム８９６部、およびジエチレングリコール１６８部をニーダー中で、内容物の温度を１１５〜１２５℃に保って１５時間湿式摩砕した。得られた内容物を２％の希硫酸水溶液中で加熱処理し、濾過、水洗を繰り返し、ろ液が中性となるまで洗浄することによって、顔料分３５％のε型銅フタロシアニン顔料組成物のウエットケーキを得た。
このウエットケーキを熱風乾燥機で乾燥、粉砕して、乾燥粉体のε型銅フタロシアニン顔料組成物１を得た。組成物１のＢＥＴ比表面積は、９０ｍ２／ｇであった。
An α-type copper phthalocyanine pigment composition containing 5 parts of oleic acid per 100 parts of α-type copper phthalocyanine pigment on a mass basis was prepared.
100 parts of this α-type copper phthalocyanine pigment composition, 5.6 parts of phthalimide alkylated copper phthalocyanine having 1 to 2 moles of phthalimidomethyl group bonded to the benzene ring, and commercially available ε-type copper phthalocyanine pigment (CI Pigment Blue) 15: 6) 5.6 parts of sodium chloride, 896 parts of sodium chloride and 168 parts of diethylene glycol were wet milled in a kneader for 15 hours while maintaining the temperature of the contents at 115-125 ° C. The obtained contents were heat-treated in a 2% dilute sulfuric acid aqueous solution, repeatedly filtered and washed with water until the filtrate became neutral. A wet cake was obtained.
The wet cake was dried and pulverized with a hot air dryer to obtain a dry powder ε-type copper phthalocyanine pigment composition 1. Composition 1 had a BET specific surface area of 90 m 2 / g.
市販ε型銅フタロシアニン顔料に代えて、有機アミンで表面処理されたε型銅フタロシアニン顔料組成物を用いた以外は、実施例１と同様にして、ε型銅フタロシアニン顔料組成物１に対応する乾燥粉体のε型銅フタロシアニン顔料組成物２を得た。組成物２のＢＥＴ比表面積は、８５ｍ２／ｇであった。 A dry solution corresponding to the ε-type copper phthalocyanine pigment composition 1 was used in the same manner as in Example 1 except that the ε-type copper phthalocyanine pigment composition surface-treated with an organic amine was used instead of the commercially available ε-type copper phthalocyanine pigment. A powdery ε-type copper phthalocyanine pigment composition 2 was obtained. Composition 2 had a BET specific surface area of 85 m 2 / g.
実施例１で得られたε型銅フタロシアニン顔料組成物１００部、ベンゼン環に１〜２モルのフタルイミドメチル基が結合したフタルイミドアルキル化銅フタロシアニン５部、塩化ナトリウム１０００部、およびジエチレングリコール２００部をニーダー中で、内容物の温度を８０〜９０℃に保って１５時間湿式摩砕した。得られた内容物を水溶液中で加熱洗浄し、濾過、ろ液が中性となるまで水洗することによって、顔料分３５％のε型銅フタロシアニン顔料組成物のウエットケーキを得た。 Kneader 100 parts of the ε-type copper phthalocyanine pigment composition obtained in Example 1, 5 parts of phthalimide alkylated copper phthalocyanine having 1-2 moles of phthalimidomethyl group bonded to the benzene ring, 1000 parts of sodium chloride, and 200 parts of diethylene glycol. Inside, the temperature of the contents was maintained at 80-90 ° C. and wet milled for 15 hours. The obtained contents were heated and washed in an aqueous solution, filtered, and washed with water until the filtrate became neutral, whereby a wet cake of an ε-type copper phthalocyanine pigment composition having a pigment content of 35% was obtained.
さらに、得られたこのウエットケーキのうち１００部を温水１０００部に再解膠後、銅フタロシアニンスルフォン酸５部を染め付け処理し、ろ過した。ろ液の比電導度が５００μＳ／ｃｍ以下になるまで水洗を繰り返した。このウエットケーキを熱風乾燥機で乾燥、粉砕して、乾燥粉体のε型銅フタロシアニン顔料組成物３を得た。組成物３のＢＥＴ比表面積は、１００ｍ２／ｇであった。 Further, 100 parts of the obtained wet cake was re-peptized into 1000 parts of warm water, and then 5 parts of copper phthalocyanine sulfonic acid was dyed and filtered. Washing with water was repeated until the specific conductivity of the filtrate reached 500 μS / cm or less. The wet cake was dried and pulverized with a hot air dryer to obtain a dry powder ε-type copper phthalocyanine pigment composition 3. The BET specific surface area of the composition 3 was 100 m 2 / g.
実施例２で得られたε型銅フタロシアニン顔料組成物１００部、ベンゼン環に１〜２モルのフタルイミドメチル基が結合したフタルイミドアルキル化銅フタロシアニン５部、塩化ナトリウム１０００部、およびジエチレングリコール２００部をニーダー中で、内容物の温度を８０〜９０℃に保って１５時間湿式摩砕した。得られた内容物を水溶液中で加熱洗浄し、濾過、ろ液が中性となるまで水洗することによって、顔料分３５％のε型銅フタロシアニン顔料組成物のウエットケーキを得た。 Kneader 100 parts of the ε-type copper phthalocyanine pigment composition obtained in Example 2, 5 parts of phthalimide alkylated copper phthalocyanine having 1 to 2 moles of phthalimidomethyl group bonded to the benzene ring, 1000 parts of sodium chloride, and 200 parts of diethylene glycol. Inside, the temperature of the contents was maintained at 80-90 ° C. and wet milled for 15 hours. The obtained contents were heated and washed in an aqueous solution, filtered, and washed with water until the filtrate became neutral, whereby a wet cake of an ε-type copper phthalocyanine pigment composition having a pigment content of 35% was obtained.
さらに、得られたこのウエットケーキのうち１００部を温水１０００部に再解膠後、銅フタロシアニンスルフォン酸５部を染め付け処理し、ろ過した。ろ液の比電導度が５００μＳ／ｃｍ以下になるまで水洗を繰り返した。このウエットケーキを熱風乾燥機で乾燥、粉砕して、乾燥粉体のε型銅フタロシアニン顔料組成物４を得た。組成物４のＢＥＴ比表面積は、１１０ｍ２／ｇであった。 Further, 100 parts of the obtained wet cake was re-peptized into 1000 parts of warm water, and then 5 parts of copper phthalocyanine sulfonic acid was dyed and filtered. Washing with water was repeated until the specific conductivity of the filtrate reached 500 μS / cm or less. The wet cake was dried and pulverized with a hot air dryer to obtain a dry powder ε-type copper phthalocyanine pigment composition 4. The BET specific surface area of the composition 4 was 110 m 2 / g.
＜比較例１＞
α型銅フタロシアニン顔料組成物に代えて、その原料のα型銅フタロシアニンだけを用いる以外は実施例１と同様の操作を行って、ε型銅フタロシアニン顔料組成物１に対応する乾燥粉体のε型銅フタロシアニン顔料組成物５を得た。組成物５のＢＥＴ比表面積は、８０ｍ２／ｇであった。
<Comparative Example 1>
Instead of the α-type copper phthalocyanine pigment composition, the same operation as in Example 1 was performed except that only the raw material α-type copper phthalocyanine was used, and ε of the dry powder corresponding to the ε-type copper phthalocyanine pigment composition 1 was obtained. Type copper phthalocyanine pigment composition 5 was obtained. The BET specific surface area of the composition 5 was 80 m 2 / g.
＜比較例２＞
特開２００２−８０７４５公報の比較例１に従い、ε型銅フタロシアニン顔料組成物を得た。組成物６のＢＥＴ比表面積は、７５ｍ２／ｇであった。
<Comparative example 2>
According to Comparative Example 1 of JP 2002-80745 A, an ε-type copper phthalocyanine pigment composition was obtained. The BET specific surface area of the composition 6 was 75 m 2 / g.
＜比較例３＞
特開２００２−１２１４２０公報の実施例３に従い、ε型銅フタロシアニン顔料組成物を得た。組成物７のＢＥＴ比表面積は、１１０ｍ２／ｇであった。
<Comparative Example 3>
According to Example 3 of JP-A-2002-121420, an ε-type copper phthalocyanine pigment composition was obtained. The BET specific surface area of the composition 7 was 110 m 2 / g.
こうして得られた実施例３〜４及び比較例１〜３のε型銅フタロシアニン顔料組成物を用いて、カラーフィルタにおける評価を行った。
<応用例１>
前記実施例３で得られたε型銅フタロシアニン組成物１を青色顔料として使用し、フォトリソグラフィー法によりカラーフィルター青色画素部を製造した。
Using the thus obtained ε-type copper phthalocyanine pigment compositions of Examples 3 to 4 and Comparative Examples 1 to 3, the color filters were evaluated.
<Application example 1>
Using the ε-type copper phthalocyanine composition 1 obtained in Example 3 as a blue pigment, a color filter blue pixel portion was manufactured by a photolithography method.
カラーフィルター青色画素部の製造方法としては、ε型銅フタロシアニン顔料組成物１０部、Ｎ，Ｎ’−ジメチルホルムアミド（有機溶剤）２．５部、ディスパービック１６１（ビックケミー社製分散剤）６．７８部、ユーカーエステルＥＥＰ（ユニオン・カーバイド社製有機溶剤）８０．８０部を０．５ｍｍφセプルビーズを加え、ペイントコンディショナー（東洋精機（株）製）で１時間分散し、顔料分散液（着色ペースト）を得た。この顔料分散液７５．００部とアロニックスＭ７１００（ポリエステルアクリレート樹脂、東亜合成化学工業（株）製、光硬化性化合物に相当する。）５．５０部、ＫＡＹＡＲＡＤ ＤＰＨＡ（ジぺンタエリスレートヘキサアクリレート、日本化薬（株）製、光硬化性化合物に相当する。）５．００部、ＫＡＹＡＣＵＲＥ ＢＰ−１００（ベンゾフェノン、日本化薬（株）製、光重合開始剤に相当する。）１．００部、ユーカーエステルＥＦＰ１３．５部を分散攪拌機で攪拌し、カラーフィルター青色画素部を形成するための光硬化性組成物を得た。該組成物は１ｍｍ厚ガラスに乾燥膜厚１μｍとなるように塗布した。 As a method for producing a blue pixel portion of the color filter, 10 parts of an ε-type copper phthalocyanine pigment composition, 2.5 parts of N, N′-dimethylformamide (organic solvent), Dispersic 161 (dispersant manufactured by BYK Chemie) 6.78 Part, 80.80 parts of Euker Ester EEP (Union Carbide organic solvent) is added with 0.5 mmφ Sepul beads, and dispersed with a paint conditioner (manufactured by Toyo Seiki Co., Ltd.) for 1 hour to obtain a pigment dispersion (colored paste). Obtained. 75.00 parts of this pigment dispersion and Aronix M7100 (polyester acrylate resin, manufactured by Toa Gosei Chemical Co., Ltd., corresponding to a photocurable compound) 5.50 parts, KAYARAD DPHA (dipentaerylate hexaacrylate, 5.00 parts by Nippon Kayaku Co., Ltd., corresponding to a photocurable compound.) 5.00 parts, KAYACURE BP-100 (benzophenone, Nippon Kayaku Co., Ltd., corresponding to a photopolymerization initiator) 1.00 parts. 13.5 parts of Euker ester EFP was stirred with a dispersion stirrer to obtain a photocurable composition for forming a blue pixel part of a color filter. The composition was applied to 1 mm thick glass so as to have a dry film thickness of 1 μm.
次いでフォトマスクを介して紫外線によるパターン露光を行った後、未露光部分を有機溶剤で洗浄することによりカラーフィルター青色画素部を製造した。 Next, pattern exposure with ultraviolet rays was performed through a photomask, and then the unexposed portion was washed with an organic solvent to produce a color filter blue pixel portion.
<応用例２>
前記実施例４で得られたε型銅フタロシアニン組成物２を青色顔料として用いた以外は応用例１と同様の操作により、カラーフィルター青色画素部を製造した。
<比較応用例１>
前記比較例１で得られたε型銅フタロシアニン組成物５を青色顔料として用いた以外は応用例１と同様の操作により、カラーフィルター青色画素部を製造した。
<比較応用例２>
前記比較例２で得られたε型銅フタロシアニン組成物６を青色顔料として用いた以外は実施例１と同様の操作により、カラーフィルター青色画素部を製造した。
<比較応用例３>
前記比較例３で得られたε型銅フタロシアニン組成物７を青色顔料として用いた以外は実施例１と同様の操作により、カラーフィルター青色画素部を製造した。
<Application example 2>
A color filter blue pixel portion was produced in the same manner as in Application Example 1 except that the ε-type copper phthalocyanine composition 2 obtained in Example 4 was used as a blue pigment.
<Comparison application example 1>
A color filter blue pixel portion was produced in the same manner as in Application Example 1 except that the ε-type copper phthalocyanine composition 5 obtained in Comparative Example 1 was used as a blue pigment.
<Comparison application example 2>
A color filter blue pixel portion was produced in the same manner as in Example 1 except that the ε-type copper phthalocyanine composition 6 obtained in Comparative Example 2 was used as a blue pigment.
<Comparative application example 3>
A color filter blue pixel portion was produced in the same manner as in Example 1 except that the ε-type copper phthalocyanine composition 7 obtained in Comparative Example 3 was used as a blue pigment.
製造した応用例１〜２および比較応用例１〜３のカラーフィルター青色画素部の塗膜の輝度、コントラストおよび光透過率をそれぞれ評価した。その結果を表１に示した。 The brightness, contrast, and light transmittance of the coating films of the produced color filter blue pixel portions of Application Examples 1-2 and Comparative Application Examples 1-3 were evaluated. The results are shown in Table 1.
輝度（Ｙ値）は、大塚電子（株）製の顕微分光光度計ＭＣＰＤ−３０００を使用して、Ｆ１０光源測色で色度座標ｘ値とｙ値を算出し、両色度座標ｘ、ｙ値を合わせてＣＩＥ発色系色度におけるＹ値を測定した。ここでは、輝度（Ｙ値）が大きいほど視覚明度が高いと評価した。また、コントラストは該カラーフィルター青色画素部を２枚の偏光板の間に設置し、一方には光源を、更にその反対側にはＣＣＤカメラを設置して輝度の測定を行った。偏光軸が平行になる時と垂直になる時との輝度（透過光強度）の比より算出した。 Luminance (Y value) is calculated by using a micro-spectrophotometer MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. to calculate chromaticity coordinate x value and y value by F10 light source colorimetry. The Y value in CIE color development system chromaticity was measured by combining the values. Here, it was evaluated that the visual brightness was higher as the luminance (Y value) was higher. Contrast was measured with the blue color pixel portion of the color filter placed between two polarizing plates, a light source on one side, and a CCD camera on the other side. It was calculated from the ratio of luminance (transmitted light intensity) between when the polarization axis was parallel and when it was vertical.
光透過率は、該カラーフィルター青色画素部を、ＪＩＳ Ｚ ８７２２に規定する第一種分光測光器（上記に記載した分光光度計）を使用して分光透過率スペクトルの光透過率が最大となる波長（λｍａｘ＝４６３ｎｍ）の光透過率（Ｔｍａｘ）を測定した。 The light transmittance of the color filter blue pixel portion is maximized by using a first-type spectrophotometer (the spectrophotometer described above) defined in JIS Z 8722. The light transmittance (Tmax) of the wavelength (λmax = 463 nm) was measured.
表１ Table 1
表１の結果から明らかな様に、実施例１〜２のカラーフィルター青色画素部においては、顔料の凝集が極めて弱く、分散性、分散安定性に優れた光硬化性組成物をより短時間で調製出来、それから得られる青色画素部は、塗膜の輝度、コントラストおよび光透過率がいずれも高かった。 As is clear from the results in Table 1, in the blue pixel portions of the color filters of Examples 1 and 2, a photocurable composition excellent in dispersibility and dispersion stability was obtained in a shorter time in which the aggregation of the pigment was extremely weak. The blue pixel portion that could be prepared and obtained therefrom had high brightness, contrast, and light transmittance of the coating film.
一方、比較例１〜３のカラーフィルター青色画素部においては、顔料の凝集が強く、分散性、分散安定性に劣る光硬化性組成物が調製され、それから得られる青色画素部は、塗膜の輝度、コントラストおよび光透過率がいずれも低かった。比較例１のε型銅フタロシアニン顔料と、オレイン酸アミドとを用いて調製したカラーフィルター青色画素部は、やはり実施例よりも前記した点において劣った性能であった。 On the other hand, in the color filter blue pixel portion of Comparative Examples 1 to 3, a photocurable composition having strong pigment agglomeration and inferior dispersibility and dispersion stability was prepared. The brightness, contrast, and light transmittance were all low. The color filter blue pixel portion prepared by using the ε-type copper phthalocyanine pigment of Comparative Example 1 and oleic acid amide was inferior in terms of the above-mentioned points as compared with the Examples.
次に塗料での評価を行った。 Next, evaluation with a paint was performed.
<応用例３>
前記実施例１で得られたε型銅フタロシアニン顔料組成物４部を、メラミンアルキッド混合ワニス（「ベッコゾールＪ−５２４−ＩＭ−６０」／「スーパーベッカミンＪ−８２０−６０」＝７／３、いずれも大日本インキ化学工業(株)製）１３部シンナー（キシレン／ブタノ−ル＝３／１）１３部及びガラスビーズ（３ｍｍφ）８０部と共に、１００ｍｌガラスビンに採り、ペイントコンディショナーにて１５分間分散させた後、前記ワニス（メラミンアルキッド混合ワニス）５０部を追加し、更に５分間分散させて青緑色塗料を得た。
<Application example 3>
4 parts of the ε-type copper phthalocyanine pigment composition obtained in Example 1 was added to a melamine alkyd mixed varnish (“Beccosol J-524-IM-60” / “Super Becamine J-820-60” = 7/3, Both are made by Dainippon Ink & Chemicals, Inc.) 13 parts thinner (xylene / butanol = 3/1) 13 parts and glass beads (3 mmφ) 80 parts, taken in a 100 ml glass bottle, and dispersed in a paint conditioner for 15 minutes. Then, 50 parts of the varnish (melamine alkyd mixed varnish) was added and further dispersed for 5 minutes to obtain a blue-green paint.
別途、ε型銅フタロシアニン顔料組成物に代えて酸化チタン顔料（ＴｉＯ2 ）を用いた以外は同様にして、白塗料を得た。得られた青色塗料を、ε型銅フタロシアニン顔料組成物／ＴｉＯ2 ＝１／１０となるように、酸化チタン顔料からなる白塗料を用いて希釈した後、フィルムアプリケーターでアート紙上に展色し、１４０℃、２０分間焼き付けて塗膜を作成した後、分光光度計を用いて、ファーストゲンブルーＥＰ−７Ｓ（大日本インキ化学工業（株）製銅フタロシニアン顔料）を標準試料に設定して、相対着色力を測定した Separately, a white paint was obtained in the same manner except that a titanium oxide pigment (TiO 2 ) was used instead of the ε-type copper phthalocyanine pigment composition. The obtained blue paint was diluted with a white paint made of a titanium oxide pigment so that ε-type copper phthalocyanine pigment composition / TiO 2 = 1/10, and then developed on art paper with a film applicator. After creating a coating film by baking at 140 ° C. for 20 minutes, using a spectrophotometer, Fast Gen Blue EP-7S (copper phthalocyanine pigment manufactured by Dainippon Ink & Chemicals, Inc.) was set as a standard sample, and relative The coloring power was measured
<応用例４>
前記実施例２で得られたε型銅フタロシアニン顔料組成物を用いた以外は応用例３と同様の操作により、相対着色力を測定した。
<Application example 4>
Relative coloring power was measured in the same manner as in Application Example 3 except that the ε-type copper phthalocyanine pigment composition obtained in Example 2 was used.
<比較応用例４>
前記比較例１で得られたε型銅フタロシアニン顔料組成物を用いた以外は応用例３と同様の操作により、相対着色力を測定した。
<Comparison application example 4>
Relative coloring power was measured by the same operation as in Application Example 3 except that the ε-type copper phthalocyanine pigment composition obtained in Comparative Example 1 was used.
<比較応用例５>
前記比較例２で得られたε型銅フタロシアニン顔料組成物を用いた以外は応用例３と同様の操作により、相対着色力を測定した。
<Comparative Application Example 5>
Relative coloring power was measured in the same manner as in Application Example 3 except that the ε-type copper phthalocyanine pigment composition obtained in Comparative Example 2 was used.
<比較応用例５>
前記比較例３で得られたε型銅フタロシアニン顔料組成物を用いた以外は応用例３と同様の操作により、相対着色力を測定した。
<Comparative Application Example 5>
Relative coloring power was measured by the same operation as in Application Example 3 except that the ε-type copper phthalocyanine pigment composition obtained in Comparative Example 3 was used.
表２ Table 2
以上より、本発明のε型銅フタロシアニン顔料組成物を使用すると、塗膜の輝度、コントラストおよび光透過率がいずれも高いカラーフィルター青色画素部及び着色力が高い塗料が得られることがわかる。
From the above, it can be seen that, when the ε-type copper phthalocyanine pigment composition of the present invention is used, a color filter blue pixel portion having high brightness, contrast and light transmittance of the coating film and a paint having high coloring power can be obtained.
Claims (6)
The method for producing an ε-type copper phthalocyanine pigment composition according to claim 4 or 5, wherein the amount is 1 to 20 parts of phthalimide alkylated phthalocyanine per 100 parts of α-type copper phthalocyanine on a mass basis.
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