JP2013061623A - Photosensitive colorant composition, and color filter and liquid crystal display device using the same - Google Patents
Photosensitive colorant composition, and color filter and liquid crystal display device using the same Download PDFInfo
- Publication number
- JP2013061623A JP2013061623A JP2012073334A JP2012073334A JP2013061623A JP 2013061623 A JP2013061623 A JP 2013061623A JP 2012073334 A JP2012073334 A JP 2012073334A JP 2012073334 A JP2012073334 A JP 2012073334A JP 2013061623 A JP2013061623 A JP 2013061623A
- Authority
- JP
- Japan
- Prior art keywords
- dye
- photosensitive
- colorant composition
- composition
- dispersion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Optical Filters (AREA)
Abstract
Description
本発明は、感光性着色剤組成物、およびそれを用いたカラーフィルタならびに液晶表示装置に関する。 The present invention relates to a photosensitive colorant composition, a color filter using the same, and a liquid crystal display device.
液晶表示装置は軽量、薄型、低消費電力等の特性を活かし、テレビ、ノートパソコン、携帯情報端末、スマートフォン、デジタルカメラ等様々な用途で使用されている。 Liquid crystal display devices are used in various applications such as televisions, notebook computers, personal digital assistants, smartphones, and digital cameras, taking advantage of characteristics such as light weight, thinness, and low power consumption.
液晶表示装置は用途に応じて、３〜６原色の最適な色が要求されるため、色性能を担うカラーフィルタ基板、ひいては着色剤組成物においても最適な色材が探索されている。 Since the liquid crystal display device is required to have an optimal color of 3 to 6 primary colors depending on the application, an optimal color material is also being searched for in the color filter substrate responsible for color performance, and in colorant composition.
従来のカラーフィルタ用着色剤組成物としては、樹脂溶液中で分散させた顔料を用いることが一般的である（顔料分散法）。顔料は色の種類が少なく、近年の求められている最適な色をだすことができない。そのため着色剤組成物により多くの種類の色がある染料を使う提案がされている。 As a conventional color filter colorant composition, a pigment dispersed in a resin solution is generally used (pigment dispersion method). There are few kinds of pigments, and it is not possible to produce the optimum color that has been demanded in recent years. For this reason, proposals have been made to use dyes with many different colors depending on the colorant composition.
着色材として染料を用いる代表的な方法として、例えば特許文献１〜２に記載されているように、溶剤に溶解させて用いる方法（染色法）が提案されている。しかしながら染色法は耐熱性や耐光性等が劣り、原理上、着色剤組成物を容器中で保存する際の温度変化や、溶剤揮発により、着色剤（染料）の析出が容易におこり、それが異物となる問題があった。 As a typical method of using a dye as a coloring material, for example, as described in Patent Documents 1 and 2, a method (dyeing method) used by dissolving in a solvent has been proposed. However, the dyeing method is inferior in heat resistance, light resistance, etc., and in principle, the colorant (dye) easily precipitates due to temperature change when the colorant composition is stored in a container or solvent volatilization. There was a problem of becoming a foreign object.
そこで、例えば特許文献３に記載されているように、染料を担体にレーキ化する、レーキ顔料を用いる方法も提案されているが、色を出すのに寄与しない担体を含むため、最適な色を出すことができなかった。 Therefore, for example, as described in Patent Document 3, a method using lake pigments in which a dye is laked on a carrier has been proposed, but since a carrier that does not contribute to color production is included, an optimum color is selected. I couldn't get it out.
また、例えば特許文献４では染料分散法が提案されているが、感光性が失われるために、エキシマレーザーでパターニングする方法が記載されている。 Further, for example, Patent Document 4 proposes a dye dispersion method, but describes a method of patterning with an excimer laser because photosensitivity is lost.
上述のとおり、色を良くしようと染料を用いた従来の染色法による感光性着色剤組成物では、耐熱性や耐光性等が劣り、また容器中での保存の際に、異物が発生する問題があった。またそれを解消しようと染料分散法を用いたとしても、充分な感光性能が得られない問題があった。本発明の染料を用いた感光性着色剤組成物は、着色剤として染料を分散したものであり、かつ充分な感光性能を有するものを得ることを目的とする。 As mentioned above, the photosensitive colorant composition by the conventional dyeing method using a dye to improve the color is inferior in heat resistance, light resistance, and the like, and foreign matter is generated when stored in a container. was there. Moreover, even if the dye dispersion method is used to solve this problem, there is a problem that sufficient photosensitive performance cannot be obtained. The photosensitive colorant composition using the dye of the present invention is obtained by dispersing a dye as a colorant and having a sufficient photosensitive performance.
本発明者らは鋭意検討した結果、従来の染料分散法は、分散と言えども、いくらか溶剤に溶解し、それが感光性能に悪影響を与えているのではないかと考えた。そして、染料の溶剤に対する溶解度に着目し、感光特性に相関があることを見出し、特定の範囲において、染料分散法であっても、十分な感光特性が得られることを見出したものである。 As a result of intensive studies, the present inventors have thought that the conventional dye dispersion method is dissolved in a solvent even though it is a dispersion, and this may have an adverse effect on the photosensitive performance. Then, paying attention to the solubility of the dye in the solvent, it has been found that there is a correlation in the photosensitivity, and in a specific range, it has been found that sufficient photosensitivity can be obtained even with the dye dispersion method.
本発明は以下の構成からなる。少なくとも、染料と、樹脂と、光重合開始剤と、溶剤を含有する着色剤感光性組成物であって、前記染料の前記溶剤に対する溶解性が０．１ｗｔ％以下である前記染料と前記溶剤の組み合わせであることを特徴とする染料含有着色剤感光性組成物。 The present invention has the following configuration. A colorant photosensitive composition containing at least a dye, a resin, a photopolymerization initiator, and a solvent, wherein the solubility of the dye in the solvent is 0.1 wt% or less. A dye-containing colorant photosensitive composition characterized by being a combination.
本発明の染料を用いた感光性着色剤組成物は、着色剤として染料を分散したものであり、かつ充分な感光性能を有する着色剤感光性組成物を提供するものである。 The photosensitive colorant composition using the dye of the present invention is obtained by dispersing a dye as a colorant and provides a colorant photosensitive composition having sufficient photosensitive performance.
本発明の感光性着色剤組成物は、少なくとも、染料と、樹脂と、光重合開始剤と、溶剤を含有する感光性着色剤組成物であって、前記染料の前記溶剤に対する溶解性が０．１ｗｔ％以下、より好ましくは０．０５ｗｔ％以下であることを特徴とする。これによって、本発明の感光性着色剤組成物は容器中での保存の際に、異物が発生しない。また十分な感光特性が得られる。 The photosensitive colorant composition of the present invention is a photosensitive colorant composition containing at least a dye, a resin, a photopolymerization initiator, and a solvent, and the solubility of the dye in the solvent is 0.00. It is characterized by being 1 wt% or less, more preferably 0.05 wt% or less. As a result, the photosensitive colorant composition of the present invention does not generate foreign matter when stored in a container. In addition, sufficient photosensitive characteristics can be obtained.
一般的な染料を用いた感光性着色剤組成物では、染料が組成物中で一部は溶解しているため、容器中で保存する際の温度変化や、溶剤揮発により、着色剤（染料）の析出が容易におこり、異物となる懸念がある。また、溶解した染料はラジカルクエンチャーとして作用し、感光特性が低下する懸念がある。 In a photosensitive colorant composition using a general dye, the dye is partially dissolved in the composition, so that the colorant (dye) may change due to temperature change during storage in a container or solvent volatilization. There is a concern that the precipitation of ash easily occurs and becomes a foreign matter. In addition, the dissolved dye acts as a radical quencher, and there is a concern that the photosensitive property is deteriorated.
一方、本発明では、感光性着色剤組成物中において、染料が溶剤に不溶であるため、異物発生が抑制でき、また充分な感度が得られる。 On the other hand, in the present invention, since the dye is insoluble in the solvent in the photosensitive colorant composition, the generation of foreign matter can be suppressed and sufficient sensitivity can be obtained.
ここでいう顔料とは、Colour Index Generic NameにおいてApplication classがPigmentであるものをさし、染料とは、それ以外（acid,Basic,Direct,Disperde,Solvent,Azoic Coupling Component,ingrain,Leather,Mordant,Natural,Reactiv,Sulphur,vat）であるものを指す。 The pigment here refers to the Color Index Generic Name whose Application class is Pigment, and the dye other than that (acid, Basic, Direct, Disperde, Solvent, Azoic Coupling Component, rain, Leather, Mordant, Natural, Reactiv, Sulfur, vat).
またこれら染料は化学構造として、フェロセン、フルオレノン、フルギド、イミダゾール、ペリレン、フェナジン、フェノチアジン、ポリエン、アゾ、キノン、インジゴ、ジフェニルメタン、トリフェニルメタン、ポリメチン、アクリジン、アクリジノン、カルボスチリル、クマリン、ジフェニルアミン、キナクリドン、キノフタロン、フェノキサジン、フタロペリノン、ポルフィン、クロロフィル、フタロシアニン等あるが、溶剤に対する溶解性が０．１質量％以下、より好ましくは０．０５ｗｔ％以下であれば任意のものを使用することができる。 These dyes have chemical structures such as ferrocene, fluorenone, fulgide, imidazole, perylene, phenazine, phenothiazine, polyene, azo, quinone, indigo, diphenylmethane, triphenylmethane, polymethine, acridine, acridinone, carbostyril, coumarin, diphenylamine, quinacridone. , Quinophthalone, phenoxazine, phthaloperinone, porphine, chlorophyll, phthalocyanine, etc., but any can be used as long as the solubility in a solvent is 0.1% by mass or less, more preferably 0.05% by weight or less.
本発明の感光性着色剤組成物に使用される溶剤としては、染料の溶解性が０．１％以下であることが好ましく、より好ましくは０．０５ｗｔ％以下であり、その限りにおいて特に限定されるものではないが、エステル系、エーテル系、ケトン系、炭化水素系の溶剤が好ましい。 The solvent used in the photosensitive colorant composition of the present invention preferably has a dye solubility of 0.1% or less, more preferably 0.05 wt% or less, and is particularly limited to that extent. Although not intended, ester, ether, ketone, and hydrocarbon solvents are preferred.
エステル系溶剤の例としては、ＰＭＡ、プロピレングリコールモノエチルエーテルアセテート、アセト酢酸エチル、メチル−３−メトキシプロピオネート、エチル−３−エトキシプロピオネート、メトキシブチルアセテート、３−メチル−３−メトキシブチルアセテート等が挙げられる。 Examples of ester solvents include PMA, propylene glycol monoethyl ether acetate, ethyl acetoacetate, methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, methoxybutyl acetate, 3-methyl-3-methoxy. Examples include butyl acetate.
エーテル系溶剤の例としては、メチルカルビトール、エチルカルビトール、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールエチルメチルエーテル、ジエチレングリコールブチルエチルエーテル等が挙げられ、ケトン系溶剤の例としては、脂肪族アルコール類、シクロペンタノン、シクロヘキサノン等が挙げられる。 Examples of ether solvents include methyl carbitol, ethyl carbitol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl ethyl Examples of the ketone solvent include aliphatic alcohols, cyclopentanone, and cyclohexanone.
炭化水素系溶剤としては、シクロヘキサン、イソオクタン等が挙げられる。 Examples of the hydrocarbon solvent include cyclohexane and isooctane.
これらの単独、あるいは２種類以上の混合溶剤も、染料の溶解性が好ましくは０．１ｗｔ％以下、より好ましくは０．０５ｗｔ％であれば用いることができる。 These alone or two or more kinds of mixed solvents can be used if the solubility of the dye is preferably 0.1 wt% or less, more preferably 0.05 wt%.
ここでいう染料の溶解性は、以下のような方法で判断することができる。５ｇの染料と９５ｇの溶剤とを混合攪拌し、５重量％の染料溶剤混合液を作製する。混合中で、溶剤不溶分は底に沈降し、溶剤溶解分は混合液中に残存するため、底の溶剤不溶性分をろ過により除去し、仮溶解液を得る。仮溶解液を１ｇサンプリングし、溶剤を乾燥させた後の染料の重量測定を行い、染料濃度を測定する。 The solubility of the dye here can be determined by the following method. 5 g of dye and 95 g of solvent are mixed and stirred to prepare a 5 wt% dye solvent mixture. During mixing, the solvent-insoluble matter settles to the bottom and the solvent-soluble matter remains in the mixed solution, so that the solvent-insoluble matter at the bottom is removed by filtration to obtain a temporary solution. 1 g of the temporary solution is sampled, the weight of the dye after drying the solvent is measured, and the dye concentration is measured.
本発明の感光性着色剤組成物における染料の粒子状態か分子状態（溶解状態）かは、例えば以下のような方法で判断することができる。粒子状態の染料は、粒径１０〜５００ｎｍであり、分子状態の染料は、分子径１ｎｍ程度であるため、粒径２〜８ｎｍ程度の透析チューブを使用することで、粒子状態と分子状態の染料を分離することができる。具体的には１００ｇの感光性着色剤組成物を透析チューブ内に注入した後、透析チューブの端と端を結ぶ。この１００ｇの感光性着色剤組成物を含む透析チューブを、３００ｇの感光性着色剤組成物に使用した溶剤中に投入する。浸透圧の関係で、分子状態の染料のみが、透析チューブの外側に流出する。よって、透析チューブ外側の溶剤が着色しているかどうかを目視で観察することで、分子状態かどうかを判断できる。 Whether the particle state or the molecular state (dissolved state) of the dye in the photosensitive colorant composition of the present invention can be determined, for example, by the following method. The particle state dye has a particle size of 10 to 500 nm, and the molecular state dye has a molecular size of about 1 nm. Therefore, by using a dialysis tube having a particle size of about 2 to 8 nm, the particle state and the molecular state dye can be used. Can be separated. Specifically, after 100 g of the photosensitive colorant composition is injected into the dialysis tube, the ends of the dialysis tube are connected. The dialysis tube containing 100 g of the photosensitive colorant composition is put into the solvent used for 300 g of the photosensitive colorant composition. Due to the osmotic pressure, only the molecular dye flows out of the dialysis tube. Therefore, it can be judged whether it is a molecular state by observing visually whether the solvent outside a dialysis tube is colored.
一方、本発明の感光性着色剤組成物中に染料が含まれているかどうかは、例えば、レーザーラマン分光法により判断することができる。すなわち、感光性着色剤組成物の塗布、溶剤乾燥、露光、現像、ポストベイクを行い、画素を作製する。この青色画素のレーザーラマン分光スペクトルと染料自体のレーザーラマン分光スペクトルを比較することで、感光性着色剤組成物中に染料が含まれているかどうかを判断できる。同様に、カラーフィルター基板のレーザーラマン分光スペクトルと染料自体のレーザーラマン分光スペクトルを比較することで、染料が含まれているかどうかを判断できる。 On the other hand, whether or not a dye is contained in the photosensitive colorant composition of the present invention can be determined by, for example, laser Raman spectroscopy. That is, application of a photosensitive colorant composition, solvent drying, exposure, development, and post-baking are performed to produce a pixel. By comparing the laser Raman spectrum of the blue pixel and the laser Raman spectrum of the dye itself, it can be determined whether or not the dye is contained in the photosensitive colorant composition. Similarly, by comparing the laser Raman spectrum of the color filter substrate with the laser Raman spectrum of the dye itself, it can be determined whether or not the dye is contained.
感光性着色剤組成物における染料の平均粒子径は、３０〜２００ｎｍであることが好ましく、３０〜１００ｎｍであることがより好ましい。平均粒子径が２００ｎｍより大きい場合、感光性着色剤組成物を基板に塗布乾燥した場合に、平坦な膜が得られず、顕微鏡観察時に粒として観察される場合がある。一方、平均粒子径が３０ｎｍより小さいと、未露光部におけるバインダー樹脂のアルカリ溶解性が低下し、パターン加工性が低下する場合がある。 The average particle size of the dye in the photosensitive colorant composition is preferably 30 to 200 nm, and more preferably 30 to 100 nm. When the average particle size is larger than 200 nm, a flat film may not be obtained when the photosensitive colorant composition is applied to a substrate and dried, and may be observed as particles during microscopic observation. On the other hand, when the average particle diameter is smaller than 30 nm, the alkali solubility of the binder resin in the unexposed area is lowered, and the pattern processability may be lowered.
サンドミル、ボールミルなどの分散機を用いて、ジルコニアビーズにより剪断応力を印加することで、染料の粉体粒子に剪断応力を印加することによって、染料の平均粒子径を上記の範囲とすることができる。 By applying a shear stress to the powder particles of the dye by applying a shear stress with zirconia beads using a disperser such as a sand mill or a ball mill, the average particle diameter of the dye can be within the above range. .
ただし、従来知られているような一般的は顔料の分散条件では、染料粒子を上記の粒径とすることは困難である。すなわち、顔料粉体は３０ｎｍ程度に造粒された１次粒子が集合し、数μｍの粉体粒子が形成されている。顔料粉体は、一次粒子同士の凝集力が小さいために、比較的弱い剪断応力で、短時間の分散で、一次粒子の凝集をほぐし、平均粒子径を３０〜２００ｎｍとすることができる。 However, it is difficult to make the dye particles have the above-mentioned particle size under the general pigment dispersion conditions as conventionally known. That is, primary particles granulated to about 30 nm are aggregated in the pigment powder, and powder particles of several μm are formed. Since the pigment powder has a small cohesion force between the primary particles, the aggregation of the primary particles can be loosened and the average particle diameter can be adjusted to 30 to 200 nm with a relatively weak shear stress and a short time dispersion.
一方、染料粉体は１ｎｍ程度の分子が集合し、数μｍの粗大粒子が形成されている。染料粉体は、分子同士の凝集力が強いため、弱い剪断応力では、平均粒子径を２００ｎｍより小さくすることが困難である。また、染料には一次粒子が存在しないため、剪断応力を強くしたり、分散時間を長くしたりすると、平均粒子径が３０ｎｍより小さくなることも懸念される。 On the other hand, molecules of about 1 nm aggregate in the dye powder, and coarse particles of several μm are formed. Since the dye powder has a strong cohesive force between molecules, it is difficult to make the average particle diameter smaller than 200 nm with a weak shear stress. In addition, since there are no primary particles in the dye, there is a concern that the average particle diameter may be smaller than 30 nm when the shear stress is increased or the dispersion time is increased.
本発明では、染料の平均粒子径を３０〜２００ｎｍとするために、ビーズ径０．３〜２．０μｍのジルコニアビーズを用いて、強い剪断応力で分散時間を３〜１０時間／ｋｇとすることが好ましい。 In the present invention, in order to set the average particle size of the dye to 30 to 200 nm, zirconia beads having a bead size of 0.3 to 2.0 μm are used, and the dispersion time is set to 3 to 10 hours / kg with a strong shear stress. Is preferred.
顔料の分散条件としては、ビーズ粒径０．１〜２．０μｍのジルコニアビーズを用いて、分散時間を１〜１０時間／ｋｇとすることが好ましい。 As pigment dispersion conditions, it is preferable to use zirconia beads having a bead particle size of 0.1 to 2.0 μm and a dispersion time of 1 to 10 hours / kg.
本発明の感光性着色剤組成物に使用される高分子分散剤としては、特に規定されないが、市販品としては、例えば、“ソルスパース”（アビシア社製）、“ＥＦＫＡ”（エフカ社製）、”アジスパー”（味の素ファインテクノ社製）、“ＢＹＫ”（ビックケミー社製）、“脂肪酸アマイド（花王社製）”等を好ましく用いることができる。 The polymer dispersant used in the photosensitive colorant composition of the present invention is not particularly defined, but examples of commercially available products include “Solsperse” (Avisia), “EFKA” (Efka), “Ajisper” (manufactured by Ajinomoto Fine Techno), “BYK” (manufactured by Big Chemie), “fatty acid amide (manufactured by Kao)” and the like can be preferably used.
本発明において高分子分散剤の添加量としては、好ましくは着色剤１００質量％に対して３０〜２００質量％が好ましい。高分子分散剤の添加量が３０質量部より少ないと、着色剤粒子の分散安定性が不良で、感光性着色剤組成物を基板上に塗布乾燥した場合に、平坦な膜が得られず、顕微鏡観察時に異物として観察される。一方、２００質量部より多いと未露光部の樹脂成分のアルカリ可溶性が低下し、パターン加工性が不良となる場合がある。 In the present invention, the addition amount of the polymer dispersant is preferably 30 to 200% by mass with respect to 100% by mass of the colorant. When the addition amount of the polymer dispersant is less than 30 parts by mass, the dispersion stability of the colorant particles is poor, and when a photosensitive colorant composition is applied and dried on a substrate, a flat film cannot be obtained, Observed as a foreign object during microscopic observation. On the other hand, when it is more than 200 parts by mass, the alkali solubility of the resin component in the unexposed part is lowered, and the pattern processability may be poor.
本発明の感光性着色剤組成物に使用される樹脂としては、アクリル系、エポキシ系、ポリイミド系等が挙げられ、カラーフィルター基板の製造コストを安くできるため感光性アクリル系樹脂が好ましい。アクリル系樹脂には、感光性を持たせるため少なくともバインダーポリマー、多官能モノマー、光重合開始剤を含有させることが一般的である。 Examples of the resin used in the photosensitive colorant composition of the present invention include acrylic, epoxy, and polyimide resins. A photosensitive acrylic resin is preferable because the manufacturing cost of the color filter substrate can be reduced. The acrylic resin generally contains at least a binder polymer, a polyfunctional monomer, and a photopolymerization initiator in order to impart photosensitivity.
なお、本発明において、樹脂としてアクリル系樹脂を用いた場合、バインダーポリマー、アクリルモノマー、および高分子分散剤を樹脂成分とし、染料を着色剤成分とする。 In the present invention, when an acrylic resin is used as the resin, a binder polymer, an acrylic monomer, and a polymer dispersant are used as a resin component, and a dye is used as a colorant component.
バインダーポリマーの例としては、不飽和カルボン酸とエチレン性不飽和化合物の共重合体等が挙げられる。不飽和カルボン酸の例としては、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、マレイン酸、フマル酸、ビニル酢酸、あるいは酸無水物等が挙げられる。 Examples of the binder polymer include a copolymer of an unsaturated carboxylic acid and an ethylenically unsaturated compound. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides.
多官能モノマーの例としては、トリメチロールプロパントリ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、トリアクリルホルマール、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、ジペンタエリスリトールペンタ（メタ）アクリレート等が挙げられる。 Examples of polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, triacryl formal, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (Meth) acrylate etc. are mentioned.
光重合開始剤の例としては、ベンゾフェノン、Ｎ，Ｎ’−テトラエチル−４，４’−ジアミノベンゾフェノン、４−メトキシ−４’−ジメチルアミノベンゾフェノン、２，２−ジエトキシアセトフェノン、α−ヒドロキシイソブチルフェノン、チオキサントン、２−クロロチオキサントン等が挙げられる。 Examples of photopolymerization initiators include benzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy-4′-dimethylaminobenzophenone, 2,2-diethoxyacetophenone, α-hydroxyisobutylphenone , Thioxanthone, 2-chlorothioxanthone and the like.
本発明の感光性着色剤組成物中の、着色剤成分と樹脂成分の質量混合比は、通常１０：９０〜６０：４０であり、好ましくは２０：８０〜５０：５０である。着色成分の量が１０質量％より少ないとカラーフィルターの色純度が低下しやすく、顔料成分が６０質量％より多いとカラーフィルターの信頼性が低下しやすい。 The mass mixing ratio of the colorant component and the resin component in the photosensitive colorant composition of the present invention is usually 10:90 to 60:40, preferably 20:80 to 50:50. If the amount of the coloring component is less than 10% by mass, the color purity of the color filter tends to be lowered, and if the amount of the pigment component is more than 60% by mass, the reliability of the color filter tends to be lowered.
本発明の感光性着色剤組成物には、界面活性剤、密着性改良剤、硬化促進剤などを添加することもできる。 A surfactant, an adhesion improver, a curing accelerator and the like can be added to the photosensitive colorant composition of the present invention.
本発明の感光性着色剤組成物において、塗工性、乾燥性などの観点から、顔料と樹脂をあわせた固形分濃度は、好ましくは５〜２０質量％の範囲で使用することが望ましい。 In the photosensitive colorant composition of the present invention, the solid content concentration of the pigment and the resin is preferably in the range of 5 to 20% by mass from the viewpoints of coating property and drying property.
本発明の感光性着色剤組成物において、着色剤として、さらに顔料を含むこともできる。染料と顔料を併用する際に特に限定はないが、それぞれ安定に分散した液を混合することが好ましい。 The photosensitive colorant composition of the present invention may further contain a pigment as the colorant. Although there is no limitation in particular when using together dye and a pigment, it is preferable to mix the liquid each disperse | distributed stably.
つぎに、本発明の感光性着色剤組成物を用いたカラーフィルター基板について説明する。
本発明のカラーフィルター基板は、上記の感光性着色剤組成物を用いて、少なくとも１色の着色画素を形成させることが必要である。
Next, a color filter substrate using the photosensitive colorant composition of the present invention will be described.
The color filter substrate of the present invention needs to form at least one color pixel using the photosensitive colorant composition.
まず、感光性着色剤組成物を基板上に塗布する方法としては、スピンコーター、バーコーター、ブレードコーター、ロールコーター、ダイコーター、インクジェット印刷法、スクリーン印刷法などで基板に塗布する方法、基板を溶液中に浸漬する方法、溶液を基板に噴霧するなどの種々の方法を用いることができる。基板としては通常、ソーダガラス、無アルカリガラス、ホウケイ酸ガラス、石英ガラスなどの透明基板が用いられる。感光性着色剤組成物を前記のような方法で透明基板上に塗布した後、風乾、加熱乾燥、真空乾燥などにより、感光性着色剤組成物の塗膜を形成する。 First, as a method of applying the photosensitive colorant composition on the substrate, a method of applying the substrate by a spin coater, a bar coater, a blade coater, a roll coater, a die coater, an ink jet printing method, a screen printing method, or the like. Various methods such as a method of immersing in a solution and spraying the solution onto a substrate can be used. As the substrate, a transparent substrate such as soda glass, alkali-free glass, borosilicate glass, or quartz glass is usually used. After the photosensitive colorant composition is applied on the transparent substrate by the method as described above, a coating film of the photosensitive colorant composition is formed by air drying, heat drying, vacuum drying or the like.
次に、感光性着色剤組成物の塗膜上にマスクを設置し、超高圧水銀灯、ケミカル灯、高圧水銀灯等を用いて、紫外線等により選択的に露光を行う。 Next, a mask is placed on the coating film of the photosensitive colorant composition, and exposure is selectively performed with ultraviolet rays or the like using an ultrahigh pressure mercury lamp, a chemical lamp, a high pressure mercury lamp, or the like.
その後、アルカリ性現像液で現像を行う。アルカリ性現像液に用いるアルカリ性物質としては、例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、アンモニア水等の無機アルカリ類、エチルアミン、ｎ−プロピルアミン等の１級アミン類、ジエチルアミン、ジ−ｎ−プロピルアミン等の２級アミン類、トリエチルアミン、メチルジエチルアミン等の３級アミン類、テトラメチルアンモニウムヒドロキシド等の有機アルカリ類等が挙げられる。 Thereafter, development is performed with an alkaline developer. Examples of the alkaline substance used in the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia, ethylamine, n-propylamine, and the like. Examples include secondary amines such as tertiary amines, diethylamine and di-n-propylamine, tertiary amines such as triethylamine and methyldiethylamine, and organic alkalis such as tetramethylammonium hydroxide.
その後、得られた塗膜パターンを加熱処理することによって画素がパターンニングされたカラーフィルター基板となる。加熱処理は通常、空気中、窒素雰囲気中、あるいは、真空中などで、１５０〜３５０℃、好ましくは１８０〜２５０℃の温度のもとで、０．５〜５時間、連続的または段階的に行われる。この加熱工程により、感光性着色剤組成物の樹脂成分の硬化が進む。 Thereafter, the obtained coating film pattern is heat-treated to form a color filter substrate on which pixels are patterned. The heat treatment is usually carried out in air, in a nitrogen atmosphere, or in a vacuum at a temperature of 150 to 350 ° C., preferably 180 to 250 ° C., for 0.5 to 5 hours, continuously or stepwise. Done. By this heating step, curing of the resin component of the photosensitive colorant composition proceeds.
上記のようなパターンニング工程を３〜６原色の各画素について順次行うと、液晶表示装置用カラーフィルターが作製できる。各色のパターンニング順序は限定されない。 When the patterning process as described above is sequentially performed for each pixel of 3 to 6 primary colors, a color filter for a liquid crystal display device can be produced. The patterning order of each color is not limited.
本発明のカラーフィルター基板の青色画素の膜厚は、１．２〜２．３μｍであることが望まれる。膜厚が１．０μｍより薄いと光の吸収が小さくなりカラーフィルターの色純度が低くなりやすい。一方、膜厚が２．５μｍより厚いと、カラーフィルターの平坦性低下、パターン加工性低下、信頼性低下等の様々な問題が生じ易くなる。 The film thickness of the blue pixel of the color filter substrate of the present invention is desirably 1.2 to 2.3 μm. If the film thickness is thinner than 1.0 μm, light absorption is reduced and the color purity of the color filter tends to be lowered. On the other hand, when the film thickness is larger than 2.5 μm, various problems such as a decrease in flatness of the color filter, a decrease in pattern workability, and a decrease in reliability are likely to occur.
以下、好ましい実施態様を用いて本発明を更に詳しく説明する。 Hereinafter, the present invention will be described in more detail using preferred embodiments.
実施例中の感光性着色剤組成物の評価を以下の方法で行った。 The photosensitive colorant composition in the examples was evaluated by the following method.
＜評価方法＞
（染料の溶解性評価）
５ｇの染料と９５ｇの溶剤とを混合攪拌し、５重量％の染料溶剤混合液を作製する。混合液中で、溶剤不溶分は底に沈降し、溶剤溶解分は混合液中に残存するため、底の溶剤不溶性分をろ過（アドバンティック製、（商品名）Ｎｏ．３）により除去する。ろ過後の染料溶液を１ｇサンプリングし、溶剤を１００℃３時間で、乾燥させた後の染料の重量測定を行い、染料濃度を測定する。
<Evaluation method>
(Dye solubility evaluation)
5 g of dye and 95 g of solvent are mixed and stirred to prepare a 5 wt% dye solvent mixture. In the mixed solution, the solvent-insoluble matter settles to the bottom, and the solvent-soluble matter remains in the mixed solution. Therefore, the solvent-insoluble matter at the bottom is removed by filtration (Advantic, (trade name) No. 3). 1 g of the dye solution after filtration is sampled, the solvent is dried at 100 ° C. for 3 hours, the weight of the dye is measured, and the dye concentration is measured.
（初期の感光性着色剤組成物の塗膜の異物評価）
感光性着色剤組成物をガラス基板上に塗布し、９０℃１０分乾燥後、１×１ｍｍの範囲を顕微鏡で１μｍ以上の大きさの異物の個数を数えた。
(Evaluation of foreign matter on coating film of initial photosensitive colorant composition)
The photosensitive colorant composition was applied on a glass substrate, dried at 90 ° C. for 10 minutes, and the number of foreign matters having a size of 1 μm or more was counted with a microscope in a range of 1 × 1 mm.
異物の個数を数え以下の基準で判定を行った。
○ ：異物が１０個以下
△ ：異物が１０〜１００個
× ：異物が１００個以上
（保管後の感光性着色剤組成物の塗膜の異物評価）
感光性着色剤組成物１００ｃｃの容器に５０ｃｃ入れ、４０℃で１日保管と５℃で１日保管を３回繰り返す。この保管後の感光性着色剤組成物をガラス基板上に塗布し、９０℃１０分乾燥後、１×１ｍｍの範囲を顕微鏡で１μｍ以上の大きさの異物の個数を数えた。
The number of foreign matters was counted and judged according to the following criteria.
○: 10 or less foreign matters Δ: 10 to 100 foreign matters ×: 100 or more foreign matters (foreign matter evaluation of the coating film of the photosensitive colorant composition after storage)
50 cc is placed in a 100 cc container of the photosensitive colorant composition, and stored at 40 ° C. for one day and at 5 ° C. for one day three times. The photosensitive colorant composition after storage was applied on a glass substrate, dried at 90 ° C. for 10 minutes, and the number of foreign matters having a size of 1 μm or more was counted with a microscope in a range of 1 × 1 mm.
異物の個数を数え以下の基準で判定を行った。
○：異物が１０個以下
△：異物が１０〜１００個
×：異物が１００個以上
（保管前後の異物の増加評価）
○：初期と保管後で異物の増加がないもの
初期○で保管後○、初期△で保管後△、初期×で保管後×
×：初期と保管後で異物の増加があること
初期が○で保管後が△もしくは×、初期が△で保管後が×
（感光特性評価）
感光性着色剤組成物をガラス基板上に塗布し、９０℃１０分乾燥し、５０μｍのライン＆スペースパターンを持つフォトマスクを介して、露光量が２００ｍｊ/ｃｍ２なるように、露光時間を調整し、紫外線露光を行った。基板とフォトマスクのＧａｐは１００μｍとした。
The number of foreign matters was counted and judged according to the following criteria.
○: 10 or less foreign objects Δ: 10 to 100 foreign objects ×: 100 or more foreign objects (increase evaluation of foreign objects before and after storage)
○: No increase in foreign matter after initial and storage After storage at initial ○, after storage at initial △, after storage at initial ×
×: There is an increase in foreign matter after initial storage and storage Initially ○, after storage △ or ×, initial △, after storage ×
(Photosensitive characteristic evaluation)
The photosensitive colorant composition is applied onto a glass substrate, dried at 90 ° C. for 10 minutes, and the exposure time is adjusted through a photomask having a 50 μm line & space pattern so that the exposure amount is 200 mj / cm 2. Then, UV exposure was performed. The gap between the substrate and the photomask was 100 μm.
次に、露光後基板を２３℃の０．２質量％水酸化テトラメチルアンモニウム水溶液中で６０秒間シャワー現像した後、純水で洗浄した。 Next, the exposed substrate was subjected to shower development for 60 seconds in a 0.2 mass% tetramethylammonium hydroxide aqueous solution at 23 ° C., and then washed with pure water.
パターン加工後の基板について、５０μｍパターンの顕微鏡観察を行い、以下の基準で判定を行った。
○：パターン幅が５０μｍ以上
△：パターン幅が４０〜５０μｍ
×：パターン幅が４０μｍ以下
（感光性着色剤組成物の着色剤の状態評価）
孔径５ｎｍの透析チューブ（富士理科工業株式会社製、（商品名）ヴィスキングチューブ）中に、１００ｇの感光性着色剤組成物を投入し透析チューブの端と端を結んだ。次に、３００ｇの、感応性着色剤組成物に使用した溶剤を投入したビーカ中に、１００ｇの感光性着色剤組成物を入りの透析チューブを投入後、２４時間放置した。
About the board | substrate after pattern processing, the microscope observation of a 50 micrometer pattern was performed and it determined by the following references | standards.
○: Pattern width is 50 μm or more Δ: Pattern width is 40 to 50 μm
X: Pattern width is 40 μm or less (evaluation of colorant state of photosensitive colorant composition)
100 g of the photosensitive colorant composition was put into a dialysis tube having a pore diameter of 5 nm (manufactured by Fuji Science Industry Co., Ltd., (trade name) Visking Tube), and the ends of the dialysis tube were connected to each other. Next, a dialysis tube containing 100 g of the photosensitive colorant composition was placed in a beaker containing 300 g of the solvent used in the sensitive colorant composition, and then left for 24 hours.
通常、粒子状態の染料は粒径３０〜２００ｎｍであり、分子状態（溶解状態）の染料は分子系１ｎｍ程度であるため、分子状態の染料のみ透析チューブを透過し、外側の溶剤に遺贈する。よって、透析チューブの外側の溶剤を目視観察し、着色が見られた場合は染料が分子状態と判断した。 Usually, the particle state dye has a particle size of 30 to 200 nm, and the molecular state (dissolved state) dye has a molecular system of about 1 nm. Therefore, only the molecular state dye passes through the dialysis tube and is left to the outer solvent. Therefore, the solvent on the outside of the dialysis tube was visually observed, and when coloring was observed, the dye was judged to be in a molecular state.
（着色剤の平均粒子径測定）
感光性着色剤組成物中における、染料濃度が０．１質量％となるように感光性着色剤組成物に使用した溶剤を用いて希釈した。この希釈液を、動的光散乱式粒形分布測定装置（（株）堀場製作所製ＬＢ−５００）を用いて、２５℃における体積基準の粒子の算術平均径を算出した。
(Measurement of average particle size of colorant)
It diluted with the solvent used for the photosensitive colorant composition so that the dye density | concentration in a photosensitive colorant composition might be 0.1 mass%. The arithmetic mean diameter of the volume-based particles at 25 ° C. was calculated for this diluted solution using a dynamic light scattering particle size distribution measuring device (LB-500, manufactured by Horiba, Ltd.).
実施例１
（染料の溶解性測定）
５０ｇのＡＲ２８９（東京化成（株）製）、９５０ｇのプロピレングリコールモノメチルエーテル（ＰＭＡ）を混合した。染料の溶解性評価を行ったところ、溶解性は０．０５質量％であった。
Example 1
(Dye solubility measurement)
50 g of AR289 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 950 g of propylene glycol monomethyl ether (PMA) were mixed. When the solubility of the dye was evaluated, the solubility was 0.05% by mass.
（無用剤バインダーポリマの作製）
バインダーポリマー（ダイセル化学製、“サイクロマー”、（商品名）ＡＣＡ２５０、４５質量％溶液）１００ｇを精製水１Ｌ中に滴下し析出させる。次に吸引ろ過で水分を取り除き、６０℃の雰囲気で２４時間真空乾燥を行い、無溶剤のバインダーを得た。
(Production of useless binder polymer)
100 g of binder polymer (manufactured by Daicel Chemical Industries, “Cyclomer”, (trade name) ACA250, 45 mass% solution) is dropped into 1 L of purified water and precipitated. Next, moisture was removed by suction filtration, and vacuum drying was performed in an atmosphere at 60 ° C. for 24 hours to obtain a solvent-free binder.
（染料分散液１の作製）
５０ｇのＡＲ２８９、５０ｇの無溶媒バインダーポリマ、５０ｇの高分子分散剤（味の素製、“アジスパーＰＢ８２１”、無溶剤、（以下ＰＢ８２１））、８５０ｇのＰＭＡを混合してスラリーを作製した。スラリーを入れたビーカーをダイノーミルとチューブでつなぎ、メディアとして直径０．５ｍｍのジルコニアビーズを使用して、周速１４ｍ／ｓで８時間の分散処理を行い、染料分散液１を作製した。染料分散液１の平均粒子径測定をしたところ、３０ｎｍであった。
(Preparation of dye dispersion 1)
A slurry was prepared by mixing 50 g of AR289, 50 g of a solventless binder polymer, 50 g of a polymer dispersant (manufactured by Ajinomoto Co., Inc., “Ajisper PB821”, solventless (hereinafter PB821)), and 850 g of PMA. The beaker containing the slurry was connected with a dyno mill and a tube, and zirconia beads having a diameter of 0.5 mm were used as media, and a dispersion treatment was performed at a peripheral speed of 14 m / s for 8 hours to prepare a dye dispersion 1. It was 30 nm when the average particle diameter measurement of the dye dispersion liquid 1 was carried out.
（感光性着色組成物１の作成）
つぎに、８０ｇの染料分散液１、１２ｇのＰＭＡ、１ｇの無溶剤バインダーポリマ、５ｇのＤＰＨＡモノマ（日本化薬製 “カヤラッドＤＰＨＡ” 無溶剤）、１．５ｇのイルガキュア９０７（ＢＡＳＦ（株）製、商品名）、および０．５ｇのカヤキュアＤＥＴＸ−Ｓ（日本化薬（株）製、商品名）を添加し、感光性着色剤組成物１を作製した。
(Preparation of photosensitive coloring composition 1)
Next, 80 g of dye dispersion 1, 12 g of PMA, 1 g of solvent-free binder polymer, 5 g of DPHA monomer (Nippon Kayaku “Kayarad DPHA” solvent-free), 1.5 g of Irgacure 907 (manufactured by BASF Corporation) ) And 0.5 g of Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd., trade name) were added to prepare photosensitive colorant composition 1.
（感光性着色組成物の状態評価）
孔径５ｎｍの透析チューブ（富士理科工業株式会社製、（商品名）ヴィスキングチューブ）中に、１００ｇの感光性着色剤組成物１を投入し透析チューブの端と端を結んだ。次に、３００ｇの、ＰＭＡを投入したビーカ中に、１００ｇの感光性着色剤組成物を入りの透析チューブを投入後、２４時間放置したところ、ＰＭＡに着色が見られず染料は粒子状態であった。
(Evaluation of state of photosensitive coloring composition)
100 g of the photosensitive colorant composition 1 was put into a dialysis tube having a pore size of 5 nm (manufactured by Fuji Science Industry Co., Ltd., (trade name) Visking tube), and the ends of the dialysis tube were connected to each other. Next, when a dialysis tube containing 100 g of a photosensitive colorant composition was placed in a 300 g beaker charged with PMA and left for 24 hours, PMA was not colored and the dye was in a particulate state. It was.
（感光性着色組成物１の評価）
この感光性着色剤組成物１の、感光特性評価、初期の塗膜の異物評価、保管後の塗膜の異物評価を行った。感光性着色剤組成物１は、線幅５２μｍで充分な感光特性を持ち、初期の異物は１個で良好あり、保管後の異物は１個で良好あり、したがって異物の増加がない良好な組成物であった。
(Evaluation of photosensitive coloring composition 1)
The photosensitive colorant composition 1 was subjected to photosensitive property evaluation, initial coating foreign matter evaluation, and storage coating foreign matter evaluation after storage. The photosensitive colorant composition 1 has a sufficient photosensitive property with a line width of 52 μm, and it is good that only one foreign substance is good, and only one foreign substance after storage, and therefore, there is no increase in foreign substances. It was a thing.
実施例２
（染料分散液２の作製）
実施例１の染料分散液１のＰＢ８２１を３０ｇにした以外は、染料分散液１と全く同様に作製した染料分散液２を作製した。染料分散液２の平均粒子径測定をしたところ、１８０ｎｍであった。
Example 2
(Preparation of dye dispersion 2)
A dye dispersion 2 prepared in exactly the same manner as the dye dispersion 1 was prepared except that 30 g of PB821 in the dye dispersion 1 of Example 1 was used. It was 180 nm when the average particle diameter measurement of the dye dispersion liquid 2 was carried out.
（感光性着色組成物２の作成）
実施例１の染料分散液１を染料分散液２に変更した以外は、全く同様に作製した感光性着色剤組成物２を作成した。
(Preparation of photosensitive coloring composition 2)
A photosensitive colorant composition 2 was prepared in exactly the same manner except that the dye dispersion 1 of Example 1 was changed to the dye dispersion 2.
（感光性着色組成物２の評価）
この感光性着色剤組成物２の、感光特性評価、初期の塗膜の異物評価、保管後の塗膜の異物評価を行った。感光性着色剤組成物２は、線幅５２μｍであり充分な感光特性を持ち、初期の異物は６個で良好あり、保管後の異物は５個で良好あり、したがって異物の増加がない良好な組成物であった。
(Evaluation of photosensitive coloring composition 2)
The photosensitive colorant composition 2 was evaluated for photosensitivity, evaluation of foreign matter on the initial coating film, and evaluation of foreign matter on the coating film after storage. Photosensitive colorant composition 2 has a line width of 52 μm and sufficient photosensitivity. Good initial foreign matter is six, good foreign matter after storage, and therefore no increase in foreign matter. It was a composition.
比較例１
（染料の溶解性測定）
５０ｇのＡＲ２８９、９５０ｇの３−メチル−３−メトキシブタノール（ＭＭＢ）を混合した。染料の溶解性評価を行ったところ、溶解性は０．３質量％であった。
Comparative Example 1
(Dye solubility measurement)
50 g of AR289 and 950 g of 3-methyl-3-methoxybutanol (MMB) were mixed. When the solubility of the dye was evaluated, the solubility was 0.3% by mass.
（染料分散液３の作製）
実施例１の染料分散液１のＰＭＡをＭＭＢにした以外は、染料分散液１と全く同様にして、染料分散液３を作製した。染料分散液３の平均粒子径測定をしたところ、１５０ｎｍであった
（感光性着色組成物３の作成）
実施例１の染料分散液１を染料分散液３に変更し、し、ＰＭＡをＭＭＢにした以外は、感光性着色組成物１と全く同様に作製した感光性着色剤組成物３を作成した。
（感光性着色組成物３の評価）
感光性着色剤組成物３は、パターン幅が４９μｍでやや低い感光特性を持ち、初期には異物が３個で良好であったものの、保管後に異物が２０個と増加した。したがって異物が増加するやや不安定な組成物であった。
(Preparation of dye dispersion 3)
A dye dispersion 3 was prepared in exactly the same manner as the dye dispersion 1, except that the PMA of the dye dispersion 1 of Example 1 was changed to MMB. The average particle diameter of the dye dispersion 3 was measured and found to be 150 nm (preparation of photosensitive coloring composition 3).
A photosensitive colorant composition 3 was prepared in exactly the same manner as the photosensitive coloring composition 1 except that the dye dispersion 1 of Example 1 was changed to the dye dispersion 3 and PMA was changed to MMB.
(Evaluation of photosensitive coloring composition 3)
The photosensitive colorant composition 3 had a slightly low photosensitive property with a pattern width of 49 μm, and although three foreign particles were good at the beginning, the number of foreign particles increased to 20 after storage. Therefore, it was a slightly unstable composition with increased foreign matter.
比較例２
（染料の溶解性測定）
５０ｇのＡＲ２８９、９５０ｇのＮ−メチルピロリドン（ＮＭＰ）を混合した。染料の溶解性評価を行ったところ、溶解性は５質量％であった。
Comparative Example 2
(Dye solubility measurement)
50 g of AR289 and 950 g of N-methylpyrrolidone (NMP) were mixed. When the solubility of the dye was evaluated, the solubility was 5% by mass.
（染料分散液４の作製）
実施例１の染料分散液１のＰＭＡをＮＭＰにした以外は、染料分散液１と全く同様にして、染料分散液４を作製した。染料分散液４の平均粒子径は５ｎｍであった。
(Preparation of dye dispersion 4)
Dye dispersion 4 was prepared in exactly the same manner as dye dispersion 1, except that PMA of dye dispersion 1 of Example 1 was changed to NMP. The average particle size of the dye dispersion 4 was 5 nm.
（感光性着色組成物４の作成）
実施例１の染料分散液１を染料分散液４に変更し、ＰＭＡをＮＭＰに変更した以外は、感光性着色組成物１と、全く同様に作製した感光性着色剤組成物４を作成した。
(Preparation of photosensitive coloring composition 4)
A photosensitive colorant composition 4 was prepared exactly in the same manner as the photosensitive color composition 1 except that the dye dispersion liquid 1 of Example 1 was changed to the dye dispersion liquid 4 and PMA was changed to NMP.
（感光性着色組成物の状態評価）
孔径５ｎｍの透析チューブ（富士理科工業株式会社製、（商品名）ヴィスキングチューブ）中に、１００ｇの感光性着色剤組成物５を投入し透析チューブの端と端を結んだ。次に、３００ｇの、ＮＭＰを投入したビーカ中に、１００ｇの感光性着色剤組成物を入りの透析チューブを投入後、２４時間放置したところ、ＮＭＰに着色が見られ染料は分子状態であった。
(Evaluation of state of photosensitive coloring composition)
100 g of the photosensitive colorant composition 5 was introduced into a dialysis tube (Fuji Rika Kogyo Co., Ltd., (trade name) Visking tube) having a pore diameter of 5 nm, and the ends of the dialysis tube were connected. Next, when a dialysis tube containing 100 g of a photosensitive colorant composition was placed in a beaker charged with 300 g of NMP and allowed to stand for 24 hours, NMP was colored and the dye was in a molecular state. .
（感光性着色組成物４の評価）
感光性着色剤組成物４は、パターン幅が３８μｍで、実施例１に比較して大幅に低い感光特性を持ち、初期には異物が１個で良好であったものの、保管後に異物が１００個以上と増加した、またこの異物は正方形の規則正しい結晶系そしていた。したがって保管中に染料の溶解析出を繰り返して、異物が増加する不安定な組成物であった。
(Evaluation of photosensitive coloring composition 4)
Photosensitive colorant composition 4 had a pattern width of 38 μm and significantly lower photosensitive properties than those of Example 1. Although only one foreign material was good at the beginning, 100 foreign materials were stored after storage. In addition, this foreign substance was a regular crystal system with a square shape. Therefore, it was an unstable composition in which foreign matter increased due to repeated dissolution and precipitation of the dye during storage.
実施例３
（顔料分散液の作製）
１００ｇの顔料ＰＢ１５：６（東洋インキ社製“リオノール”ブルー、（商品名）７６０２）、５０ｇのＰＢ８２１、５０ｇのバインダーポリマー、および８００ｇのＰＭＡ、を混合してスラリーを作製した。スラリーを入れたビーカーを循環式ビーズミル分散機（ウイリー・エ・バッコーフェン社製“ダイノーミル”ＫＤＬ−Ａ）とチューブでつなぎ、メディアとして直径０．３ｍｍのジルコニアビーズを使用して、周速１０ｍ／ｓで４時間の分散処理を行い、顔料分散液を作製した。顔料分散液中のＰＢ１５：６の平均粒子径は、４５ｎｍであった
（感光性着色組成物５の作成）
つぎに、４０ｇの顔料分散液、４０ｇの染料分散液１、１２ｇのＰＭＡ、１ｇの無溶剤バインダーポリマ、５ｇのＤＰＨＡ、１．５ｇのイルガキュア９０７、および０．５ｇのカヤキュアＤＥＴＸ−Ｓを添加し、顔料と染料を併用した感光性着色剤組成物５を作製した。
Example 3
(Preparation of pigment dispersion)
A slurry was prepared by mixing 100 g of pigment PB15: 6 (“Rionol” blue (trade name) 7602 manufactured by Toyo Ink Co., Ltd.), 50 g of PB821, 50 g of binder polymer, and 800 g of PMA. The beaker containing the slurry was connected with a circulation type bead mill disperser ("Dino Mill" KDL-A manufactured by Willy et Bacofen) and a tube, and a zirconia bead with a diameter of 0.3 mm was used as the medium, and the peripheral speed was 10 m / s. Then, a dispersion treatment was performed for 4 hours to prepare a pigment dispersion. The average particle diameter of PB15: 6 in the pigment dispersion was 45 nm (Preparation of photosensitive coloring composition 5)
Next, 40 g of pigment dispersion, 40 g of dye dispersion 1, 12 g of PMA, 1 g of solventless binder polymer, 5 g of DPHA, 1.5 g of Irgacure 907, and 0.5 g of Kayacure DETX-S were added. A photosensitive colorant composition 5 using a pigment and a dye in combination was prepared.
（感光性着色組成物５の評価）
この感光性着色剤組成物５の、感光特性評価、初期の塗膜の異物評価、保管後の塗膜の異物評価を行った。感光性着色剤組成物５は、線幅５２μｍであり充分な感光特性を持ち、初期の異物は２個で良好あり、保管後の異物は２個で良好あり、したがって顔料と染料を併用した場合においても、異物の増加がない良好な組成物であった。
(Evaluation of photosensitive coloring composition 5)
The photosensitive colorant composition 5 was subjected to photosensitive property evaluation, initial coating foreign matter evaluation, and coating foreign matter evaluation after storage. The photosensitive colorant composition 5 has a line width of 52 μm and has sufficient photosensitive characteristics. Two initial foreign matters are good and two foreign matters after storage are good. Therefore, when a pigment and a dye are used in combination. In this case, it was a good composition with no increase in foreign matter.
実施例４
（染料の溶解性測定）
５０ｇのSolvent Blue 60（有本化学（株）製“Oil Blue 5511”）、９５０ｇのイソパラフィン炭化水素（出光興産（株）、ＩＰソルベント１６２０）を混合した。染料の溶解性評価を行ったところ、溶解性は０．０８質量％であった。
Example 4
(Dye solubility measurement)
50 g of Solvent Blue 60 (“Oil Blue 5511” manufactured by Arimoto Chemical Co., Ltd.) and 950 g of isoparaffin hydrocarbon (Idemitsu Kosan Co., Ltd., IP Solvent 1620) were mixed. When the solubility of the dye was evaluated, the solubility was 0.08% by mass.
（染料分散液６の作製）
５０ｇのSolvent Blue 60、５０ｇの無溶媒バインダーポリマ、５０ｇのＰＢ８２１、８５０ｇのＩＰソルベントを混合してスラリーを作製した。スラリーを入れたビーカーをダイノーミルとチューブでつなぎ、メディアとして直径０．５ｍｍのジルコニアビーズを使用して、周速１４ｍ／ｓで８時間の分散処理を行い、染料分散液６を作製した。染料分散液６の平均粒子径測定をしたところ、１２８ｎｍであった。
(Preparation of dye dispersion 6)
A slurry was prepared by mixing 50 g of Solvent Blue 60, 50 g of solventless binder polymer, 50 g of PB821, and 850 g of IP solvent. The beaker containing the slurry was connected with a dyno mill and a tube, and zirconia beads having a diameter of 0.5 mm were used as media, and a dispersion treatment was performed at a peripheral speed of 14 m / s for 8 hours to prepare Dye Dispersion Liquid 6. It was 128 nm when the average particle diameter measurement of the dye dispersion liquid 6 was carried out.
（感光性着色組成物６の作成）
つぎに、８０ｇの染料分散液６、１２ｇのＰＭＡ、１ｇの無溶剤バインダーポリマ、５ｇのＤＰＨＡ、１．５ｇのイルガキュア９０７、
および０．５ｇのカヤキュアＤＥＴＸ−Ｓを添加し、感光性着色剤組成物６を作製した。
(Preparation of photosensitive coloring composition 6)
Next, 80 g dye dispersion 6, 12 g PMA, 1 g solventless binder polymer, 5 g DPHA, 1.5 g Irgacure 907,
And 0.5 g of Kayacure DETX-S were added to prepare photosensitive colorant composition 6.
（感光性着色組成物６の評価）
この感光性着色剤組成物６の、感光特性評価、初期の塗膜の異物評価、保管後の塗膜の異物評価を行った。感光性着色剤組成物６は、線幅５２μｍで充分な感光特性を持ち、初期の異物は７個で良好あり、保管後の異物は９個で良好あり、したがって保管によりわずかに異物が増加するものの良好な組成物であった。
(Evaluation of photosensitive coloring composition 6)
The photosensitive colorant composition 6 was subjected to photosensitive property evaluation, initial coating foreign matter evaluation, and coating foreign matter evaluation after storage. The photosensitive colorant composition 6 has a sufficient photosensitive property with a line width of 52 μm, and is good with 7 initial foreign matters and 9 good foreign materials after storage. Therefore, the foreign materials slightly increase by storage. It was a good composition.
比較例３
（染料の溶解性測定）
５０ｇのSolvent Blue 60（有本化学（株）製“Oil Blue 5511”）、９５０ｇのPMAを混合した。染料の溶解性評価を行ったところ、溶解性は５質量％であった。
Comparative Example 3
(Dye solubility measurement)
50 g of Solvent Blue 60 (“Oil Blue 5511” manufactured by Arimoto Chemical Co., Ltd.) and 950 g of PMA were mixed. When the solubility of the dye was evaluated, the solubility was 5% by mass.
（染料分散液７の作製）
実施例４の染料分散液６のＩＰソルベント１６２０をＰＭＡにした以外は、染料分散液６と全く同様にして、染料分散液７を作製した。
(Preparation of dye dispersion 7)
A dye dispersion 7 was prepared in exactly the same manner as the dye dispersion 6 except that the IP solvent 1620 of the dye dispersion 6 of Example 4 was changed to PMA.
（感光性着色組成物７の作成）
実施例４の染料分散液６を染料分散液７に変更し、ＩＰソルベント１６２０をＰＭＡにした以外は、全く同様に作製した感光性着色剤組成物７を作成した。
(Preparation of photosensitive coloring composition 7)
A photosensitive colorant composition 7 was prepared in exactly the same manner except that the dye dispersion 6 of Example 4 was changed to the dye dispersion 7 and the IP solvent 1620 was changed to PMA.
（感光性着色組成物７の評価）
感光性着色剤組成物７は、パターン幅がまったくのこらず、実施例４に比較して大幅感光特性が低下しており、初期には異物が８個で良好であったものの、保管後に異物が１００個以上と大幅に増加した、またこの異物は規則正しい結晶系をしていた。したがって保管中に染料の溶解析出を繰り返して、異物が増加する不安定な組成物であった。
(Evaluation of Photosensitive Coloring Composition 7)
The photosensitive colorant composition 7 had no pattern width at all, and the photosensitivity characteristics were greatly reduced as compared with Example 4. Although 8 foreign matters were good at the beginning, the foreign matter after storage Greatly increased to 100 or more, and this foreign material had a regular crystal system. Therefore, it was an unstable composition in which foreign matter increased due to repeated dissolution and precipitation of the dye during storage.
実施例５
（染料の溶解性測定）
５０ｇのBasic Blue 3（稲畑ファインテック（株）製“Nichilon Pure Blue”）、９５０ｇのPMAを混合した。染料の溶解性評価を行ったところ、溶解性は０．０２質量％であった。
Example 5
(Dye solubility measurement)
50 g of Basic Blue 3 (“Nichilon Pure Blue” manufactured by Inabata Finetech Co., Ltd.) and 950 g of PMA were mixed. When the solubility of the dye was evaluated, the solubility was 0.02% by mass.
（染料分散液８の作製）
５０ｇのBasic Blue 3、５０ｇの無溶媒バインダーポリマ、５０ｇのＰＢ８２１、８５０ｇのPMAを混合してスラリーを作製した。スラリーを入れたビーカーをダイノーミルとチューブでつなぎ、メディアとして直径０．５ｍｍのジルコニアビーズを使用して、周速１４ｍ／ｓで８時間の分散処理を行い、染料分散液８を作製した。染料分散液８の平均粒子径測定をしたところ、１５０ｎｍであった。
(Preparation of dye dispersion 8)
A slurry was prepared by mixing 50 g of Basic Blue 3, 50 g of a solventless binder polymer, 50 g of PB821, and 850 g of PMA. The beaker containing the slurry was connected with a dyno mill and a tube, and zirconia beads having a diameter of 0.5 mm were used as media, and a dispersion treatment was performed at a peripheral speed of 14 m / s for 8 hours to prepare a dye dispersion 8. It was 150 nm when the average particle diameter measurement of the dye dispersion liquid 8 was carried out.
（感光性着色組成物８の作成）
つぎに、８０ｇの染料分散液８、１２ｇのＰＭＡ、１ｇの無溶剤バインダーポリマ、５ｇのＤＰＨＡ、１．５ｇのイルガキュア９０７、
および０．５ｇのカヤキュアＤＥＴＸ−Ｓを添加し、感光性着色剤組成物８を作製した。
(Preparation of photosensitive coloring composition 8)
Next, 80 g of dye dispersion 8, 12 g of PMA, 1 g of solventless binder polymer, 5 g of DPHA, 1.5 g of Irgacure 907,
And 0.5 g of Kayacure DETX-S were added to prepare photosensitive colorant composition 8.
（感光性着色組成物８の評価）
この感光性着色剤組成物８の、感光特性評価、初期の塗膜の異物評価、保管後の塗膜の異物評価を行った。感光性着色剤組成物８は、線幅５１μｍで充分な感光特性を持ち、初期の異物は９個で良好あり、保管後の異物は５個で良好あり、したがって異物の増加がない良好な組成物であった。
(Evaluation of photosensitive coloring composition 8)
The photosensitive colorant composition 8 was subjected to photosensitive property evaluation, initial coating foreign matter evaluation, and coating foreign matter evaluation after storage. The photosensitive colorant composition 8 has sufficient photosensitivity with a line width of 51 μm, 9 initial foreign matters are good, and 5 foreign matters are good after storage, and therefore no good increase in foreign matters. It was a thing.
比較例４
（染料の溶解性測定）
５０ｇのBasic Blue 3（稲畑ファインテック（株）製“Nichilon Pure Blue”）、９５０ｇのNMPを混合した。染料の溶解性評価を行ったところ、溶解性は０．１８質量％であった。
Comparative Example 4
(Dye solubility measurement)
50 g of Basic Blue 3 (“Nichilon Pure Blue” manufactured by Inabata Finetech Co., Ltd.) and 950 g of NMP were mixed. When the solubility of the dye was evaluated, the solubility was 0.18% by mass.
（染料分散液９の作製）
実施例５の染料分散液８のPMAをＮＭＰにした以外は、染料分散液８と全く同様にして、染料分散液９を作製した。
(Preparation of dye dispersion 9)
Dye dispersion 9 was prepared in exactly the same manner as dye dispersion 8, except that PMA in dye dispersion 8 of Example 5 was changed to NMP.
（感光性着色組成物９の作成）
実施例５の染料分散液８を染料分散液９に変更し、ＰＭＡをＮＭＰにした以外は、全く同様に作製した感光性着色剤組成物９を作成した。
(Preparation of photosensitive coloring composition 9)
A photosensitive colorant composition 9 was prepared in exactly the same manner except that the dye dispersion 8 of Example 5 was changed to the dye dispersion 9 and PMA was changed to NMP.
（感光性着色組成物９の評価）
感光性着色剤組成物９は、パターン幅が４９μｍであり、実施例５に比較してやや感光特性が低下しており、初期には異物が７個で良好であったものの、保管後に異物が４０個とやや増加した。したがって保管中に染料の溶解析出を繰り返して、異物が増加する不安定な組成物であった。
(Evaluation of photosensitive coloring composition 9)
The photosensitive colorant composition 9 had a pattern width of 49 μm and slightly decreased photosensitive characteristics as compared with Example 5. Although 7 foreign particles were good at the beginning, 40 particles were stored after storage. Slightly increased with individuals. Therefore, it was an unstable composition in which foreign matter increased due to repeated dissolution and precipitation of the dye during storage.
実施例６
（染料の溶解性測定）
５０ｇのReactiv Blue 224（ダイスター（株）製“Lavafix Royal Blue E-FR”）、９５０ｇのPMAを混合した。染料の溶解性評価を行ったところ、溶解性は０．０２質量％であった。
Example 6
(Dye solubility measurement)
50 g of Reactiv Blue 224 (“Lavafix Royal Blue E-FR” manufactured by Dystar Co., Ltd.) and 950 g of PMA were mixed. When the solubility of the dye was evaluated, the solubility was 0.02% by mass.
（染料分散液１０の作製）
５０ｇのReactiv Blue 224、５０ｇの無溶媒バインダーポリマ、５０ｇのＰＢ８２１、８５０ｇのPMAを混合してスラリーを作製した。スラリーを入れたビーカーをダイノーミルとチューブでつなぎ、メディアとして直径０．５ｍｍのジルコニアビーズを使用して、周速１４ｍ／ｓで８時間の分散処理を行い、染料分散液１０を作製した。染料分散液１０の平均粒子径測定をしたところ、１５０ｎｍであった。
(Preparation of dye dispersion 10)
50 g of Reactiv Blue 224, 50 g of solventless binder polymer, 50 g of PB821, and 850 g of PMA were mixed to prepare a slurry. The beaker containing the slurry was connected with a dyno mill and a tube, and zirconia beads having a diameter of 0.5 mm were used as media, and a dispersion treatment was performed at a peripheral speed of 14 m / s for 8 hours to prepare a dye dispersion liquid 10. The average particle size of the dye dispersion liquid 10 was measured and found to be 150 nm.
（感光性着色組成物１０の作成）
つぎに、８０ｇの染料分散液１０、１２ｇのＰＭＡ、１ｇの無溶剤バインダーポリマ、５ｇのＤＰＨＡ、１．５ｇのイルガキュア９０７、
および０．５ｇのカヤキュアＤＥＴＸ−Ｓを添加し、感光性着色剤組成物１０を作製した。
(Preparation of photosensitive coloring composition 10)
Next, 80 g of dye dispersion 10, 12 g of PMA, 1 g of solventless binder polymer, 5 g of DPHA, 1.5 g of Irgacure 907,
And 0.5 g of Kayacure DETX-S were added to prepare photosensitive colorant composition 10.
（感光性着色組成物１０の評価）
この感光性着色剤組成物１０の、感光特性評価、初期の塗膜の異物評価、保管後の塗膜の異物評価を行った。感光性着色剤組成物１０は、線幅５１μｍで充分な感光特性を持ち、初期の異物は５個で良好あり、保管後の異物は５個で良好あり、したがって異物の増加がない良好な組成物であった。
(Evaluation of photosensitive coloring composition 10)
The photosensitive colorant composition 10 was evaluated for photosensitive properties, evaluation of foreign matter on the initial coating film, and evaluation of foreign matter on the coating film after storage. The photosensitive colorant composition 10 has sufficient photosensitivity with a line width of 51 μm, is good when there are five initial foreign matters, and is good when there are five foreign matters after storage, and therefore there is no increase in foreign matters. It was a thing.
比較例５
（染料の溶解性測定）
５０ｇのReactiv Blue 224、９５０ｇのNMPを混合した。染料の溶解性評価を行ったところ、溶解性は０．２２質量％であった。
Comparative Example 5
(Dye solubility measurement)
50 g Reactiv Blue 224 and 950 g NMP were mixed. When the solubility of the dye was evaluated, the solubility was 0.22% by mass.
（染料分散液１１の作製）
実施例６の染料分散液１０のPMAをＮＭＰにした以外は、染料分散液１０と全く同様にして、染料分散液１１を作製した。この染料分散液の平均粒子径は１５０ｎｍであった。
(Preparation of Dye Dispersion 11)
Dye dispersion 11 was prepared in exactly the same manner as dye dispersion 10 except that PMA in dye dispersion 10 of Example 6 was changed to NMP. The average particle size of this dye dispersion was 150 nm.
（感光性着色組成物１１の作成）
実施例６の染料分散液１０を染料分散液１１に変更し、ＰＭＡをＮＭＰにした以外は、全く同様に作製した感光性着色剤組成物１１を作成した。
(Preparation of photosensitive coloring composition 11)
A photosensitive colorant composition 11 was prepared in exactly the same manner except that the dye dispersion 10 of Example 6 was changed to the dye dispersion 11 and PMA was changed to NMP.
（感光性着色組成物１１の評価）
感光性着色剤組成物１１は、パターン幅が４８μｍであり、実施例６に比較してやや感光特性が低下しており、初期には異物が５個で良好であったものの、保管後に異物が２３個とやや増加した。したがって保管中に染料の溶解析出を繰り返して、異物が増加する不安定な組成物であった。
(Evaluation of photosensitive coloring composition 11)
The photosensitive colorant composition 11 had a pattern width of 48 μm and slightly decreased photosensitive characteristics as compared with Example 6. Although five foreign matters were good at the beginning, the foreign matter was 23 after storage. Slightly increased with individuals. Therefore, it was an unstable composition in which foreign matter increased due to repeated dissolution and precipitation of the dye during storage.
実施例７
（染料の溶解性測定）
５０ｇのAcid Blue ９（東京化成（株）製“Acid Blue ９”）、９５０ｇのPMAを混合した。染料の溶解性評価を行ったところ、溶解性は０．０４質量％であった。
Example 7
(Dye solubility measurement)
50 g of Acid Blue 9 (“Acid Blue 9” manufactured by Tokyo Chemical Industry Co., Ltd.) and 950 g of PMA were mixed. When the solubility of the dye was evaluated, the solubility was 0.04% by mass.
（染料分散液１２の作製）
５０ｇのAcid Blue ９、５０ｇの無溶媒バインダーポリマ、５０ｇのＰＢ８２１、８５０ｇのPMAを混合してスラリーを作製した。スラリーを入れたビーカーをダイノーミルとチューブでつなぎ、メディアとして直径０．５ｍｍのジルコニアビーズを使用して、周速１４ｍ／ｓで８時間の分散処理を行い、染料分散液１２を作製した。染料分散液１２の平均粒子径測定をしたところ、３５０ｎｍであった。
(Preparation of dye dispersion 12)
50 g Acid Blue 9, 50 g solvent-free binder polymer, 50 g PB821, and 850 g PMA were mixed to prepare a slurry. The beaker containing the slurry was connected with a dyno mill and a tube, and zirconia beads having a diameter of 0.5 mm were used as media, and a dispersion treatment was performed at a peripheral speed of 14 m / s for 8 hours to prepare a dye dispersion liquid 12. It was 350 nm when the average particle diameter measurement of the dye dispersion liquid 12 was carried out.
（感光性着色組成物１２の作成）
つぎに、８０ｇの染料分散液１２、１２ｇのＰＭＡ、１ｇの無溶剤バインダーポリマ、５ｇのＤＰＨＡ、１．５ｇのイルガキュア９０７、
および０．５ｇのカヤキュアＤＥＴＸ−Ｓを添加し、感光性着色剤組成物１２を作製した。
(Preparation of photosensitive coloring composition 12)
Next, 80 g of dye dispersion 12, 12 g of PMA, 1 g of solventless binder polymer, 5 g of DPHA, 1.5 g of Irgacure 907,
And 0.5 g of Kayacure DETX-S were added to prepare photosensitive colorant composition 12.
（感光性着色組成物１２の評価）
この感光性着色剤組成物１２の、感光特性評価、初期の塗膜の異物評価、保管後の塗膜の異物評価を行った。感光性着色剤組成物１２は、線幅５２μｍで充分な感光特性を持ち、初期の異物は２０個でやや多いものの、保管後の異物は１６個であり、したがって異物の増加がない組成物であった。
(Evaluation of Photosensitive Coloring Composition 12)
The photosensitive colorant composition 12 was subjected to photosensitive property evaluation, initial coating foreign matter evaluation, and coating foreign matter evaluation after storage. The photosensitive colorant composition 12 has a sufficient photosensitive property with a line width of 52 μm, and although there are 20 initial foreign matters, there are 16 foreign matters after storage, and therefore there is no increase in foreign matters. there were.
比較例６
（染料の溶解性測定）
５０ｇのAcid Blue ９、９５０ｇのNMPを混合した。染料の溶解性評価を行ったところ、溶解性は０．５０質量％であった。
Comparative Example 6
(Dye solubility measurement)
50 g Acid Blue 9 and 950 g NMP were mixed. When the solubility of the dye was evaluated, the solubility was 0.50% by mass.
（染料分散液１３の作製）
実施例７の染料分散液１２のPMAをＮＭＰにした以外は、染料分散液１２と全く同様にして、染料分散液１３を作製した。この染料分散液の平均粒子径は６００ｎｍであった。
(Preparation of dye dispersion 13)
A dye dispersion 13 was prepared in exactly the same manner as the dye dispersion 12, except that the PMA of the dye dispersion 12 of Example 7 was changed to NMP. The average particle size of this dye dispersion was 600 nm.
（感光性着色組成物１３の作成）
実施例７の染料分散液１２を染料分散液１３に変更し、ＰＭＡをＮＭＰにした以外は、全く同様に作製した感光性着色剤組成物１３を作成した。
(Preparation of photosensitive coloring composition 13)
A photosensitive colorant composition 13 was prepared in exactly the same manner except that the dye dispersion 12 of Example 7 was changed to the dye dispersion 13 and PMA was changed to NMP.
（感光性着色組成物１３の評価）
感光性着色剤組成物１３は、パターン幅が４８μｍであり、実施例７に比較してやや感光特性が低下しており、平均粒子径が５００ｎｍと大きいため、初期には異物が５０個でややや多く、保管後に異物が１００個以上と大幅に増加した。したがって保管中に染料の溶解析出を繰り返して、異物が増加する不安定な組成物であった。
(Evaluation of photosensitive coloring composition 13)
The photosensitive colorant composition 13 has a pattern width of 48 μm, slightly lower photosensitivity than that of Example 7, and an average particle size as large as 500 nm. In many cases, after storage, the number of foreign matters increased to 100 or more. Therefore, it was an unstable composition in which foreign matter increased due to repeated dissolution and precipitation of the dye during storage.
実施例８
（染料の溶解性測定）
５０ｇのSolvent Blue４５（有本化学（株）製、“Plast Blue DB463”）、９５０ｇのPMAを混合した。染料の溶解性評価を行ったところ、溶解性は０．０９質量％であった。
Example 8
(Dye solubility measurement)
50 g of Solvent Blue 45 (manufactured by Arimoto Chemical Co., “Plast Blue DB463”) and 950 g of PMA were mixed. When the solubility of the dye was evaluated, the solubility was 0.09% by mass.
（染料分散液１４の作製）
５０ｇのSolvent Blue４５、５０ｇの無溶媒バインダーポリマ、５０ｇのＰＢ８２１、８５０ｇのPMAを混合してスラリーを作製した。スラリーを入れたビーカーをダイノーミルとチューブでつなぎ、メディアとして直径０．５ｍｍのジルコニアビーズを使用して、周速１４ｍ／ｓで８時間の分散処理を行い、染料分散液１４を作製した。染料分散液１４の平均粒子径測定をしたところ、９８ｎｍであった。
(Preparation of dye dispersion 14)
A slurry was prepared by mixing 50 g of Solvent Blue 45, 50 g of solventless binder polymer, 50 g of PB821, and 850 g of PMA. The beaker containing the slurry was connected with a dyno mill and a tube, and zirconia beads having a diameter of 0.5 mm were used as media, and a dispersion treatment was performed at a peripheral speed of 14 m / s for 8 hours to prepare a dye dispersion liquid 14. The average particle diameter of the dye dispersion 14 was measured and found to be 98 nm.
（感光性着色組成物１４の作成）
つぎに、８０ｇの染料分散液１４、１２ｇのＰＭＡ、１ｇの無溶剤バインダーポリマ、５ｇのＤＰＨＡ、１．５ｇのイルガキュア９０７、
および０．５ｇのカヤキュアＤＥＴＸ−Ｓを添加し、感光性着色剤組成物１４を作製した。
(Preparation of photosensitive coloring composition 14)
Next, 80 g of dye dispersion 14, 12 g of PMA, 1 g of solventless binder polymer, 5 g of DPHA, 1.5 g of Irgacure 907,
And 0.5 g of Kayacure DETX-S were added to prepare photosensitive colorant composition 14.
（感光性着色組成物１４の評価）
この感光性着色剤組成物１４の、感光特性評価、初期の塗膜の異物評価、保管後の塗膜の異物評価を行った。感光性着色剤組成物１４は、線幅５１μｍで充分な感光特性を持ち、初期の異物は３個で良好であり、保管後の異物は９個であり、したがって保管によりわずかに異物が増加するものの安定性の良好な組成物であった。
(Evaluation of photosensitive coloring composition 14)
The photosensitive colorant composition 14 was subjected to photosensitive property evaluation, initial coating foreign matter evaluation, and coating foreign matter evaluation after storage. The photosensitive colorant composition 14 has sufficient photosensitivity with a line width of 51 μm, is good when three foreign matters are present, and has nine foreign matters after storage. Therefore, foreign matters slightly increase by storage. The composition had good stability.
比較例７
（染料の溶解性測定）
５０ｇのSolvent Blue４５、９５０ｇのシクロヘキサノンを混合した。染料の溶解性評価を行ったところ、溶解性は１．２質量％であった。
Comparative Example 7
(Dye solubility measurement)
50 g of Solvent Blue 45 and 950 g of cyclohexanone were mixed. When the solubility of the dye was evaluated, the solubility was 1.2% by mass.
（染料分散液１５の作製）
実施例８の染料分散液１５のPMAをシクロヘキサノンにした以外は、染料分散液１４と全く同様にして、染料分散液１５を作製した。この染料分散液の平均粒子径は２１０ｎｍであった。
(Preparation of dye dispersion 15)
A dye dispersion 15 was prepared in exactly the same manner as the dye dispersion 14 except that cyclohexanone was used as the PMA of the dye dispersion 15 of Example 8. The average particle size of this dye dispersion was 210 nm.
（感光性着色組成物１５の作成）
実施例８の染料分散液１４を染料分散液１５に変更し、ＰＭＡをシクロヘキサノンにした以外は、全く同様に作製した感光性着色剤組成物１５を作成した。
(Preparation of photosensitive coloring composition 15)
A photosensitive colorant composition 15 was prepared in exactly the same manner except that the dye dispersion 14 of Example 8 was changed to the dye dispersion 15 and PMA was changed to cyclohexanone.
（感光性着色組成物１５の評価）
感光性着色剤組成物１５は、パターン幅が３２μｍであり、実施例８に比較して大幅に感光特性が低下しており、初期には異物が１個で良好なものの、保管後に異物が６０個と大幅に増加した。したがって保管中に染料の溶解析出を繰り返して、異物が増加する不安定な組成物であった。
(Evaluation of photosensitive coloring composition 15)
The photosensitive colorant composition 15 has a pattern width of 32 μm, and the photosensitive characteristics are greatly deteriorated as compared with Example 8. Although one foreign matter is good at the beginning, the foreign matter is 60 after storage. The number increased significantly. Therefore, it was an unstable composition in which foreign matter increased due to repeated dissolution and precipitation of the dye during storage.
実施例および比較例の組成および評価結果を表１に示す。 Table 1 shows the compositions and evaluation results of Examples and Comparative Examples.
本発明の感光性着色剤組成物は、カラーフィルタ用感光性着色剤組成物に好適に使用できる。 The photosensitive colorant composition of this invention can be used conveniently for the photosensitive colorant composition for color filters.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012073334A JP2013061623A (en) | 2011-08-24 | 2012-03-28 | Photosensitive colorant composition, and color filter and liquid crystal display device using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011182205 | 2011-08-24 | ||
| JP2011182205 | 2011-08-24 | ||
| JP2012073334A JP2013061623A (en) | 2011-08-24 | 2012-03-28 | Photosensitive colorant composition, and color filter and liquid crystal display device using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2013061623A true JP2013061623A (en) | 2013-04-04 |
Family
ID=48186302
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012046243A Pending JP2013061619A (en) | 2011-08-24 | 2012-03-02 | Blue colorant composition for color filter and color filter substrate using the same |
| JP2012073334A Pending JP2013061623A (en) | 2011-08-24 | 2012-03-28 | Photosensitive colorant composition, and color filter and liquid crystal display device using the same |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012046243A Pending JP2013061619A (en) | 2011-08-24 | 2012-03-02 | Blue colorant composition for color filter and color filter substrate using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP2013061619A (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6129606B2 (en) * | 2013-03-25 | 2017-05-17 | 株式会社三共 | GAME SYSTEM AND GAME DEVICE |
| JP6129607B2 (en) * | 2013-03-25 | 2017-05-17 | 株式会社三共 | GAME SYSTEM AND GAME DEVICE |
| JP6245826B2 (en) * | 2013-03-25 | 2017-12-13 | 株式会社三共 | GAME SYSTEM AND GAME DEVICE |
| JP6245825B2 (en) * | 2013-03-25 | 2017-12-13 | 株式会社三共 | Game equipment |
| JP2014205746A (en) * | 2013-04-11 | 2014-10-30 | Jsr株式会社 | Colored composition, colored cured film and display element |
| TWI674477B (en) | 2014-12-25 | 2019-10-11 | 日商富士軟片股份有限公司 | Coloring curable composition, color filter, pattern forming method, method of manufacturing color filter, solid-state imaging element, and image display device |
| JP6152143B2 (en) * | 2015-07-31 | 2017-06-21 | 株式会社Ｄｎｐファインケミカル | White colored composition for color filter, method for producing color filter, method for producing display device, color filter and display device |
| KR102383698B1 (en) * | 2016-03-28 | 2022-04-05 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter and image display device produced using the same |
| KR101996327B1 (en) | 2017-01-23 | 2019-07-04 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter, and image display device comprising the same |
| KR102494967B1 (en) | 2017-02-01 | 2023-02-02 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter and image display device produced using the same |
| KR102510668B1 (en) | 2017-02-01 | 2023-03-16 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter and image display device produced using the same |
| CN111333830B (en) * | 2020-04-21 | 2022-06-17 | 山东凯瑞尔光电科技有限公司 | Synthesis method of blue color paste complex high-molecular red dye for color photoresist |
| KR20240099357A (en) * | 2021-12-22 | 2024-06-28 | 후지필름 가부시키가이샤 | Coloring compositions, films, optical filters, solid-state imaging devices, image display devices and compounds |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3167013B2 (en) * | 1996-11-07 | 2001-05-14 | 大日精化工業株式会社 | Dye purification method, purified dye, colorant comprising purified dye, and colored article |
| JP4492217B2 (en) * | 2004-06-04 | 2010-06-30 | 東洋インキ製造株式会社 | Pigment and pigment composition |
| JP2006265548A (en) * | 2005-02-28 | 2006-10-05 | Sumitomo Chemical Co Ltd | Color development composition |
| JP2007041239A (en) * | 2005-08-02 | 2007-02-15 | Fujifilm Corp | Method for producing color filter, the color filter and liquid crystal display |
| JP5504627B2 (en) * | 2008-07-01 | 2014-05-28 | 住友化学株式会社 | Colored photosensitive resin composition |
| JP2010144057A (en) * | 2008-12-18 | 2010-07-01 | Mitsubishi Chemicals Corp | Colored resin composition, color filter, liquid crystal displaying device, and organic el display |
| JP5523919B2 (en) * | 2009-08-31 | 2014-06-18 | 富士フイルム株式会社 | Colored composition, colored photosensitive composition, color filter, solid-state imaging device, and liquid crystal display device |
| JP2011102945A (en) * | 2009-11-12 | 2011-05-26 | Toyo Ink Mfg Co Ltd | Coloring composition for color filter, and color filter |
| JP4492760B1 (en) * | 2009-12-01 | 2010-06-30 | 東洋インキ製造株式会社 | Blue coloring composition for color filter, and color filter |
-
2012
- 2012-03-02 JP JP2012046243A patent/JP2013061619A/en active Pending
- 2012-03-28 JP JP2012073334A patent/JP2013061623A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JP2013061619A (en) | 2013-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2013061623A (en) | Photosensitive colorant composition, and color filter and liquid crystal display device using the same | |
| JP5604968B2 (en) | Green colorant composition for color filter, color filter substrate and liquid crystal display device | |
| JP4940716B2 (en) | Cleaning liquid for photosensitive coloring composition | |
| JP2011242568A (en) | Green colorant composition for color filter, and color filter substrate | |
| JP2008122750A (en) | Photosensitive resist composition for color filter, and the color filter | |
| JP5932435B2 (en) | Blue pigment dispersion composition for color filter and blue pigment dispersion resist composition for color filter containing the same | |
| JP6569220B2 (en) | Black resin composition for touch panels | |
| JP2007112919A (en) | Pigment dispersion, colorant composition and color filter | |
| JP6252001B2 (en) | Colorant composition, color filter substrate, and liquid crystal display device | |
| JP2015068893A (en) | Resin black matrix substrate | |
| JP5540649B2 (en) | Red coloring composition for color filter, color filter substrate for liquid crystal display device, and liquid crystal display device | |
| JP5262691B2 (en) | Color filter substrate for liquid crystal display device and liquid crystal display device using the same | |
| TW201800516A (en) | Coloring resin composition | |
| JP2004067715A (en) | Pigment dispersion liquid, colorant composition, color filter, and liquid crystal display panel | |
| JP2009035671A (en) | Pigment dispersion, colorant composition, and color filter | |
| JP4821316B2 (en) | Red colorant composition and color filter | |
| KR102425989B1 (en) | A red coloring agent composition for a color filter | |
| JP2009175507A (en) | Photosensitive cyan colored composition for color filter, color filter using the same and liquid crystal display device | |
| JP6654556B2 (en) | Colored photosensitive resin composition, color filter and image display device manufactured using the same | |
| JP4516412B2 (en) | Pigment-dispersed resist composition | |
| CN101604120A (en) | Photosensitive composition | |
| JPH07198933A (en) | Production of pigment dispersion liquid for color filter | |
| JP4774316B2 (en) | Color filter, manufacturing method thereof, and display device including the same | |
| JP4972953B2 (en) | Color filter and coloring composition for color filter | |
| JP2004067714A (en) | Pigment dispersion liquid, colorant composition, color filter, and liquid crystal display panel |