JP5246994B2 - Photosensitive composition and color filter - Google Patents
Photosensitive composition and color filter Download PDFInfo
- Publication number
- JP5246994B2 JP5246994B2 JP2005223361A JP2005223361A JP5246994B2 JP 5246994 B2 JP5246994 B2 JP 5246994B2 JP 2005223361 A JP2005223361 A JP 2005223361A JP 2005223361 A JP2005223361 A JP 2005223361A JP 5246994 B2 JP5246994 B2 JP 5246994B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituted
- photosensitive composition
- ethylenically unsaturated
- photopolymerization initiator
- 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.)
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Landscapes
- Optical Filters (AREA)
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Description
本発明は、感光性組成物に関するものであり、特にカラー液晶表示装置、カラー撮像素子等に用いられるカラーフィルタの製造の際に使用されるカラーフィルタ用着色組成物やオーバーコート材として好適に用いられる感光性組成物に関する。また、本発明は、カラー液晶表示装置、カラー撮像素子等に用いられるカラーフィルタに関する。 The present invention relates to a photosensitive composition, and particularly suitably used as a color filter coloring composition or an overcoat material used in the production of a color filter used in a color liquid crystal display device, a color imaging device or the like. It relates to the photosensitive composition obtained. The present invention also relates to a color filter used for a color liquid crystal display device, a color image sensor, and the like.
近年、液晶表示装置等は薄型化、大型化が進んでおり、用いられるカラーフィルタにも無欠陥薄型化が求められ、さらに耐熱性、耐光性等の諸耐性に加え、高透過率、高コントラストなどの要求特性があがってきている。また、同時にカラーフィルタの低コスト化が強く求められており、製造工程における歩留り向上や工程短縮が必要となっている。 In recent years, liquid crystal display devices are becoming thinner and larger, and the color filters used are also required to be thin and defect-free. In addition to various resistances such as heat resistance and light resistance, they also have high transmittance and high contrast. The required characteristics such as At the same time, there is a strong demand for cost reduction of the color filter, and it is necessary to improve the yield and shorten the process in the manufacturing process.
現在、カラーフィルタは、液晶表示装置の製造工程でカラーフィルタ上に透明電極や配向膜を形成する工程を経るため、一般に２００℃以上、好ましくは２３０℃以上の高温に耐えられる性能が必要である。そこで、耐熱性に優れた顔料を含むレジスト材を用いて、フォトリソグラフィー法によりカラーフィルタを形成することが主流となっている。しかし、顔料は紫外線照射時に紫外線を吸収し、感度を低下させるために、液晶表示装置等の大型化に伴う露光時間短縮、生産性向上のためには、レジスト材中に多量の光重合開始剤を配合し、レジスト材を高感度化する必要がある。 At present, since the color filter undergoes a process of forming a transparent electrode or an alignment film on the color filter in the manufacturing process of the liquid crystal display device, generally, the color filter needs to be capable of withstanding a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. . Therefore, it is a mainstream to form a color filter by a photolithography method using a resist material containing a pigment having excellent heat resistance. However, since the pigment absorbs ultraviolet rays when irradiated with ultraviolet rays and lowers the sensitivity, a large amount of photopolymerization initiator is contained in the resist material in order to shorten the exposure time and increase the productivity due to the enlargement of the liquid crystal display device etc. It is necessary to increase the sensitivity of the resist material.
従来、レジスト材の高感度化ということでは、光重合開始剤の配合比の最適化と共に、モノマーや樹脂の設計（多官能化など）と、その配合比の最適化により対応可能な部分もあった。
一方、カラーフィルタの耐熱性を補い、その他に耐湿性、耐薬品性、バリア性等の向上を図るという目的からカラーフィルタ上にオーバーコート層を設ける場合もある。このオーバーコート層形成用の感光性組成物もカラーフィルタと同様に生産性向上のためには高感度化が必要である。
On the other hand, an overcoat layer may be provided on the color filter for the purpose of supplementing the heat resistance of the color filter and improving the moisture resistance, chemical resistance, barrier property and the like. The photosensitive composition for forming the overcoat layer also needs to be highly sensitive to improve productivity, like the color filter.
レジスト材の高感度化を図る場合、光重合開始剤の配合比率は増加する傾向にあり、用いる光重合開始剤の着色によりカラーフィルタの透過率低下を招く場合がある。そこで、レジスト材に配合する光重合開始剤として、熱によって昇華するものを選択することにより、カラーフィルタ製造時のポストベイク工程（パターン形成後の加熱工程）で光重合開始剤を昇華させ、塗膜中に残存する光重合開始剤を最小限に抑えると共に、カラーフィルタの透過率低下を抑えることができる。しかし、光重合開始剤が熱によって昇華するだけでなく、光昇華性を有するものである場合には、カラーフィルタ製造時のパターン露光工程で光重合開始剤が昇華し、昇華物がマスクに付着し、パターンを覆ってしまうことで、目的のパターン形状を露光することができなくなる場合がある。一度マスクが汚れてしまうと、カラーフィルタ製造ラインを止めて、マスク洗浄を行う必要があり、製造効率の低下につながる。 When increasing the sensitivity of the resist material, the blending ratio of the photopolymerization initiator tends to increase, and coloring of the photopolymerization initiator used may cause a decrease in transmittance of the color filter. Therefore, by selecting a photopolymerization initiator to be sublimated by heat as a photopolymerization initiator to be blended in the resist material, the photopolymerization initiator is sublimated in the post-baking process (heating process after pattern formation) at the time of color filter production, and the coating film It is possible to minimize the photopolymerization initiator remaining therein and to suppress a decrease in transmittance of the color filter. However, if the photopolymerization initiator is not only sublimated by heat but also has a photosublimation property, the photopolymerization initiator sublimates in the pattern exposure process during color filter production, and the sublimate adheres to the mask. In some cases, however, the target pattern shape cannot be exposed by covering the pattern. Once the mask becomes dirty, it is necessary to stop the color filter production line and perform mask cleaning, leading to a reduction in production efficiency.
そこで、本発明は、高感度でありながら、カラーフィルタのパターン露光工程で発生するマスク汚れを低減させた、高透過率のカラーフィルタを形成できる感光性組成物、およびこれを用いた高透過率のカラーフィルタを提供することを目的とする。
また、本発明は、高感度で、高透過率の維持が可能なオーバーコート層を形成できる感光性組成物を提供することを目的とする。
Therefore, the present invention provides a photosensitive composition capable of forming a color filter with high transmittance, which is highly sensitive and has reduced mask contamination generated in the pattern exposure process of the color filter, and high transmittance using the same. An object of the present invention is to provide a color filter.
Another object of the present invention is to provide a photosensitive composition capable of forming an overcoat layer having high sensitivity and capable of maintaining high transmittance.
本発明の感光性組成物は、透明樹脂と、３つ以上のエチレン性不飽和二重結合を有する多官能モノマーと、光昇華性のある光重合開始剤とを含む感光性組成物であり、この感光性組成物中の３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの配合割合が、透明樹脂、３つ以上のエチレン性不飽和二重結合を有する多官能モノマー、光重合開始剤の合計重量を基準として３０〜５０重量％であり、かつ感光性組成物中の光重合開始剤の配合割合が、透明樹脂、３つ以上のエチレン性不飽和二重結合を有する多官能モノマー、光重合開始剤の合計重量を基準として１３〜３０重量％であり、さらに感光性組成物中の透明樹脂のＦｅｄｏｒｓの方法により、下記式で計算される溶解度パラメータが３つ以上のエチレン性不飽和二重結合を有する多官能モノマーのＦｅｄｏｒｓの方法により、下記式で計算される溶解度パラメータよりも大きく、その差が０．４〜０．９の範囲であることを特徴とする。
式
多官能モノマー、ホモポリマーのＳＰ値：δ=［Σ（原子、原子団の凝集エネルギ−×モ
ル分率）／Σ（原子、原子団の分子容積率×モル分率）］ 1/2
コポリマーのＳＰ値：δcopolymer＝（δ A 2 ×Ｘ A ＋δ B 2 ×Ｘ B ＋δ C 2 ×Ｘ C ・・・） 1/2
（ただし、コポリマーを構成するモノマーＡ、Ｂ、Ｃ・・・のホモポリマーのＳＰ値をδ
A 、δ B 、δ C ・・・，モル分率をＸ A 、Ｘ B 、Ｘ C ・・・とする。）
また、本発明のカラーフィルタは、着色材を配合した前記感光性組成物から形成されるフィルタセグメントを具備することを特徴とする。
The photosensitive composition of the present invention is a photosensitive composition comprising a transparent resin, a polyfunctional monomer having three or more ethylenically unsaturated double bonds, and a photopolymerization initiator having a photosublimation property, The blending ratio of the polyfunctional monomer having three or more ethylenically unsaturated double bonds in this photosensitive composition is a transparent resin, the polyfunctional monomer having three or more ethylenically unsaturated double bonds, photopolymerization Polyfunctional having 30 to 50% by weight based on the total weight of the initiator and having a blending ratio of the photopolymerization initiator in the photosensitive composition having a transparent resin and three or more ethylenically unsaturated double bonds Ethylene having a solubility parameter of 3 or more calculated by the following formula according to the Fedors method of the transparent resin in the photosensitive composition, based on the total weight of the monomer and the photopolymerization initiator. Unsaturated double bond By the method of Fedors polyfunctional monomer having greater than the solubility parameter calculated by the following formula, the difference is equal to or in the range of 0.4 to 0.9.
formula
SP value of polyfunctional monomer and homopolymer: δ = [Σ (agglomeration energy of atoms and atomic groups-x
Fraction) / Σ (molecular volume fraction of atoms and atomic groups x mole fraction)] 1/2
SP value of copolymer: δ copolymer = (δ A 2 × X A + δ B 2 × X B + δ C 2 × X C ...) 1/2
(However, the SP value of the homopolymer of monomers A, B, C.
A, δ B, δ C ··· , the mole fraction X A, X B, and X C · · ·. )
Moreover, the color filter of this invention comprises the filter segment formed from the said photosensitive composition which mix | blended the coloring material, It is characterized by the above-mentioned.
本発明の感光性組成物は、光重合開始剤の配合割合が高いため感度が高いが、感光性組成物中の３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの配合割合を３０〜５０重量％と高くすること、および配合する透明樹脂と前記多官能モノマーのＳＰ値が適正な範囲になるよう透明樹脂と前記多官能モノマーの組合せを選択することにより、カラーフィルタのパターン露光工程で光重合開始剤が昇華することにより発生するマスク汚れを低減させることを可能とした。これにより、長期にわたって安定なパターン形状が得られ、カラーフィルタの生産性の向上が図れる。また、感光性組成物の高感度化のために配合された多量の光重合開始剤は、最終的にカラーフィルタの製造時のポストベイク工程で昇華するため、カラーフィルタの高透過率を維持することができる。よって、本発明の感光性組成物を用いてフィルタセグメントを形成することにより、安定して高品質の透過型・反射型のカラー液晶表示装置ならびに固体撮像素子の色分解用カラーフィルタを製造することができる。 The photosensitive composition of the present invention has high sensitivity because the blending ratio of the photopolymerization initiator is high, but the blending ratio of the polyfunctional monomer having three or more ethylenically unsaturated double bonds in the photosensitive composition is Pattern exposure of a color filter by increasing it to 30 to 50% by weight, and selecting a combination of the transparent resin and the polyfunctional monomer so that the SP value of the transparent resin to be blended and the polyfunctional monomer is in an appropriate range. It was possible to reduce the mask contamination generated by sublimation of the photopolymerization initiator in the process. Thereby, a stable pattern shape can be obtained over a long period of time, and the productivity of the color filter can be improved. In addition, a large amount of the photopolymerization initiator compounded to increase the sensitivity of the photosensitive composition eventually sublimes in the post-baking process at the time of manufacturing the color filter, so that the high transmittance of the color filter must be maintained. Can do. Therefore, by forming a filter segment using the photosensitive composition of the present invention, it is possible to stably produce a high-quality transmissive / reflective color liquid crystal display device and a color filter for color separation of a solid-state imaging device. Can do.
まず、本発明の感光性組成物について説明する。
本発明の感光性組成物は、透明樹脂と、３つ以上のエチレン性不飽和二重結合を有する多官能モノマーと、光昇華性のある光重合開始剤とを含有する。
透明樹脂は、可視光領域の４００〜７００ｎｍの全波長領域において、透過率が好ましくは８０％以上、より好ましくは９５％以上の樹脂である。透明樹脂には、感光性樹脂と非感光性樹脂があるが、高感度の感光性組成物を得るには、感光性樹脂を配合することが好ましい。
First, the photosensitive composition of this invention is demonstrated.
The photosensitive composition of the present invention contains a transparent resin, a polyfunctional monomer having three or more ethylenically unsaturated double bonds, and a photopolymerization initiator having a photosublimation property.
The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a photosensitive resin and a non-photosensitive resin. In order to obtain a highly sensitive photosensitive composition, it is preferable to add a photosensitive resin.
感光性樹脂としては、水酸基、カルボキシル基、アミノ基等の反応性の置換基を有する高分子に、イソシアネート基、アルデヒド基、エポキシ基、カルボキシル基等の反応性置換基を有する（メタ）アクリル化合物やケイヒ酸を反応させて、（メタ）アクリロイル基、スチリル基等の光架橋性基を該高分子に導入した樹脂が用いられる。具体的には、例えば水酸基を有するエチレン性不飽和単量体、その他のエチレン性不飽和単量体などを数種類共重合した共重合体に、水酸基と反応可能な官能基及びエチレン性不飽和二重結合を有する化合物を反応させることにより得られるものがある。水酸基と反応可能な官能基としては、イソシアネート基、カルボキシル基等が挙げられるが、特に反応性の点でイソシアネート基が好ましい。イソシアネート基及びエチレン性不飽和二重結合を有する化合物として具体的には、２−アクリロイルエチルイソシアネート、２−メタクリロイルエチルイソシアネート等が挙げられる。また、スチレン−無水マレイン酸共重合体やα−オレフィン−無水マレイン酸共重合体等の酸無水物を含む高分子をヒドロキシアルキル（メタ）アクリレート等の水酸基を有する（メタ）アクリル化合物によりハーフエステル化したものも用いられる。 Photosensitive resins include (meth) acrylic compounds having reactive substituents such as isocyanate groups, aldehyde groups, epoxy groups, and carboxyl groups on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, and amino groups. Or a resin in which a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting with cinnamic acid. Specifically, for example, a functional group capable of reacting with a hydroxyl group and an ethylenically unsaturated dimer are obtained by copolymerizing several kinds of ethylenically unsaturated monomers having a hydroxyl group and other ethylenically unsaturated monomers. Some are obtained by reacting a compound having a heavy bond. Examples of the functional group capable of reacting with a hydroxyl group include an isocyanate group and a carboxyl group, and an isocyanate group is particularly preferred from the viewpoint of reactivity. Specific examples of the compound having an isocyanate group and an ethylenically unsaturated double bond include 2-acryloylethyl isocyanate and 2-methacryloylethyl isocyanate. In addition, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.
また、非感光性樹脂としては、本発明の感光性組成物を用いてアルカリ現像によりフィルタセグメントを形成する場合には、アルカリ可溶型非感光性樹脂を用いることが好ましい。アルカリ可溶型非感光性樹脂とは、アルカリ水溶液に溶解しラジカルにより架橋しない樹脂であり、例えば、カルボキシル基、スルホン基などの酸性官能基を有する樹脂が挙げられる。アルカリ可溶型非感光性樹脂として具体的には、酸性官能基を有するアクリル樹脂、α−オレフィン／（無水）マレイン酸共重合体、スチレン／（無水）マレイン酸共重合体、スチレン／スチレンスルホン酸共重合体、エチレン／（メタ）アクリル酸共重合体、イソブチレン／（無水）マレイン酸共重合体などが挙げられる。なかでも、酸性官能基を有するアクリル樹脂、α−オレフィン／（無水）マレイン酸共重合体、スチレン／（無水）マレイン酸共重合体およびスチレン／スチレンスルホン酸共重合体から選ばれる少なくとも１種の樹脂、特に酸性官能基を有するアクリル樹脂は、耐熱性、透明性が高いため、好適に用いられる。 In addition, as the non-photosensitive resin, when a filter segment is formed by alkali development using the photosensitive composition of the present invention, it is preferable to use an alkali-soluble non-photosensitive resin. The alkali-soluble non-photosensitive resin is a resin that dissolves in an alkaline aqueous solution and does not crosslink with radicals. Specific examples of the alkali-soluble non-photosensitive resin include an acrylic resin having an acidic functional group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / (anhydrous) maleic acid copolymer, and a styrene / styrene sulfone. Examples thereof include an acid copolymer, an ethylene / (meth) acrylic acid copolymer, and an isobutylene / (anhydrous) maleic acid copolymer. Among them, at least one selected from an acrylic resin having an acidic functional group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / (anhydrous) maleic acid copolymer, and a styrene / styrene sulfonic acid copolymer. Resins, particularly acrylic resins having an acidic functional group, are preferably used because of their high heat resistance and transparency.
アルカリ可溶型でない非感光性樹脂には、熱可塑性樹脂と熱硬化性樹脂があり、熱可塑性樹脂としては、例えば、ブチラール樹脂、塩素化ポリエチレン、塩素化ポリプロピレン、ポリ塩化ビニル、塩化ビニル−酢酸ビニル共重合体、ポリ酢酸ビニル、ポリウレタン系樹脂、ポリエステル樹脂、アクリル系樹脂、アルキッド樹脂、スチレン樹脂、ポリアミド樹脂、ゴム系樹脂、環化ゴム系樹脂、セルロース類、ポリブタジエン、ポリイミド樹脂等が挙げられる。また、熱硬化性樹脂としては、例えば、エポキシ樹脂、ベンゾグアナミン樹脂、ロジン変性マレイン酸樹脂、ロジン変性フマル酸樹脂、フェノール樹脂、メラミン樹脂、尿素樹脂等が挙げられる。 Non-photosensitive resins that are not alkali-soluble include thermoplastic resins and thermosetting resins. Examples of thermoplastic resins include butyral resin, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride-acetic acid. Examples include vinyl copolymers, polyvinyl acetate, polyurethane resins, polyester resins, acrylic resins, alkyd resins, styrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polybutadiene, and polyimide resins. . Examples of the thermosetting resin include an epoxy resin, a benzoguanamine resin, a rosin-modified maleic acid resin, a rosin-modified fumaric acid resin, a phenol resin, a melamine resin, and a urea resin.
また、透明樹脂としては、下記一般式（２）で示されるエチレン性不飽和単量体（ａ）を重合成分として含むものを用いることが好ましく、特に下記一般式（２）で示されるエチレン性不飽和単量体（ａ）と他のエチレン性不飽和単量体（ｂ）の共重合体を用いることが、着色材の分散安定性向上という面から好ましい。
一般式（２）において、アルキレン基Ｒ10は、２〜３個の炭素原子を有することが好ましい。また、Ｒ11のアルキル基の炭素数は１〜２０であるが、より好ましくは１〜１０であり、Ｒ11はベンゼン環等の置換基を含んでもよい。Ｒ11のアルキル基の炭素数が１〜１０のときはアルキル基が障害となり樹脂同士の接近を抑制し、顔料への吸着／配向を促進するが、炭素数が１０を超えると、アルキル基の立体障害効果が高くなり、ベンゼン環の顔料への吸着／配向までをも妨げる傾向を示す。この傾向は、Ｒ11のアルキル基の炭素鎖長が長くなるに従い顕著となり、炭素数が２０を超えると、ベンゼン環の吸着／配向が極端に低下する。Ｒ11で表されるベンゼン環を含むアルキル基としては、ベンジル基、２−フェニル（イソ）プロピル基等を挙げることができる。 In the general formula (2), the alkylene group R 10 preferably has 2 to 3 carbon atoms. Although the carbon number of the alkyl group of R 11 is 1 to 20, more preferably 1 to 10, R 11 may contain substituents such as benzene ring. When the carbon number of the alkyl group of R 11 is 1 to 10, the alkyl group becomes an obstacle and suppresses the approach between the resins and promotes adsorption / orientation to the pigment, but when the carbon number exceeds 10, The steric hindrance effect becomes high and shows a tendency to prevent even the adsorption / orientation of the benzene ring to the pigment. This tendency becomes more prominent as the carbon chain length of the alkyl group of R 11 becomes longer. When the carbon number exceeds 20, the adsorption / orientation of the benzene ring is extremely lowered. Examples of the alkyl group containing a benzene ring represented by R 11 include a benzyl group and a 2-phenyl (iso) propyl group.
エチレン性不飽和単量体（ａ）としては、フェノールのエチレンオキサイド（ＥＯ）変性（メタ）アクリレート、パラクミルフェノールのＥＯまたはプロピレンオキサイド（ＰＯ）変性（メタ）アクリレート、ノニルフェノールのＥＯ変性（メタ）アクリレート、ノニルフェノールのＰＯ変性（メタ）アクリレート等が挙げられる。これら化合物のうち、パラクミルフェノールのＥＯまたはＰＯ変性（メタ）アクリレートは、上記ベンゼン環のπ電子の効果ばかりでなく、その立体的な効果も加わり、顔料などの着色材に対してより良好な吸着／配向面を形成することができるので、より分散効果が高い。 Examples of the ethylenically unsaturated monomer (a) include phenol ethylene oxide (EO) modified (meth) acrylate, paracumylphenol EO or propylene oxide (PO) modified (meth) acrylate, and nonylphenol EO modified (meth). Examples thereof include acrylate, PO-modified (meth) acrylate of nonylphenol, and the like. Among these compounds, EO or PO-modified (meth) acrylate of paracumylphenol is not only effective for the π-electron of the benzene ring, but also its steric effect, which is better for coloring materials such as pigments. Since the adsorption / orientation plane can be formed, the dispersion effect is higher.
他のエチレン性不飽和単量体（ｂ）としては、（メタ）アクリル酸、メチル（メタ）アクリレート、エチル（メタ）アクリレート、（イソ）プロピル（メタ）アクリレート、（イソ）ブチル（メタ）アクリレート、（イソ）ペンチル（メタ）アクリレート、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、ベンジル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、グリシジル（メタ）アクリレート、イソボニル（メタ）アクリレート、アシッドホスホオキシエチル（メタ）アクリレート、アシッドホスホオキシプロピル（メタ）アクリレート、３−クロロ−２−アシッドホスホオキシエチル（メタ）アクリレート、アシッドホスホオキシポリエチレングリコールモノ（メタ）アクリレート等が挙げられる。 Other ethylenically unsaturated monomers (b) include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (iso) propyl (meth) acrylate, (iso) butyl (meth) acrylate , (Iso) pentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate, isobornyl (meth) Acrylate, acid phosphooxyethyl (meth) acrylate, acid phosphooxypropyl (meth) acrylate, 3-chloro-2-acid phosphooxyethyl (meth) acrylate, acid phosphooxypolyethylene glycol mono (meth) acrylate Rate, and the like.
上記一般式（２）で示されるエチレン性不飽和単量体（ａ）と他のエチレン性不飽和単量体（ｂ）とを共重合してなる透明樹脂中のエチレン性不飽和単量体（ａ）の割合は、エチレン性不飽和単量体（ａ）と他のエチレン性不飽和単量体（ｂ）の合計重量を基準（１００重量％）として、０．１〜５０重量％であることが好ましく、より好ましくは１０〜３５重量％である。エチレン性不飽和単量体（ａ）の割合が０．１重量％より少ないと顔料の分散効果が低下する。また、５０重量％より多いと疎水性が大きくなり、感光性組成物の現像性が低下したり、残渣の原因になったりすることがある。 The ethylenically unsaturated monomer in the transparent resin obtained by copolymerizing the ethylenically unsaturated monomer (a) represented by the general formula (2) and another ethylenically unsaturated monomer (b) The proportion of (a) is 0.1 to 50% by weight based on the total weight (100% by weight) of the ethylenically unsaturated monomer (a) and the other ethylenically unsaturated monomer (b). It is preferable that it is 10 to 35% by weight. When the proportion of the ethylenically unsaturated monomer (a) is less than 0.1% by weight, the pigment dispersing effect is lowered. On the other hand, when the amount is more than 50% by weight, the hydrophobicity increases, and the developability of the photosensitive composition may be lowered or a residue may be caused.
３つ以上のエチレン性不飽和二重結合を有する多官能モノマーとしては、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、ジペンタエリスリトールヘキサ（メタ）アクリレート、エチレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート、プロピレンオキサイド変性トリメチロールプロパントリ（メタ）アクリレート等の各種アクリル酸エステルおよびメタクリル酸エステル等が代表例に挙げられ、これらを単独でまたは２種類以上混合して用いることができる。3つ以上のエチレン性不飽和二重結合を有する多官能モノマーの官能基数は、好ましくは３〜１２であり、より好ましくは３〜１０である。官能基数が３未満では、感光性組成物の十分な感度が得られず、官能基数が１２を超えると、カラーフィルタのパターニング性が不良となる場合があり好ましくない。 Examples of the polyfunctional monomer having three or more ethylenically unsaturated double bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-modified trimethylol. Typical examples include various acrylic esters and methacrylic esters such as propane tri (meth) acrylate and propylene oxide-modified trimethylolpropane tri (meth) acrylate, and these may be used alone or in combination of two or more. it can. The number of functional groups of the polyfunctional monomer having three or more ethylenically unsaturated double bonds is preferably 3 to 12, and more preferably 3 to 10. If the number of functional groups is less than 3, sufficient sensitivity of the photosensitive composition cannot be obtained, and if the number of functional groups exceeds 12, the patterning property of the color filter may be deteriorated.
感光性組成物中の透明樹脂の溶解度パラメータと、３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの溶解度パラメータは、透明樹脂の溶解度パラメータが３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの溶解度パラメータよりも大きく、その差が０．４〜０．９の範囲である。溶解度パラメータの差が０．４よりも小さい場合には、感光性組成物を塗工した時の３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの塗膜表面への偏析が十分でなく、塗膜表面付近での硬化性、架橋密度が低下し、パターン露光工程で光重合開始剤の昇華をおさえることができない。一方、溶解度パラメータの差が０．９よりも大きい場合には、感光性組成物の塗膜内での相分離挙動が助長され、感光性組成物を用いてフィルタセグメントを形成する場合に、諸耐性が十分でなくなったり、パターニング性が不良となったりする。 The solubility parameter of the transparent resin in the photosensitive composition and the solubility parameter of the polyfunctional monomer having three or more ethylenically unsaturated double bonds are the ethylenically unsaturated double having the solubility parameter of the transparent resin of 3 or more. The solubility parameter is larger than the solubility parameter of the polyfunctional monomer having a bond, and the difference is in the range of 0.4 to 0.9 . When the difference in solubility parameter is smaller than 0.4, segregation of the polyfunctional monomer having three or more ethylenically unsaturated double bonds on the coating surface is sufficient when the photosensitive composition is applied. In addition, the curability near the coating film surface and the crosslink density are reduced, and the photopolymerization initiator cannot be sublimated in the pattern exposure step. On the other hand, when the difference in solubility parameter is greater than 0.9 , the phase separation behavior of the photosensitive composition in the coating film is promoted, and various filter segments are formed when the photosensitive composition is used to form a filter segment. Resistance may not be sufficient or patterning properties may be poor.
感光性組成物中の透明樹脂と、３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの溶解度パラメータ（ＳＰ値）は、Ｆｅｄｏｒｓの方法（文献：「Ｒ.Ｆ.Ｆｅｄｏｒｓ，Ｐｏｌｙｍｅｒ.Ｅｎｇ.，１４，（２）１４７（１９７４）」）により、下記式で計算される値を用いた。
多官能モノマー、ホモポリマーのＳＰ値：δ=［Σ（原子、原子団の凝集エネルギ−×モル分率）／Σ（原子、原子団の分子容積率×モル分率）］1/2
コポリマーのＳＰ値：δcopolymer＝（δA 2×ＸA＋δB 2×ＸB＋δC 2×ＸC・・・）1/2
ただし、コポリマーを構成するモノマーＡ、Ｂ、Ｃ・・・のホモポリマーのＳＰ値をδA、δB、δC・・・，モル分率をＸA、ＸB、ＸC・・・とする。
The solubility parameter (SP value) of the transparent resin in the photosensitive composition and the polyfunctional monomer having three or more ethylenically unsaturated double bonds was determined by the method of Fedors (reference: “RF Fedors, Polymer. Eng., 14, (2) 147 (1974) "), the value calculated by the following formula was used.
Polyfunctional monomers, SP value of a homopolymer: δ = [Σ (atoms, aggregation energy of atomic - × mole fraction) / sigma (atomic, molecular volume factor × mole fraction of atomic group)] 1/2
SP value of copolymer: δ copolymer = (δ A 2 × X A + δ B 2 × X B + δ C 2 × X C ...) 1/2
However, the SP value of the homopolymers of the monomers A, B, C,... Constituting the copolymer is δ A , δ B , δ C , and the molar fraction is X A , X B , X C, and so on. To do.
感光性組成物中の３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの配合割合は、透明樹脂、３つ以上のエチレン性不飽和二重結合を有する多官能モノマー、光重合開始剤の合計重量を基準（１００重量％）として、好ましくは３０〜５０重量％であり、より好ましくは３５〜５０重量％であり、さらにより好ましくは４０〜５０重量％である。３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの配合割合が３０重量％より少ない場合は、感光性組成物中の３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの偏析量が十分でなく、光重合開始剤の昇華を押さえられなくなる。一方、３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの配合割合が５０重量％より多い場合には、感光性組成物の粘度安定性、現像性が低下してしまう。 The blending ratio of the polyfunctional monomer having 3 or more ethylenically unsaturated double bonds in the photosensitive composition is a transparent resin, the polyfunctional monomer having 3 or more ethylenically unsaturated double bonds, and the start of photopolymerization. Based on the total weight of the agent (100% by weight), it is preferably 30 to 50% by weight, more preferably 35 to 50% by weight, and even more preferably 40 to 50% by weight. When the blending ratio of the polyfunctional monomer having 3 or more ethylenically unsaturated double bonds is less than 30% by weight, the polyfunctional monomer having 3 or more ethylenically unsaturated double bonds in the photosensitive composition The amount of segregation is not sufficient and sublimation of the photopolymerization initiator cannot be suppressed. On the other hand, when the blending ratio of the polyfunctional monomer having three or more ethylenically unsaturated double bonds is more than 50% by weight, the viscosity stability and developability of the photosensitive composition are lowered.
光昇華性のある光重合開始剤としては、ヨードニウム塩、アンモニウム塩、ジアゾニウム塩を始めとする各種オニウム塩（特許第２８３０５２７号公報参照）、トリハロメチルトリアジン系光重合開始剤（特開平０８−３４８０７号公報、特開平０８−２１７８１２号公報参照）、オルト−キノンジアジド系光重合開始剤（特開２００１−２２６４２０号公報、特開２００１−２３３９１１号公報参照）、過酸化物系光重合開始剤（特開平０５−２７４２２号公報、特開平０６−１２２８５６号公報参照）、オキシムエステル系光重合開始剤（特開２００４−３００３６７号公報参照）、ベンジル系光重合開始剤、N−フェニルグリシン系光重合開始剤（特開平０８−７６３６９号公報参照）、チタノセン系光重合開始剤（特開平０８−２８６３７９号公報、特開２００４−３０１９４１号公報参照）、アセトフェノン系光重合開始剤、アシルフォスフィンオキサイド系光重合開始剤、スルホニウム有機ホウ素錯体またはオキソスルホニウム有機ホウ素錯体等が挙げられる。上記の中でも、感光性組成物調整後の感度や色度特性への影響を考慮すると、アセトフェノン系重合開始剤、アシルフォスフィンオキサイド系重合開始剤、スルホニウム有機ホウ素錯体またはオキソスルホニウム有機ホウ素錯体が好ましい。 As photopolymerization initiators having photosublimation properties, various onium salts including iodonium salts, ammonium salts, diazonium salts (see Japanese Patent No. 2830527), trihalomethyltriazine photopolymerization initiators (Japanese Patent Laid-Open No. 08-34807). No., JP-A-08-217812), ortho-quinonediazide photopolymerization initiator (see JP-A-2001-226420, JP-A-2001-233911), peroxide photopolymerization initiator (special Kaihei 05-27422, JP 06-122856 A), oxime ester photopolymerization initiator (JP 2004-3000367 A), benzyl photopolymerization initiator, N-phenylglycine photopolymerization start Agent (see JP-A-08-76369), titanocene photopolymerization initiator (JP-A-08-286) 379, JP-A-2004-301941), acetophenone photopolymerization initiator, acylphosphine oxide photopolymerization initiator, sulfonium organic boron complex, oxosulfonium organic boron complex, and the like. Among the above, in consideration of the effect on sensitivity and chromaticity characteristics after adjusting the photosensitive composition, an acetophenone polymerization initiator, an acyl phosphine oxide polymerization initiator, a sulfonium organic boron complex, or an oxosulfonium organic boron complex is preferable. .
アセトフェノン系光重合開始剤の具体例としては、ジエトキシアセトフェノン、４−フェノキシジクロロアセトフェノン、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−ヒドロキシシクロヘキシルフェニルケトン、２−ベンジル−２−ジメチルアミノ−１−（４−モルフォリノフェニル）−ブタン−１−オン、２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン、１−［４−（２−ヒドロキシエトキシ）−フェニル］−２−ヒドロキシ−２−メチル−１−プロパン−１−オン等が挙げられる。アシルフォスフィンオキサイド系光重合開始剤の具体例としては、２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド、ビス（２，４，６−トリメチルベンゾイル）−フェニルフォスフィンオキサイド等が挙げられる。スルホニウム有機ホウ素錯体またはオキソスルホニウム有機ホウ素錯体等は、下記一般式（１）で表されるものである。
感光性組成物中の光重合開始剤の配合割合は、透明樹脂、３つ以上のエチレン性不飽和二重結合を有する多官能モノマー、光重合開始剤の合計重量を基準（１００重量％）として、好ましくは１３〜３０重量％であり、より好ましくは１５〜３０重量％である。光重合開始剤の配合割合が１３重量％よりも少ない場合には、感光性組成物の感度が低下してしまう。一方、光重合開始剤の配合割合が３０重量％よりも多い場合には、感光性組成物中の透明樹脂、３つ以上のエチレン性不飽和二重結合を有する多官能モノマーとの配合バランスが崩れてしまい、塗工膜の表面近くの光重合開始剤濃度が上昇するため、光重合開始剤の昇華を押さえられなくなる。 The blending ratio of the photopolymerization initiator in the photosensitive composition is based on the total weight (100% by weight) of the transparent resin, the polyfunctional monomer having three or more ethylenically unsaturated double bonds, and the photopolymerization initiator. , Preferably it is 13-30 weight%, More preferably, it is 15-30 weight%. When the blending ratio of the photopolymerization initiator is less than 13% by weight, the sensitivity of the photosensitive composition is lowered. On the other hand, when the blending ratio of the photopolymerization initiator is more than 30% by weight, there is a blending balance between the transparent resin in the photosensitive composition and the polyfunctional monomer having three or more ethylenically unsaturated double bonds. It collapses and the concentration of the photopolymerization initiator near the surface of the coating film increases, so that sublimation of the photopolymerization initiator cannot be suppressed.
光重合開始剤は、単独であるいは２種以上混合して用いるが、増感剤として、α−アシロキシエステル、アシルフォスフィンオキサイド、メチルフェニルグリオキシレート、ベンジル−９，１０−フェナンスレンキノン、カンファーキノン、エチルアンスラキノン、４，４’−ジエチルイソフタロフェノン、３，３’，４，４’−テトラ（ｔ−ブチルパーオキシカルボニル）ベンゾフェノン、４，４’−ジエチルアミノベンゾフェノン等の化合物を併用することもできる。 The photopolymerization initiator is used alone or in combination of two or more. As a sensitizer, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl-9,10-phenanthrenequinone are used. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.
本発明の感光性組成物には着色材を配合することができ、着色材を配合した感光性着色組成物は、カラーフィルタを構成するフィルタセグメントの形成に用いることができる。着色材としては、有機または無機の顔料を、単独でまたは２種類以上混合して用いることができる。顔料は、発色性が高く、且つ耐熱性の高い顔料、特に耐熱分解性の高い顔料が好ましく、通常は有機顔料が用いられる。
以下に、本発明の感光性着色組成物に使用可能な有機顔料の具体例を、カラーインデックス番号で示す。
A colorant can be blended in the photosensitive composition of the present invention, and the photosensitive color composition blended with the colorant can be used for forming a filter segment constituting a color filter. As the colorant, organic or inorganic pigments can be used alone or in admixture of two or more. The pigment is preferably a pigment having a high color developability and a high heat resistance, particularly a pigment having a high heat decomposition resistance, and an organic pigment is usually used.
Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition of this invention is shown with a color index number.
赤色組成物には、例えばＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ ７、１４、４１、４８：１、４８：２、４８：３、４８：４、８１：１、８１：２、８１：３、８１：４、１４６、１６８、１７７、１７８、１８４、１８５、１８７、２００、２０２、２０８、２１０、２４６、２５４、２５５、２６４、２７０、２７２、２７９等の赤色顔料を用いることができる。赤色組成物には、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｏｒａｎｇｅ ４３、７１、７３等の橙色顔料を併用することができる。 Examples of red compositions include C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 81: 4, 146, 168, 177, 178, 184, Red pigments such as 185, 187, 200, 202, 208, 210, 246, 254, 255, 264, 270, 272, and 279 can be used. The red composition includes C.I. I. An orange pigment such as Pigment Orange 43, 71, 73 can be used in combination.
緑色組成物には、例えば、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｇｒｅｅｎ ７、１０、３６、３７等の緑色顔料を用いることができる。緑色組成物には、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １、２、３、４、５、６、１０、１２、１３、１４、１５、１６、１７、１８、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４２、４３、５３、５５、６０、６１、６２、６３、６５、７３、７４、７７、８１、８３、９３、９４、９５、９７、９８、１００、１０１、１０４、１０６、１０８、１０９、１１０、１１３、１１４、１１５、１１６、１１７、１１８、１１９、１２０、１２３、１２６、１２７、１２８、１２９、１３８、１３９、１４７、１５０、１５１、１５２、１５３、１５４、１５５、１５６、１６１、１６２、１６４、１６６、１６７、１６８、１６９、１７０、１７１、１７２、１７３、１７４、１７５、１７６、１７７、１７９、１８０、１８１、１８２、１８５、１８７、１８８、１９３、１９４、１９８、１９９、２１３、２１４等の黄色顔料を併用することができる。 Examples of green compositions include C.I. I. Green pigments such as Pigment Green 7, 10, 36, and 37 can be used. Green compositions include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 , 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214 and the like can be used in combination.
青色組成物には、例えばＣ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、２２、６０、６４等の青色顔料を用いることができる。青色組成物には、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ １、１９、２３、２７、２９、３０、３２、３７、４０、４２、５０等の紫色顔料を併用することができる。
マゼンタ色組成物には、例えば、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｖｉｏｌｅｔ １、１９、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｒｅｄ １４４、１４６、１７７、１６９、８１等の紫色顔料および赤色顔料を用いることができる。
Examples of the blue composition include C.I. I. Blue pigments such as Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, and 64 can be used. Blue compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination.
Examples of magenta color compositions include C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 144, 146, 177, 169, 81, and red pigments can be used.
イエロー色組成物には、例えば、Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｙｅｌｌｏｗ １、２、３、４、５、６、１０、１２、１３、１４、１５、１６、１７、１８、２４、３１、３２、３４、３５、３５：１、３６、３６：１、３７、３７：１、４０、４２、４３、５３、５５、６０、６１、６２、６３、６５、７３、７４、７７、８１、８３、９３、９４、９５、９７、９８、１００、１０１、１０４、１０６、１０８、１０９、１１０、１１３、１１４、１１５、１１６、１１７、１１８、１１９、１２０、１２３、１２６、１２７、１２８、１２９、１３８、１３９、１４７、１５０、１５１、１５２、１５３、１５４、１５５、１５６、１６１、１６２、１６４、１６６、１６７、１６８、１６９、１７０、１７１、１７２、１７３、１７４、１７５、１７６、１７７、１７９、１８０、１８１、１８２、１８５、１８７、１８８、１９３、１９４、１９８、１９９、２１３、２１４等の黄色顔料を用いることができる。 Examples of yellow color compositions include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180 , 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, and the like can be used.
シアン色組成物には、例えば Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ １５：１、１５：２、１５：３、１５：４、１５：６、１６、８１等の青色顔料を用いることができる。
また、無機顔料としては、群青、紺青等が挙げられる。無機顔料は、彩度と明度のバランスを取りつつ良好な塗布性、感度、現像性等を確保するために、有機顔料と組み合わせて用いられる。
本発明の感光性着色組成物には、調色のため、耐熱性を低下させない範囲内で染料を含有させることができる。
Examples of the cyan composition include C.I. I. Blue pigments such as Pigment Blue 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, and 81 can be used.
Examples of the inorganic pigment include ultramarine blue and bitumen. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The photosensitive coloring composition of the present invention may contain a dye within a range that does not reduce heat resistance for color matching.
顔料は、感光性着色組成物中に、透明樹脂、多官能モノマー、光重合開始剤、分散助剤、溶剤の全量を基準（１００重量％）として、０．５〜１０重量％の割合で含有されることが好ましい。また、顔料は、最終フィルタセグメント中に好ましくは１０〜６０重量％、より好ましくは２０〜５０重量％の割合で含有され、その残部は透明樹脂、モノマー等により提供される樹脂質バインダーから実質的になる。
本発明の感光性着色組成物は、遠心分離、焼結フィルタ、メンブレンフィルタ等の手段にて、５μｍ以上の粗大粒子、好ましくは１μｍ以上の粗大粒子、さらに好ましくは０．５μｍ以上の粗大粒子および混入した塵の除去を行うことが好ましい。
The pigment is contained in the photosensitive coloring composition in a proportion of 0.5 to 10% by weight based on the total amount (100% by weight) of the transparent resin, polyfunctional monomer, photopolymerization initiator, dispersion aid and solvent. It is preferred that Further, the pigment is preferably contained in the final filter segment in a proportion of 10 to 60% by weight, more preferably 20 to 50% by weight, and the remainder is substantially composed of a resinous binder provided by a transparent resin, a monomer or the like. become.
The photosensitive coloring composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust.
着色材を含む感光性着色組成物は、透明樹脂を含む組成物中に、着色材を三本ロールミル、二本ロールミル、サンドミル、ニーダー、アトライター、ペイントコンディショナー等の各種分散手段を用いて微細に分散して顔料分散体を製造し、これに３つ以上のエチレン性不飽和二重結合を有する多官能モノマーと光昇華性のある光重合開始剤等を配合することで製造することができる。 The photosensitive coloring composition containing a coloring material is finely divided into a composition containing a transparent resin by using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, an attritor, and a paint conditioner. A pigment dispersion can be produced by dispersing, and it can be produced by blending a polyfunctional monomer having three or more ethylenically unsaturated double bonds, a photopolymerization initiator having a photosublimation property, and the like.
着色材として顔料を感光性組成物中に分散する際には、適宜、樹脂型顔料分散剤、色素誘導体、界面活性剤等の分散助剤を用いることができる。分散助剤は、顔料の分散に優れ、分散後の顔料の再凝集を防止する効果が大きいので、分散助剤を用いて顔料を感光性組成物中に分散してなる感光性着色組成物を用いた場合には、透明性に優れたカラーフィルタが得られる。分散助剤は、顔料１００重量部に対して、０．１〜４０重量部の量で用いることができる。 When the pigment is dispersed in the photosensitive composition as the colorant, a dispersion aid such as a resin-type pigment dispersant, a dye derivative, or a surfactant can be appropriately used. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing reaggregation of the pigment after dispersion, a photosensitive coloring composition obtained by dispersing the pigment in the photosensitive composition using the dispersion aid is used. When used, a color filter excellent in transparency can be obtained. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight with respect to 100 parts by weight of the pigment.
樹脂型顔料分散剤は、顔料に吸着する性質を有する顔料親和性部位と、顔料担体と相溶性のある部位とを有し、顔料に吸着して顔料の感光性組成物への分散を安定化する働きをするものである。樹脂型顔料分散剤として具体的には、ポリウレタン、ポリアクリレートなどのポリカルボン酸エステル、不飽和ポリアミド、ポリカルボン酸、ポリカルボン酸（部分）アミン塩、ポリカルボン酸アンモニウム塩、ポリカルボン酸アルキルアミン塩、ポリシロキサン、長鎖ポリアミノアマイドリン酸塩、水酸基含有ポリカルボン酸エステルや、これらの変性物、ポリ（低級アルキレンイミン）と遊離のカルボキシル基を有するポリエステルとの反応により形成されたアミドやその塩などが用いられる。また、（メタ）アクリル酸−スチレン共重合体、（メタ）アクリル酸−（メタ）アクリル酸エステル共重合体、スチレン−マレイン酸共重合体、ポリビニルアルコール、ポリビニルピロリドンなどの水溶性樹脂や水溶性高分子化合物、ポリエステル系、変性ポリアクリレート、エチレンオキサイド／プロピレンオキサイド付加物等が用いられる。これらは、単独でまたは２種以上を混合して用いることができる。 The resin-type pigment dispersant has a pigment affinity part that has the property of adsorbing to the pigment and a part that is compatible with the pigment carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment into the photosensitive composition. It works to do. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Salt or the like is used. In addition, water-soluble resins such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, and polyvinylpyrrolidone, and water-soluble Polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and the like are used. These can be used alone or in admixture of two or more.
具体的には、ビックケミー社製のＤｉｓｐｅｒｂｙｋまたはＤｉｓｐｅｒｂｙｋ−１０１、１０３、１０７、１０８、１１０、１１１、１１６、１３０、１４０、１５４、１６１、１６２、１６３、１６４、１６５、１６６、１７０、１７１、１７４、１８０、１８１、１８２、１８３、１８４、１８５、１９０、２０００、２００１またはＡｎｔｉ−Ｔｅｒｒａ−Ｕ、２０３、２０４またはＢＹＫ−Ｐ１０４、Ｐ１０４Ｓ、２２０ＳまたはＬａｃｔｉｍｏｎ、Ｌａｃｔｉｍｏｎ−ＷＳまたはＢｙｋｕｍｅｎ等、アビシア社製のＳＯＬＳＰＥＲＳＥ−３０００、９０００、１３２４０、１３６５０、１３９４０、１７０００、１８０００、２００００、２１０００、２４０００、２６０００、２７０００、２８０００、３１８４５、３２０００、３２５００、３２６００、３４７５０、３６６００、３８５００、４１０００、４１０９０、５３０９５等、エフカケミカルズ社製のＥＦＫＡ−４６、４７、４８、４５２、ＬＰ４００８、４００９、ＬＰ４０１０、ＬＰ４０５０、ＬＰ４０５５、４００、４０１、４０２、４０３、４５０、４５１、４５３、４５４０、４５５０、ＬＰ４５６０、１２０、１５０、１５０１、１５０２、１５０３等が挙げられる。 Specifically, Disperbyk or Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174 manufactured by Big Chemie , 180, 181, 182, 183, 184, 185, 190, 2000, 2001 or Anti-Terra-U, 203, 204 or BYK-P104, P104S, 220S or Lactimon, Lactimon-WS or Bykumen, etc., manufactured by Avicia SOLPERSE-3000, 9000, 13240, 13650, 13940, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 3200 , 32500, 32600, 34750, 36600, 38500, 41000, 41090, 53095, etc., EFKA-46, 47, 48, 452, LP4008, 4009, LP4010, LP4050, LP4055, 400, 401, 402, manufactured by Efka Chemicals 403, 450, 451, 453, 4540, 4550, LP4560, 120, 150, 1501, 1502, 1503 and the like.
色素誘導体は、有機色素に置換基を導入した化合物である。有機色素には、一般に色素と呼ばれていないナフタレン系、アントラキノン系等の淡黄色の芳香族多環化合物も含まれる。色素誘導体としては、特開昭６３−３０５１７３号公報、特公昭５７−１５６２０号公報、特公昭５９−４０１７２号公報、特公昭６３−１７１０２号公報、特公平５−９４６９号公報等に記載されているものを使用でき、これらは単独で、または２種類以上を混合して用いることができる。 A pigment derivative is a compound in which a substituent is introduced into an organic pigment. Organic dyes include light yellow aromatic polycyclic compounds such as naphthalene and anthraquinone which are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used singly or in combination of two or more.
界面活性剤としては、ポリオキシエチレンアルキルエーテル硫酸塩、ドデシルベンゼンスルホン酸ナトリウム、スチレン−アクリル酸共重合体のアルカリ塩、アルキルナフタリンスルホン酸ナトリウム、アルキルジフェニルエーテルジスルホン酸ナトリウム、ラウリル硫酸モノエタノールアミン、ラウリル硫酸トリエタノールアミン、ラウリル硫酸アンモニウム、ステアリン酸モノエタノールアミン、ステアリン酸ナトリウム、ラウリル硫酸ナトリウム、スチレン−アクリル酸共重合体のモノエタノールアミンなどのアニオン性界面活性剤；ポリオキシエチレンオレイルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンソルビタンモノステアレート、ポリエチレングリコールモノラウレートなどのノニオン性界面活性剤；アルキル４級アンモニウム塩やそれらのエチレンオキサイド付加物などのカオチン性界面活性剤；アルキルジメチルアミノ酢酸ベタインなどのアルキルベタイン、アルキルイミダゾリンなどの両性界面活性剤が挙げられ、これらは単独でまたは２種以上を混合して用いることができる。 Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer; polyoxyethylene oleyl ether, polyoxyethylene Lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate, polyethylene glycol Nonionic surfactants such as monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines These may be used alone or in combination of two or more.
また、感光性着色組成物には、着色材の経時粘度を安定化させるために貯蔵安定剤を含有させることができる。貯蔵安定剤としては、例えばベンジルトリメチルクロライド、ジエチルヒドロキシアミンなどの４級アンモニウムクロライド、乳酸、シュウ酸などの有機酸およびそのメチルエーテル、ｔ−ブチルピロカテコール、テトラエチルホスフィン、テトラフェニルフォスフィンなどの有機ホスフィン、亜リン酸塩等が挙げられる。貯蔵安定剤は、着色材１００重量部に対して、０．１〜１０重量部の量で用いることができる。 The photosensitive coloring composition can contain a storage stabilizer in order to stabilize the viscosity of the coloring material with time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.
また、感光性着色組成物には、着色材を十分に感光性組成物中に分散させ、ガラス基板等の透明基板上に乾燥膜厚が０．２〜５μｍとなるように塗布してフィルタセグメントを形成することを容易にするために溶剤を含有させることができる。溶剤としては、例えばシクロヘキサノン、エチルセロソルブアセテート、ブチルセロソルブアセテート、プロピレングリコールモノメチルエーテルアセテート、ジエチレングリコールジメチルエーテル、エチルベンゼン、エチレングリコールジエチルエーテル、キシレン、エチルセロソルブ、メチル−ｎアミルケトン、プロピレングリコールモノメチルエーテル、トルエン、メチルエチルケトン、酢酸エチル、メタノール、エタノール、イソプロピルアルコール、ブタノール、イソブチルケトン、石油系溶剤等が挙げられ、これらを単独でもしくは混合して用いる。溶剤は、着色材１００重量部に対して、８００〜４０００重量部の量で用いることができる。 In the photosensitive coloring composition, the colorant is sufficiently dispersed in the photosensitive composition, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. In order to make it easier to form, a solvent can be included. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether, toluene, methyl ethyl ketone, acetic acid Examples of the solvent include ethyl, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, and petroleum solvents. These are used alone or in combination. The solvent can be used in an amount of 800 to 4000 parts by weight with respect to 100 parts by weight of the colorant.
次に、本発明のカラーフィルタについて説明する。
本発明のカラーフィルタは、着色材を含む本発明の感光性組成物を用いて形成されたフィルタセグメントを具備するカラーフィルタである。カラーフィルタには、少なくとも１つの赤色フィルタセグメント、少なくとも１つの緑色フィルタセグメント、および少なくとも１つの青色フィルタセグメントを具備する加法混色型、および少なくとも１つのマゼンタ色フィルタセグメント、少なくとも１つのシアン色フィルタセグメント、および少なくとも１つのイエロー色フィルタセグメントを具備する減法混色型のものがある。
各色のフィルタセグメントは、各色顔料、前記透明樹脂、前記３つ以上のエチレン性不飽和二重結合を有する多官能モノマー、前記光重合開始剤を含有する各色感光性組成物を用いて形成することができる。
Next, the color filter of the present invention will be described.
The color filter of this invention is a color filter which comprises the filter segment formed using the photosensitive composition of this invention containing a coloring material. The color filter includes an additive color mixture comprising at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and at least one magenta filter segment, at least one cyan filter segment, And a subtractive color type with at least one yellow filter segment.
Each color filter segment is formed by using each color photosensitive composition containing each color pigment, the transparent resin, the polyfunctional monomer having three or more ethylenically unsaturated double bonds, and the photopolymerization initiator. Can do.
本発明のカラーフィルタは、フォトリソグラフィー法により、着色材を含む本発明の感光性組成物を用いて、基板上に各色のフィルタセグメントを形成することにより製造することができる。
基板としては、ガラス板や、ポリカーボネート、ポリメタクリル酸メチル、ポリエチレンテレフタレートなどの透明樹脂板が用いられる。
フォトリソグラフィー法による各色フィルタセグメントの形成は、下記の方法で行う。すなわち、溶剤現像型あるいはアルカリ現像型着色組成物として調製した感光性組成物を、基板上に、スプレーコートやスピンコート、スリットコート、ロールコート等の塗布方法により、乾燥膜厚が０．２〜５μｍとなるように塗布する。必要により乾燥された膜には、この膜と接触あるいは非接触状態で設けられた所定のパターンを有するマスクを通して紫外線露光を行う。その後、溶剤またはアルカリ現像液に浸漬するか、もしくはスプレーなどにより現像液を噴霧して未硬化部を除去し所望のパターンを形成したのち、同様の操作を他色について繰り返してカラーフィルタを製造することができる。さらに、感光性組成物の重合を促進するため、必要に応じて加熱を施すこともできる。フォトリソグラフィー法によれば、印刷法より精度の高いカラーフィルタが製造できる。
The color filter of this invention can be manufactured by forming the filter segment of each color on a board | substrate using the photosensitive composition of this invention containing a coloring material by the photolithographic method.
As the substrate, a transparent resin plate such as a glass plate, polycarbonate, polymethyl methacrylate, polyethylene terephthalate is used.
The formation of each color filter segment by photolithography is performed by the following method. That is, the photosensitive film prepared as a solvent-developable or alkaline-developable coloring composition has a dry film thickness of 0.2 to 0.2 on a substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. Apply to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate | stimulate superposition | polymerization of the photosensitive composition, it can also heat as needed. According to the photolithography method, a color filter with higher accuracy than the printing method can be manufactured.
現像に際しては、アルカリ現像液として炭酸ナトリウム、水酸化ナトリウム等の水溶液が使用され、ジメチルベンジルアミン、トリエタノールアミン等の有機アルカリを用いることもできる。また、現像液には、消泡剤や界面活性剤を添加することもできる。
なお、紫外線露光感度を上げるために、上記感光性組成物を塗布乾燥後、水溶性あるいはアルカリ可溶性樹脂、例えばポリビニルアルコールや水溶性アクリル樹脂等を塗布乾燥し酸素による重合阻害を防止する膜を形成した後、紫外線露光を行うこともできる。
また、本発明の感光性組成物をカラーフィルタのオーバーコート層の形成に用いる場合、一般的には感光性組成物に溶剤を含有させ、溶液濃度を１０〜４０重量％程度に調整して使用する。溶剤を含有する感光性組成物を、カラーフィルタ層が形成された透明基板上に、ロールコータ、スピンコータ等により任意の厚さに塗布し、露光後、１５０℃〜２５０℃の温度で、０．５〜２時間程度硬化させるとオーバーコート層が形成される。
In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase UV exposure sensitivity, after coating and drying the photosensitive composition, a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.
In addition, when the photosensitive composition of the present invention is used for forming an overcoat layer of a color filter, it is generally used by adding a solvent to the photosensitive composition and adjusting the solution concentration to about 10 to 40% by weight. To do. A photosensitive composition containing a solvent is applied onto a transparent substrate on which a color filter layer has been formed by using a roll coater, a spin coater, or the like, and after exposure, at a temperature of 150 ° C. to 250 ° C. When cured for about 5 to 2 hours, an overcoat layer is formed.
以下に、本発明を実施例に基づいて説明するが、本発明はこれによって限定されるものではない。なお、実施例および比較例中、「部」とは「重量部」を意味する。透明樹脂の分子量は、GPC（ゲルパーミエーションクロマトグラフィ）により測定したポリスチレン換算の重量平均分子量であり、透明樹脂、３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの溶解度パラメータは、Ｆｅｄｏｒｓの方法により算出した値である。
（透明樹脂合成例１）
反応容器にシクロヘキサノン３７０部を入れ、容器に窒素ガスを注入しながら８０℃に加熱して、同温度でメタクリル酸３２．０部、メチルメタクリレート１０．０部、ｎ−ブチルメタクリレート４４．０部、２−ヒドロキシエチルメタクリレート１４．０部、２，２’−アゾビスイソブチロニトリル４．０部の混合物を１時間かけて滴下して重合反応を行った。滴下終了後、さらに８０℃で３時間反応させた後、アゾビスイソブチロニトリル１．０部をシクロヘキサノン５０部に溶解させたものを添加し、さらに８０℃で１時間反応を続けて、非感光性透明樹脂の溶液を得た。室温まで冷却した後、非感光性透明樹脂の溶液約２ｇをサンプリングして１８０℃、２０分加熱乾燥して不揮発分を測定し、先に合成した非感光性透明樹脂の溶液に不揮発分が２０重量％になるようにシクロヘキサノンを添加して非感光性透明樹脂溶液を調製した。
Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples and comparative examples, “parts” means “parts by weight”. The molecular weight of the transparent resin is a polystyrene-equivalent weight average molecular weight measured by GPC (gel permeation chromatography), and the solubility parameter of the transparent resin and the polyfunctional monomer having three or more ethylenically unsaturated double bonds is Fedors. It is a value calculated by the method.
(Transparent resin synthesis example 1)
370 parts of cyclohexanone was placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 32.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 44.0 parts of n-butyl methacrylate, A mixture of 14.0 parts of 2-hydroxyethyl methacrylate and 4.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A solution of photosensitive transparent resin was obtained. After cooling to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and the previously synthesized non-photosensitive transparent resin solution had a non-volatile content of 20 A non-photosensitive transparent resin solution was prepared by adding cyclohexanone in an amount of% by weight.
（透明樹脂合成例２）
反応容器にシクロヘキサノン４００部を入れ、容器に窒素ガスを注入しながら８０℃に加熱して、同温度でｎ−ブチルメタクリレート２３．２部、２−ヒドロキシエチルメタクリレート１４．３部、メタクリル酸２６．５部、パラクミルフェノールエチレンオキサイド変性アクリレート（東亜合成株式会社製「アロニックスＭ１１０」）３６．０部、２，２’−アゾビスイソブチロニトリル４．０部の混合物を２時間かけて滴下して重合反応を行った。滴下終了後、さらに８０℃で３時間反応させた後、アゾビスイソブチロニトリル１．０部をシクロヘキサノン５０部に溶解させたものを添加し、さらに８０℃で１時間反応を続けて、非感光性透明樹脂の溶液を得た。
室温まで冷却した後、非感光性透明樹脂の溶液約２ｇをサンプリングして１８０℃、２０分加熱乾燥して不揮発分を測定し、先に合成した非感光性透明樹脂の溶液に不揮発分が２０重量％になるようにシクロヘキサノンを添加して非感光性透明樹脂溶液を調製した。
(Transparent resin synthesis example 2)
Put 400 parts of cyclohexanone in a reaction vessel, heat to 80 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 23.2 parts of n-butyl methacrylate, 14.3 parts of 2-hydroxyethyl methacrylate, 26. methacrylic acid. 5 parts, a mixture of 36.0 parts paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) and 4.0 parts 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. The polymerization reaction was carried out. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A solution of photosensitive transparent resin was obtained.
After cooling to room temperature, about 2 g of the non-photosensitive transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and the previously synthesized non-photosensitive transparent resin solution had a non-volatile content of 20 A non-photosensitive transparent resin solution was prepared by adding cyclohexanone in an amount of% by weight.
（透明樹脂合成例３）
反応容器にシクロヘキサノン５６０部を入れ、容器に窒素ガスを注入しながら８０℃に加熱して、同温度でメタクリル酸５．０部、ｎ−ブチルメタクリレート、２３．０部、パラクミルフェノールエチレンオキサイド変性アクリレート（東亜合成株式会社製「アロニックスＭ１１０」）１５．０部、グリセロールモノメタクリレート５７．０部、２，２’−アゾビスイソブチロニトリル４．０部の混合物を１時間かけて滴下して重合反応を行った。滴下終了後、さらに８０℃で３時間反応させた後、アゾビスイソブチロニトリル１．０部をシクロヘキサノン５５部に溶解させたものを添加し、さらに８０℃で１時間反応を続けて、非感光性透明樹脂の溶液を得た。
次に、得られた非感光性透明樹脂の溶液３６０部に対して、２−メタクロイルエチルイソシアネート３０．０部、ラウリン酸ジブチル錫０．４部、シクロヘキサノン１２０．０部の混合物を７０℃で３時間かけて滴下し、感光性透明樹脂の溶液を得た。室温まで冷却した後、感光性透明樹脂の溶液約２ｇをサンプリングして１８０℃、２０分加熱乾燥して不揮発分を測定し、先に合成した感光性透明樹脂の溶液に不揮発分が２０重量％になるようにシクロヘキサノンを添加して感光性透明樹脂溶液を調製した。
(Transparent resin synthesis example 3)
560 parts of cyclohexanone is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and 5.0 parts of methacrylic acid, n-butyl methacrylate, 23.0 parts, modified paracumylphenol ethylene oxide at the same temperature. A mixture of 15.0 parts of acrylate ("Aronix M110" manufactured by Toa Gosei Co., Ltd.), 57.0 parts of glycerol monomethacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 1 hour. A polymerization reaction was performed. After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 1.0 part of azobisisobutyronitrile dissolved in 55 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour. A solution of photosensitive transparent resin was obtained.
Next, a mixture of 30.0 parts of 2-methacryloylethyl isocyanate, 0.4 parts of dibutyltin laurate, and 120.0 parts of cyclohexanone was added at 70 ° C. to 360 parts of the obtained non-photosensitive transparent resin solution. The solution was added dropwise over 3 hours to obtain a photosensitive transparent resin solution. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and the previously synthesized photosensitive transparent resin solution had a nonvolatile content of 20% by weight. Cyclohexanone was added so that a photosensitive transparent resin solution was prepared.
［実施例１］
（顔料分散体の製造方法）
下記の組成の混合物を均一に撹拌混合した後、直径１ｍｍのジルコニアビーズを用いて、アイガーミル（アイガージャパン社製「ミニモデルＭ−２５０ ＭＫII」）で２時間分散した後、５μｍのフィルタで濾過し、顔料分散体を作製した。
ε型銅フタロシアニン顔料（Ｃ．Ｉ．Ｐｉｇｍｅｎｔ Ｂｌｕｅ１５：６）
（ＢＡＳＦ製「ヘリオゲンブルーＬ−６７００Ｆ」） １１．０部
フタロシアニン系顔料誘導体 １．０部
シクロヘキサノン ４８．０部
[Example 1]
(Method for producing pigment dispersion)
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A pigment dispersion was prepared.
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6)
("Heliogen Blue L-6700F" manufactured by BASF) 11.0 parts 1.0 part of phthalocyanine pigment derivative
（感光性着色組成物の製造方法）
ついで、下記組成の混合物を均一になるように攪拌混合した後、１μｍのフィルタで濾過して、青色の感光性着色組成物を得た。
顔料分散体 ４５．０部
合成例１の非感光性透明樹脂溶液 ５．０部
３つ以上のエチレン性不飽和二重結合を有する多官能モノマー ６．６部
（トリメチロールプロパントリアクリレート）
光重合開始剤 ２．９部
（２−メチル−１−［４−（メチルチオ）フェニル］−２−モルフォリノプロパン−１−オン）
増感剤（保土ヶ谷化学社製「ＥＡＢ−Ｆ」） ０．３部
シクロヘキサノン ４０．２部
(Method for producing photosensitive coloring composition)
Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a blue photosensitive coloring composition.
Pigment dispersion 45.0 parts Non-photosensitive transparent resin solution of Synthesis Example 1 5.0 parts Polyfunctional monomer having 3 or more ethylenically unsaturated double bonds 6.6 parts (trimethylolpropane triacrylate)
2.9 parts of photopolymerization initiator (2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one)
Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.3 parts Cyclohexanone 40.2 parts
［実施例２〜１３および比較例１〜６］
感光性透明樹脂溶液、非感光性透明樹脂溶液、３つ以上のエチレン性不飽和二重結合を有する多官能モノマーを、感光性組成物中における各成分の割合が表４に示す割合（固形分の重量比）となるように配合し、実施例1と同様にして青色の感光性着色組成物を得た。透明樹脂の重量平均分子量およびＳＰ値を表１に、使用した３つ以上のエチレン性不飽和二重結合を有する多官能モノマーの一覧を表２に、使用した光重合開始剤の一覧を表３示す。
[Examples 2 to 13 and Comparative Examples 1 to 6]
Photosensitive transparent resin solution, non-photosensitive transparent resin solution, polyfunctional monomer having 3 or more ethylenically unsaturated double bonds, the ratio of each component in the photosensitive composition shown in Table 4 (solid content The blue photosensitive coloring composition was obtained in the same manner as in Example 1. Table 1 shows the weight average molecular weight and SP value of the transparent resin, Table 2 lists the polyfunctional monomers having three or more ethylenically unsaturated double bonds, and Table 3 lists the photopolymerization initiators used. Show.
（粘度安定性評価）
感光性着色組成物を配合した翌日の初期粘度と４０℃で１週間、経時促進させた経時粘度をＥ型粘度計（東機産業社製「ＥＬＤ型粘度計」）を用いて、回転数２０ｒｐｍという条件で測定した。この初期粘度から経時粘度への変化率を算出した。
［経時粘度変化率］＝｜（［初期粘度］−［経時粘度］）／［初期粘度］×１００｜
(Viscosity stability evaluation)
Using an E-type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.), the initial viscosity of the next day in which the photosensitive coloring composition was blended and the time-lapse viscosity accelerated at 40 ° C. for 1 week was rotated at 20 rpm. It measured on condition of. The rate of change from this initial viscosity to the time-dependent viscosity was calculated.
[Viscosity change rate with time] = | ([initial viscosity] − [viscosity with time]) / [initial viscosity] × 100 |
（感度評価）
感光性着色組成物を１００ｍｍ×１００ｍｍ、１．１ｍｍ厚のガラス基板上に、スピンコータを用いて塗布し、厚さ２.０μｍの塗膜を形成した。次に、７０℃で２０分間のプリベイクを行った後、５０μｍの細線パターンを露光するようなマスクを介して紫外線露光を行った。１０ｍＪ／ｃｍ2〜２００ｍＪ／ｃｍ2間の８水準の露光量で露光を行った。露光後、アルカリ現像液にて９０秒間現像して、ストライプ形状のフィルタセグメントを形成した。なお、アルカリ現像液としては、炭酸ナトリウム１．５重量％ 炭酸水素ナトリウム０．５重量％ 陰イオン系界面活性剤（花王社製「ペリレックスＮＢＬ」）８．０重量％および水９０重量％からなるものを用いた。得られたフィルタセグメントの膜厚を未露光・未現像部分を１００とした時の各露光量水準での露光・現像後の残膜率を算出した。得られた残膜率曲線から、残膜率が飽和に達する露光量を飽和露光量と定めた。得られた飽和露光量と残膜率とを表５に示す。高感度用途での使用を目的としているため、飽和露光量が５０ｍＪ／ｃｍ2以下のものが良好である。
(Sensitivity evaluation)
The photosensitive coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater to form a coating film having a thickness of 2.0 μm. Next, after prebaking at 70 ° C. for 20 minutes, ultraviolet exposure was performed through a mask that exposes a 50 μm fine line pattern. It was exposed with an exposure amount of 8 levels between 10mJ / cm 2 ~200mJ / cm 2 . After exposure, the film was developed with an alkaline developer for 90 seconds to form a stripe-shaped filter segment. The alkali developer is 1.5% by weight of sodium carbonate, 0.5% by weight of sodium bicarbonate, 8.0% by weight of an anionic surfactant (“PERILEX NBL” manufactured by Kao Corporation) and 90% by weight of water. What was used. The residual film ratio after exposure / development at each exposure level when the film thickness of the obtained filter segment was defined as 100 for the unexposed / undeveloped portion was calculated. From the obtained residual film rate curve, the exposure amount at which the residual film rate reached saturation was determined as the saturated exposure amount. Table 5 shows the obtained saturation exposure and remaining film ratio. Since it is intended for use in high-sensitivity applications, a saturated exposure amount of 50 mJ / cm 2 or less is good.
（光重合開始剤の昇華性評価）
カラーフィルタの製造工程で、パターン露光を行う際に感光性着色組成物から発生する光重合開始剤の昇華物がマスクに付着し、パターンを覆ってしまうことで、目的のパターン形状を露光できなくなる現象を定量的に捉えることは難しい。そのため、感光性着色組成物の塗工膜の露光前後での膜厚変化の測定を、感光性着色組成物からの光重合開始剤の昇華性の代用評価として行った。感光性着色組成物を１００ｍｍ×１００ｍｍ、１．１ｍｍ厚のガラス基板上に、スピンコータを用いて塗布し、厚さ約４.０μｍの塗膜を形成した。塗膜の乾燥を減圧乾燥により行い、この時点の膜厚を測定しておく。その後、紫外線露光を１０分間行い、再度膜厚測定を行う。減圧乾燥後と紫外線露光後の塗膜の膜厚測定結果から膜厚変化率を算出した。膜厚変化率は５％以下であるものを良好である。
［膜厚変化率］＝｜（［減圧乾燥後膜厚］−［紫外線露光後膜厚］）／［減圧乾燥後膜厚］×１００｜
(Sublimation evaluation of photopolymerization initiator)
In the manufacturing process of the color filter, when the pattern exposure is performed, the sublimation product of the photopolymerization initiator generated from the photosensitive coloring composition adheres to the mask and covers the pattern, so that the target pattern shape cannot be exposed. It is difficult to quantitatively capture the phenomenon. Therefore, the measurement of the film thickness change before and after the exposure of the coating film of the photosensitive coloring composition was performed as a substitute evaluation of the sublimation property of the photopolymerization initiator from the photosensitive coloring composition. The photosensitive coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater to form a coating film having a thickness of about 4.0 μm. The coating film is dried under reduced pressure, and the film thickness at this point is measured. Thereafter, UV exposure is performed for 10 minutes, and the film thickness is measured again. The film thickness change rate was calculated from the film thickness measurement results of the coating film after drying under reduced pressure and after UV exposure. The film thickness change rate is preferably 5% or less.
[Thickness change rate] = | ([film thickness after drying under reduced pressure] − [film thickness after UV exposure]) / [film thickness after drying under reduced pressure] × 100 |
（パターニング性評価）
感度評価において、紫外線の露光量を飽和露光量＋５０ｍＪ／ｃｍ2、アルカリ現像液での現像時間をそれそれのレジスト塗膜の未露光部を洗い流すのに適正な時間とした以外は、同様の方法で基板を作成後、２３０℃で６０分間加熱処理をし、その細線パターンの形状を、パタ−ンの断面形状により評価した。パターンの断面形状は、走査型電子顕微鏡（ＳＥＭ）を用いて評価を行った。評価のランクは、○：順テーパー形状、△：ノンテーパー形状、×：逆テーパー形状。
(Patternability evaluation)
In the sensitivity evaluation, the same method except that the exposure amount of ultraviolet rays is a saturated exposure amount + 50 mJ / cm 2 , and the development time with an alkali developer is set to an appropriate time to wash away the unexposed portions of the resist coating film. Then, after the substrate was prepared, heat treatment was performed at 230 ° C. for 60 minutes, and the shape of the fine line pattern was evaluated by the cross-sectional shape of the pattern. The cross-sectional shape of the pattern was evaluated using a scanning electron microscope (SEM). The evaluation ranks are: ○: forward taper shape, Δ: non-taper shape, x: reverse taper shape.
表５に示すように、感光性組成物中の各成分の配合比を最適化し、透明樹脂と３つ以上のエチレン性不飽和二重結合を有する多官能モノマーのＳＰ値が適正であるものを選択した実施例においては、感光性着色組成物塗工膜の減圧乾燥後と紫外線露光後の膜厚変化率は小さくなっており、これはすなわち光重合開始剤の昇華による膜厚変化がおさえられていることを意味する。一方、比較例においては、感光性着色組成物塗工膜の減圧乾燥後と紫外線露光後の膜厚変化率は小さくなっているものもあるが、透明樹脂と３つ以上のエチレン性不飽和二重結合を有する多官能モノマーのＳＰ値の差が大きかったり（比較例３）、３つ以上のエチレン性不飽和二重結合を有する多官能モノマー、光昇華性の開剤の配合量が適正でないために（比較例５、７）、モノマーの偏析が過度となりパターニング性が不良となる。 As shown in Table 5, the mixing ratio of each component in the photosensitive composition is optimized, and the SP value of the polyfunctional monomer having a transparent resin and three or more ethylenically unsaturated double bonds is appropriate. In the selected example, the rate of change in the thickness of the photosensitive coloring composition coating film after drying under reduced pressure and after UV exposure is small, that is, the film thickness change due to sublimation of the photopolymerization initiator is suppressed. Means that On the other hand, in the comparative examples, the rate of change in film thickness after drying under reduced pressure and exposure to ultraviolet light of the photosensitive coloring composition coating film is small, but the transparent resin and three or more ethylenically unsaturated dioxygens are present. The difference in SP value of the polyfunctional monomer having a heavy bond is large (Comparative Example 3). The blending amount of the polyfunctional monomer having three or more ethylenically unsaturated double bonds and the photosublimable opener is not appropriate. For this reason (Comparative Examples 5 and 7), the segregation of the monomer becomes excessive and the patterning property becomes poor.
Claims (6)
式
多官能モノマー、ホモポリマーのＳＰ値：δ=［Σ（原子、原子団の凝集エネルギ−×モル分率）／Σ（原子、原子団の分子容積率×モル分率）］1/2
コポリマーのＳＰ値：δcopolymer＝（δA 2×ＸA＋δB 2×ＸB＋δC 2×ＸC・・・）1/2
（ただし、コポリマーを構成するモノマーＡ、Ｂ、Ｃ・・・のホモポリマーのＳＰ値をδA、δB、δC・・・，モル分率をＸA、ＸB、ＸC・・・とする。） A photosensitive composition comprising a transparent resin, a polyfunctional monomer having three or more ethylenically unsaturated double bonds, and a photopolymerization initiator having a photosublimation property. Three of the photosensitive compositions The blending ratio of the above polyfunctional monomer having an ethylenically unsaturated double bond is 30 based on the total weight of the transparent resin, the polyfunctional monomer having three or more ethylenically unsaturated double bonds, and the photopolymerization initiator. The blending ratio of the photopolymerization initiator in the photosensitive composition is ˜50% by weight, and the total weight of the transparent resin, the polyfunctional monomer having three or more ethylenically unsaturated double bonds, and the photopolymerization initiator Is a polyfunctional compound having an ethylenically unsaturated double bond whose solubility parameter is calculated by the following formula by the Fedors method of the transparent resin in the photosensitive composition. Monomeric The method of Edors, greater than the solubility parameter calculated by the following formula, a photosensitive composition the difference is equal to or in the range of 0.4 to 0.9.
SP value of polyfunctional monomer and homopolymer of formula: δ = [Σ (agglomeration energy of atoms and atomic groups × molar fraction) / Σ (molecular volume fraction of atoms and atomic groups × molar fraction)] 1/2
SP value of copolymer: δ copolymer = (δ A 2 × X A + δ B 2 × X B + δ C 2 × X C ...) 1/2
(However, the SP values of the homopolymers of the monomers A, B, C... Constituting the copolymer are δ A , δ B , δ C ..., And the molar fractions are X A , X B , X C. And)
［式（１）において、Ｒ1は、ベンジル基、置換されたベンジル基、フェナシル基、置換されたフェナシル基、アリールオキシ基、置換されたアリールオキシ基、アルケニル基、置換されたアルケニル基から選ばれる基を表し、Ｒ2およびＲ3は、それぞれ独立に、Ｒ1 を構成できる基と同じ基か、またはアルキル基、置換されたアルキル基、アリール基、置換されたアリール基、アラルキル基、置換されたアラルキル基、アルキニル基、置換されたアルキニル基、脂環基、置換された脂環基、アルコキシ基、置換されたアルコキシ基、アルキルチオ基、置換されたアルキルチオ基、アミノ基、置換されたアミノ基、またはＲ2とＲ3が相互に結合した環状構造を表し、Ｒ4は酸素原子または孤立電子対を表し、Ｒ5、Ｒ6、Ｒ7およびＲ8は、それぞれ独立に、アルキル基、置換されたアルキル基、アリール基、置換されたアリール基、アラルキル基、置換されたアラルキル基、アルキニル基、置換されたアルキニル基を表す（但し、Ｒ5、Ｒ6、Ｒ7およびＲ8の全てが、アリール基または置換されたアリール基となることはない。）］ The photopolymerization initiator having a photosublimation property is an acetophenone photopolymerization initiator, an acyl phosphine oxide initiator, or a sulfonium organic boron complex or an oxosulfonium organic boron complex represented by the following general formula (1) The photosensitive composition according to claim 1.
[In the formula (1), R 1 is selected from a benzyl group, a substituted benzyl group, a phenacyl group, a substituted phenacyl group, an aryloxy group, a substituted aryloxy group, an alkenyl group, and a substituted alkenyl group. R 2 and R 3 are each independently the same group as that capable of constituting R 1 , or an alkyl group, a substituted alkyl group, an aryl group, a substituted aryl group, an aralkyl group, a substituted group Aralkyl group, alkynyl group, substituted alkynyl group, alicyclic group, substituted alicyclic group, alkoxy group, substituted alkoxy group, alkylthio group, substituted alkylthio group, amino group, substituted amino group group or represents a cyclic structure R 2 and R 3 are bonded to each other, R 4 represents an oxygen atom or a lone pair of electrons, R 5, R 6, R 7 and R 8, is its The respective independently, alkyl group, substituted alkyl group, aryl group, substituted aryl group, an aralkyl group, substituted aralkyl group, an alkynyl group, a substituted alkynyl group (provided that, R 5, R 6 , R 7 and R 8 are not all aryl groups or substituted aryl groups.]]
［式（２）において、Ｒ9は、水素原子またはメチル基を表し、Ｒ10は、アルキレン基を表し、Ｒ11は、水素原子またはベンゼン環を含んでも良い炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。］ 4. The photosensitive composition according to claim 1, wherein the transparent resin contains an ethylenically unsaturated monomer represented by the following general formula (2) as a polymerization component.
[In the formula (2), R 9 represents a hydrogen atom or a methyl group, R 10 represents an alkylene group, and R 11 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. Represent. n represents an integer of 1 to 15. ]
A color filter comprising a filter segment formed from the photosensitive composition according to claim 5.
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| JP2008261947A (en) * | 2007-04-10 | 2008-10-30 | Toppan Printing Co Ltd | Photosensitive color composition for translucent liquid crystal display, color filter for translucent liquid crystal display using photosensitive color composition and its manufacturing method, and translucent liquid crystal display |
| JP5075510B2 (en) * | 2007-07-20 | 2012-11-21 | 東洋インキＳｃホールディングス株式会社 | Coloring composition and color filter using the same |
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| JPH1010724A (en) * | 1996-06-27 | 1998-01-16 | Hitachi Chem Co Ltd | Color image forming photosensitive liquid, production of color filter using that, and color filter |
| JP2000284478A (en) * | 1999-03-31 | 2000-10-13 | Showa Denko Kk | Photocuring composition |
| JP3726627B2 (en) * | 2000-03-15 | 2005-12-14 | 株式会社村田製作所 | Photosensitive conductor paste, electronic component, electronic device |
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| JP4047588B2 (en) * | 2002-01-17 | 2008-02-13 | 互応化学工業株式会社 | Negative photosensitive resin composition for lift-off method and dry film |
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