JPH05333207A - Color filter - Google Patents
Color filterInfo
- Publication number
- JPH05333207A JPH05333207A JP16162892A JP16162892A JPH05333207A JP H05333207 A JPH05333207 A JP H05333207A JP 16162892 A JP16162892 A JP 16162892A JP 16162892 A JP16162892 A JP 16162892A JP H05333207 A JPH05333207 A JP H05333207A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- dye
- color filter
- parts
- colored
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、カラーフィルターに関
する。更に詳しくは、特定の染料を含有し、固体撮像素
子又はカラー液晶表示等に使用されうるカラーフィルタ
ーに関する。FIELD OF THE INVENTION The present invention relates to a color filter. More specifically, it relates to a color filter which contains a specific dye and can be used for a solid-state image pickup device, a color liquid crystal display, or the like.
【０００２】[0002]
【従来の技術】ＶＴＲ用カメラ等に用いられる固体撮像
素子又は、カラー液晶表示等に用いられるカラーフィル
ターは２種以上の色相に着色された微細な領域を画素と
して、固体撮像素子又は透明基板上に設けることによっ
て形成されている。カラーフィルターは、三原色、即
ち、赤、緑、青から成るものと黄、マジエンタ、シアン
の補色系からなるものがある。カラーフィルターの分光
特性が、カラーテレビ等の色再現性や、カラーフィルタ
ーの耐熱、耐光性が製品の耐久性の良否を決定している
事は、言うまでもなく、使用目的等により、さまざまな
染料又は顔料による着色が試みられてきた。2. Description of the Related Art A solid-state image pickup device used in a VTR camera or the like, or a color filter used in a color liquid crystal display or the like has fine regions colored in two or more kinds of hues as pixels and is formed on a solid-state image pickup device or a transparent substrate. It is formed by providing. There are three primary color filters, namely, ones composed of three primary colors, that is, red, green and blue, and ones composed of a complementary color system of yellow, magenta and cyan. It goes without saying that the spectral characteristics of color filters determine the color reproducibility of color TVs, and the heat and light resistance of color filters determine the durability of the product. Coloring with pigments has been tried.
【０００３】熱硬化性樹脂溶液又は、光硬化性樹脂溶液
に、染料を溶解して用いる方法の場合、染料は樹脂が可
溶である溶剤と同一の溶剤に、可溶でなければならな
い。しかしながら、従来用いられてきた染料は溶剤への
溶解性が良いものは、耐熱性及び／又は耐光性に劣り、
又逆に耐熱性及び／又は耐光性がよいものは、概して溶
剤への溶解性に劣るという性質がある。特に、耐熱性、
耐光性に優れた緑色（グリーン）のカラーフィルターを
得るのに有用な染料がなく、その開発が望まれていた。In the case of using a dye in a thermosetting resin solution or a photocurable resin solution, the dye must be soluble in the same solvent in which the resin is soluble. However, conventionally used dyes having good solubility in a solvent have poor heat resistance and / or light resistance,
On the contrary, those having good heat resistance and / or light resistance generally have the property of being poor in solubility in a solvent. Especially heat resistance,
There is no dye useful for obtaining a green color filter having excellent light resistance, and its development has been desired.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記した
ような課題を解決するため、鋭意努力した結果、本発明
に至った。即ち、本発明は熱硬化性樹脂又は光硬化性樹
脂溶液に染料を溶解した着色樹脂溶液を用いるカラーフ
ィルターに於いて、染料として下記式（１）で示される
対イオンで造塩された染料で、着色されている事を特徴
とする耐熱、耐光性に優れたカラーフィルターを提供す
る。DISCLOSURE OF THE INVENTION The inventors of the present invention have made earnest efforts to solve the above-mentioned problems and, as a result, arrived at the present invention. That is, the present invention relates to a color filter using a colored resin solution in which a dye is dissolved in a thermosetting resin or a photocurable resin solution, and a dye salted with a counterion represented by the following formula (1) is used as the dye. A color filter having excellent heat resistance and light resistance, which is characterized by being colored.
【０００５】〔Ａ〕+ （１） （式（１）中、Ａは炭素数１〜１８の直鎖又は枝分れし
た１個の酸素原子によって中断されていても良いアルキ
ルアンモニウム、炭素数２乃至６のアルカノールアンモ
ニウム又はシクロヘキシルアンモニウムを表す。）殊に
緑色（グリーン）のカラーフィルターとして上記式
（１）で示される対イオンで造塩された含金属フタロシ
アニン染料と黄色（イエロー）染料及び／又はニトロ化
合物の使用が耐熱性、耐光性の優れたカラーフィルター
を得る上で好ましい。[A] + (1) (In the formula (1), A is an alkylammonium having 1 to 18 carbon atoms which may be interrupted by a linear or branched oxygen atom, or 2 carbon atoms. To 6 of alkanol ammonium or cyclohexyl ammonium). Particularly, as a green color filter, a metal-containing phthalocyanine dye salted with a counter ion represented by the above formula (1) and a yellow dye and / or Use of a nitro compound is preferable for obtaining a color filter having excellent heat resistance and light resistance.
【０００６】式（１）で示される対イオンを少くとも１
個含むアニオン染料は、通常の方法で合成された染料の
反応液又は、酸析または塩析により分離されたアニオン
染料の結晶を水に溶解した水溶液に、下記式（２）で表
されるアミンを、染料１モルに対し、１モル以上添加
し、酸性〜中性で反応させることにより得られる。 〔Ｂ〕 （２） （式（２）において、Ｂは炭素数１〜１８の直鎖又は枝
分れした１個の酸素原子によって中断されていてもよい
アミン又は炭素数２乃至６のアルカノールアミン又はシ
クロヘキシルアミンを表す。）At least 1 counter ion represented by the formula (1) is used.
The anionic dye containing a compound is obtained by adding an amine represented by the following formula (2) to a reaction solution of a dye synthesized by an ordinary method or an aqueous solution in which crystals of an anion dye separated by acid precipitation or salting out are dissolved in water. Can be obtained by adding 1 mol or more to 1 mol of the dye and reacting it in an acidic to neutral manner. [B] (2) (In the formula (2), B is an amine which may be interrupted by a linear or branched oxygen atom having 1 to 18 carbon atoms or an alkanolamine having 2 to 6 carbon atoms. Or represents cyclohexylamine.)
【０００７】式（２）で表されるアミンの具体例として
は、例えば、メチルアミン、エチルアミン、ｎ−プロピ
ルアミン、ｉｓｏ−プロピルアミン、ブチルアミン、ペ
ンチルアミン、ヘキシルアミン、シクロヘキシルアミ
ン、ヘプシルオクチルアミン、デシルアミン、ラウリル
アミン、ミリスチルアミン、パルミチルアミン、セチル
アミン、エチルヘキシルオキシプロピルアミン、ラウロ
キシプロピルアミン、カプロキシプロピルアミン、オク
タデシルアミン、ジエタノールアミン、トリエタノール
アミン、イソプロパノールアミン、シクロヘキシルアミ
ン等が挙げられるがこの限りでない。又、使用するアミ
ンは１種又は２種以上の混合物であってもよい。Specific examples of the amine represented by the formula (2) include, for example, methylamine, ethylamine, n-propylamine, iso-propylamine, butylamine, pentylamine, hexylamine, cyclohexylamine, heptyloctylamine. , Decylamine, laurylamine, myristylamine, palmitylamine, cetylamine, ethylhexyloxypropylamine, lauroxypropylamine, caproxypropylamine, octadecylamine, diethanolamine, triethanolamine, isopropanolamine, cyclohexylamine and the like. Not limited. The amine used may be one kind or a mixture of two or more kinds.
【０００８】塩を形成するためのアニオン染料として
は、カラーインデックス（Society ofDyers and Colour
ist 発行）に記載されているアゾ染料、アゾ金属錯塩染
料アンスラキノン染料、含金属フタロシアニン染料、オ
キサジン染料、トリフェニル−メタン染料、キサンチン
染料、インジゴイド染料が挙げられるが、耐熱性、耐光
性の点から、アゾ染料、アゾ金属錯塩染料、アンスラキ
ノン染料、銅、亜鉛、ニッケル、等を含む金属含有フタ
ロシアニン染料、オキサジン染料が好ましい。As an anionic dye for forming a salt, a color index (Society of Dyers and Color
Issu), azo metal complex salt dyes, anthraquinone dyes, metal-containing phthalocyanine dyes, oxazine dyes, triphenyl-methane dyes, xanthine dyes, indigoid dyes, but they are heat-resistant and light-resistant. Therefore, azo dyes, azo metal complex salt dyes, anthraquinone dyes, metal-containing phthalocyanine dyes containing copper, zinc, nickel and the like, and oxazine dyes are preferable.
【０００９】又、必要により含金属フタロシアニン染料
と組み合わせて使用する黄色染料の例としては、対イオ
ンがＮａ+ の状態で、純水に溶解し、純水をリファレン
スとして吸光度を測定した場合、最大吸収波長に於ける
光学密度を３．０に合わせた透過率が４００ｎｍ、４２
０ｎｍ、４５０ｎｍ、５００ｎｍ、５００〜７００ｎｍ
で各々１．０％以下、１．０％以下、１０％以下、５０
％以下、９０％以下であるアゾ染料、アゾ金属錯塩染料
が好ましい。Further, as an example of a yellow dye used in combination with a metal-containing phthalocyanine dye, if necessary, when the counter ion is Na + , it is dissolved in pure water and the absorbance is measured using pure water as a reference, the maximum The optical density at the absorption wavelength is adjusted to 3.0, the transmittance is 400 nm, 42
0 nm, 450 nm, 500 nm, 500-700 nm
1.0% or less, 1.0% or less, 10% or less, 50
% Or 90% or less, and azo dyes and azo metal complex salt dyes are preferable.
【００１０】又、必要により含金属フタロロシアニン染
料と組み合わせて使用するニトロ化合物としては、４，
４′−ジニトロスチルベン、２，２′−ジスルホン酸の
式（１）で示される対イオンで造塩された化合物ニトロ
フェノール類、ニトロナフタレン類、ニトロアンスラキ
ノン類が挙げられるがこの限りではない。好ましいニト
ロ化合物としては、４，４′−ジニトロスチルベン、
２，２′−ジスルホン酸の式（１）で示される対イオン
て造塩された化合物２，４−ジニトロフェノール、メタ
ニトロフェノール、２−ニトロナフタレンが挙げられ
る。If necessary, the nitro compound used in combination with the metal-containing phthalocyanine dye is 4,
Examples thereof include, but are not limited to, 4'-dinitrostilbene and 2,2'-disulfonic acid salt-ionized compounds nitrophenols, nitronaphthalenes, and nitroanthraquinones. Preferred nitro compounds are 4,4'-dinitrostilbene,
Examples include the salt-forming compound 2,4-dinitrophenol, metanitrophenol, and 2-nitronaphthalene of the counterion represented by the formula (1) of 2,2′-disulfonic acid.
【００１１】熱硬化性樹脂としては、ノボラック、ポリ
イミド、エポキシ、ポリエステル、ユリア、メラミン樹
脂等が使用されうる。殊に好ましい樹脂としては、アル
カリ性水溶液に溶解容易なノボラック、ポリイミド前駆
体が挙げられる。光硬化樹脂としては、感光基がポリマ
ーに結合しており光により橋かけするもの、感光基がポ
リマーに結合していないが、重合開始剤、感光剤、増感
剤を添加し橋かけするもの等が使用しうる好ましい態様
としてはエチレン性不飽和二重結合をすくなくとも１つ
以上有する光重合性化合物と皮膜形成性高分子結合剤と
光重合開始剤とからなる樹脂組成物として使用する。As the thermosetting resin, novolac, polyimide, epoxy, polyester, urea, melamine resin and the like can be used. Particularly preferred resins include novolaks and polyimide precursors that are easily dissolved in an alkaline aqueous solution. As the photo-curing resin, one having a photosensitive group bonded to a polymer to be cross-linked by light, and one having no photosensitive group bonded to the polymer but having a polymerization initiator, a photosensitizer, and a sensitizer added thereto to be cross-linked And the like are preferably used as a resin composition comprising a photopolymerizable compound having at least one ethylenically unsaturated double bond, a film-forming polymer binder and a photopolymerization initiator.
【００１２】ここでエチレン性不飽和二重結合を少くと
も１個以上有する光重合性化合物とは、光の作用により
重合しうるもので、かつエチレン性不飽和二重結合を有
する化合物であり、例えば、光架橋又は光重合可能な、
モノマー、オリゴマー、プレポリマーとして、１価又は
多価アルコールのアクリル酸又はメタアクリル酸のエス
テル類、多価アルコールと一塩基酸又は多塩基酸を縮合
して得られるポリエステルプレポリマーに、（メタ）ア
クリル酸を反応して得られるポリエステル（メタ）アク
リレート、ポリオール基と２個のイソシアネート基をも
つ化合物を反応させた後（メタ）アクリル酸を反応させ
て得られるポリウレタン（メタ）アクリレート、エポキ
シ樹脂と（メタ）アクリル酸を反応させて得られるエポ
キシ（メタ）アクリレート、The photopolymerizable compound having at least one ethylenically unsaturated double bond is a compound which can be polymerized by the action of light and has an ethylenically unsaturated double bond. For example, photocrosslinkable or photopolymerizable,
As monomers, oligomers and prepolymers, acrylic acid or methacrylic acid esters of monohydric or polyhydric alcohols, polyester prepolymers obtained by condensing polyhydric alcohols with monobasic acids or polybasic acids, (meth) Polyester (meth) acrylate obtained by reacting acrylic acid, polyurethane (meth) acrylate obtained by reacting a compound having two isocyanate groups with a polyol group, and (meth) acrylate obtained by reacting (meth) acrylic acid, and an epoxy resin Epoxy (meth) acrylate obtained by reacting (meth) acrylic acid,
【００１３】[0013]
【化１】 [Chemical 1]
【００１４】を主鎖に有するポリエステル、シンナミリ
デン基を側鎖又は末端に有するポリマーなどが挙げられ
る。皮膜形成高分子化合物としては、前記の光重合化合
物に相溶性のある有機高分子重合体が使用できる。その
具体例としてはポリメタアクリル酸エステル又はその部
分加水分解物、スチレンと無水マレイン酸の共重合体又
はそのハーフエステル、アクリル酸、アクリル酸エステ
ル、メタアクリル酸アクリルニトリルなどの共重合可能
なモノマー群から選ばれたガラス転移点３５℃以上であ
る共重合体などが挙げられるが、これらのうちアルカリ
性水溶液での現像を可能にするカルボキシル基等の酸性
基をもつものが特に好ましい。皮膜形成高分子化合物の
使用量は光重合性化合物に対し、重量比で１〜４倍量で
使用するのが好ましい。重合開始剤としては、チオキサ
ントン系化合物、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）−ブタノン等が使用
できる。Examples thereof include polyesters having a main chain, and polymers having a cinnamylidene group on the side chain or terminal. As the film-forming polymer compound, an organic polymer polymer compatible with the above photopolymerizable compound can be used. Specific examples thereof include polymethacrylic acid ester or a partial hydrolyzate thereof, a copolymer of styrene and maleic anhydride or a half ester thereof, acrylic acid, an acrylic acid ester, a copolymerizable monomer such as methacrylic acid acrylonitrile. Examples thereof include copolymers having a glass transition point of 35 ° C. or higher selected from the group, and among these, those having an acidic group such as a carboxyl group that enables development with an alkaline aqueous solution are particularly preferable. The amount of the film-forming polymer compound used is preferably 1 to 4 times the weight of the photopolymerizable compound. As the polymerization initiator, thioxanthone compounds, 2-benzyl-2-dimethylamino-
1- (4-morpholinophenyl) -butanone and the like can be used.
【００１５】熱硬化性樹脂又は光硬化性樹脂の溶液を調
製するための溶媒としては、メチルセロソルブ、エチル
セロソルブ、エチルセロソルブアセテート、イソプロピ
ルセロソルブ、イソプロピ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、ジプロピレン
グリコールモノメチルエーテル、ジグライム、Ｎ−メチ
ルピロリドン、ジメチルホルムアミド等が挙げられるが
この限りではない。これらの溶媒は固型分に対して重量
比で１．５〜１５倍量使用するのが好ましい。染料の使
用量としては、熱硬化性樹脂に対して３０〜１５０重量
％好ましくは、４０〜１２０重量％である。又、光硬化
性樹脂の場合は、光重合性化合物と皮膜形成性高分子結
合剤との総量に対し、１０〜６０重量％、好ましくは２
０〜５０重量％の範囲内で使用するのが好ましい。Solvents for preparing a thermosetting resin or photocurable resin solution include methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, isopropyl cellosolve, isopropyl cellosolve acetate, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether. , Diglyme, N-methylpyrrolidone, dimethylformamide and the like, but not limited thereto. It is preferable to use these solvents in an amount of 1.5 to 15 times by weight relative to the solid content. The amount of the dye used is 30 to 150% by weight, preferably 40 to 120% by weight, based on the thermosetting resin. Further, in the case of a photocurable resin, it is 10 to 60% by weight, preferably 2 to the total amount of the photopolymerizable compound and the film-forming polymer binder.
It is preferably used in the range of 0 to 50% by weight.
【００１６】本発明の染料を用いたカラーフィルター
は、例えば次のようにして製造される。熱硬化性樹脂を
使用する場合は、例えば、ノボラック樹脂等の熱硬化性
樹脂と、光活性溶解度抑制剤（置換ナフトキノンジアジ
ド化合物：例えば２，３，４−トリヒドロキシベンゾフ
ェノンの１，２−ナフトキノンジアジド−５−スルホニ
ルトリエステル等）と、染料を含む溶液を前記溶媒を用
いて調製し、洗滌した基板（ガラス板、又はＣＣＤのウ
エハプロセス済みのウエハ等）にスピンコーター等を用
いて塗布し、プリベーク後、塗膜にマスクを当て光照射
し、次にアルカリ剤を含む現像液にて処理し、未硬化部
を洗い流す。十分に水洗を行い乾燥してカラーフィルタ
ーをえるという方法で製造される。A color filter using the dye of the present invention is manufactured, for example, as follows. When a thermosetting resin is used, for example, a thermosetting resin such as a novolac resin and a photoactive solubility suppressor (substituted naphthoquinonediazide compound: 1,2-naphthoquinonediazide of 2,3,4-trihydroxybenzophenone, for example) are used. -5-sulfonyltriester, etc.) and a solution containing a dye are prepared using the solvent, and are applied to a washed substrate (glass plate, CCD wafer processed wafer, etc.) using a spin coater or the like, After prebaking, a mask is applied to the coating film to irradiate it with light, and then the coating film is treated with a developing solution containing an alkaline agent to wash away the uncured portion. It is manufactured by a method of thoroughly washing with water and drying to obtain a color filter.
【００１７】又、熱硬化性樹脂としてポリイミド前駆体
を使用する場合は、ポリイミド前駆体と染料を含む液を
前記同様に基板に塗付、プリベーク後、ポジタイプのフ
ォトレジストをスピンコーター等で塗付し、プリベーク
後、塗膜にマスクを当て光照射し、次にアルカリ剤を含
む現像液にて処理した後、フォトレジストを剥離する。
その後、ポストベークを行いカラーフィルターを得る。
一方、光硬化性樹脂の場合には、光重合性化合物と皮膜
形成性高分子結合剤、光重合開始剤と染料を含む溶液を
前記溶媒を用いて調製し基板にスピンコーター等で塗
付、プリベーク後マクスを当て光照射し、次に光照射さ
れた塗膜を、アルカリ剤を含む現像液にて処理し、未硬
化部を洗い流す。十分に水洗を行い乾燥してカラーフィ
ルターを得る。これらの方法において乾燥時の膜厚とし
ては１．５μｍ以下が好ましい。When a polyimide precursor is used as the thermosetting resin, a liquid containing the polyimide precursor and the dye is applied to the substrate in the same manner as above, prebaked, and then a positive type photoresist is applied by a spin coater or the like. Then, after the pre-baking, a mask is applied to the coating film to irradiate it with light, and then the coating film is treated with a developer containing an alkali agent, and then the photoresist is peeled off.
Then, post baking is performed to obtain a color filter.
On the other hand, in the case of a photocurable resin, a solution containing a photopolymerizable compound and a film-forming polymer binder, a photopolymerization initiator and a dye is prepared using the solvent and coated on a substrate with a spin coater or the like. After pre-baking, a mask is applied and light is irradiated, and then the light-irradiated coating film is treated with a developer containing an alkaline agent to wash away the uncured portion. Thoroughly wash with water and dry to obtain a color filter. In these methods, the film thickness when dried is preferably 1.5 μm or less.
【００１８】本発明のカラーフィルターにおいては使用
する染料にＮａ、Ｋ等の金属を含まぬことから金属イオ
ンの液晶等への溶出によるトラブルを防止することが出
来る。又、本発明のカラーフィルターにおいて金属フタ
ロシアニンと黄色染料又は芳香族ニトロ化合物とから得
られるグリーンの膜はそれらの染料又は化合物による着
色濃度がたかいので染色法によってグリーンの膜を作成
したときのようにグリーンの膜だけを特に厚膜にする必
要がないという利点がある。更に本発明のカラーフィル
ターは耐熱性、耐光性にすぐれるという特徴がある。In the color filter of the present invention, since the dye used does not contain metals such as Na and K, troubles due to elution of metal ions into liquid crystal and the like can be prevented. Further, in the color filter of the present invention, the green film obtained from the metal phthalocyanine and the yellow dye or the aromatic nitro compound has a high coloring density due to those dyes or compounds. There is an advantage that only the green film need not be particularly thick. Further, the color filter of the present invention is characterized by excellent heat resistance and light resistance.
【００１９】[0019]
【実施例】実施例によって、本発明を更に詳細に説明す
る。実施例に於いて、部は重量部を示す。The present invention will be described in more detail by way of examples. In the examples, "part" means "part by weight".
【００２０】実施例１ ポリイミド前駆体溶液セミコファイン９１０（東レ社
製、商品名）７部、エチルセロソルブ１０部、式（２）
で表される染料０．７部、式（３）で表される染料１．
０部シランカップリング剤ＫＢＭ５７３が、０．０３部
から成る着色ポリイミド樹脂溶液をガラス基板上にスピ
ンコート法によりコーティングし着色被膜を形成し、次
いで、そのガラス基板をオーブンで８０℃、３０分加熱
した後、１５０℃、２０分プリベークした。これに、ポ
ジタイプのフォトレジストであるマイクロポジット１４
００−２７（シープレイ・ファーイースト社製、商品
名）を用いてスピンコーターでコーティングし１１０℃
で３分間熱処理して紫外線露光後、アルカリ現像液ＭＦ
−３１２（シープレイファスト社製）で現像した後、セ
ロソルブアセテートにデイッピングしてフォトレジスト
を剥離後、２００℃で３０分加熱し緑色の着色パターン
を得た。この着色パターンの最大透過率波長５３４ｎｍ
に於ける透過率は７８％であり、膜厚は１．０μｍであ
った。Example 1 7 parts of polyimide precursor solution Semicofine 910 (trade name, manufactured by Toray Industries, Inc.), 10 parts of ethyl cellosolve, formula (2)
0.7 part of the dye represented by the formula 1, and the dye represented by the formula (3) 1.
0 part of the silane coupling agent KBM573 is coated with 0.03 parts of a colored polyimide resin solution on a glass substrate by spin coating to form a colored film, and then the glass substrate is heated in an oven at 80 ° C. for 30 minutes. After that, it was prebaked at 150 ° C. for 20 minutes. In addition to this, a positive type micro resist 14
00-27 (manufactured by Seaplay Far East Co., Ltd., trade name) is coated with a spin coater at 110 ° C.
Heat treatment for 3 minutes at 37 ° C and after UV exposure, use alkaline developer MF
After development with -312 (manufactured by Seaplay Fast Co., Ltd.), the photoresist was peeled by dipping it in cellosolve acetate and then heated at 200 ° C. for 30 minutes to obtain a green colored pattern. The maximum transmittance wavelength of this colored pattern is 534 nm.
The transmittance was 78% and the film thickness was 1.0 μm.
【００２１】[0021]
【化２】 [Chemical 2]
【００２２】式（２）に於いて、Ｘ1 はＮＨ3 （Ｃ
Ｈ2 )3ＯＣＨ2 ＣＨ（Ｃ2 Ｈ5)（Ｃ4 Ｈ9 ）を表す。
又、Ｃｕ、Ｐｃは銅フタロシアニン骨格を示す。In the formula (2), X 1 is NH 3 (C
H 2) 3 OCH 2 CH ( C 2 H 5) represents a (C 4 H 9).
Cu and Pc represent a copper phthalocyanine skeleton.
【００２３】[0023]
【化３】 [Chemical 3]
【００２４】こうして得られた緑色のカラーフィルター
の耐光試験は次の様に行った。フィルターの表面をセロ
テープ（ニチバン社製、商品名）でおおい、酸素カット
の状態にした後、ＵＶカットフィルター（ＨＯＹＡ
（株）製１−４０）を介して、スガ試験機製 カーボン
アークフェドメーターにて１時間露光試験をしたとこ
ろ、最大透過率波長５３４ｎｍの透過率は、露光剤の７
８％が７７％になったにすぎず、極めて優れた耐光性で
あった。又、２５０℃、１時間のオーブン中での耐熱性
テストでも同様な優れた結果が得られた。式（２）で表
される染料は以下の様にして合成した。The light resistance test of the green color filter thus obtained was carried out as follows. After covering the surface of the filter with cellophane tape (product name, manufactured by Nichiban Co., Ltd.) and setting it in an oxygen cut state, a UV cut filter (HOYA
When the exposure test was carried out for 1 hour with a carbon arc fedometer manufactured by Suga Test Instruments Co., Ltd. through 1-40), the maximum transmittance wavelength of 534 nm was 7% of that of the exposure agent.
Only 8% was 77%, which was extremely excellent light resistance. Also, the same excellent result was obtained in a heat resistance test in an oven at 250 ° C. for 1 hour. The dye represented by the formula (2) was synthesized as follows.
【００２５】通常の方法で合成された式（４）の染料１
０．８部を純水３００部に溶解した溶液に、アミン（Ｎ
Ｈ2 （ＣＨ2)3 ＣＨ（Ｃ2 Ｈ5)（Ｃ4 Ｈ9)７．９部と塩
酸４．７部とからなる水溶液３００部を添加し、５０〜
６０℃で１時間攪拌後、固液分離し、得られた結晶を、
乾燥する事により得られる。Dye 1 of formula (4) synthesized by conventional methods
A solution of 0.8 parts dissolved in 300 parts of pure water was added with amine (N
H 2 (CH 2) 3 CH (C 2 H 5) (C 4 H 9) was added an aqueous solution 300 parts consisting of 7.9 parts of hydrochloric acid 4.7 parts, 50
After stirring at 60 ° C. for 1 hour, solid-liquid separation was performed, and the obtained crystals were
Obtained by drying.
【００２６】[0026]
【化４】 [Chemical 4]
【００２７】（式（４）に於いてＣｕ、Ｐｃは、銅フタ
ロシアニン骨格を表す。）又式（３）の染料は、式
（５）の染料５７．５部を純水に溶解した溶液に、アミ
ン（ＮＨ2 （ＣＨ2)3 ＣＨ（Ｃ2 Ｈ5)（Ｃ4 Ｈ9)１９．
６部と塩酸１１．７部を純水に溶解した溶液を添加し、
５０〜６０℃で１時間攪拌後、固液分離し、得られた結
晶を乾燥する事により得られる。(In the formula (4), Cu and Pc represent a copper phthalocyanine skeleton.) The dye of the formula (3) is a solution prepared by dissolving 57.5 parts of the dye of the formula (5) in pure water. , amine (NH 2 (CH 2) 3 CH (C 2 H 5) (C 4 H 9) 19.
Add a solution of 6 parts and 11.7 parts of hydrochloric acid in pure water,
After stirring for 1 hour at 50 to 60 ° C., solid-liquid separation is performed, and the obtained crystals are dried.
【００２８】[0028]
【化５】 [Chemical 5]
【００２９】比較例１ 実施例１に於いて、式（２）、（３）で表される染料の
代わりに式（４）で表される染料のみを使用する以外
は、実施例に準じて操作を行い、緑色のパターンを得
た。しかし、式（４）で表される染料は、ポリイミド前
駆体溶液７部とエチルセロソルブ１０部の溶液に対し、
０．３部しか溶けず、最大透過率波長５３０ｎｍに於け
る透過率は８９．５％であり、最大透過率波長より長波
長域に於ける最小透過率は、実施例１における値４．８
％に対し、１１．７％と高く、実施例１と同様な分光特
性を得るには、膜厚を実施例１の２倍以上にする必要が
あった。Comparative Example 1 According to Example 1, except that only the dye represented by the formula (4) is used in place of the dye represented by the formulas (2) and (3). The operation was performed to obtain a green pattern. However, the dye represented by the formula (4) is added to a solution of 7 parts of polyimide precursor solution and 10 parts of ethyl cellosolve,
Only 0.3 part is melted, the transmittance at the maximum transmittance wavelength of 530 nm is 89.5%, and the minimum transmittance in the wavelength region longer than the maximum transmittance wavelength is 4.8 in Example 1.
%, Which is as high as 11.7%, and in order to obtain the same spectral characteristics as in Example 1, the film thickness had to be twice or more that in Example 1.
【００３０】又、実施例１と同様な方法で耐光試験を行
ったところ、最大吸収波長５３４ｎｍに於ける透過率は
７８．８％となり、極めて大きな劣化状態となった。Further, when a light resistance test was conducted in the same manner as in Example 1, the transmittance at the maximum absorption wavelength of 534 nm was 78.8%, which was an extremely large deterioration state.
【００３１】実施例２ ポリイミド前駆体溶液セミコファイン９１０（東レ社製
商品名）７部、式（６）で表される染料０．８４部を
含むＮ−メチルピロリドン溶液５．６部、ジニトロフェ
ノール０．２５部から成る着色ポリイミド溶液をガラス
基板上にスピンコート法によりコーテイングし着色被膜
を形成し、次いで、そのガラス基板をオーブンで８０
℃、３０分加熱した後、１５０℃、２０分プリベーキン
グした。これに、ポジタイプのフォトレジストであるマ
イクロポジット１４００−２７（シープレイ・ファーイ
ースト社製 商品名）を用いてスピンコーターでコーテ
ィングし１１０℃で３分間熱処理して紫外線露光後、ア
ルカリ現像液ＭＦ−３１２で現像後セロソルブアセテー
トにディッピングしてフォトレジストを剥離し、２００
℃で３０分間加熱して緑色の着色パターンを得た。この
着色パターンの最大透過率波長５３３ｎｍに於ける透過
率は７８％であり、膜厚は１．０μｍであった。Example 2 7 parts of a polyimide precursor solution Semicofine 910 (trade name, manufactured by Toray Industries, Inc.), 5.6 parts of an N-methylpyrrolidone solution containing 0.84 part of the dye represented by the formula (6), and dinitrophenol. A colored polyimide solution consisting of 0.25 parts is coated on a glass substrate by a spin coating method to form a colored film, and then the glass substrate is heated in an oven at 80 ° C.
After heating at 30 ° C for 30 minutes, prebaking was performed at 150 ° C for 20 minutes. This is coated with a spin coater using Microposit 1400-27 (trade name, manufactured by Seaplay Far East Co., Ltd.), which is a positive type photoresist, and heat-treated at 110 ° C. for 3 minutes to be exposed to ultraviolet rays, and then alkali developer MF- After development at 312, the photoresist is peeled off by dipping in cellosolve acetate.
It was heated at 0 ° C. for 30 minutes to obtain a green colored pattern. The transmittance of this colored pattern at the maximum transmittance wavelength of 533 nm was 78%, and the film thickness was 1.0 μm.
【００３２】[0032]
【化６】 [Chemical 6]
【００３３】式（６）において、Ｘ2 は、オクタデシル
アンモニウムＮＨ3 （ＣＨ2)17ＣＨ3 を表わし、Ｃｕ．
Ｐｃは、銅フタロシアニン骨格を表す。こうして得られ
た緑色のカラーフィルターの耐光試験を実施例１と同様
に行ったところ、実施例１と同様に極めて優れた結果が
得られた。耐熱性についても同様であった。In the formula (6), X 2 represents octadecyl ammonium NH 3 (CH 2 ) 17 CH 3 , and Cu.
Pc represents a copper phthalocyanine skeleton. When the light resistance test of the green color filter thus obtained was conducted in the same manner as in Example 1, extremely excellent results were obtained as in Example 1. The same applies to heat resistance.
【００３４】式（６）で表した化合物は、以下の様にし
て合成した。通常の方法で合成された実施例１に於ける
式（４）の染料１０．８部を純水３００部に溶解した溶
液に、ドデシルアミンＮＨ2 （ＣＨ2)17ＣＨ3 １０部と
塩酸４．７部を純水３００部に溶解した溶液３００部を
添加し、５０〜６０℃で１時間攪拌後、固液分離し得ら
れた結晶を乾燥する事により得られる。The compound represented by the formula (6) was synthesized as follows. To a solution prepared by dissolving 10.8 parts of the dye of the formula (4) in Example 1 synthesized by a usual method in 300 parts of pure water was added 10 parts of dodecylamine NH 2 (CH 2 ) 17 CH 3 and 4 parts of hydrochloric acid. It can be obtained by adding 300 parts of a solution prepared by dissolving 0.7 part in 300 parts of pure water, stirring the mixture at 50 to 60 ° C. for 1 hour, and performing solid-liquid separation to dry the obtained crystals.
【００３５】実施例３ ポリイミド前駆体溶液セミコファイン９１０（東レ社製
商品名）７部、メチルセロソルブ１２部、式（７）で
表される染料０．６６部、式（８）で表される染料０．
９部から成る着色ポリイミド樹脂溶液をガラス基板上に
スピンコート法によりコーティングし着色被膜を形成
し、次いでそのガラス基板をオーブンで８０℃、３０分
加熱した後に１５０℃、２０分プリベークした。Example 3 7 parts of polyimide precursor solution Semicofine 910 (trade name, manufactured by Toray Industries, Inc.), 12 parts of methyl cellosolve, 0.66 parts of the dye represented by the formula (7), and represented by the formula (8). Dye 0.
A colored polyimide resin solution consisting of 9 parts was coated on a glass substrate by a spin coating method to form a colored film, and then the glass substrate was heated in an oven at 80 ° C. for 30 minutes and then prebaked at 150 ° C. for 20 minutes.
【００３６】これに、ポジタイプのフォトレジストであ
るマイクロポジット１４００−２７（シープレイ・ファ
ーイースト社製 商品名）を用いて、スピンコーターで
コーティングし１１０℃で３分間熱処理した紫外線露光
後、アルカリ現像液ＭＦ−３１２（シープレイファスト
社製）で現像した後、セロソルブアセテートにディッピ
ングして、フォトレジストを剥離後、２００℃で３０分
加熱し緑色の着色パターンを得た。この着色パターンの
最大透過率波長５４０ｎｍに於ける透過率は、８０％で
あり膜厚は０．９８μｍであった。A positive type photoresist, Microposit 1400-27 (trade name, manufactured by Seaplay Far East Co., Ltd.) was coated on this with a spin coater and heat-treated at 110 ° C. for 3 minutes. After development with the liquid MF-312 (manufactured by Seaplay Fast), the photoresist was peeled off by dipping in cellosolve acetate and then heated at 200 ° C. for 30 minutes to obtain a green colored pattern. The transmittance of this colored pattern at the maximum transmittance wavelength of 540 nm was 80%, and the film thickness was 0.98 μm.
【００３７】[0037]
【化７】 [Chemical 7]
【００３８】式（７）に於いてＸ3 は、ＮＨ3 ＣＨ2 Ｃ
Ｈ2 ＣＨ2 ＣＨ3 を表しＺｎ．Ｐｃは亜鉛フタロシアニ
ン骨格を表す。In the formula (7), X 3 is NH 3 CH 2 C
H 2 CH 2 CH 3 represents Zn. Pc represents a zinc phthalocyanine skeleton.
【００３９】[0039]
【化８】 [Chemical 8]
【００４０】こうして得られた緑色のカラーフィルター
の耐光試験を実施例１と同様な方法で行ったところ、最
大吸収波長５４０ｎｍの透過率は、露光前の８０％が７
８％になったに過ぎず極めて優れた結果が得られた。A light resistance test of the green color filter thus obtained was carried out in the same manner as in Example 1, and the transmittance at the maximum absorption wavelength of 540 nm was 7% at 80% before exposure.
Very good results were obtained with only 8%.
【００４１】式（７）の染料は、通常の方法で合成され
た式（９）の染料１０部を水３００部に溶解した溶液
に、アミンＮＨ2 ＣＨ2 （ＣＨ2)2 ＣＨ3 ２．３部を塩
酸３．５部とからなる水溶液３００部を添加し５０〜６
０℃で１時間攪拌し、固液分離し得られた結晶を乾燥す
る事により得られる。式（８）の化合物は、通常の方法
で合成された式（１０）の染料より、アミンとの反応に
より同様に得られる。The dye of the formula (7) is prepared by dissolving 10 parts of the dye of the formula (9) synthesized by a usual method in 300 parts of water, and adding the amine NH 2 CH 2 (CH 2 ) 2 CH 3 2. Add 300 parts of an aqueous solution containing 3 parts of hydrochloric acid and 3.5 parts of 50 to 6
It can be obtained by stirring at 0 ° C. for 1 hour, solid-liquid separation, and drying the obtained crystal. The compound of formula (8) is similarly obtained from the dye of formula (10) synthesized by a conventional method by reaction with an amine.
【００４２】[0042]
【化９】 [Chemical 9]
【００４３】[0043]
【化１０】 [Chemical 10]
【００４４】実施例４ 実施例３に於いて、式（１１）のニトロ化合物を使用す
る以外は、実施例３と同様にして緑色のカラーフィルタ
ーを得た。最大透過率の波長５３９ｎｍに於ける透過率
は８０％であり、実施例１と同様な耐光性試験を行った
ところ、耐光テスト後の最大透過率波長５３９ｎｍに於
ける透過率は７６％と極めて優れた結果が得られた。Example 4 A green color filter was obtained in the same manner as in Example 3 except that the nitro compound of the formula (11) was used. The maximum transmittance at a wavelength of 539 nm was 80%, and the same light resistance test as in Example 1 was conducted. As a result, the maximum transmittance at a wavelength of 539 nm after the light resistance test was 76%, which was extremely high. Excellent results have been obtained.
【００４５】[0045]
【化１１】 [Chemical 11]
【００４６】（式（１１）に於いて、Ｘ4 はＮＨ（ＣＨ
2 ＣＨ2 ＯＨ)3を表す。）式（１１）のニトロ化合物
は、通常の方法でつくられた式（１２）のニトロ化合物
４．７部とトリエタノールアミン０．２部と塩酸０．２
部純水３００部から成る溶液を、７０℃で１０時間、ｐ
Ｈ７．２を保ちながら攪拌し得られる。(In the formula (11), X 4 is NH (CH
2 CH 2 OH) 3 . ) The nitro compound of formula (11) comprises 4.7 parts of the nitro compound of formula (12), 0.2 parts of triethanolamine and 0.2 parts of hydrochloric acid prepared by a conventional method.
Solution consisting of 300 parts of pure water at 70 ° C. for 10 hours, p
It can be obtained by stirring while maintaining H7.2.
【００４７】実施例５ ポジ型フォトレジストＨｕｎｔ２５６ Positive Photor
esist (Philips ＡHunt chemical Corporation)に実施
例１に於ける式（２）の染料６重量％、式（３）の染料
５重量％、並びにメタニトロフェノール２重量％を含む
着色樹脂液をガラス基板上にスピンコーターでコーティ
ングする事によって緑色の着色被膜を形成し、そのガラ
ス基板を、加熱したホットプレート上で、９５℃で５分
間乾燥させ、次に、所定パターンを有するマスクを介し
て面照度７．５ｍｗ／ｃｍ2 のＵＶ照射を４５秒間行っ
た後、現像液Ｈ−４２７（Philips Ａ Hunt chemicalCo
rporation)を用いて、１２０秒間の浸漬により行い純水
で４０秒間すすぎ、次いでホットプレートで１８０℃、
３分間加熱し、緑色のカラーフィルターを得た。Example 5 Positive Photoresist Hunt256 Positive Photor
A colored resin solution containing 6% by weight of the dye of the formula (2), 5% by weight of the dye of the formula (3) and 2% by weight of meta-nitrophenol in Example 1 was applied to esist (Philips AHunt chemical Corporation) on a glass substrate. A green colored film is formed by coating with a spin coater on the glass substrate, the glass substrate is dried on a heated hot plate at 95 ° C. for 5 minutes, and then the surface illuminance is 7 through a mask having a predetermined pattern. After UV irradiation of 0.5 mw / cm 2 for 45 seconds, the developing solution H-427 (Philips A Hunt chemical Co
rporation), dipping for 120 seconds, rinsing with pure water for 40 seconds, then 180 ° C on a hot plate,
After heating for 3 minutes, a green color filter was obtained.
【００４８】この様にして得た緑色のカラーフィルター
の最大透過率の波長５３９ｎｍに於ける透過率は８１％
であり、膜厚は１．１μｍであった。実施例１と同様な
方法で、耐光テストを行ったところ、耐光テスト後の最
大透過率波長５３９ｎｍに於ける透過率は７９％となり
極めて優れた耐光性が得られた。The maximum transmittance of the green color filter thus obtained has a transmittance of 81% at a wavelength of 539 nm.
And the film thickness was 1.1 μm. A light resistance test was conducted in the same manner as in Example 1. As a result, the transmittance at the maximum transmittance wavelength of 539 nm after the light resistance test was 79%, and extremely excellent light resistance was obtained.
【００４９】実施例６ ポリイミド前駆体溶液セミコファイン９１０（東レ社製
商品名）７部、Ｎ−メチルピロリドン１０部、式（１
２）で表される染料０．６部から成る着色ポリイミド樹
脂溶液をガラス基板上にスピンコート法によりコーティ
ングし着色被膜を形成し、次いで、そのガラス基板をオ
ーブンで８０℃、３０分加熱した後、１５０℃、２０分
プリベークした。これに、ポジタイプのフォトレジスト
であるマイクロポジット１４００−２７（シープレイ、
ファーイースト社製 商品名）を用いてスピンコーター
でコーティングし１１０℃で３分間熱処理して紫外線露
光後、アルカリ現像液ＭＦ−３１２（シープレイファス
ト社製）を用いて現像した後、セロソルブアセテートに
ディッピングしてフォトレジストを剥離し赤色の着色パ
ターンを得た。Example 6 Polyimide precursor solution Semicofine 910 (trade name, manufactured by Toray Industries, Inc.) 7 parts, N-methylpyrrolidone 10 parts, formula (1)
A colored polyimide resin solution consisting of 0.6 part of the dye represented by 2) is coated on a glass substrate by a spin coating method to form a colored film, and then the glass substrate is heated in an oven at 80 ° C. for 30 minutes. Prebaked at 150 ° C. for 20 minutes. In addition to this, a positive type photoresist, Microposit 1400-27 (Seaplay,
Far East Co., Ltd. product name) was coated with a spin coater, heat-treated at 110 ° C. for 3 minutes, exposed to ultraviolet light, and then developed with an alkaline developer MF-312 (manufactured by Seaplay Fast Co., Ltd.), and then converted to cellosolve acetate. The photoresist was peeled off by dipping to obtain a red colored pattern.
【００５０】[0050]
【化１２】 [Chemical formula 12]
【００５１】赤色着色部の分光透過率曲線を測定したと
ころ、４５０〜５５０ｎｍの領域に於ける透過率は１％
以下で透過率５０％を示す波長λT ５０は５９７ｎｍで
あった。膜厚は、０．６５μｍであり、好ましい薄膜が
得られた。実施例１に於ける方法と同一の方法により、
耐光、耐熱性のテストを行ったところ、最大吸収波長に
於ける低下率は、１％以下で優れた耐性を示した。When the spectral transmittance curve of the red colored portion was measured, the transmittance in the region of 450 to 550 nm was 1%.
The wavelength λ T 50 showing a transmittance of 50% below was 597 nm. The film thickness was 0.65 μm, and a preferable thin film was obtained. By the same method as in Example 1,
When the light resistance and heat resistance were tested, the decrease rate at the maximum absorption wavelength was 1% or less, and excellent resistance was exhibited.
【００５２】式（１２）の染料は、以下の様にして合成
した。通常の方法で合成された式（１３）の染料１６部
を含む水溶液５００部アミンＮＨ2 Ｃ14Ｈ29 ４．７
部、塩酸２．３部を含む水溶液２００部を添加し、５５
〜６５℃で１時間攪拌後、固液分離し得られた結晶を固
液分離する事により得られる。The dye of formula (12) was synthesized as follows. Aqueous solution containing 16 parts of dye of formula (13) synthesized by conventional methods 500 parts amine NH 2 C 14 H 29 4.7
Part, 200 parts of an aqueous solution containing 2.3 parts of hydrochloric acid were added, and
It can be obtained by solid-liquid separation of the crystals obtained by solid-liquid separation after stirring at ˜65 ° C. for 1 hour.
【００５３】[0053]
【化１３】 [Chemical 13]
【００５４】実施例７ ポジ型フォトレジストＨｕｎｔ２５６ Positive Photo
resist(Philips ＡHunt chemical Corporation)に、実
施例６に於ける式（１２）の染料９重量％を含む着色樹
脂液をガラス基板上にスピンコーターでコーティングす
る事によって赤色の着色被膜を形成し、そのガラス基板
を加熱したホットプレート上で９５℃５分間乾燥させ、
次に所定のパターンを有するマスクを介して、面照度
７．５ｍｗ／ｃｍ2 のＵＶ照射を４５秒行った。現像
は、Ｈ−４２７（Philips Ａ Huntchemical Corporati
on) を用いて１２０秒間の浸漬により行い、純水で４０
秒間すすぎ、次いでホットプレートで１８０℃、３分間
加熱し、実施例６と同様な赤色のカラーフィルターを得
た。この赤色のカラーフィルターの膜厚は０．６５μｍ
であり、耐光性、耐熱性共に、実施例６と同様に優れて
いた。Example 7 Positive Photoresist Hunt256 Positive Photo
A resist (Philips AHunt chemical Corporation) was coated with a colored resin solution containing 9% by weight of the dye of the formula (12) in Example 6 on a glass substrate by a spin coater to form a red colored film. Dry the glass substrate on a heated hot plate at 95 ° C for 5 minutes,
Next, UV irradiation with a surface illuminance of 7.5 mw / cm 2 was performed for 45 seconds through a mask having a predetermined pattern. Developed by H-427 (Philips A Huntchemical Corporati
on) and soak for 120 seconds in pure water.
Rinse for 2 seconds and then heat on a hot plate at 180 ° C. for 3 minutes to obtain a red color filter similar to that in Example 6. The thickness of this red color filter is 0.65 μm
Thus, both light resistance and heat resistance were excellent as in Example 6.
【００５５】実施例８ 実施例6 に於いて式（１２）で表わされる染料の代わり
に式（１４）で表される染料０．５部を使用する以外は
実施例６と同じ方法により、青色の着色パターンを得
た。Example 8 Blue color was obtained in the same manner as in Example 6 except that 0.5 part of the dye represented by the formula (14) was used in place of the dye represented by the formula (12). A colored pattern of
【００５６】[0056]
【化１４】 [Chemical 14]
【００５７】青色着色部の分光透過率曲線を測定したと
ころ、４５０ｎｍに於ける透過率は、７８％であり、５
４０ｎｍに於ける透過率は２％であった。膜厚は０．６
２μｍとなり、好ましい薄膜が得られた。実施例１に於
ける方法と同一の方法により、耐光、耐熱性のテストを
行ったところ、４５０ｎｍに於ける透過率は、７８％が
７６％になったにすぎず優れた耐性を示した。When the spectral transmittance curve of the blue colored portion was measured, the transmittance at 450 nm was 78%.
The transmittance at 40 nm was 2%. The film thickness is 0.6
The thickness was 2 μm, and a preferable thin film was obtained. When the light resistance and the heat resistance were tested by the same method as in Example 1, the transmittance at 450 nm was 78% at 76%, which was excellent resistance.
【００５８】式（１４）で表される染料は、式（１５）
の染料１１．６部を含む水溶液３００部に、イソプロパ
ノールアミン１．７部、塩酸２．４部を含む水溶液２０
０部を添加し、６０〜７０℃で、ｐＨ７．２を保ちなが
ら２時間攪拌後、固液分離し、固形分を乾燥し得られ
る。The dye represented by the formula (14) has the formula (15)
20 parts of an aqueous solution containing 1.7 parts of isopropanolamine and 2.4 parts of hydrochloric acid in 300 parts of an aqueous solution containing 11.6 parts of the dye
0 parts is added, and the mixture is stirred at 60 to 70 ° C. for 2 hours while maintaining pH 7.2, then solid-liquid separated, and the solid content is dried.
【００５９】[0059]
【化１５】 [Chemical 15]
【００６０】実施例９ 実施例７に於いて式（１２）で表される染料の代わりに
式（１６）の染料を用いる以外は、実施例７と同じ操作
を行い青色の着色パターンを得た。青色着色部の分光透
過率曲線を測定したところ、４５０ｎｍに於ける透過率
は、７７％であり、５４０ｎｍに於ける透過率は５％で
あった。膜厚は０．６５μｍであった。実施例１と同一
の方法により耐光、耐熱性のテストを行ったところ、４
５０ｎｍに於ける透過率は７７％が７６％になったにす
ぎず、優れた耐性を示した。Example 9 A blue colored pattern was obtained by performing the same operation as in Example 7 except that the dye of the formula (16) was used in place of the dye of the formula (12). .. When the spectral transmittance curve of the blue colored portion was measured, the transmittance at 450 nm was 77% and the transmittance at 540 nm was 5%. The film thickness was 0.65 μm. When a light resistance and heat resistance test was conducted in the same manner as in Example 1, it was 4
The transmittance at 50 nm was only 76% from 77%, indicating excellent resistance.
【００６１】[0061]
【化１６】 [Chemical 16]
【００６２】式（１６）の染料は、式（１７）の染料１
３．８部を含む４００部の水溶液に、ｎ−プロピルアミ
ン１．３部と塩酸２．４部を含む水溶液２００部を添加
し、５５〜６５℃で２時間攪拌後、固液分離し得られ
る。The dye of formula (16) is the dye 1 of formula (17)
200 parts of an aqueous solution containing 1.3 parts of n-propylamine and 2.4 parts of hydrochloric acid were added to 400 parts of an aqueous solution containing 3.8 parts, and the mixture was stirred at 55 to 65 ° C. for 2 hours, and then solid-liquid separation was possible. Be done.
【００６３】[0063]
【化１７】 [Chemical 17]
【００６４】実施例１０ アーコケミカル製 ＳＭＡ−２６２５、（スチレンマレ
イン酸共重合ハーフエステル体）１０ｇ、ジペンタエリ
スリトール、ヘキサアクリレート５ｇ、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）−ブタノン０．３ｇ、２，４−ジエチルチオキサン
トン０．２ｇ、エチルセロソルブアセテート３３ｇから
なる溶液に、式（１８）で表される染料６．５ｇを溶解
した溶液をガラス基板上にスピンコート法によりコーテ
ィングし着色被膜を形成し、１００℃で５分間乾燥し
た。得られた塗膜上に１０％ポリビニルアルコール水溶
液をスピンコーターにて塗布し、１００℃で５分間乾燥
した。この様にして得られた塗膜を、所定のパターンを
有するマスクを介して面照度７．５ｍｗ／ｃｍ2 のＵＶ
照射を２０秒間行った後、１００℃で１５分間プリベイ
クした。その後、現像液である１％の炭酸ナトリウム水
溶液に１分間浸漬後、純水で４０秒間すすぎ黒色のカラ
ーフィルターを得た。この様にして得た黒色のカラーフ
ィルターの最大透過率は０．１％であり、ブラックマス
ク用の優れたフイルターが得られた。Example 10 SMA-2625 manufactured by Arco Chemical Co., Ltd. (styrene maleic acid copolymerized half ester body) 10 g, dipentaerythritol, hexaacrylate 5 g, 2-benzyl-
5. A dye consisting of 2-dimethylamino-1- (4-morpholinophenyl) -butanone (0.3 g), 2,4-diethylthioxanthone (0.2 g) and ethyl cellosolve acetate (33 g). A solution in which 5 g was dissolved was coated on a glass substrate by a spin coating method to form a colored film and dried at 100 ° C. for 5 minutes. A 10% polyvinyl alcohol aqueous solution was applied onto the obtained coating film by a spin coater, and dried at 100 ° C. for 5 minutes. The coating film thus obtained was subjected to UV with a surface illuminance of 7.5 mw / cm 2 through a mask having a predetermined pattern.
After irradiation for 20 seconds, prebaking was performed at 100 ° C. for 15 minutes. After that, it was immersed in a 1% aqueous solution of sodium carbonate as a developing solution for 1 minute and then rinsed with pure water for 40 seconds to obtain a black color filter. The maximum transmittance of the black color filter thus obtained was 0.1%, and an excellent filter for a black mask was obtained.
【００６５】[0065]
【化１８】 [Chemical 18]
【００６６】式（１８）の染料は以下の様にして合成し
た。通常の方法で合成された式（１９）の染料１．１部
を含む水溶液５００部に、アミンＮＨ2 Ｃ14Ｈ29 ４．
７部、塩酸２．３部を含む水溶液２００部を添加し、５
５〜６５℃で１時間攪拌後、得られた結晶を固液分離す
る事により得られる。The dye of formula (18) was synthesized as follows. The amine NH 2 C 14 H 29 was added to 500 parts of an aqueous solution containing 1.1 parts of the dye of the formula (19) synthesized by a usual method.
Add 200 parts of an aqueous solution containing 7 parts and 2.3 parts of hydrochloric acid, and add 5 parts.
After stirring at 5 to 65 ° C for 1 hour, the obtained crystals are obtained by solid-liquid separation.
【００６７】[0067]
【化１９】 [Chemical 19]
【００６８】[0068]
【発明の効果】熱硬化性樹脂溶液、又は光硬化性樹脂溶
液に染料を溶解した着色樹脂溶液から、つくられるカラ
ーフィルターが薄膜であり、かつ、耐熱、耐光性に優れ
ているものが得られる。EFFECTS OF THE INVENTION A color filter produced from a thermosetting resin solution or a colored resin solution obtained by dissolving a dye in a photocurable resin solution has a thin film and is excellent in heat resistance and light resistance. ..
Claims (2)
（１）式で示される対イオンで造塩された染料で着色さ
れてなるカラーフィルター。 〔Ａ〕+ （１） （式（１）に於いて、Ａは１個の酸素原子によって中断
されていてもよい直鎖又は分枝した炭素数１乃至１８の
アルキルアンモニウム、炭素数２乃至６のアルカノール
アンモニウム又はシクロヘキシルアンモニウムを表
す。）1. A color filter in which a thermosetting resin or a photocurable resin is colored with a dye salted with a counter ion represented by the following formula (1). [A] + (1) (In the formula (1), A is a linear or branched alkylammonium having 1 to 18 carbon atoms, which may be interrupted by one oxygen atom, and 2 to 6 carbon atoms. Represents alkanol ammonium or cyclohexyl ammonium).
に記載の式（１）で示される対イオンで造塩された含金
属フタロシアニン染料、黄色染料及び／又は芳香族ニト
ロ化合物で着色されてなるカラーフィルター。2. A thermosetting resin or a photocurable resin as claimed in claim 1.
A color filter, which is colored with a metal-containing phthalocyanine dye, a yellow dye and / or an aromatic nitro compound, which are salted with a counter ion represented by the formula (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16162892A JPH05333207A (en) | 1992-05-29 | 1992-05-29 | Color filter |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16162892A JPH05333207A (en) | 1992-05-29 | 1992-05-29 | Color filter |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05333207A true JPH05333207A (en) | 1993-12-17 |
Family
ID=15738802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16162892A Pending JPH05333207A (en) | 1992-05-29 | 1992-05-29 | Color filter |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05333207A (en) |
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