JP4373520B2 - Manufacturing method of color filter - Google Patents

Description

【００５１】
上に示した化学試薬を反応器に入れる。その混合物を窒素雰囲気下に高温で攪拌して反応を行わせる。エステル化および減圧で脱水の後、重合を停止する。得られた樹脂の分析結果は下記のようである。
【００５２】
不揮発性成分（１５０℃、１時間、重量％） ７５．４
酸価（ｍｇＫＯＨ／ｇ、固体） ４８．７
粘度（２５℃、ｃｐｓ） ４５．２
【００５３】
例２−低酸価のポリエステル樹脂を含有する電着塗料の製造
低酸価ポリエステル樹脂の成分の種類と量は、下記のとおりである。
【００５４】
成分 Ａ−１ Ａ−２ Ａ−３
アニオンポリエステル樹脂 ９５．０ ９５．０ ９５．０
メラミン樹脂
（Ｎｉｋａｒａｋｋｕ^TM ＭＸ−４０） ８．０ ８．０ ８．０
２−エトキシエタノールブチルエーテル ２５．０ ２５．０ ２５．０
２−エトキシエタノールエチルエーテル ５．０ ５．０ ５．０
ｎ−ブタノール １８．０ １８．０ １８．０
トリエチルアミン ２．５ ２．５ ２．５
脱イオン水 ８１３．５ ８１３．５ ８１３．５
フタロシアニンブルー（ＳＲ−１５００） ５．０ − −
フタロシアニングリーン（ＳＡＸ） − ５．０ −
アゾレーキ顔料（ＣＡＲＭＩＮＥ ＦＢ） − − ５．０
合計 １０００ １０００ １０００
【００５５】
低酸価ポリエステル樹脂を含有する電着塗料を調製するため次の工程を使用する。
１）上記に示した量のアニオンポリエステル樹脂、メラミン樹脂（Ｎｉｋａｒａｋｋｕ^TM ＭＸ−４０）、２−エトキシエタノールブチルエーテル、２−エトキシエタノールエチルエーテル、ｎ−ブタノールおよびトリエチルアミンを秤量し、それらの試薬を一つの容器に入れ、攪拌して混合する。
【００５６】
２）上記に示した量の顔料を秤量し、それらを前記の混合物に添加し、攪拌して混合する。
３）ミルにより前記の混合物を磨砕分散する。使用する磨砕用ビーズ球は０．８〜１．２μｍの平均粒径を有する。
４）攪拌しながら脱イオン水を加えて前記の混合物を乳化させる。そして
５）その混合物を５μｍのフィルターで濾過する。
【００５７】
例 ３
２．２μｍの厚みの米国特許第５，６４５，９７０号明細書に開示されている弱塩基性現像液に相当するポジ型フォトレジストを導電性透明ガラス基板上に形成した。その基板の厚みは０．７ｍｍであり、予め配置されたブラックマトリックスを有していた。僅かに三分の一の光透過面積を有するフォトマスクを注意深く動かすことにより使用して、それぞれ２５０、１５０および５０ｍＪ／ｃｍ² のエネルギー露光（１００％、 ６０％および２０％）を行い、異なる初期準位の三つの区域を形成した。
【００５８】
０．５％Ｎａ₂ ＳｉＯ₃ を含む現像液を使用して、２５０ｍＪ／ｃｍ² の初期の露光区域（即ち、１００％初期露光区域）を現像して除いた。次に、赤い顔料を含む熱硬化性樹脂をその導電性基板の露出表面の上に電着した。電着工程は、２５℃において５０Ｖの電圧で２０秒間行われた。電着工程が完了した後、基板を脱イオン水で洗浄し、９０℃で１０分間乾燥した。次に、１００ｍＪ／ｃｍ² の増分露光エネルギーを受けるように、フォトレジスト全体を光源で露光した。これは第２区域（初めに１５０ｍＪ／ｃｍ² 、即ち６０％初期露光エネルギー）および第３区域（初めに５０ｍＪ／ｃｍ² 、即ち１０％初期露光エネルギー）において蓄積露光エネルギーをもたらして、それぞれ２５０ｍＪ／ｃｍ² （完全露光）および１５０ｍＪ／ｃｍ² （完全露光の６０％）に上昇させた。次に、同様にして、同じ０．５％Ｎａ₂ ＳｉＯ₃ を含む現像液を使用して、前記の完全露光された区域を現像および除去した。これに続いて同様の条件下に緑の顔料を含む熱硬化性樹脂をその導電性基板の露出表面の上に電着し、次いで乾燥した。さらに１００ｍＪ／ｃｍ² の増分露光エネルギーを受けるように、フォトレジスト全体を再び光源で露光した。これは第３区域において蓄積露光エネルギーをもたらして、２５０ｍＪ／ｃｍ² （１００％露光）に上昇させた。同じ０．５％Ｎａ₂ ＳｉＯ₃ を含む現像液を使用してこの区域を現像および除去した。これに続いて再び同様な条件下で青の顔料を含む熱硬化性樹脂をその導電性基板の露出表面上に電着し、乾燥した。最後に、基板全体を１００ｍＪ／ｃｍ² のエネルギーで露光し、残存フォトレジストを０．５％Ｎａ₂ ＳｉＯ₃ 現像液で除去し、基板を２６０℃で１時間完全硬化させ、赤、緑、青、三画素の処理を完了した。
【００５９】
本発明の好ましい実施態様の上記の説明は、例示と説明の目的で提供されたものである。自明な修正ないし変更は上記の教示により可能である。これらの実施態様は本発明の原理とその実際的応用の最良の例による説明を提供するために選択して記述したので、それにより当業者は意図する特定の用途に適するように本発明をいろいろな実施態様において或いはいろいろな修正を加えて利用することができる。そのような修正及び変更のすべては、添付の特許請求の範囲を正当に、合法的に、かつ公正に権利を付与されている範囲に従って解釈されるならば、該特許請求の範囲によって規定された本発明の範囲内に入る。
【図面の簡単な説明】
【図１Ａ】（ａ）〜（ｆ）は、本発明に従ってカラーフィルターを製造する方法のいろいろな段階を示す略線図であり、その中で透明導電性基板にはブラックマトリックスが予め配置されている。
【図１Ｂ】（ａ）〜（ｆ）は、本発明に従ってカラーフィルターを製造する別の方法のいろいろな段階を示す略線図であり、その中で透明導電性基板にはブラックマトリックスが予め配置されている。
【図２】（ａ）〜（ｆ）は、本発明に従ってカラーフィルターを製造する他の方法のいろいろな段階を示す略線図であり、その中で透明導電性基板にはブラックマトリックスは配置されていない。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a color filter using a colored electrodeposition paint containing a low acid value anion electrodeposition resin. The method includes: applying a positive photoresist layer on a transparent conductive substrate; exposing the substrate under a photomask to form areas of initial levels having different exposure energies; Exposing each area in a manner that increases energy so that sufficient energy is sequentially achieved on all areas of the substrate to fully expose the photoresist over the corresponding area, each area being developed identically A step of developing using a liquid to expose a conductive substrate in a corresponding area, and a colored electrodeposition paint containing a low acid value anionic electrodeposition resin is electrodeposited in the area to form a pixel of a desired color Finishing the arrangement and fully exposing the substrate. The low acid value anion electrodeposition resin used in the present invention has an acid value of 70 mgKOH / g or less.
[0002]
The method of the present invention has an advantage that the degree of freedom of the pattern shape is high and the manufacturing method (operation) tolerance is wide. Furthermore, it is possible to produce a color filter with a large surface area and to obtain a very high yield of the product.
[0003]
[Prior art]
Flat panel displays (FPDs, flat display devices) are optoelectronic industry products that combine semiconductor, photology, and chromatics technologies. The tendency for FPDs to gradually replace traditional cathode ray tubes (CRT, CRT) is becoming increasingly prominent. Among various flat panel displays, liquid crystal displays (LCDs) have been considered a step forward because they are lightweight, thin and can be made into full color displays. A color filter is a key element to make an image bright and lively.
[0004]
The color filter includes three main components. That is, a black matrix, a color filter layer, and a protective film. The manufacturing method of the color filter currently in practical use is
(1) dyeing process,
(2) Etching process,
(3) Pigment dispersion step,
(4) electrodeposition process, and
(5) Printing process
There is.
[0005]
In dyeing and etching methods, dyes are mainly used as filter element materials. The advantages of using dyes as filter element materials are that they are of various types, have a uniform color density, high dyeability, high color purity, and high light transmittance. Suitable dyes are disclosed in U.S. Pat. Nos. 4,820,619 and 4,837,098. Since these dye materials are relatively inferior in light resistance and heat resistance, the dyeing method and the etching method have been almost replaced by the pigment dispersion method and electrodeposition method using a pigment as an element material of a filter. The pigment has excellent light resistance and heat resistance. By simply controlling the size of the pigment particles to less than 0.1 μm using a general-purpose pigment dispersion technique, the above two methods can achieve a color purity and light transmittance close to or substantially equal to those when using a dye. Can be achieved. For the above reasons, the pigment dispersion method and the electrodeposition method have become mainstream methods for producing color filters.
[0006]
In the pigment dispersion as disclosed in US Pat. Nos. 5,085,973 and 4,786,148 and JP-A-60-129739, a photosensitive resin uniformly dispersed in the pigment is used. And the use of photolithography techniques to achieve the goals of high resolution and pattern design flexibility. This method is currently the main manufacturing technology. However, (1) the application efficiency of the material is low (1% to 2%), (2) it is difficult to apply to a large area glass substrate, and (3) an expensive precision alignment machine is not used frequently. For example, the manufacturing cost by such a method will not be able to meet the trend toward larger LCDs and lower prices.
[0007]
An electrodeposition coating process such as that disclosed in US Pat. No. 4,812,387 can be used to electrodeposit a uniformly dispersed electrodeposition resin and pigment in water onto a patterned transparent electrode substrate. Use electrophoresis techniques. A filter layer having a uniform thickness and excellent smoothness can be obtained. The electrodeposition coating technology has its application limit. From the electrode design, the electrodeposition coating method can use only a substrate having a strip-shaped electrodeposition conductive film for implementation. Therefore, it is impossible to arrange the pixels freely.
[0008]
Among all color filter manufacturing methods, the printing method is the cheapest method. However, the printing method has a problem of poor positional precision, smoothness and reliability. Printing methods are not well accepted by the high quality electronic product manufacturing industry and are commonly used in the manufacture of low-end products.
[0009]
In order to address the above-mentioned problems without impairing the advantages of the pigment dispersion and electrodeposition coating methods, Nippon Oil Co., Ltd. has developed an electrodeposition method combining electrodeposition (ED) coating method and lithography method (litho). An ED) lithography method (ED-litho) was proposed. As disclosed in US Pat. Nos. 5,214,541 and 5,214,542 (the contents of these specifications are a part of the description of this application), Co., Ltd. first disclosed the electrodeposition lithography method. The method includes a step of forming regions of different exposure energies at a time under a photomask having a pattern having a light transmittance of more than three steps on a photoresist layer on a transparent conductive layer, and using different developers. A step of removing the resist layer stepwise, and a step of sequentially depositing red, green, and blue on the exposed conductive substrate. The above electrodeposition lithography method has the following advantages.
(1) Since this method combines the electrodeposition technique and the lithography technique, it is possible to obtain a pattern with high precision better than that obtained by the electrodeposition coating method.
(2) The degree of freedom of the pattern shape is high, and a stripe pattern or a non-stripe pattern can be created. and
(3) Since this method utilizes the advantageous features of the electrodeposition method, the coating film has a uniform thickness and excellent smoothness.
[0010]
However, the electrodeposition lithography method has at least three levels so that the exposed photoresist can be selectively removed at different stages of the development process and red, green and blue (R, G, B) can be electrodeposited thereon. Since different concentrations of developers are required, only a relatively narrow operational (acceptable) range within the acceptable range is possible. Furthermore, it is known to use a basic developing aqueous solution for positive photoresists. Under such circumstances, there are very limited options for selecting an appropriate electrodeposition resin. Moreover, there is still photoresist on the substrate before completing the electrodeposition of all desired colors. A curing operation at high temperature is not possible. In the examples of this document, a colored electrodeposition paint containing an anion electrodeposition resin is used. The acid value of this resin is in the range of 100 to 500 mg KOH / g. Such type of anion electrodeposition resin is easily affected by the developer. Therefore, a high concentration developer cannot be applied. As a result, the allowable range for the developer is narrowed. Cationic electrodeposition resins have better base resistance, but have the disadvantage of being easily yellowed and having low transmittance. During the electrodeposition process, such type of resin tends to reduce ITO (indium tin oxide), which is a transparent conductive material commonly used for transparent conductive substrates, to black spots. The technical limitations listed above are believed to be the main reason why no commercialized product has been produced from this method.
[0011]
Another method for producing a color filter that combines an electrodeposition (ED) coating method and a lithography (litho) technique is disclosed in US Pat. No. 5,641,595. This color filter manufacturing method uses the energy storage characteristics of a positive photoresist combined with a photo-curable electrodeposition resin. The method includes the steps of applying a positive photoresist layer on a transparent conductive substrate and exposing the positive photoresist layer to form areas of fine pixels having different exposures. One of these areas has reached an exposure that can be developed with a particular developer. After the development step, the photoresist on this area is removed to expose the corresponding conductive substrate. Next, electrodeposition is performed on this area to form pixels of a desired color. When this step is completed, the substrate is subjected to an exposure step without positioning the substrate. The previously electrodeposited pixels are then cured by light. By this step, it is possible to protect the electrodeposition dye from attack by the developer in the next stage. The second area that has not been developed with a particular developer is then exposed until development is reached. Thereafter, development and electrodeposition are advanced for each pixel and repeated until the required colored pixel area is completed.
[0012]
This incremental energy method has the function of sequentially developing areas of different levels of exposure energy. This method uses an anionically electrodeposited photocurable resin, configures the exposure energy so that each area reaches the total exposure energy of the positive photoresist, and cures the film formed by the electrodeposition paint. Since these advantages are combined, the influence of a basic developer used thereafter on the electrodeposited pixels is eliminated, and the development process is simplified. However, the electrodeposited photocurable resin requires a sufficient amount of exposure energy to cure the electrodeposited film and protect it from attack by the developer. In order to provide a function as a filter, the pigment particles are dispersed in the electrodeposited film. Thus, the energy required to expose the coating becomes more and more, which narrows the exposure tolerance of the photoresist. Furthermore, the addition of photosensitive groups in the electrodeposited coating makes it more difficult to achieve good dispersion and stability, which has an adverse effect on product yield.
[0013]
[Problems to be solved by the invention]
The present invention intends to overcome the above-mentioned problems while retaining the advantages of the method for producing a color filter by the pigment dispersion and electrodeposition coating method. The present invention develops an excellent technique for producing a color filter by using a colored electrodeposition paint containing a low acid value anion electrodeposition resin together with a weakly basic development positive photoresist solution. Since the present invention uses a low acid value anion electrodeposition resin in combination with a weakly basic development positive photoresist solution, the pixels in the corresponding area previously electrodeposited do not affect the function of the photoresist, It can be baked at normal heat drying temperatures to protect against attack by the developer used subsequently to develop other desired color pixels. The method of the present invention has the advantage of having a high degree of freedom in pattern shape and a wide operating tolerance. Furthermore, it is possible to produce a color filter with a large surface area and obtain the product in a very high yield.
[0014]
[Means for Solving the Problems]
The present invention
(A) A step of applying a positive photoresist layer on a transparent conductive substrate and exposing the positive photoresist layer to form three or four areas of initial levels having different exposure energies [in each case The exposure energy of the area is sequentially D₁, D₂, D_Three(And D_Four) And D₁Represents the total exposure energy of a positive photoresist, D₁> D₂> D_Three(> D_Four)
(B) D using developer₁And develop and remove areas of the photoresist layer having an exposure energy of 70 mg KOH / d so that the corresponding areas of the conductive substrate under the photoresist are exposed and the areas are finished in the desired color pixel arrangement. a step of electrodepositing a colored electrodeposition paint containing an anionic electrodeposition resin having an acid value of g or less,
(C) Energy IE on the entire surface of the substrate_nExposing the entire area of the substrate to an incremental amount of energy [in this case IE_nIs D_nAnd D_{n + 1}And the definition of n is as follows:
(I) When three areas of initial levels with different exposure energies are formed on the substrate, n is 1 and 2 in sequence,
(Ii) When four areas of initial levels with different exposure energies are formed on the substrate, n is 1, 2 and 3 in sequence],
(D) After each exposure in step (c) (i) or (ii), develop and develop the photoresist in the area where full exposure is achieved using the same developer used in step (b). Colored electrodeposition comprising a low acid number anionic electrodeposition resin so as to remove and thereby expose a corresponding area of the conductive substrate under the photoresist, and then finish the area into a pixel arrangement of another desired color The process of electrodeposition of paint,
(E) repeating steps (c) and (d) until all of the pixel placement is achieved; and
(F) forming a protective film on the substrate;
The present invention relates to a method for producing a color filter including
[0015]
The transparent conductive substrate of the present invention can be selected from the group consisting of oxides of tin, indium and antimony, such as indium tin oxide (ITO) and mixtures thereof, or a conductive glass in practical use.
[0016]
The material forming the black matrix is chromium, nickel or other alloy or oxide, or a mixture thereof. Alternatively, the black matrix can be formed from an organic polymer coating composition (including black pigment dispersed therein). For example, the materials may be conductive, such as acrylic resins and epoxy resins, or may not be conductive.
[0017]
The positive photoresist (PR) used in the present invention can be selected from novolak resins, naphthylanthraquinone diazo compounds and derivatives thereof. Suitable positive photoresists are those disclosed in US Pat. No. 5,645,970. These energy-storable amounts of these materials allow for selective development of areas of different initial exposure energy. A positive photoresist works on the principle that its solubility increases after exposure to light energy, ie it can be developed with a basic solution. The precision of the photoresist pattern is high and the dimensional accuracy is high. Preferably, the photoresist used in the method of the present invention should have a high contrast so as to minimize film loss in unexposed or underexposed areas.
[0018]
The technique for applying the photoresist may be any of those conventionally known to those skilled in the art, such as spraying, dipping, screen printing, roll coating, and spin coating. The thickness of the photoresist layer is preferably 1 to 10 μm, more preferably 1.5 to 5 μm.
[0019]
If the photoresist layer forms areas of three different exposure energy degrees after exposure, the exposure energy of each area, D₁, D₂And D_ThreeRepresents from 100% to 40%, from 85% to 20% and from 70% to 0%, respectively. Preferably, D₁, D₂And D_ThreeRepresents from 100% to 70%, from 70% to 40% and from 40% to 0%, respectively. If the photoresist layer forms areas of four different exposure energy degrees after exposure, the exposure energy of each area, D₁, D₂, D_ThreeAnd D_FourRepresents from 100% to 40%, from 85% to 20%, from 70% to 5% and from 50% to 0%, respectively. Preferably, each D₁, D₂, D_ThreeAnd D_FourRepresents from 100% to 80%, from 80% to 50%, from 50% to 30% and from 30% to 0%.
[0020]
The total exposure energy required in photoresist production is 80-1500 mJ / cm.²It is. 80-1500mJ / cm²This energy can be obtained by a single exposure process using a photomask having a multiple exposure density. Alternatively, it can be achieved by using one photomask having a predetermined exposure pattern. By carefully moving the photomask, areas of different exposure energy levels can be formed on the photoresist. Another alternative method is to use multiple (three or four) photomasks to form the desired three areas of different initial exposure energy degrees by using the incremental exposure method disclosed in the present invention, and then It is to develop. The area pattern may be a stripe shape, but may be a stripe pattern that is not a stripe shape (for example, a mosaic or a triangle).
[0021]
Positive photoresists are typically developed in basic developers such as aqueous solutions of one or a mixture of two or more of sodium carbonate, sodium bicarbonate, sodium metasilicate, tetraalkylammonium hydroxide, sodium hydroxide and potassium hydroxide. Developed. A preferred concentration of the developer is in the range of 0.2 to 4% by weight. The development temperature is generally 10 to 70 ° C, preferably 15 to 40 ° C. The time required for development is typically 5 to 600 seconds.
[0022]
A colorant consisting of a crosslinkable curing agent, an organic solvent, a neutralizing agent or dye, a pigment, or a mixture thereof can be added to the color electrodeposition paint containing the low acid value anionic electrodeposition resin used in the present invention.
[0023]
The low acid value anion electrodeposition resin used in the present invention is preferably a polyester resin having a carboxyl group. This resin can be dissolved or dispersed with a neutralizing agent. The acid value of this resin is preferably 70 mgKOH / g or less, more preferably 20 to 70 mgKOH / g, and the solid content is about 75.0%. The monomer constituting the polyester resin may contain a monomer selected from the group consisting of neopentyl glycol, adipic acid, isophthalic acid, isodecanol, trimellitic anhydride, butyl cellosolve and 2-butanol.
[0024]
The neutralizing agent can be selected from one or more of dimethylethanolamine, diethylethanolamine, diisopropanolamine and triethylamine. The crosslinkable curing agent used in the present invention can be selected from the group consisting of methylated melamine resin, butylated melamine resin, methylated methanol melamine resin, butylated methanol melamine resin, and benzoguanamine resin.
[0025]
The colorant of the present invention can be a dye, a pigment or a mixture thereof. As a rule, suitable dyes may be selected from one or more of azo dyes, anthraquinone dyes, benzodifuranone dyes and concentrated methine dyes. Pigments are azo lake organic pigment, quinacridone organic pigment, phthalocyanine organic pigment, isoindolinone organic pigment, anthraquinone organic pigment, thioindigo organic pigment, chrome yellow, chrome blue, iron oxide, chrome vermilion, chrome green, ultramarine, pulshan It can be selected from one or more of blue, cobalt green, emerald green, titanium white and carbon black.
[0026]
According to the method of the present invention, when three areas having different exposure levels are formed on a substrate, a black matrix is previously arranged on the substrate, and a colored electrodeposition paint containing red, green, and blue is selectively used on the substrate. Paint sequentially. When four areas of initial levels with different exposure energies are formed on the substrate, a black resin is applied to the last area of the substrate (four times) after selectively or sequentially applying a colored electrodeposition paint containing red, green and blue to the substrate. Electrodeposition on the second area). The development process and the entire exposure process are repeated until the arrangement of all the pixels is completed. Once all pixel arrangements are achieved in accordance with the present invention, it is preferable to bake the substrate in order to fully cure the electrodeposition resin.
[0027]
The anion electrodeposition resin exhibits excellent storage stability (non-yellowing property), emulsion stability and pigment dispersibility (particularly pigment dispersibility at a high concentration). When an anionic electrodeposition resin is used in combination with a photoresist, the photoresist still exists on the substrate until all desired color electrodepositions have been achieved, and there is no baking and curing at that high temperature. For anionic electrodeposition resins there is still the possibility of being attacked by the developer used later.
[0028]
In order to avoid such disadvantages, in the present invention, a colored electrodeposition paint containing an anion electrodeposition resin having an acid value of 70 mgKOH / g or less is used in combination with a weakly basic development positive photoresist solution. The method of the present invention utilizes a method of incremental energy to develop the photoresist stepwise with a single concentration developer. After exposing the colored area of the conductive substrate, a dye is electrodeposited on the area to form a pixel. In short, the present invention is characterized in that an electrodeposition paint containing an anion electrodeposition resin having an acid value of 70 mgKOH / g or less is used in combination with a positive photoresist technique having an energy gradual increase function. For example, a weakly basic development positive photoresist solution disclosed in US Pat. No. 5,645,970 can be used. Thus, the pre-deposited colored area pixels protect against developer attack that is subsequently used to develop other desired color pixels without being affected by the function of the photoresist. Therefore, it can be baked at a standard baking drying temperature such as 80 to 120 ° C.
[0029]
【The invention's effect】
The method of the present invention shows the advantage of having a high degree of pattern shape freedom and good workability. Furthermore, it is possible to produce large surface area color filters and to obtain products in very high yields.
[0030]
DETAILED DESCRIPTION OF THE INVENTION
Each of FIGS. 1A and 1B represents a preferred embodiment according to the present invention. Both of these two embodiments are directed to a method of manufacturing a color filter in which a black matrix is previously disposed on a transparent conductive substrate. This method includes the following steps.
[0031]
1. A step of pre-forming a black matrix on the transparent conductive substrate (2) [the black matrix is conductive as shown in (3) of FIG. 1A (a) and (13) of FIG. 1B (a), respectively] Can be made from conductive or non-conductive materials].
[0032]
2. Applying a layer of positive photoresist onto the transparent conductive substrate (2) and exposing the photoresist layer under a photomask to form three areas of different initial levels of exposure energy; In this case, the exposure energy of each area is D, as shown in FIGS. 1A (a) and 1B (a).₁(5), D₂(6) and D_Three(7) where D₁Represents the total exposure energy of a positive photoresist, D₁> D₂> D_ThreeIs].
[0033]
3. D using developer₁An area of the photoresist layer having the exposure energy of (5) is developed and removed, thereby exposing a corresponding area of the conductive substrate under the photoresist, and anionic electrodeposition having a low acid number in the area A step of electrodepositing a colored electrodeposition paint containing a resin, that is, a step of performing an electrodeposition process on the first pixel (8) as shown in FIGS. 1A (b) and 1B (b).
[0034]
4). Energy IE on the entire surface of the substrate₁Exposing the entire area of the substrate to an incremental amount of energy [in this case IE₁Is D₁And D₂At this time, as shown in FIGS. 1A (b) and 1B (b), the initial exposure energy is D₂The exposure energy for the area is the amount of full exposure (D₂+ IE₁= D₁) (6 '), and the initial exposure energy is D_ThreeThe exposure energy of the area which is is not accumulated to the amount of full exposure (D_Three+ IE₁Only) (7 ').
[0035]
5). Develop and remove the photoresist (6 ') in the area (6') that has achieved full exposure using the same developer as in step 3, thereby exposing the corresponding area of the conductive substrate under the photoresist. The step of electrodepositing a colored electrodeposition coating containing an anionic electrodeposition resin having a low acid value in the area, that is, as shown in FIG. 1A (c) / (d) and FIG. And a step of performing an electrodeposition process on the second pixel (9, 19).
[0036]
6). Energy IE on the entire surface of the substrate₂Exposing the entire area of the substrate to an incremental amount of energy [in this case IE₂Is D₂And D_ThreeAt this time, as shown in FIGS. 1A (b) and 1B (b), the initial exposure energy is D_ThreeThe exposure energy for the area (7) is the amount of full exposure (D₂+ IE₁+ IE₂= D₁) (7 ").]
[0037]
7. Develop and remove the photoresist in the area (7 ″) that has achieved full exposure using the same developer as in step 3, thereby exposing the corresponding area of the conductive substrate under the photoresist. Step, that is, a step of performing electrodeposition processing of the third pixel (10, 20) as shown in FIGS. 1A (e) and 1B (e).
[0038]
8). Finally, as shown in FIGS. 1A (f) and 1B (f), a protective film is formed on the substrate.
[0039]
FIG. 2 is a schematic diagram showing various stages of another method for manufacturing a color filter according to the present invention, in which a black matrix is not disposed on a transparent conductive substrate. This method includes the following steps.
[0040]
1. Applying a layer of positive photoresist onto the transparent conductive substrate (2) and exposing the photoresist layer under a photomask to form four areas of different initial levels of exposure energy. The exposure energy in each area is D, as shown in FIG.₁(22), D₂(23), D_Three(24) and D_Four(25) where D₁Represents the total exposure energy of a positive photoresist, D₁> D₂> D_Three> D_FourIs].
[0041]
2. D using developer₁An area of the photoresist layer having an exposure energy of (22) is developed and removed, thereby exposing a corresponding area of the conductive substrate under the photoresist, and anionic electrodeposition having a low acid number in the area A step of electrodepositing a colored electrodeposition paint containing a resin, that is, a step of performing an electrodeposition process on the first pixel (26) as shown in FIG.
[0042]
3. Energy IE on the entire surface of the substrate₁Exposing the entire area of the substrate to an incremental amount of energy [in this case IE₁Is D₁And D₂At this time, as shown in FIG. 2 (b), the initial exposure energy is D₂The exposure energy for the area (23) is the amount of full exposure (D₂+ IE₁= D₁) (23 '), and the initial exposure energy is D._Three(24) and D_FourThe exposure energy in the area that is (25) was not accumulated to the amount of full exposure [each (D_Three+ IE₁) (24 ') and (D_Four+ IE₁) (25 ') only]].
[0043]
4). Develop and remove the photoresist (23 ') that has achieved full exposure using the same developer as in Step 2, thereby exposing the corresponding area of the conductive substrate under the photoresist. , Electrodepositing a colored electrodeposition paint containing an anionic electrodeposition resin having a low acid value in the area, that is, as shown in FIGS. 2 (c) / (d), the second pixel (27) A process of performing an electrodeposition process.
[0044]
5). Energy IE on the entire surface of the substrate₂Exposing the entire area of the substrate to an incremental amount of energy [in this case IE₂Is D₂And D_ThreeAt this time, as shown in FIGS. 2 (c) / (d), the initial exposure energy is D_ThreeThe exposure energy of the area which is (24) is the amount of full exposure (D_Three+ IE₁+ IE₂= D₁) (24 ″), but the initial exposure energy is D_FourThe exposure energy in the area (25) was not accumulated to the amount of full exposure (D_Four+ IE₁+ IE₂Only) (25 ")].
[0045]
6). Develop and remove the photoresist in the area (24 ″) that has achieved full exposure using the same developer as in step 2, thereby exposing the corresponding area of the conductive substrate under the photoresist. , Electrodepositing a colored electrodeposition paint containing an anionic electrodeposition resin having a low acid value in the area, that is, as shown in FIGS. 2 (c) / (d), the third pixel (28) A process of performing an electrodeposition process.
[0046]
7. Energy IE on the entire surface of the substrate_ThreeTo give an incremental amount of energy to all areas of the substrate [in this case IE_ThreeIs D_ThreeAnd D_FourThe initial exposure energy is D at this time._FourThe exposure energy of the area which is (25) is the amount of full exposure (D_Three+ IE₁+ IE₂+ IE_Three= D₁) (According to 25 ″ ′)], then using the same developer as in Step 2 to develop and remove the photoresist in the area (25 ″ ′) where full exposure has been achieved, Thereby, the corresponding area of the conductive substrate under the photoresist is exposed, the area is coated with a layer of black resin, and the back side of the conductive substrate is irradiated with ultraviolet light to thereby cure the cured resin. Curing the black matrix (29) that fills the pores in the area under the shielding effect given by (26, 27, 28) [the material forming the black matrix and its manufacturing method comprises the following three steps: (1) A method in which a black matrix is formed on an area having a smaller initial exposure energy using a thermosetting positive photoresist in which a black colorant is dispersed, (2) A method of processing a black electrodeposition resin on a conductive substrate using an electrodeposition method using a black electrodeposition resin which is the same type as that contained in the electrodeposition paint; (3) photosensitivity 2 is used, and the pixel (26, 27, 28) and the black matrix (29) are completely cured by baking the substrate at a high temperature using the conductive black electrodeposition resin, as shown in FIG. ].
[0047]
8). Finally, as shown in FIGS. 1A (f) and 2 (f), a step of forming a protective film on the substrate.
[0048]
【Example】
Examples of the present invention are described below. It is believed that other objects, features and advantages of the present invention will be more clearly understood through the description of the following examples.
[0049]
Example 1 Synthesis of Low Acidity Polyester Resin
In order to synthesize a low acid value polyester resin, conventionally known esterification condensation polymerization is used. The types and amounts of monomers and solvents used are as follows.
[0050]

[0051]
Place the chemical reagents shown above into the reactor. The mixture is stirred at a high temperature under a nitrogen atmosphere to cause the reaction. After esterification and dehydration at reduced pressure, the polymerization is stopped. The analysis results of the obtained resin are as follows.
[0052]
Nonvolatile components (150 ° C., 1 hour, wt%) 75.4
Acid value (mgKOH / g, solid) 48.7
Viscosity (25 ° C., cps) 45.2
[0053]
Example 2-Manufacture of electrodeposition paint containing low acid value polyester resin
The types and amounts of the components of the low acid value polyester resin are as follows.
[0054]
Component A-1 A-2 A-3
Anionic polyester resin 95.0 95.0 95.0
Melamine resin
(Nikarakuku^TM  MX-40) 8.0 8.0 8.0
2-Ethoxyethanol butyl ether 25.0 25.0 25.0
2-Ethoxyethanol ethyl ether 5.0 5.0 5.0
n-butanol 18.0 18.0 18.0
Triethylamine 2.5 2.5 2.5
Deionized water 813.5 813.5 813.5
Phthalocyanine blue (SR-1500) 5.0 − −
Phthalocyanine green (SAX)-5.0-
Azo lake pigment (CARMINE FB)--5.0
Total 1000 1000 1000
[0055]
The following steps are used to prepare an electrodeposition paint containing a low acid value polyester resin.
1) Anionic polyester resin and melamine resin (Nikarakuku) in the amounts indicated above^TM  MX-40), 2-ethoxyethanol butyl ether, 2-ethoxyethanol ethyl ether, n-butanol and triethylamine are weighed and placed in one container and mixed with stirring.
[0056]
2) Weigh the amount of pigment indicated above, add them to the mixture and mix with stirring.
3) The above mixture is ground and dispersed by a mill. The grinding bead spheres used have an average particle size of 0.8 to 1.2 μm.
4) Add deionized water with stirring to emulsify the mixture. And
5) Filter the mixture through a 5 μm filter.
[0057]
Example 3
A positive photoresist corresponding to the weakly basic developer disclosed in US Pat. No. 5,645,970 having a thickness of 2.2 μm was formed on a conductive transparent glass substrate. The substrate had a thickness of 0.7 mm and had a pre-arranged black matrix. Using carefully moved photomasks having a light transmission area of only one third, 250, 150 and 50 mJ / cm respectively²Energy exposures (100%, 60% and 20%) were made to form three areas of different initial levels.
[0058]
0.5% Na₂SiO_Three250 mJ / cm using a developer containing²The initial exposure area (ie 100% initial exposure area) was developed and removed. Next, a thermosetting resin containing a red pigment was electrodeposited on the exposed surface of the conductive substrate. The electrodeposition process was performed at 25 ° C. and a voltage of 50 V for 20 seconds. After the electrodeposition process was completed, the substrate was washed with deionized water and dried at 90 ° C. for 10 minutes. Next, 100 mJ / cm²The entire photoresist was exposed with a light source to receive an incremental exposure energy of. This is the second zone (initially 150 mJ / cm², Ie 60% initial exposure energy) and the third zone (initially 50 mJ / cm²I.e., 10% initial exposure energy), resulting in stored exposure energy of 250 mJ / cm each²(Complete exposure) and 150 mJ / cm²(60% of full exposure). Next, similarly, the same 0.5% Na₂SiO_ThreeThe fully exposed areas were developed and removed using a developer containing. This was followed by electrodeposition of a thermosetting resin containing a green pigment under similar conditions onto the exposed surface of the conductive substrate and then dried. 100mJ / cm²The entire photoresist was again exposed with a light source to receive the incremental exposure energy of. This results in accumulated exposure energy in the third zone, 250 mJ / cm²(100% exposure). Same 0.5% Na₂SiO_ThreeThis area was developed and removed using a developer containing. Subsequently, a thermosetting resin containing a blue pigment was again electrodeposited on the exposed surface of the conductive substrate under similar conditions and dried. Finally, the entire substrate is 100 mJ / cm²The remaining photoresist is exposed to 0.5% Na.₂SiO_ThreeThe substrate was removed with a developing solution, and the substrate was completely cured at 260 ° C. for 1 hour to complete the processing of red, green, blue, and three pixels.
[0059]
The above description of preferred embodiments of the present invention has been provided for purposes of illustration and description. Obvious modifications or changes can be made by the above teachings. These embodiments have been chosen and described in order to provide a description of the principles of the invention and the best examples of its practical application, thereby enabling those skilled in the art to vary the invention to suit the particular application intended. Can be used in various embodiments or with various modifications. All such modifications and changes are defined by the appended claims if they are to be construed according to the scope to which they are legally, legally and fairly entitled. Within the scope of the present invention.
[Brief description of the drawings]
FIGS. 1A to 1F are schematic diagrams illustrating various stages of a method of manufacturing a color filter according to the present invention, in which a black matrix is pre-arranged on a transparent conductive substrate. Yes.
FIGS. 1A to 1F are schematic diagrams showing various stages of another method of manufacturing a color filter according to the present invention, in which a black matrix is pre-arranged on a transparent conductive substrate. Has been.
2 (a) to (f) are schematic diagrams showing various stages of another method for producing a color filter according to the present invention, in which a black matrix is arranged on a transparent conductive substrate; Not.

Claims (18)

(A) A step of applying a positive photoresist layer on a transparent conductive substrate and exposing the positive photoresist layer to form three or four areas of initial levels having different exposure energies [in each case The exposure energy of the area is sequentially D ₁ , D ₂ , D ₃ (and D ₄ ), D ₁ represents the total exposure energy of the positive photoresist, and D ₁ > D ₂ > D ₃ (> D ₄ ) is there,]
(B) using a developer to develop and remove areas of the photoresist layer having an exposure energy of D ₁ , thereby exposing the corresponding areas of the conductive substrate under the photoresist, which areas are desired A step of electrodepositing a colored electrodeposition coating material containing an anionic electrodeposition resin having an acid value of 70 mgKOH / g or less so as to finish a color pixel arrangement;
(C) exposing the entire surface of the substrate with energy IE _n to give an incremental amount of energy to all areas of the substrate [where IE _n is the energy difference between D _n and D _{n + 1} , n The definition is as follows:
(I) When three areas of initial levels with different exposure energies are formed on the substrate, n is 1 and 2 in sequence,
(Ii) When four areas of initial levels with different exposure energies are formed on the substrate, n is 1, 2, and 3 in sequence.
(D) After each exposure in step (c) (i) or (ii), develop and develop the photoresist in the area where full exposure is achieved using the same developer used in step (b). Colored electrodeposition comprising a low acid number anionic electrodeposition resin so as to remove and thereby expose a corresponding area of the conductive substrate under the photoresist, and then finish the area into a pixel arrangement of another desired color The process of electrodeposition of paint,
(E) repeating steps (c) and (d) until all of the pixel placement is achieved, and (f) forming a protective film on the substrate;
A method for producing a color filter comprising: The method for producing a color filter according to claim 1, wherein the anion electrodeposition resin is a polyester resin having a carboxyl group. The method for producing a color filter according to claim 1, wherein the anion electrodeposition resin has an acid value of 20 to 70 mg KOH / g. The method for producing a color filter according to claim 1, wherein the anionic electrodeposition resin further comprises a colorant comprising a crosslinkable curing agent, an organic solvent, a neutralizing agent or a dye, a pigment, or a mixture thereof. The color filter production according to claim 4, wherein the crosslinkable curing agent comprises one or more of a methylated melamine resin, a butylated melamine resin, a methylated methanol melamine resin, a butylated methanol melamine resin and a benzoguanamine resin. Method. The pigment is an azo lake organic pigment, quinacridone organic pigment, phthalocyanine organic pigment, isoindolinone organic pigment, anthraquinone organic pigment, thioindigo organic pigment, chrome yellow, chrome blue, iron oxide, chrome vermilion, chrome green, ultramarine, pull The manufacturing method of the color filter of Claim 4 which consists of 1 type, or 2 or more types of a champagne blue, cobalt green, emerald green, titanium white, and carbon black. The method for producing a color filter according to claim 4, wherein the dye comprises one or more of an azo dye, an anthraquinone dye, a benzodifuranone dye, and a concentrated methine dye. In the case where three regions of initial levels with different exposure energies are formed on the substrate, D ₁ , D ₂ and D ₃ are respectively 100% to 40%, 85% to 20% and 70% to 0%. The method for producing a color filter according to claim 1, wherein The method for producing a color filter according to claim 8, wherein D ₁ , D _2, and D ₃ represent from 100% to 70%, from 70% to 40%, and from 40% to 0%, respectively. In the case where four areas of initial levels having different exposure energies are formed on the substrate, D ₁ , D ₂ , D ₃ and D ₄ are respectively 100% to 40%, 85% to 20%, 70% and more. The method for producing a color filter according to claim 1, which represents up to 5% and from 50% to 0%. In the case where four areas of initial levels having different exposure energies are formed on the substrate, D ₁ , D ₂ , D ₃ and D ₄ are from 100% to 80%, from 80% to 50%, from 50%, respectively. The method for producing a color filter according to claim 10, which represents up to 30% and from 30% to 0%. Step (a) is a one-time exposure process using one photomask having a multiple exposure density, and exposure is performed on a photoresist on a substrate by moving the photomask using one photomask having a predetermined exposure pattern. A single exposure step of forming areas of different energy levels, or a single exposure step of forming a desired three areas of different initial exposure energies on a substrate photoresist using a plurality of photomasks. Item 2. A method for producing a color filter according to Item 1. The developer of step (c) comprises one or more aqueous solutions of sodium carbonate, sodium bicarbonate, sodium metasilicate, tetraalkylammonium hydroxide, sodium hydroxide and potassium hydroxide. A method for producing a color filter. The method for producing a color filter according to claim 1, wherein in step (e), the substrate is selectively or sequentially coated with a colored electrodeposition paint containing red, green and blue. The method for producing a color filter according to claim 1, wherein a black matrix is arranged in advance on the substrate when three areas of initial levels having different exposure energies are formed on the substrate. 2. The material forming the black matrix is an alloy or oxide of chromium and / or nickel or a mixture thereof or an organic polymer coating composition in which a black pigment is dispersed. The manufacturing method of the color filter of description. In the case where four areas of initial levels having different exposure energies are formed on the substrate, steps (c) and (d) are repeated until the electrodeposition of all pixels is completed, and black resin is added to the last area of the substrate. The manufacturing method of the color filter of Claim 1 apply | coated on top. The method for producing a color filter according to claim 1, further comprising a step of baking the substrate again after the step (e) in order to completely cure the electrodeposition resins of all colors.

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