TW200804974A

TW200804974A - Curable composition, color filters, and liquid crystal displays

Info

Publication number: TW200804974A
Application number: TW096108440A
Authority: TW
Inventors: Kouji Yamauchi; Naoto Sekiguchi
Original assignee: Mitsubishi Chem Corp
Priority date: 2006-03-10
Filing date: 2007-03-12
Publication date: 2008-01-16
Also published as: TWI405034B; KR20080108966A; WO2007105649A1; CN101379132B; CN101379132A; KR101167868B1

Abstract

The invention provides a curable composition which little generates aggregate contaminants and is excellent in storage stability; and high-quality color filters and liquid crystal displays which are made by using the composition and which little suffer from defects due to fragmentary exfoliated contaminants. A curable composition comprising (A) a binder, (B) a monomer, (C) a solvent, and (D) a pigment, characterized by having a water content of 0.4 to 2.0wt%, a quantity (a) of matter adhering to one edge of a glass test piece of 2 μg or below as determined by applicability test (I) comprising specific four steps, and a viscosity increase of 1.0cps or below after the storage at 35 DEG C for 2 weeks under normal pressure; and color filters and liquid crystal displays, made by using the same.

Description

200804974 (1) 九、發明說明【發明所屬之技術領域】本發明係關於硬化性組成物'彩色濾光片、及液晶顯示裝置。詳細而言，形成使用於液晶顯示裝置（液晶面板）等之顯示構件的製造之畫素或黑色矩陣等之硬化性組成物 (光阻）、彩色濾光片、及液晶顯示裝置。[Technical Field] The present invention relates to a curable composition 'color filter' and a liquid crystal display device. Specifically, a curable composition (photoresist) such as a pixel or a black matrix which is used for manufacturing a display member such as a liquid crystal display device (liquid crystal panel), a color filter, and a liquid crystal display device are formed.

【先前技術】液晶顯示裝置等之顯示構件的製造所使用的畫素、黑色矩陣、光阻間隔物、稜（rib)材、保護膜等，一般而言，經由將硬化性組成物塗佈於基板，形成硬化性組成物層之步驟被形成。於上述塗佈步驟中，可使用先前技術旋轉塗佈法，但近年來因爲基板的大型化與省液化的必要性，而轉移至狹縫及旋轉式塗佈法（slit and spin coating)或擠壓式塗佈法 (die coating)。特別是藉由擠壓式塗佈法完全無藉由旋轉塗佈法進行塗佈時附著重霧等之影響、及異物發生被抑制等，由綜合的觀點而言較佳。惟’狹縫及旋轉式塗佈法或擠壓式塗佈法，因爲硬化性組成物乾掉而在配料機噴嘴的先端所發生的凝聚異物，附著於塗佈膜上後變成剝離異物而降低產率之問題變嚴重。爲了解決此問題，例如專利文獻1係揭示將使用著色畫像形成用感光液所形成的乾燥膜，浸漬於該感光液所包 -4- (2) 200804974 含的溶劑時，可使其於5分鐘以內被解溶（以下，形成乾燥膜，將其溶解於與原組成物中所包含的者相同的溶劑這件事，稱爲「再溶解」，亦將符合於此之性質稱爲「再溶解性」。）之著色影像形成用感光液與其方法。惟，在實際的製造過程，則因爲一度發生的凝聚異物未等待再溶解的時間而被散佈於塗佈面，所專利文獻1所記載的技術的重複性低，不足以改善因爲凝聚異物所造成的產率降低。[Prior Art] A pixel, a black matrix, a photoresist spacer, a rib material, a protective film, or the like used for the production of a display member such as a liquid crystal display device is generally applied to a curable composition. The substrate is formed by forming a layer of a hardenable composition. In the above coating step, the prior art spin coating method can be used, but in recent years, it has been transferred to a slit and a spin and spin coating or extrusion because of the necessity of enlargement of the substrate and liquefaction. Die coating. In particular, it is preferable from the viewpoint of synthesis that the influence of heavy fog or the like during coating is not caused by the spin coating method, and the occurrence of foreign matter is suppressed by the extrusion coating method. However, in the slit, rotary coating method or extrusion coating method, the cohesive foreign matter generated at the tip end of the nozzle of the batching machine due to the drying of the curable composition is adhered to the coating film, and the foreign matter is peeled off to reduce the yield. The problem of the rate has become serious. In order to solve this problem, for example, Patent Document 1 discloses that a dried film formed by using a photosensitive liquid for forming a colored image is immersed in a solvent contained in the photosensitive liquid -4-(2) 200804974, and can be made in 5 minutes. It is dissolved in the inside (hereinafter, a dry film is formed and dissolved in the same solvent as that contained in the original composition, which is called "redissolution", and the property corresponding to this is also called "redissolution". "Sensitivity". The coloring solution for color image formation and its method. However, in the actual manufacturing process, the condensed foreign matter that has once occurred does not wait for re-dissolution, and is dispersed on the coated surface. The technique described in Patent Document 1 has low repeatability and is insufficient to improve the aggregation due to foreign matter. The yield is reduced.

此外，專利文獻2係揭示清掃噴嘴先端之裝置，惟，在實際的製造過程，很難完全的去除銳利形狀的噴嘴先端的異物，此外會有因爲噴嘴的清掃而必須中斷塗佈動作，而阻礙製造生產之問題。而且，清掃不完全則噴嘴先端發生擦拭殘留的液體池，而會有導致塗佈的不均勻性（斑）的問題。專利文獻1 :特開2002-23 3 52號公報專利文獻2 :特開平9_ 1 92566號公報專利文獻3 :特開2006-343 648號公報【發明內容】 [發明所欲解決之課題] 本發明鑑於上述的先前技術，發現可適當的評估在狹縫及旋轉式塗佈法或擠壓式塗佈法中凝聚異物的產生量之硬化性組成物的塗佈適性評估方法，此外，具有特定的組成’而且發現用該評估方法可得到優良的結果之硬化性組成物，非常適用於狹縫及旋轉式塗佈法或擠壓式塗佈法。 -5- 200804974 (3) 本發明的目的在於提供適合藉由狹縫及旋轉式塗佈法或擠壓式塗佈法塗佈之硬化性組成物，而且使用其所形成的局品質的彩色減光片、及液晶顯不裝置。 [用以解決課題之手段]Further, Patent Document 2 discloses a device for cleaning the tip end of the nozzle. However, in the actual manufacturing process, it is difficult to completely remove the foreign matter at the tip end of the sharp shape of the nozzle, and the coating operation must be interrupted due to the cleaning of the nozzle, which hinders Manufacturing production issues. Further, if the cleaning is incomplete, the liquid pool at the tip end of the nozzle is wiped off, and there is a problem of unevenness (spot) which causes coating. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2006-343. In view of the above-described prior art, it has been found that a coating suitability evaluation method for a curable composition in which a generation amount of agglomerated foreign matter is generated in a slit and a spin coating method or a squeeze coating method can be appropriately evaluated, and further, has a specific The composition of the composition of the hardening composition which is excellent in the results of the evaluation method is very suitable for the slit and the rotary coating method or the extrusion coating method. -5- 200804974 (3) An object of the present invention is to provide a hardenable composition suitable for coating by a slit and a rotary coating method or a squeeze coating method, and to use the color quality of the local quality formed by the method. Light film, and liquid crystal display device. [Means to solve the problem]

本發明者等經過精心硏究的結果，發現藉由利用非依賴硬化性組成物的塗佈適性，而是著重於凝聚異物的發生過程之適當的評估方法，可解決上述課題，而逹成成本發明。亦即，本發明的要旨如下述。 (i)一種硬化物組成物，係含有（A)黏合劑樹脂、（B)單體、（C)溶劑及（D)顏料之硬化性組成物，其特徵爲該硬化性組成物的水分含量爲〇 . 4重量％以上2 · 0重量％以下’藉由特定下述（1)〜（4)的步驟所成的塗佈適性評估方法（I)之被形成於玻璃試驗片的一稜線上的附著物U)爲2 pg以下，而且將該硬化性組成物在常壓下以35 °C保存2週時的黏度上升爲l.Ocps以下。 [塗佈適性評估方法（I)] (1) 在氣體環境溫度23°C，將長度lOOmmx寬度5mmx 厚度0.7mm的玻璃試驗片的縱方向的前端部份20mm，以 12.5mm/秒的速度浸漬於硬化性組成物中，然後維持4秒之步驟 (2) 將該玻璃試驗片，以12.5mm/秒的速度從硬化性組成物取出，將該玻璃試驗片的前端往下保持垂直後，在氣體環境溫度23°C、濕度55%、風速0·5±0·2πι/秒的條件下 -6- (4) 200804974 使其乾燥5 2秒之步驟 (3) 重複步驟（1)及（2)合計250次，該玻璃試驗片上形成源自硬化性組成物的附著物之步驟 (4) 該玻璃試驗片的4稜線中，選擇該附著物量最多的稜線之步驟（再者，被選擇的稜線上的附著物被稱爲「附著物（a)」。） (Π)使用上述（i)所記載的硬化性組成物所形成的彩色As a result of careful investigation, the inventors of the present invention have found that by utilizing the coating suitability of the non-hardening composition, it is possible to solve the above problems by focusing on an appropriate evaluation method for the occurrence of agglomerated foreign matter. invention. That is, the gist of the present invention is as follows. (i) a cured composition comprising (A) a binder resin, (B) a monomer, (C) a solvent, and (D) a curable composition of a pigment, characterized by a moisture content of the curable composition 4% by weight or more and 2·0% by weight or less 'The coating suitability evaluation method (I) obtained by the steps (1) to (4) described below is formed on the ridge line of the glass test piece. The adhering material U) was 2 pg or less, and the viscosity of the curable composition was increased to 1. Ocps or less when stored at 35 ° C for 2 weeks under normal pressure. [Coating suitability evaluation method (I)] (1) The tip end portion of the glass test piece having a length of 100 mm x width 5 mm x thickness 0.7 mm in the longitudinal direction was 20 mm at a gas ambient temperature of 23 ° C, and was impregnated at a rate of 12.5 mm / sec. In the curable composition, the step of maintaining the film for 4 seconds (2), the glass test piece was taken out from the curable composition at a rate of 12.5 mm/sec, and the front end of the glass test piece was held vertically downward. Gas ambient temperature 23 ° C, humidity 55%, wind speed 0 · 5 ± 0 · 2πι / s -6 - (4) 200804974 to dry it for 5 seconds (3) Repeat steps (1) and (2 a total of 250 times, the step of forming a deposit derived from the curable composition on the glass test piece (4) The step of selecting the ridge line having the largest amount of attached matter among the 4 ridge lines of the glass test piece (again, the selected ridge line) The deposit on the top is called "attachment (a)".) (Π) The color formed by using the curable composition described in (i) above

(iii)使用上述（ii)所記載的硬化性組成物所形成的液晶顯不裝置。 [發明之效果](iii) A liquid crystal display device formed using the curable composition described in the above (ii). [Effects of the Invention]

依據本發明，可提供較少發生凝聚異物、具有優異的保存安定性之硬化性組成物；此外，藉由使用如此的硬化性組成物，可較少發生因爲剝離片異物所造成的缺陷且高品質的彩色濾光片、及液晶顯示裝置。 [實施發明之最佳形態] 以下詳細說明本發明的實施形態，此等乃爲本發明的實施形態的其中一例，本發明並不限定於此等內容。 [1]硬化性組成物本發明的硬化性組成物，係含有（A)黏合劑樹脂、（B) 單體、（C)溶劑及（D)顏料之硬化性組成物，其特徵爲該硬化性組成物的水分含量爲〇 · 4重量％以上2.0重量％以下， 200804974 (5) 藉由特定下述（1)〜（4)的步驟所成的塗佈適性評估方法⑴ 中，被形成於玻璃試驗片的一稜線上的附著物（a)爲2 μ g 以下，而且將該硬化性組成物在常壓下以3 5 °C保存2週時的黏度上升爲l.Ocps以下。 [1 _ 1 ]硬化性組成物的水分含量According to the present invention, it is possible to provide a hardenable composition which is less likely to cause agglomerated foreign matter and has excellent storage stability; moreover, by using such a hardenable composition, defects due to foreign matter peeling off the sheet can be less and high. Quality color filters and liquid crystal display devices. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail, and these are examples of the embodiments of the present invention, and the present invention is not limited thereto. [1] Curable composition The curable composition of the present invention contains (A) a binder resin, (B) a monomer, (C) a solvent, and (D) a curable composition of a pigment, which is characterized by the hardening. The water content of the composition is 〇·4% by weight or more and 2.0% by weight or less, and 200804974 (5) is formed by the coating suitability evaluation method (1) which is specific to the following steps (1) to (4). The adhesion (a) on the ridge line of the glass test piece was 2 μg or less, and the viscosity of the curable composition was increased to 1.0 cp or less when stored at 35 ° C for 2 weeks under normal pressure. [1 _ 1 ] Moisture content of the hardening composition

本發明的硬化性組成物，該組成物中的水分含量爲〇 . 4重量％以上，較佳爲〇 · 5重量％以上，更佳爲〇 . 6重量 %以上，特別佳爲〇·7重量％以上，以及0.2重量％以下，較佳爲1.5重量％以下，更佳爲1.2重量％以下，特別佳爲〇·9重量％以下。水分含量太少則無法表現出異物降低效果，太多則在硬化性或長期保存性方面會有問題。再者，硬化性組成物中的水分量，可藉由習知的手段測量及調整，例如將使用後述方法所調製的硬化性組成物的水分量，用卡爾-費歇法測量，不足部分藉由於硬化性組成物中滴入水而補償，過剩部分可將預先用烘箱等被真空乾燥的分子篩（例如，和光純藥工業公司製「Molecular Sieves 3A 1/16」等，加進硬化物組成物後藉由攪拌脫水0 其他的脫水的手段，可列舉使用矽膠、氧化鋁等之多孔質材料，或亞硫酸鈉（Na2S03)、氯化鈣等之脫水劑之方法’但並不限定於此等方法。 [1-2]附著物（a) 本發明的硬化性組成物，於下述（1 )〜（4)的步驟所成的塗佈適性評估方法（I)，被形成於玻璃試驗片的一稜線 -8- (6) 200804974 上的附著物（a)爲2 pg以下。 [塗佈適性評估方法（1)1 (1) 將l〇〇mmx5mmx〇.7mm的玻璃試驗片的前端部份 20mm，在氣溫23 °C的條件下，於硬化物組成物中浸漬4 秒之步驟In the curable composition of the present invention, the moisture content in the composition is 〇. 4% by weight or more, preferably 〇·5% by weight or more, more preferably 〇. 6% by weight or more, particularly preferably 〇·7 by weight. % or more and 0.2% by weight or less, preferably 1.5% by weight or less, more preferably 1.2% by weight or less, particularly preferably 9% by weight or less. If the moisture content is too small, the effect of reducing foreign matter cannot be exhibited, and too much may cause problems in hardenability or long-term preservation. Further, the amount of water in the curable composition can be measured and adjusted by a conventional means. For example, the moisture content of the curable composition prepared by the method described later is measured by the Karl Fischer method. It is compensated by the dripping of the water in the hardening composition, and the molecular sieve which was previously vacuum-dried in an oven or the like (for example, "Molecular Sieves 3A 1/16" manufactured by Wako Pure Chemical Industries, Ltd.) is added to the hardened composition. In the meantime, a method of using a porous material such as tannin or alumina, or a dehydrating agent such as sodium sulfite (Na2S03) or calcium chloride is used, but the method is not limited thereto. [1-2] Attachment (a) The curable composition of the present invention is a coating suitability evaluation method (I) formed in the following steps (1) to (4), and is formed on one of the glass test pieces. The ridge line -8- (6) The attachment (a) on 200804974 is 2 pg or less. [Applicability evaluation method (1) 1 (1) The front end portion of the glass test piece of l〇〇mmx5mmx〇.7mm is 20mm. , at a temperature of 23 ° C, in the hardened composition The impregnation step 4 seconds

(2) 將該玻璃試驗片，從硬化性組成物取出，將前端往下保持垂直後，在氣溫23 °C、濕度55%、風速〇.5m/秒的條件下使其乾燥52秒之步驟 (3) 重複步驟（1)及（2)合計250次，該玻璃試驗片上形成源自硬化性組成物的附著物之步驟 (4) 該玻璃試驗片的4稜線中，選擇該附著物量最多的棱線之步驟。 (再者，被選擇之稜線上的附著物被稱爲「附著物 (a)」。） [1-2-1]硬化性組成物的塗佈適性評估方法（I) 以下，說明關於各步驟。步驟（1): 「在氣體環境溫度23°C，將長度lOOmmx 寬度5mmx厚度0.7mm的玻璃試驗片的縱方向的前端部份 20mm，以12.5mm/秒的速度浸漬於硬化物組成物中，然後維持4秒之步驟。」浸漬步驟的氣體環境溫度，亦即本發明實施浸漬步驟之室溫爲23 °C，所浸漬的硬化性組成物的液溫，可爲該硬化性組成物通常存在於上述室溫下之液溫。液溫太低則會有黏度變高的傾向，太高則會有產生溫度劣化之虞。 -9- (7) 200804974 將試驗片浸漬於硬化性組成物中時之速度爲12.5mm/ 秒，被浸漬時之速度，爲了使試驗片的浸漬時間均勻’使其爲與後述之取出速度相同之速度較佳。浸漬時間爲4秒，此處之浸漬時間之意，係指將玻璃試驗片的縱方向的前端部份20mm浸漬於硬化性組成物中後，維持浸漬狀態之時間。會有浸漬時間太短則重複性易發生問題，太長則異物不易形成之傾向。(2) The glass test piece was taken out from the curable composition, and the front end was kept vertical, and then dried at a temperature of 23 ° C, a humidity of 55%, and a wind speed of 5 5 m / sec for 52 seconds. (3) Steps (1) and (2) are repeated 250 times in total, and the step of forming a deposit derived from the curable composition on the glass test piece (4) is selected from the four ridge lines of the glass test piece. The steps of the ridge line. (Further, the attached matter on the selected ridgeline is referred to as "attachment (a)".) [1-2-1] Evaluation method of coating suitability of curable composition (I) Hereinafter, each step will be described. . Step (1): "In the gas ambient temperature of 23 ° C, the longitudinal end portion of the glass test piece having a length of 100 mm x a width of 5 mm x a thickness of 0.7 mm is immersed in the cured composition at a rate of 12.5 mm / sec. Then, the step of maintaining the gas for 4 seconds. The gas ambient temperature of the impregnation step, that is, the room temperature at which the impregnation step of the present invention is carried out is 23 ° C, and the liquid temperature of the hardened composition to be impregnated may be such that the curable composition is usually present. The liquid temperature at the above room temperature. If the liquid temperature is too low, the viscosity tends to be high, and if it is too high, there is a tendency for temperature deterioration. -9- (7) 200804974 The speed at which the test piece was immersed in the curable composition was 12.5 mm/sec, and the speed at the time of immersion was made to make the immersion time of the test piece uniform, so that it was the same as the take-up speed described later. The speed is better. The immersion time is 4 seconds, and the immersion time here means the time during which the immersion state is maintained after immersing the tip end portion of the glass test piece in the longitudinal direction of 20 mm in the curable composition. If the immersion time is too short, repeatability tends to cause problems, and if it is too long, foreign matter tends to be difficult to form.

步驟（2) : 「將該玻璃試驗片，以12.5mm/秒的速度從硬化性組成物取出，將該玻璃試驗片的前端往下保持垂直後，在氣體環境溫度23°C、濕度55%、風速0.5±0.2m/秒的條件下使其乾燥52秒之步驟。」將步驟（1)中浸漬的試驗片，從硬化性組成物取出、乾燥。取出試驗片時之取出速度，與使其浸漬時的速度相同，爲12.5mm/秒。會有取出速度太慢則試驗片偕同的液體太少而附著物（a)不易被形成，太快則試驗片偕同的液體太多而異物的判別不易之虞。取出的玻璃試驗片，將其前端往下保持垂直後，在氣體環境溫度23°C、濕度55%、風速0.5±0.2m/秒的條件下使其乾燥52秒之步驟。此時，從保持垂直的試驗片的上側往下側，藉由氣流垂直的流動下之強制對流乾燥（藉由氣流在一定的方向上用一定的風速作用之條件進行乾燥），因爲在試驗片的4稜線上附著物（a)均等地被形成，故較佳。會有乾燥風速太慢則附著物（a)不易形成，太快則試驗片振動之虞，此外，強制對流乾燥時的風速的振幅 -10 - 200804974Step (2): "The glass test piece was taken out from the curable composition at a rate of 12.5 mm/sec, and the front end of the glass test piece was kept vertical, and the gas atmosphere temperature was 23 ° C and the humidity was 55%. The step of drying for 52 seconds under a condition of a wind speed of 0.5 ± 0.2 m/sec. The test piece immersed in the step (1) was taken out from the curable composition and dried. The take-up speed at the time of taking out the test piece was 12.5 mm/sec as the speed at which the test piece was immersed. If the take-up speed is too slow, the test piece has too little liquid and the attached material (a) is not easily formed. Too fast, the test piece has too many liquids and the foreign matter is difficult to discriminate. The taken-out glass test piece was subjected to a step of drying it for 52 seconds under the conditions of a gas atmosphere temperature of 23 ° C, a humidity of 55%, and a wind speed of 0.5 ± 0.2 m / sec. At this time, from the upper side to the lower side of the test piece which is kept perpendicular, forced convection drying by the vertical flow of the air flow (drying by a certain wind speed in a certain direction by the air flow), because in the test piece It is preferable that the attachments (a) on the four rib lines are formed equally. If the drying wind speed is too slow, the attached material (a) is not easy to form, too fast, the test piece vibrates, and in addition, the amplitude of the wind speed during forced convection drying -10 - 200804974

爲土 0.2m/秒。本發明中，乾燥速度之意，係指從硬化性組成物完全取出試驗片後，維持乾燥狀態之時間。再者，使乾燥溫度爲23 °C，會有太低則異物不易形成，太高則產生硬化之虞。步驟（3): 「重複步驟（1)及（2)合計250次，該玻璃試驗片上形成源自硬化性組成物的附著物之步驟。」For soil 0.2m / sec. In the present invention, the meaning of the drying speed means the time during which the test piece is completely taken out from the curable composition and maintained in a dry state. Further, when the drying temperature is 23 ° C, the foreign matter is too low to be easily formed, and if it is too high, the hardening is caused. Step (3): "Repeat steps (1) and (2) for a total of 250 times, and the step of forming a deposit derived from the curable composition on the glass test piece."

藉由複數次重複上述步驟（1)及（2)(本發明爲 250 次），在試驗片上形成源自硬化性組成物的附著物。步驟（4) : 「該玻璃試驗片的4稜線中，選擇該附著物量最多的稜線之步驟（再者，被選擇的稜線上的附著物被稱爲「附者物（a)」。）上述附著物特別容易形成於試驗片的稜線部份（參考圖1〜3 )。本發明的硬化性組成物，係玻璃試驗片的縱方向的4 稜線中，選擇該附著物量最多的稜線，以使該稜線上所形成的附著物的量（亦即「附著物（a)的量」）成爲2 pg以下爲條件。可藉由測量此附著物（a)的量，判斷硬化性組成物的塗佈適性。附著物（a)的重量的測量方法並沒有特別的限制’例如可測量從試驗片刮取的重量，亦可預先使用該硬化物組成物測量所形成的膜的比重備用，用3維雷射顯微鏡等測量附著物（a)的體積，由此等之積計算。附著物（a)的重量爲2μ§以下，較佳爲低於bg ’附著 -11 - 200804974 (9) 物（a)的重量太大則凝聚異物的發生可能性變大，此外附著物（a)的重量一般〇·ΐμβ以上左右，但愈少愈好。要將附著物（a)的量控制在上述範圍內，例如進行調整（D)顏料的分散條件、顏料濃度、黏合劑樹脂的種類或其分子量、分散劑的種類或其含量、溶劑組成、及硬化性組成物的水分量等爲有效的作法。By repeating the above steps (1) and (2) in a plurality of times (250 times in the present invention), deposits derived from the curable composition are formed on the test piece. Step (4): "In the four ridge lines of the glass test piece, the step of selecting the ridge line having the largest amount of attached matter (hereinafter, the attached matter on the selected ridge line is referred to as "attachment (a)"). The attached matter is particularly easily formed on the ridge portion of the test piece (refer to Figs. 1 to 3). In the curable composition of the present invention, among the four ridge lines in the longitudinal direction of the glass test piece, the ridge line having the largest amount of attached matter is selected so that the amount of the deposit formed on the ridge line (that is, the "attachment (a)" The amount ") is a condition of 2 pg or less. The coating suitability of the curable composition can be judged by measuring the amount of the adhering substance (a). The method for measuring the weight of the attached matter (a) is not particularly limited. For example, the weight scraped from the test piece can be measured, and the specific gravity of the formed film can be measured by using the cured composition in advance, and a 3-dimensional laser is used. The volume of the attached matter (a) is measured by a microscope or the like, and is calculated by the product. The weight of the deposit (a) is 2 μ§ or less, preferably less than bg 'attachment-11 - 200804974 (9) The weight of the substance (a) is too large, and the possibility of occurrence of agglomerated foreign matter becomes large, and the deposit (a) The weight of the product is generally about ΐ·ΐμβ or so, but the less the better. To control the amount of the attached matter (a) within the above range, for example, adjusting (D) the dispersion condition of the pigment, the pigment concentration, the kind of the binder resin or the molecular weight thereof, the kind or content of the dispersing agent, the solvent composition, and The moisture content of the curable composition or the like is an effective method.

顏料分散係以可得到品質充分安定的顏料分散液之條件進行較佳。分散不充分之意，係指附著於顏料的分散劑的附著量不足。如此狀態的顏料分散液，一度固化成爲塗膜，則顏料的露出部份變多，即使再度浸漬於溶劑亦不會溶解；相反的分散過度時’分散劑頑固且緊密地附著於顏料表面。認爲如此的顏料分散液一度固化成爲塗膜，則即使再度浸漬於溶劑，具有分散劑分子之tail構造（後述）之間溶劑不易進入，顏料分散體（顏料、與附著在其周圍的分散劑之並稱）形成附著物。此外顏料濃度太高，則硬化性組成物的塗佈膜乾燥時’膜中的顏料分散體的含量太多，依然因爲溶劑變得不易滲入膜中，而易成爲附著物。硬化物組成物中所含有的黏合劑樹脂的分子量，愈小者愈易與溶劑溶在一起，塗膜化後再浸漬於溶劑時易再分散。惟，分子量愈小，因爲顏料彼此易凝聚而分散變不安定，故一度乾燥則易成爲附著物。硬化物組成物中所含有的分散劑相對於顏料之含量亦 -12- 200804974 (10) 重要，太少則分散體不安定，而顏料易凝聚，容易變成異物，而且，如同後述，附著劑（a)的量亦隨著分散劑或溶劑的種類而改變。特別是使硬化性組成物的水分量在上述[1 -1 ]所記載的範圍，對於逹成本發明之上述的數値範圍而言有效果。The pigment dispersion is preferably carried out in such a manner that a pigment dispersion having a sufficiently stable quality can be obtained. Insufficient dispersion means that the amount of the dispersing agent attached to the pigment is insufficient. When the pigment dispersion liquid in this state is once cured into a coating film, the exposed portion of the pigment is increased, and even if it is immersed in a solvent again, it does not dissolve; when the dispersion is excessively excessive, the dispersant adheres to the surface of the pigment retentively and closely. When such a pigment dispersion liquid is once cured into a coating film, even if it is immersed in a solvent again, the solvent does not easily enter between the tail structure (described later) having a dispersant molecule, and the pigment dispersion (pigment, and a dispersant attached thereto) It is said to form an attachment. Further, when the concentration of the pigment is too high, the content of the pigment dispersion in the film is too large when the coating film of the curable composition is dried, and the solvent tends to be infiltrated into the film, which tends to become a deposit. The smaller the molecular weight of the binder resin contained in the cured composition, the easier it is to dissolve with the solvent, and it is easily dispersed after being immersed in a solvent after coating. However, the smaller the molecular weight, the more the pigments are easily agglomerated and the dispersion becomes unstable, so that once dried, it tends to become an adherent. The content of the dispersant contained in the hardened composition relative to the pigment is also -12-200804974 (10). If the dispersion is too small, the dispersion is unstable, and the pigment tends to aggregate and easily become foreign matter, and, as will be described later, the adhesive agent ( The amount of a) also varies with the type of dispersant or solvent. In particular, the moisture content of the curable composition is in the range described in the above [1 - 1 ], and is effective for the above-described range of the invention.

像這樣藉由適當調整硬化性組成物的水分量、或上述的各種構成成份的種類或量、或顏料分散條件等，可得到於本發明的塗佈適性評估方法（I)中附著量（a)成爲2pg以下之硬化性組成物。 [1-3]黏度本發明的硬化性組成物，係在常壓下以3 5 °C保存2 週時的黏度上升爲l.Ocps以下，較佳爲低於0.5cps。黏度增加的硬化性組成物，因爲容易產生塗佈不均勻或乾燥不均勻，又在極端情況下要塗佈於基板上這件事困難或不可能，故事實上無法製造彩色濾光片。硬化性組成物之保存後的黏度上升多於l.Ocps，則很難使用其製造商業用的彩色濾光片。再者，本發明中「黏度」之意，係指用E型黏度計在測量試料量1.0ml、測量溫度23°C、旋轉數20rpm所測量的數値。硬化性組成物的黏度增加的原因有幾個，可列舉例如磷酸丙烯酸酯與水分共存。如專利文獻3等所記載，爲提高使用硬化性組成物所形成的畫素對基板的密合性，會有使硬化性組成物中含有磷酸丙烯酸酯的情況。惟，含有磷 -13- 200804974 (11) 酸丙烯酸酯之硬化性組成物，再含有水’則該硬化性組成物會隨著保存而黏度上升，因而降低影像形成性。具體而言，發生例如無法從擠壓式塗佈法的噴嘴均句地噴出硬化生組成物而發生塗佈不均勻或塗佈條紋、旋轉塗佈時滴下液無法充分均勻地擴散而發生放射狀的不均勻或塗佈殘留、無法充分地進行乾燥時的塗平而變成不均勻等之問題。By appropriately adjusting the moisture content of the curable composition, the type or amount of the above various constituent components, or the pigment dispersion conditions, etc., the amount of adhesion in the coating suitability evaluation method (I) of the present invention can be obtained (a). ) is a curable composition of 2 pg or less. [1-3] Viscosity The curable composition of the present invention has a viscosity increase of 1.0 cp or less, preferably less than 0.5 cps, when stored at 35 ° C for 2 weeks under normal pressure. The hardenable composition having an increased viscosity is difficult or impossible to apply due to uneven coating or uneven drying, and it is difficult or impossible to apply it to a substrate in an extreme case, so that a color filter cannot be manufactured in fact. It is difficult to use a commercial color filter for the viscosity increase of the hardenable composition after the retention of the viscosity is more than 1.0 cps. Further, the term "viscosity" in the present invention means a number measured by an E-type viscometer measuring a sample amount of 1.0 ml, a measurement temperature of 23 ° C, and a number of revolutions of 20 rpm. There are several reasons why the viscosity of the curable composition increases, and for example, phosphoric acid acrylate and moisture coexist. In the case of improving the adhesion of the pixel formed using the curable composition to the substrate, the phosphoric acid acrylate may be contained in the curable composition. However, if the curable composition containing phosphorus -13-200804974 (11) acid acrylate contains water, the curable composition will increase in viscosity as it is stored, thereby lowering image formation properties. Specifically, for example, it is not possible to uniformly eject the cured raw material from the nozzle of the extrusion coating method to cause coating unevenness or coating streaks, and the dripping liquid cannot be sufficiently uniformly diffused during spin coating to be radially formed. There is a problem that unevenness or coating remains, and the coating at the time of drying cannot be sufficiently performed to become uneven.

本發明的硬化性組成物，不含有磷酸丙烯酸酯、或磷酸丙烯酸酯的含量爲5重量％以下爲佳’更佳爲3重量％以下，最佳爲0重量％(不含）。由抑制黏度上升之觀點而言，磷酸丙烯酸酯的含量愈少愈好。此外黏度上升的原因，可列舉因爲過度的顏料分散而顯示出結構黏性、因爲樹脂或單體的暗反應而產生聚合等。不管原因爲任何一種，狀況皆相同，硬化性組成物的保存後的黏度大幅上升至大於l.Ocps，則在商業上製造彩色濾光片方面變成大的問題。接著，詳細說明關於本發明的硬化性組成物的構成成份。本發明的硬化性組成物，係含有（A)黏合劑樹脂、（B) 單體、(C)溶劑及（D)顏料之硬化性組成物，其特徵爲該硬化性組成物的水分含量爲0.4重量％以上2.0重量％以下，於下述的塗佈適性評估方法（I)中，被形成於玻璃試驗片的一稜線上的附著物（a)爲2 以下，而且在常壓下以35 -14- (12) 200804974 t保存2週時的黏度上升爲l.Ocps以下。此外，必要時可再含有（E)分散劑、其他的成份等。The curable composition of the present invention contains no phosphoric acid acrylate or phosphoric acid acrylate in an amount of preferably 5% by weight or less, more preferably 3% by weight or less, and most preferably 0% by weight (excluding). From the viewpoint of suppressing the increase in viscosity, the less the content of the phosphoric acid acrylate is, the better. Further, the reason for the increase in viscosity is that the structure is sticky due to excessive pigment dispersion, and polymerization occurs due to a dark reaction of a resin or a monomer. Regardless of the cause, the conditions are the same, and the viscosity of the curable composition after storage is greatly increased to more than 1.0 cps, which becomes a big problem in the commercial manufacture of color filters. Next, the constituent components of the curable composition of the present invention will be described in detail. The curable composition of the present invention contains (A) a binder resin, (B) a monomer, (C) a solvent, and (D) a curable composition of a pigment, wherein the curable composition has a moisture content of 0.4% by weight or more and 2.0% by weight or less, in the coating suitability evaluation method (I) described below, the deposit (a) formed on the ridge line of the glass test piece is 2 or less, and 35 at normal pressure. -14- (12) 200804974 t The viscosity at 2 weeks of storage was increased to below 1.0 cps. Further, if necessary, (E) a dispersant, other components, and the like may be contained.

再者，「（甲基）丙烯基」、「（甲基）丙烯酸酯」等之意，係指「丙烯基及/或甲基丙烯基」、「丙烯酸酯及/或甲基丙烯酸酯」等，例如「（甲基）丙烯酸」之意係指「丙烯酸及/或甲基丙烯酸」。此外「總固體成份」之意，係指後述之溶劑成份以外的本發明的硬化性組成物的總成份。 [1-4](A)黏合劑樹脂本發明的硬化性組成物以黏合劑樹脂作爲必須成份，黏合劑樹脂例如可使用特開平7-20721 1號、特開平8-259876號、特開平10-300922號、特開平11-140144號、特開平1 1 - 1 74224號、特開2000-56 1 1 8號、特開2003- 23 3 1 79號等之各公報等中所記載的習知的高分子化合物，惟關於作爲（A)黏合劑樹脂特別佳者，說明如下。 (A-1) : 「相對於含環氧基之（甲基）丙烯酸酯、與其他的自由基聚合性單體之共聚物，於該共聚物所具有的環氧基的至少一部份上加成不飽和一元酸，再於藉由該加成反應所產生的羥基的至少一部份上加成多元酸後所得到的鹼可溶性樹脂」特別佳的樹脂的其中之一，可列擧「相對於含環氧基之（甲基）丙烯酸酯5〜90莫耳％、與其他的自由基聚合性單體10〜95莫耳％之共聚物，於該共聚物所具有的環氧基的10〜100莫耳％上加成不飽和一元酸，再於藉由該加 -15- 200804974 (13) 成反應所產生的羥基的10〜100莫耳％上加成多元酸後所得到的鹼可溶性樹脂」。In addition, "(meth)acrylyl", "(meth)acrylate", etc. mean "acrylic and / or methacryl", "acrylate, / / methacrylate", etc. For example, "(meth)acrylic" means "acrylic acid and/or methacrylic acid". Further, the meaning of "total solid content" means the total amount of the curable composition of the present invention other than the solvent component described later. [1-4] (A) Adhesive Resin The curable resin of the present invention has an adhesive resin as an essential component, and the adhesive resin can be, for example, JP-A-7-20721 No. 1, No. 8-259876, and No. 10 Conventions described in each of the publications of Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The polymer compound is particularly preferred as the (A) binder resin. (A-1): "copolymer with respect to an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, at least a part of the epoxy group of the copolymer Addition of an unsaturated monobasic acid to an alkali-soluble resin obtained by adding a polybasic acid to at least a portion of a hydroxyl group produced by the addition reaction", one of which is particularly preferable. a copolymer of 5 to 90 mol% with respect to the epoxy group-containing (meth) acrylate and 10 to 95 mol% with respect to the other radical polymerizable monomer, and an epoxy group of the copolymer a base obtained by adding an unsaturated monobasic acid to 10 to 100 mol%, and then adding a polybasic acid to 10 to 100 mol% of the hydroxyl group produced by the reaction of the addition of -15-200804974 (13) Soluble resin".

此含環氧基之（甲基）丙烯酸酯，可列舉例如（甲基）丙烯酸環氧丙酯、（甲基）丙烯酸3,4-環氧基丁酯、（甲基）丙烯酸（3,4-環氧基環己基）甲酯、（甲基）丙烯酸4-羥基丁酯環氧丙基醚等。其中又以（甲基）丙烯酸環氧丙酯爲佳，此等含環氧基之（甲基）丙烯酸酯可單獨使用1種或可倂用2 種以上。與上述含環氧基之（甲基）丙烯酸酯共聚合之其他的自由基聚合性單體，較佳爲具有下述一般式（1)所表示的結構之單（甲基）丙烯酸酯。Examples of the epoxy group-containing (meth) acrylate include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and (meth)acrylic acid (3,4). -Epoxycyclohexyl)methyl ester, 4-hydroxybutyl (meth)acrylate, epoxypropyl ether, and the like. Further, the epoxy group-containing (meth) acrylate is preferable, and the epoxy group-containing (meth) acrylate may be used singly or in combination of two or more. The other radical polymerizable monomer which is copolymerized with the above epoxy group-containing (meth) acrylate is preferably a mono(meth)acrylate having a structure represented by the following general formula (1).

(1) 式（1)中，Rl〜R6各自獨立地表示氫原子、或碳數1 〜3的烷基，R7及R8各自獨立地表示氫原子、碳數1〜3 的烷基，或可連結後形成環。式（1)中，R7及R8連結後所形成的環，以脂肪族環爲佳，可爲飽和或不飽和，或碳數5〜6者較佳。其中，一般式（1)所表不的結構，以下述式（1 a)、 -16- 200804974 (14) (lb)、或（1c)所表示的結構爲佳。藉由於黏合劑樹脂導入此等的結構，將本發明的硬化性組成物使用於彩色濾光片或液晶顯示元件時，可提高該硬化性組成物的耐熱性，及增加使用該硬化性組成物所形成的畫素的強度。再者’具有一般式（1)所表示的結構之單（甲基）丙烯酸酯’可單獨使用1種，或可並倂用2種以上。(1) In the formula (1), R1 to R6 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R7 and R8 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; After the connection, a ring is formed. In the formula (1), the ring formed by the combination of R7 and R8 is preferably an aliphatic ring, and may be saturated or unsaturated, or preferably having a carbon number of 5 to 6. Among them, the structure represented by the general formula (1) is preferably a structure represented by the following formula (1 a), -16-200804974 (14) (lb), or (1c). When the curable resin is introduced into the color filter or the liquid crystal display element by the introduction of the adhesive resin, the heat resistance of the curable composition can be improved, and the use of the curable composition can be increased. The intensity of the formed pixels. Further, the mono(meth)acrylates having the structure represented by the general formula (1) may be used singly or in combination of two or more.

[化2][Chemical 2]

具有上述一般式（1)所表示的結構之單（甲基）丙烯酸酯’只要具有該結構者即可，可使用各種習知者，特別是下述一般式（2)所表示者爲佳。 [化3] (2) CH2= C— C 一Ο一The mono(meth)acrylate having the structure represented by the above general formula (1) may be any one as long as it has such a structure, and it is preferable to use it in particular, as shown by the following general formula (2). [2] (2) CH2=C-C

II 0 -17- 200804974 (15) 式（2)中，R9表示氫原子或甲基，Ri〇表示上述一般式 (1)的結構。II 0 -17- 200804974 (15) In the formula (2), R9 represents a hydrogen atom or a methyl group, and Ri 〇 represents a structure of the above general formula (1).

於上述含環氧基之（甲基）丙烯酸酯、與其他的自由基聚合性單體之共聚物中，源自具有一般式（丨)所表示的結構之單（甲基）丙烯酸酯之重複單元，係在源自「其他的自由基單體」的重複單元中，含有5〜90莫耳者爲佳，含有 1 0〜7 0莫耳％者更佳’含有1 5〜5 0莫耳者特別佳。再者’具有一般式（1)所表示的結構之單（甲基）丙烯酸酯以外之其他的自由基單體」，並沒有特別的限制，具體而言’可列舉例如苯乙烯、苯乙烯的Q -、〇_、m-、P-烷基、硝基、氰基、醯胺基、酯衍生物等之乙烯芳香族類；丁二烯、2,3·二甲基丁二烯、異戊二烯、氯丁二烯等之二烯類；（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸-n_丙酯、（甲基）丙烯酸-iS0·丙酯、（甲基）丙烯酸 η-丁酯、（甲基）丙嫌酸-sec_ 丁酯、（甲基）丙烯酸-tert· 丁酯、（甲基）丙烯酸戊酯、（甲基）丙烯酸新戊酯、（甲基）丙烯酸異戊酯、（甲基）丙烯酸己酯、（甲基）丙烯酸-2-乙基己酯、（甲基）丙烯酸月桂酯、（甲基）丙烯酸十二烷酯、（甲基）丙烯酸環戊酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸-2-甲基環己酯、（甲基）丙烯酸二環己酯、（甲基）丙烯酸異冰片酯、（甲基）丙烯酸金剛烷酯、（甲基）丙烯酸炔丙酯、（甲基）丙烯酸苯酯、（甲基）丙烯酸萘酯、（甲基）丙烯酸蒽酯、（甲基）丙烯酸蒽醌酯、（甲基）丙烯酸胡椒酯、（甲基）丙烯酸水 -18- (16) 200804974In the copolymer of the above epoxy group-containing (meth) acrylate and another radical polymerizable monomer, a repeat of a mono(meth) acrylate derived from a structure represented by the general formula (丨) The unit is preferably in the repeating unit derived from "other radical monomers", preferably containing 5 to 90 moles, and containing 10 to 70 moles per mole of the more 'containing 1 5 to 5 0 moles. Especially good. Further, the radical monomer other than the mono(meth)acrylate having the structure represented by the general formula (1) is not particularly limited, and specific examples thereof include styrene and styrene. Ethylene aromatics such as Q-, 〇_, m-, P-alkyl, nitro, cyano, decylamine, ester derivatives; butadiene, 2,3·dimethylbutadiene, a diene such as pentadiene or chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, (meth)acrylic acid-n-propyl ester, (meth)acrylic acid-iS0·c Ester, η-butyl (meth)acrylate, (meth)acrylic acid-sec-butyl ester, (meth)acrylic acid-tert. butyl ester, amyl (meth)acrylate, neopentyl (meth)acrylate Ester, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, (Methyl) cyclopentyl acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate , isobornyl (meth)acrylate, adamantyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, bismuth (meth)acrylate Ester, decyl (meth)acrylate, piperonyl (meth)acrylate, water (meth)acrylate-18- (16) 200804974

楊酯、（甲基）丙烯酸呋喃酯、（甲基）丙烯酸糠酯、（甲基）丙烯酸四氫呋喃酯、（甲基）丙燏酸吡喃酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸苯乙酯、（甲基）丙烯酸甲酚酯、（甲基）丙烯酸-1，1，1 -三氟乙酯、（甲基）丙烯酸全氟乙酯、（甲基）丙烯酸全氟-n_丙酯、（甲基）丙烯酸全氟-iso-丙酯、（甲基）丙烯酸三苯基甲酯、（甲基）丙烯酸枯烯酯、（甲基）丙烯酸 3-(N，N-二甲基胺基）丙酯、（甲基）丙烯酸-2-羥基乙酯、（甲基）丙烯酸-2-羥基丙酯等之（甲基）丙烯酸酯類；（甲基）丙烯酸醯胺、（甲基）丙烯酸N，N-二甲基醯胺、(甲基）丙烯酸 N，N-二乙基醯胺、（甲基）丙烯酸N，N-二丙基醯胺、（甲基）丙烯酸N，N-二-iso-丙基醯胺、（甲基）丙烯酸蒽基醯胺等之 (甲基）丙烯酸醯胺；（甲基）丙烯酸苯胺、（甲基）丙烯醯腈、丙烯醛、氯乙烯、偏氯乙烯、氟乙烯、偏氟乙烯、N-乙烯吡咯烷酮、乙烯吡啶、乙酸乙烯等之乙烯化合物類；檸康酸二乙酯、馬來酸二乙酯、富馬酸二乙酯、衣康酸二乙酯等之不飽和二羧酸二酯類；N-苯基馬來酸酐縮亞胺、 N-環己基馬來酸酐縮亞胺、N-月桂基馬來酸酐縮亞胺、N-(4·羥基苯基）馬來酸酐縮亞胺等之單馬來酸酐縮亞胺；N-(甲基）丙烯醯基酞醯亞胺等。此等「其他的自由基單體」之中，爲了對硬化性組成物賦予優異的耐熱性及強度，使用至少一種選自苯乙烯、 (甲基）丙烯酸苄酯、及單馬來酸酐縮亞胺爲有效的作法。特別是源自「其他的自由基單體」之重複單元中，此等源自苯乙烯、（甲基）丙烯酸苄酯、及單馬來酸酐縮亞胺所選 -19 -Salicylate, furyl (meth)acrylate, decyl (meth)acrylate, tetrahydrofuran (meth)acrylate, pyryl (meth)propionate, benzyl (meth)acrylate, (methyl) Phenylethyl acrylate, cresyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoro-n (meth)acrylate _propyl ester, perfluoro-iso-propyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-di(meth)acrylate a (meth) acrylate such as methylamino)propyl ester, 2-hydroxyethyl (meth)acrylate or 2-hydroxypropyl (meth)acrylate; decyl (meth)acrylate; N,N-dimethyl decylamine, methyl N,N-diethyl decylamine (meth) acrylate, N,N-dipropyl decylamine (meth) acrylate, (meth)acrylic acid N , N-di-iso-propyl decylamine, (meth)acrylic acid decylamine, etc.; (meth)acrylic acid aniline, (meth)acrylonitrile, propylene , vinyl compounds such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, etc.; diethyl citrate, diethyl maleate, diethyl fumarate An unsaturated dicarboxylic acid diester such as ester or diethyl itaconate; N-phenyl maleic anhydride imide, N-cyclohexyl maleic anhydride imide, N-lauryl maleic anhydride A monomaleic acid anhydride imide such as an amine or N-(4-hydroxyphenyl)maleic acid imide; N-(meth)acrylonitrile ruthenium imine or the like. Among these "other radical monomers", at least one selected from the group consisting of styrene, benzyl (meth) acrylate, and monomaleic anhydride is used in order to impart excellent heat resistance and strength to the curable composition. Amines are an effective practice. In particular, in the repeating unit derived from "other radical monomers", such sources are selected from styrene, benzyl (meth) acrylate, and monomaleic anhydride.

200804974 (17) 的至少一種之重複單元的含有比例，1〜70莫耳佳，3〜5 0莫耳％更佳。再者’上述含環氧基之（甲基）丙烯酸酯、與上的自由基聚合性單體之共聚合反應，適合使用習知聚合法’所使用的溶劑只要是對自由基聚合爲惰可，並未限制爲何物，可使用一般所使用的有機溶此溶劑的具體例子，可列舉乙酸乙酯、乙酸異溶纖劑乙酸酯、丁基溶纖劑乙酸酯等之乙二醇單烷酸酯類；二乙二醇單甲基醚乙酸酯、卡必醇乙酸酯卡必醇乙酸酯等之二乙二醇單烷基醚乙酸酯類；丙烷基醚乙酸酯類；二丙二醇單烷基醚乙酸酯類等之類；乙二醇二烷基醚類；甲基卡必醇、乙基卡必醇卡必醇等之二乙二醇二烷基醚類；二乙二醇二烷基丙二醇二烷基醚類；二丙二醇二烷基醚類；1，4-二四氫呋喃等之醚類；丙酮、甲基乙基酮、甲基異丁環己酮等之酮類；苯、甲苯、二甲苯、辛烷、癸烷類；石油醚、石腦油、氫化石腦油、溶劑石腦油等系溶劑；乳酸甲酯、乳酸乙酯、乳酸丁酯等之乳酸二甲基甲醯胺、N-甲基吡咯烷酮等。此等溶劑可用，亦可倂用2種以上，此等的溶劑的使用量，相得到的共聚物100重量份，通常爲30〜1 000重量佳爲50〜800重量份，溶劑的使用量在此範圍外則的分子量控制變難。此外，共聚反應所使用的自由基聚合起始劑， %者爲述其他的溶液性者即劑。丙酯、基醚乙、丁基二醇單乙酸酯、丁基醚類；嚼院、基酮、等之烴之石油酯類；單獨使對於所份，較共聚物只要是 -20 - 200804974 (18)200804974 (17) The proportion of the repeating unit of at least one of the types is preferably from 1 to 70 mol, and more preferably from 3 to 50 mol%. Further, the copolymerization of the above epoxy group-containing (meth) acrylate and the above radical polymerizable monomer is preferably a solvent used in the conventional polymerization method as long as it is inert to the radical polymerization. Specific examples of the organic solvent to be used in general use may be used, and examples thereof include ethylene glycol monoalkanoic acid such as ethyl acetate, isocyanuric acid acetate, and butyl cellosolve acetate. Ethylene ester; diethylene glycol monomethyl ether acetate such as diethylene glycol monomethyl ether acetate; carbitol acetate carbitol acetate; propane ether acetate; dipropylene glycol Monoalkyl ether acetates and the like; ethylene glycol dialkyl ethers; di-glycol dialkyl ethers such as methyl carbitol and ethyl carbitol carbitol; diethylene glycol Dialkyl propylene glycol dialkyl ethers; dipropylene glycol dialkyl ethers; ethers such as 1,4-ditetrahydrofuran; ketones such as acetone, methyl ethyl ketone, methyl isobutyl cyclohexanone; , toluene, xylene, octane, decane; petroleum ether, naphtha, hydrogenated naphtha, solvent naphtha, etc. ; Methyl lactate, ethyl lactate, butyl lactate, etc. dimethylformamide, N- methylpyrrolidone and the like. These solvents may be used, and two or more kinds may be used. The amount of the solvent used is 100 parts by weight of the copolymer obtained, usually 30 to 1,000 weights, preferably 50 to 800 parts by weight, and the solvent is used in an amount of Molecular weight control outside this range becomes difficult. Further, as the radical polymerization initiator used in the copolymerization reaction, % is the other solution agent. Propyl ester, ethyl ether, butyl glycol monoacetate, butyl ether; petroleum esters of chewable, ketone, and the like; alone, for the portion, the copolymer is only -20 - 200804974 (18)

可使自由基聚合開始者即可，並沒有特別的限制’可使用一般所使用的有機過氧化物催化劑或偶氮化合物催化劑。此有機過氧化物催化劑，可列舉被分類爲習知的酮過氧化物、過氧化酮縮醇、氫過氧化物、二烯丙基過氧化物、二醯基過氧化物、過氧化酯、過氧化二碳酸酯者。其具體例子，可列舉苯甲醯過氧化物、二枯烯基過氧化物、二異丙基過氧化物、二-t-丁基過氧化物、t-丁基過氧化苯甲酸酯、t -己基過氧化苯甲酸酯、t -丁基過氧化-2-乙基己酸酯、t-己基過氧化-2-乙基乙酸酯、1，1-雙（t-丁基過氧化）_ 3,3,5-三甲基環己烷、2,5-二甲基-2,5-雙（t-丁基過氧化）己基-3,3-異丙基氫過氧化物、t-丁基氫過氧化物、二枯稀基過氧化物、二枯烯基氫過氧化物、乙醯基過氧化物、雙 (4_t_ 丁基環己基）過氧化二碳酸酯、二異丙基過氧化二碳酸酯、異丁基過氧化物、3,3,5-三甲基己醯基過氧化物、月桂基過氧化物、1，1-雙（t·丁基過氧化）3,3,5-三甲基環己烷、1，1_雙（t-己基過氧化）3,3,5-三甲基環己烷等。此外，偶氮化合物催化劑，可列舉偶氮雙異丁腈、偶氮雙碳醯胺等。此等中依聚合溫度，適當的半衰期的自由基聚合起始劑使用1種或2種以上，自由基聚合起始劑的使用量，相對於共聚反應所使用的單體的合計100重量份，爲0.5〜 20重量份，較佳爲1〜1〇重量份。共聚反應，可將共聚反應所使用的單體及自由基聚合起始劑溶解於溶劑，一邊攪拌一邊昇溫，亦可將添加自由基聚合起始劑的單體滴於經昇溫、攪拌的溶劑中，反應條 -21 - 200804974 (19) 件可依目標的分子量而自由改變。The radical polymerization can be started, and it is not particularly limited. An organic peroxide catalyst or an azo compound catalyst which is generally used can be used. The organic peroxide catalyst may be exemplified by a conventional ketone peroxide, a ketal ketal, a hydroperoxide, a diallyl peroxide, a decyl peroxide, a peroxyester, Peroxydicarbonate. Specific examples thereof include benzamidine peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, T-hexylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethyl acetate, 1,1-bis(t-butyl Oxidation)_3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyl-3,3-isopropylhydroperoxide , t-butyl hydroperoxide, di- lysyl peroxide, di- cumenyl hydroperoxide, ethoxylated peroxide, bis(4_t-butylcyclohexyl)peroxydicarbonate, diiso Propyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexyl peroxide, lauryl peroxide, 1,1-bis(t-butylperoxide) 3,3,5-trimethylcyclohexane, 1,1-bis(t-hexylperoxy) 3,3,5-trimethylcyclohexane, and the like. Further, examples of the azo compound catalyst include azobisisobutyronitrile and azobiscarbamide. In this case, one or two or more kinds of radical polymerization initiators having an appropriate half-life are used, and the amount of the radical polymerization initiator used is 100 parts by weight based on the total of the monomers used in the copolymerization reaction. It is 0.5 to 20 parts by weight, preferably 1 to 1 part by weight. In the copolymerization reaction, the monomer used in the copolymerization reaction and the radical polymerization initiator may be dissolved in a solvent, and the temperature may be raised while stirring, or the monomer to which the radical polymerization initiator is added may be dropped into a solvent which is heated and stirred. , Reaction Strip-21 - 200804974 (19) Pieces can be freely changed depending on the molecular weight of the target.

於本發明，上述含環氧基之（甲基）丙烯酸酯、與上述其他的自由基聚合性單體之共聚物，較佳爲由源自含環氧基之（甲基）丙烯酸酯的重複單元5〜90莫耳％、與源自其他的自由基聚合性單體的重複單元1 0〜9 5莫耳％所成者，由前者20〜80莫耳％、與後者80〜20莫耳％所成者更佳，由前者30〜70莫耳％、與後者70〜30莫耳％所成者特別佳。含環氧基之（甲基）丙烯酸酯太少，則會有後述之聚合成份及鹼可溶性成份的加成量變不足之虞，另一方面，含環氧基之（甲基）丙烯酸酯太多，而其他的自由基聚合性單體太少，則會有耐熱性或強度變不足的可能性。接著，使含環氧基之（甲基）丙烯酸酯、與其他的自由基聚合性單體之共聚物的環氧基部份，與不飽和一元酸 (聚合性成份）、及多元酸酐（鹼可溶性成份）反應。加成於環氧基之不飽和一元酸，可使用習知者，可列舉例如乙烯性不飽和雙鍵之不飽和羧酸。具體例子可列舉（甲基）丙烯酸、巴豆酸、〇·、m-、ρ· 乙烯苯甲酸、α -位被鹵烷基、烷氧基、鹵原子、硝基、或氰基等取代之（甲基）丙烯酸等之單羧酸等。其中較佳者爲（甲基）丙烯酸，此等可單獨使用1種，或可倂用2種以上。藉由加成如此成份，可對本發明所使用的黏合劑樹脂賦予聚合性。 -22- 200804974 (20) 此等的不飽和一元酸，一般被加成於上述共聚物所具有的環氧基的10〜100莫耳％，但較佳爲加成於30〜100 莫耳％，更佳爲加成於 5 〇〜1 〇〇莫耳％。不飽和一元酸的加成比例太少，則關於硬化性組成物的經時安定性等，擔心會因爲殘留環氧基而造成壞的影響。再者，於共聚物的環氧基加成不飽和一元酸之方法，可使用習知的方法。In the present invention, the copolymer of the epoxy group-containing (meth) acrylate and the other radical polymerizable monomer described above is preferably a repeat derived from an epoxy group-containing (meth) acrylate. The unit 5 to 90% by mole, and the repeating unit derived from other radical polymerizable monomers, 10 to 9.5 % by mole, from the former 20 to 80 mol%, and the latter 80 to 20 mol % is better, from the former 30 to 70 mol%, and the latter 70 to 30 mol% is particularly good. When the epoxy group-containing (meth) acrylate is too small, the amount of addition of the polymerization component and the alkali-soluble component described later becomes insufficient, and on the other hand, the epoxy group-containing (meth) acrylate is too much. On the other hand, when other radical polymerizable monomers are too small, there is a possibility that heat resistance or strength is insufficient. Next, an epoxy group of an epoxy group-containing (meth) acrylate and a copolymer of another radical polymerizable monomer, an unsaturated monobasic acid (polymerizable component), and a polybasic acid anhydride (alkali) Soluble component) reaction. As the unsaturated monobasic acid to be added to the epoxy group, a conventional one may be used, and an unsaturated carboxylic acid such as an ethylenically unsaturated double bond may be listed. Specific examples include (meth)acrylic acid, crotonic acid, hydrazine, m-, ρ·vinylbenzoic acid, α-position substituted by haloalkyl group, alkoxy group, halogen atom, nitro group, or cyano group ( A monocarboxylic acid or the like such as methyl)acrylic acid. The preferred one is (meth)acrylic acid, and these may be used alone or in combination of two or more. By adding such a component, the adhesive resin used in the present invention can be imparted with polymerizability. -22- 200804974 (20) These unsaturated monobasic acids are generally added to 10 to 100 mol% of the epoxy group of the above copolymer, but preferably added to 30 to 100 mol%. More preferably, it is added to 5 〇~1 〇〇耳 %. When the addition ratio of the unsaturated monobasic acid is too small, the stability of the curable composition with respect to time and the like may be adversely affected by the residual epoxy group. Further, a conventional method can be used for the method of adding an unsaturated monobasic acid to the epoxy group of the copolymer.

而且，加成於共聚物的環氧基加成不飽和一元酸時所產生的羥基之多元酸酐，可使用習知者。可列舉例如馬來酸酐、琥珀酸酐、衣康酸酐、酞酸酐、四氫酞酸酐、六氫酞酸酐、氯菌酸酐等之二元酸酐；偏苯三酸酐、均苯四甲酸酐、二苯甲酮四竣酸野、聯苯四羧酸酐等之三元以上的酸之酐。其中又以四氫酞酸酐、及 /或琥珀酸酐爲佳，此等的多元酸酐可單獨使用1種，或可倂用2種以上。藉由加成如此的成份，可對本發明所使用的黏合劑樹脂賦予鹼可溶性。此等的多元酸酐，通常被加成於藉由使該共聚物所具有的環氧基加成不飽和一元酸所產生的羥基的10〜100莫耳％，惟較佳加成於2 0〜9 0莫耳％，更佳爲加成於3 〇〜 8 0莫耳％。此加成比例太多則會有顯影時的殘膜率降低之虞，太少則會有溶解性變不足的可能性，再者，作爲於該羥基加成多元酸酐之方法’可採用習知的方法。而且，爲了提高光感度，加成上述多元酸酐後，亦可在所生成的羧基的一部份加成具有（甲基）丙烯酸環氧丙酯 -23· 200804974 (21) 或聚合性不飽和基之環氧丙基醚化合物。此外，爲了提高顯影性，亦可在所生成的羧基的一部份加成不具有聚合性不飽和基之環氧丙基醚化合物。又，亦可加成此兩者。Further, a polybasic acid anhydride which is added to the hydroxyl group which is produced when the epoxy group of the copolymer is added to the unsaturated monobasic acid can be used. Examples thereof include dibasic acid anhydrides such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chloric anhydride; trimellitic anhydride, pyromellitic anhydride, and benzophenone tetramine. An acid anhydride of a trivalent or higher acid such as acid field or biphenyl tetracarboxylic anhydride. Further, tetrahydrofurfuric anhydride and/or succinic anhydride are preferable. These polybasic acid anhydrides may be used alone or in combination of two or more. By adding such a component, the binder resin used in the present invention can be made alkali-soluble. These polybasic acid anhydrides are usually added in an amount of 10 to 100 mol% of a hydroxyl group produced by adding an epoxy group having an unsaturated monobasic acid to the copolymer, but preferably added to 2 0~ 9 0% by mole, more preferably added to 3 〇~8 0% by weight. If the addition ratio is too large, the residual film ratio at the time of development may be lowered. If the addition ratio is too small, the solubility may be insufficient. Further, as a method of adding a polybasic acid anhydride to the hydroxyl group, conventional methods may be employed. Methods. Further, in order to increase the photosensitivity, after the addition of the polybasic acid anhydride, a part of the generated carboxyl group may be added with a glycidyl (meth)acrylate-23· 200804974 (21) or a polymerizable unsaturated group. The epoxy propyl ether compound. Further, in order to improve the developability, a glycidyl ether compound having no polymerizable unsaturated group may be added to a part of the produced carboxyl group. Also, you can add both.

不具有聚合性不飽和基之環氧丙基醚化合物之具體例子，可列舉具有苯基或烷基之環氧丙基醚化合物等。市售品可列舉例如Nagase化成工業公司製的商品名「Denacol EX-111」、「Denacol EX-121」、「Denacol EX-141」、「Denacol EX-145」、「Denacol EX-146」、「Denacol EX-171」、「Denacol EX-192」等。再者，關於如此的樹脂的結構，例如特開平 8-2973 66號公報或特開200 1 -895 3 3號公報所記載，皆爲習知者。上述的黏合劑樹脂之以GPC測量的聚苯乙烯換算的重量平均分子量（Mw)較佳爲 3 000〜1 00000，特別佳爲 5000〜50000。分子量低於3000則會有耐熱性或膜強度差可能性，超過1 00000，則會有對於顯影液的溶解性不足的傾向。此外，以分子量分佈爲簡單的標準，重量平均分子量（Mw)/數平均分子量（Μη)之比爲2.0〜5.0較佳。 (Α-2):含羧基之直鏈狀鹼可溶性樹脂含羧基之直鏈狀鹼可溶性樹脂，只要是具有羧基者即可，並沒有特別的限制，可使含羧基之聚合性單體進行聚合後得到。. 含羧基之聚合性單體，可列舉例如（甲基）丙烯酸、馬 -24- 200804974 (22)Specific examples of the glycidyl ether compound having no polymerizable unsaturated group include a epoxidized propyl ether compound having a phenyl group or an alkyl group. For example, the product names "Denacol EX-111", "Denacol EX-121", "Denacol EX-141", "Denacol EX-145", "Denacol EX-146", and "" manufactured by Nagase Chemical Industry Co., Ltd." Denacol EX-171", "Denacol EX-192", etc. In addition, the structure of such a resin is described in the Japanese Patent Publication No. Hei. The polystyrene-equivalent weight average molecular weight (Mw) of the above-mentioned binder resin measured by GPC is preferably from 3,000 to 10,000, particularly preferably from 5,000 to 50,000. When the molecular weight is less than 3,000, the heat resistance or the film strength may be poor. When the molecular weight is more than 10,000, the solubility in the developer tends to be insufficient. Further, in terms of a simple molecular weight distribution, the ratio of the weight average molecular weight (Mw) / number average molecular weight (?η) is preferably 2.0 to 5.0. (Α-2): a linear alkali-soluble resin having a carboxyl group and a carboxyl group-containing linearly soluble resin, as long as it has a carboxyl group, and is not particularly limited, and a carboxyl group-containing polymerizable monomer can be polymerized. After getting it. The carboxyl group-containing polymerizable monomer may, for example, be a (meth)acrylic acid or a horse -24-200804974 (22)

來酸、巴豆酸、衣康酸、富馬酸、2-(甲基）丙烯醯基氧基乙基琥珀酸、2-(甲基）丙烯醯基氧基乙基己二酸、2-(甲基）丙烯醯基氧基乙基馬來酸、2·(甲基）丙烯醯基氧基乙基六氫酞酸、2-(甲基）丙烯醯基氧基乙基酞酸、2-(甲基）丙烯醯基氧基丙基琥珀酸、2-(甲基）丙烯醯基氧基丙基己二酸、2-(甲基）丙烯醯基氧基丙基馬來酸、2-(甲基）丙烯醯基氧基丙基氫酞酸、2-(甲基）丙烯醯基氧基丙基酞酸、2-(甲基）丙烯醯基氧基丁基琥珀酸、2-(甲基）丙烯醯基氧基丁基己二酸、2-(甲基）丙烯醯基氧基丁基馬來酸、2-(甲基）丙烯醯基氧基丁基氫酞酸、2-(甲基）丙烯醯基氧基丁基酞酸等之乙烯系單體；於丙烯酸加成ε-己內酯、丙內酯、r-丁內酯、5-戊內酯等之內酯類之單體；於羥基烷基（甲基）丙烯酸酯加成琥珀酸、馬來酸、衣康酸、富馬酸、或此等的酐等之酸或酐之單體，此等可使用複數種。其中較佳者爲（甲基）丙烯酸、2-(甲基）丙烯醯基氧基乙基琥珀酸，更佳爲（甲基）丙烯酸。此外，含羧基之直鏈狀鹼可溶性樹脂，亦於上述含羧基之聚合性單體，共聚不含羧基之其他的聚合性單體。其他的聚合性單體，並沒有特別的限制，但可列舉 (甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、（甲基）丙烯酸異丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸苯酯、（甲基）丙稀酸環己酯、（甲基）丙烯酸苯氧基乙酯、（甲基）丙烯酸苯氧基甲酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸 -25- (23) 200804974Acid, crotonic acid, itaconic acid, fumaric acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(methyl) propylene decyloxyethyl adipate, 2-( Methyl) propylene decyloxyethyl maleic acid, 2·(methyl) propylene decyloxyethyl hexahydrophthalic acid, 2-(methyl) propylene decyloxyethyl decanoic acid, 2- (Meth) propylene decyloxypropyl succinic acid, 2-(methyl) propylene methoxy propyl adipic acid, 2-(methyl) propylene methoxy propyl maleic acid, 2- (methyl) propylene decyloxypropyl hydroquinone, 2-(methyl) propylene methoxy propyl decanoic acid, 2-(methyl) propylene decyl oxy butyl succinic acid, 2- Methyl)propenyloxybutyl adipate, 2-(methyl)propenyloxybutyl maleic acid, 2-(methyl)propenyloxybutyl hydroquinone, 2- a vinyl monomer such as (meth)acryloyloxybutyl phthalic acid; a lactone such as ε-caprolactone, propyl lactone, r-butyrolactone or 5-valerolactone a monomer; a hydroxyalkyl (meth) acrylate addition succinic acid, maleic acid, itaconic acid, fumaric acid, or an anhydride thereof Of the acid or anhydride monomer, plural kinds of these can be used. Preferred among them are (meth)acrylic acid and 2-(methyl)acrylonitrile-based oxyethyl succinic acid, and more preferably (meth)acrylic acid. Further, the linear alkali-soluble resin having a carboxyl group is also copolymerized with another polymerizable monomer having no carboxyl group in the above carboxyl group-containing polymerizable monomer. The other polymerizable monomer is not particularly limited, and examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and isopropyl (meth)acrylate. Methyl)butyl acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxy (meth)acrylate Ethyl ethyl ester, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic acid-25- (23) 200804974

異冰片酯、（甲基）丙烯酸2-羥基乙酯、單（甲基）丙烯酸甘油酯、（甲基）丙烯酸四氫糠酯等之（甲基）丙烯酸酯類；苯乙烯及其衍生物等之乙烯芳香族類；N-乙烯吡咯烷酮等之乙烯化合物類；N-環己基馬來酸酐縮亞胺、N-苄基馬來酸酐縮亞胺等之N_取代馬來酸酐縮亞胺類；聚（甲基）丙烯酸甲酯巨單體、聚苯乙烯巨單體、聚（甲基）丙烯酸2-羥基乙酯巨單體、聚乙二醇巨單體、聚丙二醇巨單體、聚己內酯巨單體等之巨單體類等；此等可倂用複數種。特別佳者可列舉苯乙烯、（甲基）丙烯酸甲酯、（甲基）丙烯酸環己酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸4-羥基丁酯、（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸羥基丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸異丁酯、N-環己基馬來酸酐縮亞胺、N-苄基馬來酸酐縮亞胺、N-苯基馬來酸酐縮亞胺。含羧基之直鏈狀鹼可溶性樹脂，可再具有羥基。含有羥基之單體，可列舉（甲基）丙烯酸2-羥基乙酯、（甲基）丙烯酸羥基丙酯、（甲基）丙烯酸4-羥基丁酯等之（甲基）丙烯酸羥基烷酯、單（甲基）丙烯酸甘油酯。藉由使此等與上述各種單體共聚，可得到含有羧基及羥基之樹脂。含羧基之直鏈狀鹼可溶性樹脂，具體而言，可列舉例如（甲基）丙烯酸，與（甲基）丙烯酸甲酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸環己酯、環己基馬來酸酐縮亞胺等之不含羥基之聚合性單體，與（甲基）丙烯酸2_羥基乙酯、（甲基）丙烯酸羥基 -26- 200804974 (24) 丙酯、（甲基）丙烯酸4-羥基丁酯等之含有羥基之單體之共聚物；（甲基）丙烯酸，與（甲基）丙烯酸甲酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸異丁酯、（甲基）丙烯酸2-羥基乙酯等之（甲基）丙烯酸酯之共聚物；（甲基）丙烯酸與苯乙烯之共聚物；（甲基）丙烯酸與苯乙烯與α — 甲基苯乙烯之共聚物；（甲基）丙烯酸與環己基馬來酸酐縮亞胺之共聚物等。(meth)acrylates such as isobornyl ester, 2-hydroxyethyl (meth)acrylate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate; styrene and its derivatives, etc. a vinyl aromatic compound; an ethylene compound such as N-vinylpyrrolidone; an N-substituted maleic anhydride imide such as N-cyclohexylmaleic acid imide or N-benzyl maleic anhydride; Polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly(meth)acrylic acid 2-hydroxyethyl macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polyhexyl Macromonomers such as lactone giant monomers; etc.; Particularly preferred are styrene, methyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid 2 -hydroxyethyl ester, hydroxypropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, N-cyclohexylmaleic anhydride imide, N-benzyl maleic anhydride Imine, N-phenylmaleic anhydride imine. The linear alkali-soluble resin having a carboxyl group may further have a hydroxyl group. Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. (meth)acrylic acid glyceride. By copolymerizing these with the above various monomers, a resin containing a carboxyl group and a hydroxyl group can be obtained. Specific examples of the linear alkali-soluble resin having a carboxyl group include (meth)acrylic acid, methyl (meth)acrylate, benzyl (meth)acrylate, and butyl (meth)acrylate. a hydroxyl group-free polymerizable monomer such as isobutyl acrylate, cyclohexyl (meth) acrylate, cyclohexyl maleic anhydride, or the like, and 2-hydroxyethyl (meth) acrylate, (methyl) Acrylic acid hydroxy-26- 200804974 (24) a copolymer of a hydroxyl group-containing monomer such as propyl ester or 4-hydroxybutyl (meth)acrylate; (meth)acrylic acid, and methyl (meth)acrylate; a copolymer of (meth) acrylate such as benzyl methacrylate, butyl (meth) acrylate, isobutyl (meth)acrylate or 2-hydroxyethyl (meth)acrylate; (methyl) a copolymer of acrylic acid and styrene; a copolymer of (meth)acrylic acid and styrene and α-methylstyrene; a copolymer of (meth)acrylic acid and cyclohexylmaleic anhydride imide.

由具有優異的顏料分散性之觀點而言，特別佳爲含有 (甲基）丙烯酸苄酯之共聚物樹脂。本發明中之含羧基之直鏈狀鹼可溶性樹脂的酸値，一般爲 30〜5 00KOHmg/g，較佳爲 40〜3 5 0KOHmg/g，更佳爲 50 〜3 00KOHmg/g。此外，以GPC測量的聚苯乙烯換算的重量平均分子量（Mw)通常爲 2000〜80000，較佳爲 3 000〜50000，更佳爲4000〜30000。重量平均分子量太少則會有硬化性組成物的安定性差的傾向，太大則使用於後述彩色濾光片或液晶顯示裝置時會有對於顯影液的溶解性變差的傾向。 (A-3):於（A-2)樹脂的羧基部份上加成含環氧基的不飽和化合物之樹脂於上述（A-2)含羧基之樹脂的羧基部份上加成含環氧基的不飽和化合物之樹脂亦特別佳。含環氧基的不飽和化合物，只要是分子內具有乙烯性不飽和基及環氧基者即可，並爲特別限定爲何物。可列舉例如（甲基）丙烯酸環氧丙酯、烯丙基環氧丙基 -27· 200804974 (25) 醚、環氧丙基-α-乙基丙烯酸酯、巴豆醯基環氧丙基醚、 (異）巴豆酸環氧丙基醚、Ν-(3,5-二甲基-4-環氧丙基）苄基丙烯醯胺、4-羥基丙基（甲基）丙烯酸酯環氧丙基醚等之含有非環式環氧基之不飽和化合物，但由耐熱性、或後述的顏料的分散性的觀點而言，以含有脂環式環氧基之不飽和化合物爲佳。From the viewpoint of having excellent pigment dispersibility, a copolymer resin containing benzyl (meth)acrylate is particularly preferred. The acid hydrazine of the carboxyl group-containing linear alkali-soluble resin in the present invention is usually 30 to 500 KOH mg/g, preferably 40 to 3 5 KOH mg/g, more preferably 50 to 300 KOH mg/g. Further, the weight average molecular weight (Mw) in terms of polystyrene measured by GPC is usually from 2,000 to 80,000, preferably from 3,000 to 50,000, more preferably from 4,000 to 30,000. When the weight average molecular weight is too small, the stability of the curable composition tends to be poor, and when it is too large, the solubility in the developing solution tends to be deteriorated when used in a color filter or a liquid crystal display device to be described later. (A-3): a resin obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group of the (A-2) resin to form a ring-containing ring on the carboxyl group of the above (A-2) carboxyl group-containing resin The resin of the oxy unsaturated compound is also particularly preferred. The epoxy group-containing unsaturated compound is not particularly limited as long as it has an ethylenically unsaturated group and an epoxy group in the molecule. Examples thereof include glycidyl (meth)acrylate, allyl epoxypropyl-27·200804974 (25) ether, epoxypropyl-α-ethyl acrylate, and crotonyl epoxypropyl ether. (iso)crotonic acid epoxidized propyl ether, hydrazine-(3,5-dimethyl-4-epoxypropyl)benzyl acrylamide, 4-hydroxypropyl (meth) acrylate epoxy propyl The unsaturated compound containing an acyclic epoxy group, such as an ether, is preferably an unsaturated compound containing an alicyclic epoxy group from the viewpoint of heat resistance or dispersibility of a pigment to be described later.

此處之含有脂環式環氧基之不飽和化合物，此脂環式環氧基可列舉例如2,3-環氧基環戊基、3,4-環氧基環己基' 7,8 -環氧[三環[5.2.1.0]癸-2基]基等。此外，乙烯性不飽和基，以源自（甲基）丙烯醯基者爲佳，較適合的含脂環式環氧基不飽和化合物，可列舉下述一般式（3a)〜（3m) 所表示的化合物。Here, the alicyclic epoxy group-containing unsaturated compound may, for example, be a 2,3-epoxycyclopentyl group or a 3,4-epoxycyclohexyl group 7,8- Epoxy [tricyclo[5.2.1.0]癸-2yl] group and the like. Further, the ethylenically unsaturated group is preferably a (meth) acrylonitrile-based group, and a more preferable alicyclic epoxy group-containing unsaturated compound is exemplified by the following general formulas (3a) to (3m). The compound represented.

-28- 200804974 (26) [化4]-28- 200804974 (26) [Chem. 4]

R"0 I IIR"0 I II

Cft =c—c 一οCft = c - c one o

(3 a)(3 a)

RuORuO

I III II

Cft =C-C - O-R* RliO I II r CHr «C-C-O-R1 (3 b) (3 c)Cft = C-C - O-R* RliO I II r CHr «C-C-O-R1 (3 b) (3 c)

κιιο 〇 CH2=C—C-f〇-Rt3-C%O-R R"0 I II , ch2 -c一c-o一ri2-o R^O CH* «C-C-O-R^-CH X> (3d)Κιιο 〇 CH2=C—C-f〇-Rt3-C%O-R R"0 I II , ch2 -c a c-o-ri2-o R^O CH* «C-C-O-R^-CH X> (3d)

(3e) (3 f) R"0 I II CHt «—0-(3e) (3 f) R"0 I II CHt «—0-

tzp> OH RllO 0 I II 4,八 II CHt «-O- rmo H O (3g) CHi *C-C-0-R* HO R，_〇 I II CH* -C-C-0Tzp> OH RllO 0 I II 4, eight II CHt «-O- rmo H O (3g) CHi *C-C-0-R* HO R,_〇 I II CH* -C-C-0

CHt -O-C O〇 (3 h) (3CHt -O-C O〇 (3 h) (3

(3 j)(3 j)

Rll〇 I II CH: =C—C-0 HO R"0 R11 I II t Cft =C-C—N—R1Rll〇 I II CH: =C—C-0 HO R"0 R11 I II t Cft =C-C—N—R1

(3 k) ，t> (3 I) R"0 R1 I II f CHt «C-C-N-Rn-0-：(3 k) ,t> (3 I) R"0 R1 I II f CHt «C-C-N-Rn-0-:

R,iO (3 m) 式（3 a)〜（3 m)中，R11表示氫原子或甲基，R12表示伸烷基、R13表示2價的烴基，n爲1〜10的整數。於一般式（3 a)〜（3 m)，R 12之伸烷基，較佳爲碳數1〜 -29- (27) 200804974 1 0者，具體而言，可舉例伸甲基、伸乙基、伸丙基、伸丁基，但較佳爲伸甲基、伸乙基、伸丙基。又，R13的烴基，以碳數1〜1 〇者爲佳，可列舉伸院基、伸苯基等。含有此等的脂環式環氧基之不飽和化合物，可單獨使用1種，或可倂用2種以上。其中又以一般式（3c)所表示的化合物爲佳，特別佳爲 (甲基）丙烯酸3,4-環氧基環己基甲酯。R, iO (3 m) In the formula (3 a) to (3 m), R11 represents a hydrogen atom or a methyl group, R12 represents an alkylene group, R13 represents a divalent hydrocarbon group, and n is an integer of 1 to 10. In the general formula (3 a) to (3 m), an alkylene group of R 12 , preferably a carbon number of 1 to -29-(27) 200804974 1 0, specifically, a methyl group, a stretching type B can be exemplified. Base, propyl, butyl, but preferably methyl, ethyl, propyl. Further, the hydrocarbon group of R13 is preferably a carbon number of 1 to 1, and examples thereof include a stretching base and a stretching phenyl group. The unsaturated compound containing the alicyclic epoxy group may be used singly or in combination of two or more. Among them, a compound represented by the general formula (3c) is preferred, and a 3,4-epoxycyclohexylmethyl (meth)acrylate is particularly preferred.

於上述（A-2)含羧基之樹脂的羧基部份，加成上述含環氧基之不飽和化合物，可使用習知的方法，例如藉由使含羧基之樹脂與含環氧基不飽和化合物，在三乙胺、苄基甲胺等之3級胺；十二烷基三甲基銨氯化物、四甲基銨氯化物、四乙基銨氯化物、四丁基銨氯化物、苄基三乙基銨氯化物等之4級銨鹽；吡啶、三苯基膦等之解媒的存在下，在有機溶劑，以反應溫度50〜150°C進行數小時〜數十小時反應，可於樹脂的羧基導入含環氧基之不飽和化合物。導入含環氧基之不飽和化合物之含羧基之樹脂的酸値，一般爲 10 〜200KOHmg/g，較佳爲 20 〜150KOHmg/g ，更佳爲 30 〜150KOHmg/g。此外，以GPC測量的聚苯乙烯換算的重量平均分子量通常爲 2000〜100000，較佳爲 4000〜50000，更佳爲 5000〜30000 ° (A-4”丙烯酸系樹脂 (A-4)丙烯酸系樹脂，可謂以丙烯酸及/或丙烯酸酯作 -30- 200804974 (28) 爲單體成份，使此等進行聚合所成的聚合物。較佳的丙嫌酸系樹脂，可列舉例如（A-4-1):使含有（甲基）丙烯酸及 (甲基）丙烯酸苄酯之單體成份進行聚合所成的單體、及 (A-4-2):使以下述一般式（4)及/或（5)所表示的化合物爲必須成份之單體進行聚合所成的聚合物。 [化5]The above-mentioned (A-2) carboxyl group-containing resin may be added to the above epoxy group-containing unsaturated compound by a conventional method, for example, by subjecting a carboxyl group-containing resin to an epoxy group-containing unsaturated group. a compound, a tertiary amine such as triethylamine or benzylmethylamine; dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, benzyl a tertiary ammonium salt such as a triethylammonium chloride or the like; in the presence of a crystallization medium such as pyridine or triphenylphosphine, the reaction is carried out in an organic solvent at a reaction temperature of 50 to 150 ° C for several hours to several tens of hours. An epoxy group-containing unsaturated compound is introduced into the carboxyl group of the resin. The hydrazine of the carboxyl group-containing resin to which the epoxy group-containing unsaturated compound is introduced is usually 10 to 200 KOHmg/g, preferably 20 to 150 KOHmg/g, more preferably 30 to 150 KOHmg/g. Further, the polystyrene-equivalent weight average molecular weight measured by GPC is usually from 2,000 to 100,000, preferably from 4,000 to 50,000, more preferably from 5,000 to 30,000 ° (A-4" acrylic resin (A-4) acrylic resin. It is a polymer obtained by polymerizing such acrylic acid and/or acrylate as -30-200804974 (28). A preferred acrylic acid is exemplified by (A-4- 1): a monomer obtained by polymerizing a monomer component containing (meth)acrylic acid and benzyl (meth)acrylate, and (A-4-2): using the following general formula (4) and/or (5) The compound represented by the polymerization of a monomer which is an essential component. [Chemical 5]

式（4)中，111&及R2a各自獨立地表示氫原子或可具有取代基之碳數1〜25的烴基。 [化6]In the formula (4), 111 & and R2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. [Chemical 6]

X 式（5)中，Rlb表示氫原子或可具有取代基之院基，L, 表示2價的連結基或直接鍵結，X表示下述式^ (6)表示之基或可被取代之金剛烷基。 -31 - •…（6) 200804974 (29) [化7]In the formula (5), Rlb represents a hydrogen atom or a substituent group which may have a substituent, L represents a divalent linking group or a direct bond, and X represents a group represented by the following formula (6) or may be substituted Adamantyl. -31 - •...(6) 200804974 (29) [Chem. 7]

式（6)中，R2b、R3b及R4b各自獨立地表示氫原子、羥基、鹵素原子、胺基、或有機基，L1、L2表示2價的連結基，L3表示2價的連接基或直接結合鍵，L1、L2、L3的 2個以上可互相鍵結而形成環。 (A_4-l):使含有（甲基）丙烯酸及（甲基）丙烯酸苄酯之單體成份進行聚合所成的單體使含有（甲基）丙烯酸及（甲基）丙烯酸苄酯之單體成份進行聚合所成的單體，由與顏料的親和性高的觀點而言，較適合被使用。於單體成份中之上述（甲基）丙烯酸及（甲基）丙烯酸苄酯的比例，並無特別限制，惟總單體成份中（甲基）丙烯酸通常爲10〜90重量％，較佳爲15〜80重量％，更佳爲20 〜7 0重量％。此外，（甲基）丙烯酸苄酯，在總單體成份中通常爲5〜90重量％，較佳爲15〜80重量％，更佳爲20 〜70重量％。（甲基）丙烯酸的量太多，則顯影時會有塗膜表面易變乾裂，太少則會有無法顯影之情況。此外，（甲基）丙烯酸苄酯的量，太多或太少皆會有分散變困難的傾向。 (A - 4 · 2):使以下述一般式（4)及/或（5 )所表示的化合物爲必須成份之單體成份進行聚合所成的聚合物 -32- 200804974 (30) 首先，說明關於一般式（4)的化合物。In the formula (6), R2b, R3b and R4b each independently represent a hydrogen atom, a hydroxyl group, a halogen atom, an amine group or an organic group, L1 and L2 represent a divalent linking group, and L3 represents a divalent linking group or a direct bond. Two or more of the keys L1, L2, and L3 may be bonded to each other to form a ring. (A_4-l): a monomer obtained by polymerizing a monomer component containing (meth)acrylic acid and benzyl (meth)acrylate to form a monomer containing (meth)acrylic acid and benzyl (meth)acrylate The monomer obtained by polymerizing the component is preferably used from the viewpoint of high affinity with the pigment. The ratio of the above (meth)acrylic acid and benzyl (meth)acrylate in the monomer component is not particularly limited, but the total monomer component (meth)acrylic acid is usually 10 to 90% by weight, preferably 15 to 80% by weight, more preferably 20 to 70% by weight. Further, benzyl (meth)acrylate is usually 5 to 90% by weight, preferably 15 to 80% by weight, more preferably 20 to 70% by weight based on the total monomer component. If the amount of (meth)acrylic acid is too large, the surface of the coating film may be easily cracked during development, and if it is too small, development may not be possible. Further, the amount of benzyl (meth) acrylate, too much or too little, tends to be difficult to disperse. (A - 4 · 2): a polymer obtained by polymerizing a monomer represented by the following general formula (4) and/or (5) as an essential component - 32 - 200804974 (30) First, description Regarding the compound of the general formula (4).

一般式（4)所表示的醚二聚物，Rla及R2a各自獨立地表不氫原子或可具有取代基之碳數1〜2 5的烴基，並沒_ 別的限制，但可列舉例如甲基、乙基、η-丙基、異丙基、 η · 丁基、異丁基、t - 丁基、t -戊基、硬脂釀基、月桂甚 2_乙基己基等之直鏈狀或支鏈狀的烷基；苯基等之芳基，環己基、t-丁基環己基、二環戊二烯、三環癸基、異冰片基、金剛烷基、2-甲基-2-金剛烷基等之脂環式基；被ι 甲氧基乙基、1-乙氧基乙基等之烷氧基取代之烷基；被节基等之芳基取代之院基等。此等中又以如甲基、乙基、 % 己基、苄基等之用酸或熱不易脫離的1級或2級碳的取代基，由耐熱性的觀點而言特別佳。再者，Rl a及R2a可爲同種類的取代基，或可爲相異的取代基。上述醚二聚物的具體例子，可列舉例如二甲基_2,2，_ [氧基雙（伸甲基）]雙-2-丙烯酸酯、二乙基_2,2，-[氧基雙（伸甲基）]雙-2-丙烯酸酯、二（η -丙基）-2,2，-[氧雙（伸甲基）]雙-2_丙烯酸酯、二（異丙基）-2,2，-[氧雙（伸甲基雙丙烯酸醋、一-丁基）-2,2 -[_雙（伸甲基）]雙-2 -丙燦酸醋、二 (異丁基）-2,2’-[氧雙（伸甲基）]雙-2-丙烯酸酯、二（t_丁基卜 2,2’-[氧雙（伸甲基）]雙-2-丙烯酸酯、二（t·戊基）_2,2，·[氧雙（伸甲基）]雙-2-丙烯酸酯、二（硬脂醯基）-2,2，_[氧雙（伸甲基）]雙-2-丙烯酸酯、二（月桂基）_2,2，-[氧雙（伸甲基）] 雙-2-丙烯酸酯、二（2-乙基己基）-2,2，-[氧雙（伸甲基）]雙_ 2 -丙烯酸酯、二（1-甲氧基乙基）-2,2，-[氧雙（伸甲基）]雙- 2- -33- (31) 200804974In the ether dimer represented by the general formula (4), Rla and R2a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent, and are not particularly limited, but may, for example, be a methyl group. , ethyl, η-propyl, isopropyl, η·butyl, isobutyl, t-butyl, t-pentyl, stearyl, laurel, 2-ethylhexyl, etc. Branched alkyl; aryl group such as phenyl, cyclohexyl, t-butylcyclohexyl, dicyclopentadiene, tricyclodecyl, isobornyl, adamantyl, 2-methyl-2- An alicyclic group such as an adamantyl group; an alkyl group substituted with an alkoxy group such as an methoxymethyl group or a 1-ethoxyethyl group; or a substituted group substituted with an aryl group such as a benzyl group; Further, in the above, a substituent such as a methyl group, an ethyl group, a hexyl group or a benzyl group which is difficult to remove with an acid or heat is particularly preferred from the viewpoint of heat resistance. Further, Rl a and R2a may be the same kind of substituents or may be different substituents. Specific examples of the above ether dimer include, for example, dimethyl-2,2,-[oxybis(methyl)]bis-2-acrylate, diethyl-2,2,-[oxy Bis (methyl) bis-2-acrylate, bis(η-propyl)-2,2,-[oxybis(methyl)]bis-2-acrylate, di(isopropyl)- 2,2,-[oxybis(methyl bis-acrylic acid vinegar, mono-butyl)-2,2-[_bis(methyl)]bis-2-propanol vinegar, di(isobutyl) -2,2'-[oxybis(methyl)]bis-2-acrylate, di(t-butyl 2,2'-[oxybis(methyl))bis-2-acrylate, Bis(t.pentyl)_2,2,·[oxybis(methyl)]bis-2-acrylate, bis(stearyl)-2,2,_[oxybis(methyl)] Bi-2-acrylate, bis(lauryl)_2,2,-[oxybis(methyl)]bis-2-acrylate, di(2-ethylhexyl)-2,2,-[oxygen double (methyl) bis- 2 -acrylate, bis(1-methoxyethyl)-2,2,-[oxo(methyl)]bis- 2-33- (31) 200804974

丙烯酸酯、二（1-乙氧基乙基）·2,2，-[氧雙（伸甲基）]雙-2-丙烯酸酯、二苄基-2,2’-[氧雙（伸甲基雙-2-丙烯酸酯、二苯基_2,2’-[氧雙（伸甲基）]雙_2-丙烯酸酯、二環己基-2,2，-[氧雙（伸甲基）]雙-2-丙烯酸酯、二（t-丁基環己基）-2,2，-[氧雙（伸甲基）]雙-2-丙烯酸酯、二（二環戊二烯基）-2,2，-[氧雙（伸甲基）]雙-2-丙烯酸酯、二（三環癸基）_2,2，_[氧雙 (伸甲基）]雙-2-丙烯酸酯、二（異冰片基>2,2，-[氧雙（伸甲基）]雙-2-丙烯酸酯、二金剛烷基-2,2，-[氧雙（伸甲基）]雙_ 2-丙烯酸酯、二（2-甲基-2-金剛烷基）一2,2，-[氧雙（伸甲基）] 雙-2-丙烯酸酯等。此等中特別佳爲二甲基-2,2，_[氧雙（伸甲基）]雙-2-丙烯酸酯、二乙基_2,2，_[氧雙（伸甲基）]雙- 2-丙烯酸酯、二環己基-2,2’·[氧雙（伸甲基）]雙-2-丙烯酸酯、二苄基-2,2’-[氧雙（伸甲基雙-2_丙烯酸酯，此等醚二聚物可僅單獨使用1種，或可倂用2種以上。得到該該（A-4)丙烯酸系樹脂時之單體成份中之該醚一聚物’並沒有特別的限制，但在總單體成份中，通常爲 2〜60重量％，較佳爲5〜55重量％，更佳爲5〜50重量 %。醚二聚物的量太多，則會有聚合時很難得到低分子量者’或變得不易凝朦化之虞，另一方面，太多則會有透明性或耐熱性等之塗膜性能不足之虞。接著，說明關於一般式（5)的化合物。一般式（5 )中，11115較佳爲表示氫原子、碳數1〜5的烷基，再更佳爲氫原子、甲基。一般式（6)中，R2b、11315及尺^的有機基，可各自獨立 -34-Acrylate, bis(1-ethoxyethyl)·2,2,-[oxybis(methyl)]bis-2-acrylate, dibenzyl-2,2'-[oxybis (extension) Bis-2-acrylate, diphenyl-2,2'-[oxybis(methyl)]bis_2-acrylate, dicyclohexyl-2,2,-[oxybis(methyl) Bis-2-acrylate, bis(t-butylcyclohexyl)-2,2,-[oxybis(methyl)]bis-2-acrylate, bis(dicyclopentadienyl)-2 , 2,-[oxybis(methyl)]bis-2-acrylate, bis(tricyclodecyl)_2,2,_[oxybis(methyl)]bis-2-acrylate, Isobornyl group>2,2,-[oxybis(methyl)]bis-2-acrylate, diamantyl-2,2,-[oxybis(methyl)]bis-2-acrylate Ester, bis(2-methyl-2-adamantyl)-2,2,-[oxybis(methyl)]bis-2-acrylate, etc. Particularly preferred in this class is dimethyl-2. 2, _[oxybis(methyl))bis-2-acrylate, diethyl-2,2,_[oxybis(methyl)]bis-2-acrylate, dicyclohexyl-2, 2'·[Oxobis(methyl))bis-2-acrylate, dibenzyl-2,2'-[oxybis(methyl-bis-2-propene) The ester dimer may be used alone or in combination of two or more. The ether monomer in the monomer component when the (A-4) acrylic resin is obtained is not particularly preferable. The limitation, but in the total monomer component, is usually 2 to 60% by weight, preferably 5 to 55% by weight, more preferably 5 to 50% by weight. If the amount of the ether dimer is too large, polymerization may occur. When it is difficult to obtain a low molecular weight one, or it becomes difficult to coagulate, on the other hand, if too much, there is a lack of film properties such as transparency or heat resistance. Next, the general formula (5) is explained. In the general formula (5), 11115 is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group. In the general formula (6), R2b, 11315 and a ruler ^ Organic base, can be independent -34-

200804974 (32) 地列舉例如烷基、環烷基、烯基、環烯基基、羧基、或醯氧基等，較佳爲碳數1〜18 3〜18的環烷基、碳數2〜18的烯基、碳數基、碳數1〜15的烷氧基、碳數1〜15的疼〜15的醯基、碳數1的羧基、或碳數1〜更佳爲碳數1〜10的烷基、或碳數3〜15的 R2b、、R4b中較佳的取代基爲氫原數1〜1 〇的烷基。 L1、L2爲2價的連結基，L3只要是2 直接結合鍵即可，沒有受到特別的限制，至一者爲碳數1以上的連結基爲佳，L1、L2、爲直接結合鍵、碳數1〜15的伸院基、-0_ 、碳數1〜1 5的伸烯基、伸苯基、或此等的。、。、：^的較佳的組合^系^爲德數1〜5的伸烷基、或與R3b、R4b鍵結後充爲碳數1〜5的伸烷基。此外’ 一般式（6)的較佳者，可列舉下表示的化合物。 [化8] 、烷硫基、醯的烷基、碳數 3〜1 8的環烯 S硫基、碳數1 1 5的醯氧基，環烷基。子、羥基、碳價的連結基或少L1或L2任 L3各自獨立地、-S-、-c( = 0)- 組合亦可。 :接結合鍵、碳多成環，L1、L2 述一般式（7)所200804974 (32), for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, a carboxyl group, a decyloxy group or the like, preferably a cycloalkyl group having a carbon number of 1 to 18 3 to 18, and a carbon number of 2~ 18 alkenyl group, carbon number group, alkoxy group having 1 to 15 carbon atoms, fluorenyl group having a carbon number of 1 to 15 and having a carbon number of 1 or a carbon number of 1 or more preferably a carbon number of 1 to 1. A preferred substituent among the alkyl group of 10 or R2b and R4b having 3 to 15 carbon atoms is an alkyl group having a hydrogen number of 1 to 1 Torr. L1 and L2 are a divalent linking group, and L3 is not particularly limited as long as it is a direct bonding bond. It is preferable that one is a linking group having a carbon number of 1 or more, and L1 and L2 are direct bonding bonds and carbon. Number 1 to 15 of the stretching base, -0_, carbon number 1 to 15 of the alkenyl group, phenyl group, or the like. ,. A preferred combination of :, ^ is an alkylene group having a number of 1 to 5 or an alkylene group having a carbon number of 1 to 5 bonded to R3b and R4b. Further, the preferred ones of the general formula (6) include the compounds shown below. An alkyl group of an alkylthio group or an anthracene, a cycloolefin having a carbon number of 3 to 18, a sulfenyl group having 1 to 5 carbon atoms, or a cycloalkyl group. The linking group of a sub-, a hydroxyl group or a carbon valence may be a combination of L1 or L2 or L3, and -S-, -c(= 0)- may be used independently. : Connect the bond, carbon to form a ring, L1, L2, the general formula (7)

-35- 200804974 (33) 式 7 中，R2b、R3b、R4b、L·1、L2 與式（6)相同，R5b、 R6b各自獨立表示氫原子、羥基、鹵素原子、胺基、或有機基。-35- 200804974 (33) In the formula 7, R2b, R3b, R4b, L·1, and L2 are the same as those in the formula (6), and each of R5b and R6b independently represents a hydrogen atom, a hydroxyl group, a halogen atom, an amine group, or an organic group.

一般式（7)中，R5b及R6b的有機基，可各自獨立地列舉例如烷基、環烷基、烯基、環烯基、烷氧基、烷硫基、醯基、羧基、或醯氧基等，較佳爲碳數1〜18的烷基、碳數3〜18的環烷基、碳數2〜18的烯基、碳數3〜18的環烯基、碳數1〜15的烷氧基、碳數1〜15的烷硫基、碳數 1〜15的醯基、碳數1的羧基、或碳數1〜15的醯氧基，更佳爲碳數1〜10的烷基、或碳數3〜15的環烷基。 R5b、R6b中較佳的取代基爲氫原子、羥基、碳數1〜 1 〇的烷基。此外，Rlb的烷基、R2b、R3b、R4b的各有機基、L1、 L2、L3的2價連結基、X的金剛烷基，各自獨立，可具有取代基，具體而言可列舉以下的取代基。鹵素原子；羥基；硝基；氰基；甲基、乙基、η-丙基、異丙基、η-丁基、異丁基、卜丁基、戊基、t-戊基、 n -己基、η-庚基、η -辛基、t -羊基等之碳數1〜18的直鏈或支鏈的烷基；環丙基、環丁基、環戊基、環己基、金剛烷基等之碳數3〜1 8的環烷基；乙烯基、丙烯基、己烯基等之碳數2〜18的直鏈或支鏈的烯基；環戊烯、環己烯等之碳數3〜18的環烯基；甲氧基、乙氧基、丙氧基、異丙氧基、η-丁氧基、s-丁氧基、t-丁氧基、戊氧基、卜戊氧基、η-己氧基、η-庚氧基、η·辛氧基、t-辛氧基等之碳 -36- (34) 200804974In the general formula (7), the organic groups of R5b and R6b may each independently give, for example, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkoxy group, an alkylthio group, a decyl group, a carboxyl group, or a ruthenium oxide. The group or the like is preferably an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a cycloalkenyl group having 3 to 18 carbon atoms, and a carbon number of 1 to 15 An alkoxy group, an alkylthio group having 1 to 15 carbon atoms, a mercapto group having 1 to 15 carbon atoms, a carboxyl group having 1 carbon number, or a decyloxy group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms. a base or a cycloalkyl group having a carbon number of 3 to 15. Preferred substituents in R5b and R6b are a hydrogen atom, a hydroxyl group, and an alkyl group having 1 to 1 carbon atom. Further, the alkyl group of R1b, the respective organic groups of R2b, R3b, and R4b, the divalent linking group of L1, L2, and L3, and the adamantyl group of X may each independently have a substituent, and specifically, the following substitutions may be mentioned. base. Halogen atom; hydroxy; nitro; cyano; methyl, ethyl, η-propyl, isopropyl, η-butyl, isobutyl, butyl, pentyl, t-pentyl, n-hexyl, η a linear or branched alkyl group having 1 to 18 carbon atoms such as a heptyl group, an η-octyl group or a t-羊 group; a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group or the like. a cycloalkyl group having 3 to 18 carbon atoms; a linear or branched alkenyl group having 2 to 18 carbon atoms such as a vinyl group, a propenyl group or a hexenyl group; a carbon number of 3 to 18 of a cyclopentene or a cyclohexene; a cycloalkenyl group of 18; methoxy, ethoxy, propoxy, isopropoxy, η-butoxy, s-butoxy, t-butoxy, pentyloxy, pentyloxy, Carbon of η-hexyloxy, η-heptyloxy, η-octyloxy, t-octyloxy, etc. -36- (34) 200804974

數1〜18的直鏈或支鏈的烷氧基；甲硫基、乙硫基、η-丙硫基、異丙硫基、η -丁硫基、s -丁硫基、t -丁硫基、戊硫基、t -戊硫基、η -己硫基、η·庚硫基、η -辛硫基、t -辛硫基等之碳數1〜18的直鏈或支鏈的烷硫基；苯基、甲苯基、二甲苯基、米基等之碳數6〜18的芳基；苄基、苯乙基等之碳數7〜18的芳烷基；乙烯氧基、丙烯氧基、己烯氧基等之碳數2〜18的直鏈或支鏈的燒氧基；乙j：希硫基、戊烯硫基、己烯硫基等之碳數2〜1 8的直鏈或支鏈的烯硫基；-COR17所表示的醯基；竣基；-OCOR18所表示的酸氧基；-NR19R2()所表示的胺基；-NHCOR21所表示的醯胺基；-NHCOOR22所表示的胺基甲酸酯；-CONR23R24所表示的胺基甲醯基；-COOR25所表示的羧酸酯基； -S〇3NR26R27所表示的胺磺醯基；-S〇3R28所表示的磺酸酯基’ 2 _噻嗯基、2 -啦B定基、呋喃基、B惡嗤基、苯並螺口坐基、噻U坐基、苯並噻唑基、嗎啉代基、吡咯院基、四氫噻吩二氧化物基等之飽和或不飽和的雜環基；三甲基矽垸基等之三烷基矽烷基等。再者’ R17〜R18各自表示氫原子、可具有取代基之烷基、可具有取代基之嫌基、可具有取代基之芳基、或可具有取代基之芳烷基。此外’上述取代基的位置關係並沒有特別的限制，但具有複數的取代基時，可同種類或不同種類。一般式（5)所表示化合物的具體例子例舉如下。 -37- (35) 200804974 [化9]a straight or branched alkoxy group of 1 to 18; methylthio, ethylthio, η-propylthio, isopropylthio, η-butylthio, s-butylthio, t-butyl sulfide a linear or branched alkane having a carbon number of 1 to 18, such as a thiol group, a pentylthio group, a t-pentylthio group, an η-hexylthio group, a η-heptylthio group, a η-octylthio group, a t-octylthio group or the like a thio group; an aryl group having a carbon number of 6 to 18 such as a phenyl group, a tolyl group, a xylyl group or a methylene group; an aralkyl group having a carbon number of 7 to 18 such as a benzyl group or a phenethyl group; a vinyloxy group and a propylene oxide; a straight or branched alkoxy group having a carbon number of 2 to 18, such as a hexenyloxy group; a straight carbon or a branched alkoxy group having a carbon number of 2 to 18; and a carbon number of 2 to 18 such as a heptylthio group, a pentenethio group or a hexenethio group; Alkylthio group of a chain or a branched chain; an indenyl group represented by -COR17; an anthracene group; an acidoxy group represented by -OCOR18; an amine group represented by -NR19R2(); an amidino group represented by -NHCOR21; -NHCOOR22 a carbazate represented by the formula; an aminocarbenyl group represented by -CONR23R24; a carboxylate group represented by -COOR25; an aminesulfonyl group represented by -S〇3NR26R27; a sulfon represented by -S〇3R28; Acid ester group ' 2 _ thiophene group, 2 - 啦 B group, furyl group, B oxime group, benzopyro a saturated or unsaturated heterocyclic group such as a thiol group, a benzothiazolyl group, a morpholino group, a pyrrole group or a tetrahydrothiophene dioxide group; a trialkyl decane such as a trimethyl fluorenyl group; Base. Further, 'R17 to R18' each represent a hydrogen atom, an alkyl group which may have a substituent, a substituent which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent. Further, the positional relationship of the above substituents is not particularly limited, but when it has a plurality of substituents, it may be of the same type or different types. Specific examples of the compound represented by the general formula (5) are exemplified below. -37- (35) 200804974 [Chemistry 9]

Μ— 1Μ-1

Μ—12Μ-12

ΟΟ

Ο -38- 200804974(36) [化 10]Μ—13Ο -38- 200804974(36) [化 10]Μ—13

構成本發明相關的（A-4-2)聚合物之單體般式（5 )的比例並沒特別的限制，但一般爲總 0.5〜60重量％，較佳爲1〜55重量％，更佳爲 % °太多則會有作爲分散劑使用時分散體的分之虞，另一方面，太少則會有底面污染適性降份中，一體成份中〜5 0重量安定降低之虞。 -39- 200804974 (37) (A-4-3)關於（A-4)丙烯酸系樹脂The proportion of the monomer (5) constituting the (A-4-2) polymer of the present invention is not particularly limited, but is generally 0.5 to 60% by weight, preferably 1 to 55% by weight, more preferably If the % is too much, the dispersion of the dispersion may be used as a dispersing agent. On the other hand, if there is too little, there will be a decrease in the bottom surface contamination, and the weight of the integral component is reduced by ~50 weight stability. -39- 200804974 (37) (A-4-3) About (A-4) Acrylic Resin

於本發明之（A-4)丙烯酸系樹脂，係含有（A-4-1)及（A-4-2)所述的聚合物，且任一者皆具有酸基爲佳。因爲具有酸基，所得到的硬化性組成物，可成爲藉由酸基與環氧基反應後形成酯鍵之交聯反應（以下，簡稱爲酸-環氧硬化）而可硬化之硬化性組成物，或可用鹼顯影使未硬化部顯影之組成物。該酸基並沒有特別的限制，但可列舉例如竣基、苯酚性羥基、羧酸酐基等。此等酸基可僅爲一種或可爲2種以上。於丙烯酸系樹脂導入酸基，例如可使用具有酸基的單體及/或「聚合後可授與酸基之單體」（以下亦稱爲「用於導入酸基之單體」）作爲單體成份，再者，使用「聚合後可授與酸基之單體」作爲單體成份時，聚合後需要如後述之用於授與酸基的處理。具有該酸基之單體，可列舉例如（甲基）丙烯酸或衣康酸等之具有羧基的單體；N-羥基苯基馬來酸酐縮亞胺等之具有苯酚性羥基的單體；馬來酸酐、衣康酸酐等之具有羧酸酐基的單體等，但此等中又以（甲基）丙烯酸特別佳。作爲該聚合後可授與酸基之單體，可列舉例如（甲基）丙儲酸2 -羥基乙酯等之具有經基的單體；（甲基）丙嫌酸環氧丙酯等之具有環氧基的單體；（甲基）丙烯酸2-異氰酸酯乙酯等之具有異氰酸酯基之單體等。用於導入此等酸基之單體，可僅爲1種，或爲2種以上。 -40- 200804974 (38) 得到丙烯酸系樹脂時之單體成份，亦包括該用於^ _ λ 酸基之單體時，此含有比例並沒有特別的限制，彳旦胃胃胃總單體成份中5〜70重量％，較佳爲1〇〜60重量％。此外（A - 4)丙嫌酸系樹脂，亦可爲具有自由基聚合性雙鍵者。The (A-4) acrylic resin of the present invention contains the polymers described in (A-4-1) and (A-4-2), and any of them has an acid group. Because of having an acid group, the obtained curable composition can be a hardenable composition which can be hardened by a crosslinking reaction (hereinafter, abbreviated as acid-epoxy hardening) of an ester bond after reacting an acid group with an epoxy group. The composition, which may be developed with alkali to develop the uncured portion. The acid group is not particularly limited, and examples thereof include a mercapto group, a phenolic hydroxyl group, and a carboxylic anhydride group. These acid groups may be one type or two or more types. When an acid group is introduced into the acrylic resin, for example, a monomer having an acid group and/or a "monomer capable of imparting an acid group after polymerization" (hereinafter also referred to as "a monomer for introducing an acid group") may be used as a single substance. In the case of using a monomer component which is a monomer which can impart an acid group after polymerization, a treatment for imparting an acid group as described later is required after the polymerization. Examples of the monomer having the acid group include a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid; and a monomer having a phenolic hydroxyl group such as N-hydroxyphenylmaleic anhydride imide; A monomer having a carboxylic anhydride group such as phthalic anhydride or itaconic anhydride, etc., but particularly preferably (meth)acrylic acid. Examples of the monomer capable of imparting an acid group after the polymerization include a monomer having a trans group such as (meth)propionic acid 2-hydroxyethyl ester; (meth)acrylic acid glyphosate; a monomer having an epoxy group, a monomer having an isocyanate group such as 2-isocyanate ethyl (meth)acrylate, or the like. The monomer for introducing these acid groups may be used alone or in combination of two or more. -40- 200804974 (38) When the monomer component of the acrylic resin is obtained, and the monomer for the _ λ acid group is also included, the content ratio is not particularly limited, and the total stomach component of the stomach and stomach is not limited. 5 to 70% by weight, preferably 1 to 60% by weight. Further, the (A - 4) acrylic acid resin may be a radical polymerizable double bond.

於該丙烯酸系樹脂導入自由基聚合性雙鍵，例j $α ^ 「聚合後可授與自由基聚合性雙鍵之單體」（以下亦稱爲「用於導入自由基聚合性雙鍵之單體」）作爲單體成份聚合後’可進行如後之用於授與自由基聚合性雙鍵的處理。聚合後可授與自由基聚合性雙鍵之單體，可列舉例如 (甲基）丙烯酸酯、衣康酸等之具有羧基的單體；馬來酸酐、衣康酸酐等之具有羧酸酐基的單體；（甲基）丙烯酸環氧丙酯、（甲基）丙烯酸3,4-環氧基環己基甲酯、〇_(或m-、或P-)乙烯苄基環氧基丙基醚等之具有環氧基的單體等。此等用於導入自由基聚合性雙鍵之單體，可僅爲i 種，或可爲2種以上。得到丙嫌酸系樹脂時之單體成份，亦包括該用於導入自由基聚合性雙鍵之單體時，此含有比例並沒有特別的限制’但通常爲總單體成份中5〜7 0重量％，較佳爲1 〇〜6 0 重量％。本發明之（A-4)丙烯酸系樹脂，爲以（A-4-2)項所說明的上述一般式（4)的化合物作爲必須的單體成份之聚合物時，具有環氧基較佳。導入環氧基，例如將具有環氧基之單體（以下亦稱爲 -41 - 200804974 (39) 「用於導入環氧基之單體」）作爲單體成份聚合即可。上述具有環氧基之單體，可列舉例如（甲基）丙烯酸環氧丙酯、（甲基）丙烯酸3,4-環氧環己基甲酯、〇·(或m-、或P-)乙烯苄基環氧丙基醚等。此等用於導入環氧基之單體，可僅爲1種，或可爲2種以上。Into the acrylic resin, a radical polymerizable double bond is introduced, and j $α ^ "a monomer capable of imparting a radical polymerizable double bond after polymerization" (hereinafter also referred to as "introduction of a radical polymerizable double bond" After the monomer ") is polymerized as a monomer component, the treatment for imparting a radical polymerizable double bond can be carried out as follows. The monomer which can impart a radically polymerizable double bond after the polymerization may, for example, be a monomer having a carboxyl group such as (meth) acrylate or itaconic acid; or a carboxylic anhydride group such as maleic anhydride or itaconic anhydride. Monomer; glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 〇_(or m-, or P-)vinylbenzylepoxypropyl ether A monomer having an epoxy group or the like. These monomers for introducing a radically polymerizable double bond may be used alone or in combination of two or more. When the monomer component of the acrylic acid-based resin is obtained, and the monomer for introducing the radical polymerizable double bond is also included, the content ratio is not particularly limited 'but usually 5 to 70 in the total monomer component. The weight % is preferably from 1 6 to 60% by weight. When the (A-4) acrylic resin of the present invention is a polymer of the above general formula (4) described in the item (A-4-2) as a polymer of an essential monomer component, it is preferred to have an epoxy group. . To introduce an epoxy group, for example, a monomer having an epoxy group (hereinafter also referred to as -41 - 200804974 (39) "monomer for introducing an epoxy group") may be polymerized as a monomer component. The monomer having an epoxy group may, for example, be a glycidyl (meth)acrylate, a 3,4-epoxycyclohexylmethyl (meth)acrylate, or an anthracene (or m-, or P-) ethylene. Benzylepoxypropyl ether and the like. These monomers for introducing an epoxy group may be used alone or in combination of two or more.

得到（A-4)丙烯酸系樹脂時之單體成份，亦包括該用於導入環氧基之單體時，此含有比例並沒有特別的限制，但通常爲總單體成份中5〜70重量％，較佳爲10〜60重量％。得到（A-4)丙烯酸酯樹脂時的單體成份，除了上述必須的單體成份以外，必要時可含有其他可共聚的單體。其他可共聚的單體，可列舉例如（甲基）丙烯酸甲酯、 (甲基）丙烯酸乙酯、（甲基）丙烯酸η -丙酯、（甲基）丙烯酸異丙酯、（甲基）丙儲酸η -丁酯、（甲基）丙嫌酸異丁酯、（甲基）丙烯酸t-丁酯、（甲基）丙烯酸甲基2-乙基己酯、（甲基）丙嫌酸壤己酯、（甲基）丙烯酸节酯、（甲基）丙嫌酸2 -經基乙酯等之（甲基）丙烯酸酯類；苯乙烯、乙烯甲苯、3-甲基苯乙烯等之芳香族乙烯化合物·，N -苯基馬來酸酐縮亞胺、N-環己基馬來酸酐縮亞胺等之N-取代馬來酸酐縮亞胺類；丁二烯、異戊二烯等之丁二烯或取代丁二烯化合物；乙烯、丙烯、氯乙烯、丙烯腈等之乙烯或取代乙烯化合物；乙酸乙烯酯等之乙烯酯類等。此等中又以（甲基）丙烯酸甲酯、（甲基）丙燒酸環己酯、（甲基）丙烯酸苄酯、苯乙烯，由透明性優良且不易損 -42· 200804974 (40) 及耐熱性的觀點而言較佳。此等可共聚的其他聚合物，可僅使用1種，或可倂用2種以上。此外’特別是將（A-4)丙烯酸系樹脂的一部份或全部如後述作爲分散劑使用時，較佳爲使用（甲基）丙烯酸苄酯’其含量通常爲總單體成份中1〜70重量％，較佳爲5 〜6 0重量％。When the monomer component of the (A-4) acrylic resin is obtained, and the monomer for introducing an epoxy group is also included, the content ratio is not particularly limited, but is usually 5 to 70% by weight of the total monomer component. % is preferably from 10 to 60% by weight. The monomer component in the case of obtaining the (A-4) acrylate resin may contain other copolymerizable monomers as necessary in addition to the above-mentioned necessary monomer components. Examples of other copolymerizable monomers include methyl (meth)acrylate, ethyl (meth)acrylate, η-propyl (meth)acrylate, isopropyl (meth)acrylate, and (meth)acrylic acid. Acid storage η-butyl ester, (meth)acrylic acid isobutyl ester, (meth)acrylic acid t-butyl ester, (meth)acrylic acid methyl 2-ethylhexyl ester, (methyl) acrylic acid (meth)acrylates such as hexyl ester, (meth)acrylate, (meth)acrylic acid, 2-phenylethyl, etc.; aromatics such as styrene, vinyl toluene, 3-methylstyrene N-substituted maleic anhydride imide, such as ethylene compound, N-phenylmaleic anhydride imide, N-cyclohexylmaleic acid imide, etc.; butadiene, isoprene, etc. An ene or substituted butadiene compound; an ethylene or substituted ethylene compound of ethylene, propylene, vinyl chloride, acrylonitrile or the like; a vinyl ester such as vinyl acetate or the like. Among them, methyl (meth)acrylate, cyclohexyl (meth)propionate, benzyl (meth)acrylate, and styrene are excellent in transparency and are not easily damaged -42·200804974 (40) It is preferable from the viewpoint of heat resistance. These other polymerizable copolymers may be used alone or in combination of two or more. Further, in particular, when a part or all of the (A-4) acrylic resin is used as a dispersing agent, it is preferred to use benzyl (meth) acrylate, which is usually in the total monomer composition. 70% by weight, preferably 5 to 60% by weight.

得到上述丙烯酸系樹脂時之單體成份，亦包括上述可共聚之其他單體時，此含有比例並沒有特別的限制，但 9 5重量％以下爲佳，8 5重量％以下更佳。接著，說明關於（A-4)丙烯酸系樹脂之製造方法（聚合方法）。上述單體成份的聚合方法並沒特別的限制，可採用先前技術習知的各種方法，特別是藉由溶液聚合法爲佳。再者，聚合溫度或聚合濃度（聚合濃度=[單體成份的總重量 /(單體成份的總重量+溶劑重量）]x 1〇〇)，依所使用的單體成份的種類或比率、目標之聚合物的分子量而不同。關於聚合溫度，較佳爲40〜150°C，更佳爲聚合溫度60〜130 t，此外關於聚合濃度，較佳的聚合濃度爲5〜5 〇%，更佳爲1 〇〜4 0 %。此外，聚合時使用溶劑時，可使用通常的自由基聚合反應所使用的溶劑，具體而言，可列舉例如四氫呋喃、二噁烷、乙二醇二甲基醚、二乙二醇二甲基醚等之醚類；丙酮、甲基乙基酮、甲基異丁酮、環己酮等之酮類；乙酸乙酯、乙酸丁酯、丙二醇單甲基醚乙酸酯、3 -甲氧基丁基乙 -43- 200804974 (41) 酸酯等之酯類；甲醇、乙醇、異丙醇、η-丁醇、乙二醇單甲基醚、丙二醇單甲基醚等之醇類；甲苯、二甲苯、乙基苯等之芳香族烴類；氯仿；二甲基亞颯等。此等溶劑可僅使用1種或可倂用2種以上。When the monomer component in the case where the acrylic resin is obtained also includes the other monomer copolymerizable, the content ratio is not particularly limited, but preferably 5% by weight or less, more preferably 5% by weight or less. Next, a method (polymerization method) for producing the acrylic resin (A-4) will be described. The polymerization method of the above monomer component is not particularly limited, and various methods conventionally known in the art can be employed, particularly by solution polymerization. Further, the polymerization temperature or polymerization concentration (polymerization concentration = [total weight of monomer component / (total weight of monomer component + solvent weight)] x 1 〇〇), depending on the type or ratio of monomer components used, The molecular weight of the target polymer varies. With respect to the polymerization temperature, it is preferably 40 to 150 ° C, more preferably the polymerization temperature is 60 to 130 t, and further preferably, the polymerization concentration is 5 to 5 %, more preferably 1 to 40%. Further, when a solvent is used for the polymerization, a solvent used in a usual radical polymerization reaction can be used, and specific examples thereof include tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether. Ethers such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl Base B-43- 200804974 (41) Esters of esters, etc.; alcohols such as methanol, ethanol, isopropanol, η-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether; toluene, An aromatic hydrocarbon such as toluene or ethylbenzene; chloroform; dimethyl hydrazine or the like. These solvents may be used alone or in combination of two or more.

聚合上述單體成份時，必要時可使用聚合起始劑，聚合起始劑並沒有特別限制，但可列舉例如枯烯基氫過氧化物、二異丙基苯氫過氧化物、二-t-丁基過氧化物、月桂醯基過氧化物、苯甲醯過氧化物、t-丁基過氧化異丙基碳酸酯、t-戊基過氧化-2-乙基己酸酯、t-丁基過氧化-2 _乙基己酸酯等之有機過氧化物；2,2’·偶氮雙（異丁腈）、1，1’-偶氮雙（環己烷腈）、2,2’-偶氮雙（2,4-二甲基戊腈）、二甲基 2，2’-偶氮雙（2-甲基丙酸酯）等之偶氮化合物。此等聚合起始劑可僅使用1種或可倂用2種以上。再者，起始劑的使用量，只要依所使用的單體的組合、或反應條件、目標之聚合物分子量而適當設定即可，並無特別限制，但由在不凝膠化下可得到重量平勻分子量爲數千〜數萬的聚合物之觀點而言，通常相對於總單體成份而言爲〇 · 1〜1 5重量％，較佳爲0 · 5〜1 0重量％。此外爲了分子量調整，亦可添加鏈轉移劑，鏈轉移劑可列舉例如η-十二烷硫醇、硫醇乙酸、硫醇乙酸甲酯等之硫醇系鏈轉移劑、α -甲基苯乙烯二聚物等，但較佳爲鏈轉移效果高、可減少殘留單體、容易取得之十二烷硫醇、硫醇乙酸。使用鏈移動劑時，其使用量只要依所使用的單體的組合、或反應條件、目標之聚合物分子量而適 -44- 200804974 (42) 當設定即可，並無特別限制，但由在不凝膠化下可得到重量平勻分子量爲數千〜數萬的聚合物之觀點而言，通常相對於總單體成份而言爲〇 . 1〜1 5重量％，較佳爲0.5〜1 0 重量％。When the above monomer component is polymerized, a polymerization initiator may be used as necessary, and the polymerization initiator is not particularly limited, and examples thereof include cumenyl hydroperoxide, diisopropylbenzene hydroperoxide, and di-t. -butyl peroxide, lauryl peroxide, benzamidine peroxide, t-butyl peroxy isopropyl carbonate, t-pentyl peroxy-2-ethylhexanoate, t- An organic peroxide such as butyl peroxy-2-ethylhexanoate; 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2, An azo compound such as 2'-azobis(2,4-dimethylvaleronitrile) or dimethyl 2,2'-azobis(2-methylpropionate). These polymerization initiators may be used alone or in combination of two or more. In addition, the amount of the initiator to be used is not particularly limited as long as it is appropriately set depending on the combination of the monomers to be used, the reaction conditions, and the molecular weight of the target polymer, but it can be obtained without gelation. From the viewpoint of a polymer having a weight-average molecular weight of from several thousands to several tens of thousands, it is usually from 1 to 15% by weight, preferably from 0.5 to 10% by weight, based on the total monomer component. Further, in order to adjust the molecular weight, a chain transfer agent may be added. Examples of the chain transfer agent include a thiol-based chain transfer agent such as η-dodecyl mercaptan, thiol acetic acid, and methyl thiol acetate, and α-methyl styrene. A dimer or the like, but preferably has a high chain transfer effect, can reduce residual monomers, and is easily obtained as dodecanethiol or thiol acetic acid. When a chain shifting agent is used, the amount of use thereof depends on the combination of the monomers to be used, or the reaction conditions, and the molecular weight of the target polymer. -44-200804974 (42) When setting, there is no particular limitation, but From the viewpoint of obtaining a polymer having a weight-average molecular weight of from several thousands to several tens of thousands without gelation, it is usually from 1 to 15% by weight, preferably from 0.5 to 1%, based on the total monomer component. 0% by weight.

再者，一般式（4)的化合物作爲必須的單體成份使用時，於上述聚合反應，認爲醚二聚物的環化反應同時進行，但認爲此時的醚二聚物的環化率不一定非爲1 00%不可，在得到上述丙烯酸系樹脂時，藉由使用上述之授與酸基之單體作爲單體成份時，聚合後必須進行用於授與酸基之處理。該處理係依所使用的單體種類而不同，但例如使用（甲基）丙烯酸2-羥基乙酯之具有羥基的單體時，亦可加成琥珀酸酐、四氫酞酸酐、馬來酸酐等之酸酐。使用（甲基）丙烯酸環氧丙酯等之具有環氧基的單體時，可加成N-甲基胺基苯甲酸、N-甲基戊基苯酚等之具有胺基與酸基之化合物，或者先加成如（甲基）丙烯酸之酸，於結果產生的羥基上，加成琥珀酸酐、四氫酞酸酐、馬來酸酐等之酸酐。使用（甲基）丙烯酸2-異氰酸酯乙酯等之具有異氰酸酯之單體時，例如可加成具有2-羥基丁酸等之羥基與酸基之化合物。得到上述丙烯酸系樹脂時，藉由使用上述的授與自由基聚合性雙鍵之單體，導入自由基聚合性雙鍵時，聚合後必須進行用於授與自由基聚合性雙鍵的處理。該處理係依所使用的單體種類而不同，但例如使用 (甲基）丙烯酸或衣康酸等之具有羧基之單體時，可加成 -45- 200804974 (43)Further, when the compound of the general formula (4) is used as an essential monomer component, it is considered that the cyclization reaction of the ether dimer proceeds simultaneously in the above polymerization reaction, but it is considered that the cyclization of the ether dimer at this time is considered. The rate is not necessarily 100%. When the above acrylic resin is obtained, by using the above-mentioned monomer which imparts an acid group as a monomer component, it is necessary to carry out a treatment for imparting an acid group after polymerization. Although this treatment differs depending on the type of the monomer to be used, for example, when a monomer having a hydroxyl group of 2-hydroxyethyl (meth)acrylate is used, succinic anhydride, tetrahydrophthalic anhydride, maleic anhydride, or the like may be added. Anhydride. When an epoxy group-containing monomer such as glycidyl (meth)acrylate is used, a compound having an amine group and an acid group such as N-methylaminobenzoic acid or N-methylpentylphenol may be added. Alternatively, an acid such as (meth)acrylic acid may be added first, and an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride or maleic anhydride may be added to the resulting hydroxyl group. When a monomer having an isocyanate such as 2-isocyanate ethyl (meth)acrylate is used, for example, a compound having a hydroxyl group and an acid group of 2-hydroxybutyric acid or the like can be added. When the above-mentioned acrylic resin is obtained, when a radical polymerizable double bond is introduced by using the above-mentioned monomer which imparts a free radical polymerizable double bond, it is necessary to carry out a treatment for imparting a radical polymerizable double bond after the polymerization. This treatment differs depending on the type of the monomer to be used, but for example, when a monomer having a carboxyl group such as (meth)acrylic acid or itaconic acid is used, it can be added -45-200804974 (43)

(甲基）丙烯酸環氧丙酯、（甲基）丙烯酸3,4-環氧基環己基甲酯、〇-(或m-、或p-)乙烯苄基環氧丙基醚等之具有自由基聚合性雙鍵之化合物。使用馬來酸酐、衣康酸酐等之具有羧酸酐基的單體時，可加成（甲基）丙烯酸2-羥基乙酯等之具有羥基與自由基聚合性雙鍵之化合物；使用（甲基）丙烯酸環氧丙酯、（甲基）丙烯酸3,4-環氧環己基甲酯、〇-(或 m-、或p-)乙烯苄基環氧丙基醚等之具有環氧基的單體時，可加成具有（甲基）丙烯酸等之酸基與自由基聚合性雙鍵之化合物。本發明的（A-4)丙烯酸系樹脂的重量平均分子量，並沒有特別的限制，但較佳爲用GPC測量的苯乙烯換算的重量平均分子量爲 2000〜200000，較佳爲 4000〜 1 00000，重量平均分子量超過200000時，會有因爲黏度變過高而不易形成塗膜之情況，另一方面低於2 0 0 0則會有不易表現出充分的耐熱性。該具有丙烯酸系樹脂時，較佳的酸價爲3 〇〜 500mgKOH/g，更佳爲 50 〜400mgKOH/g，酸價低於 30 mgKOH/g時，會有很難適用於鹼顯影之情況，超過 500mgKOH/g時，會有黏度變過高而不易形成塗膜。再者，上述丙烯酸系樹脂成份中，一般式（4)所表示的化合物作爲單體成份之聚合物，其本身爲習知的化合物，可列舉例如特開2004-300203號及特開2004-300204 號公報所記載的化合物。 (A-5):含羧基之環氧基丙烯酸酯樹脂 -46- 200804974 (44) 環氧基丙烯酸酯樹脂，對環氧樹脂加成α，θ -不飽和單羧酸或酯部份具有羧基之不飽和單羧酸酯，而且，藉由使多元酸酐反應而合成。該相關的反應生成物係在化學結構上實質不具有環氧基，而且並非限定於「丙烯酸酯」，但環氧樹脂爲原料，而且「丙烯酸酯」爲代表例子，故依循慣用而命多者。Freedom of glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, hydrazine-(or m-, or p-)vinylbenzylepoxypropyl ether A compound of a polymeric double bond. When a monomer having a carboxylic anhydride group such as maleic anhydride or itaconic anhydride is used, a compound having a hydroxyl group and a radical polymerizable double bond such as 2-hydroxyethyl (meth)acrylate may be added; a single epoxy group such as glycidyl acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, hydrazine-(or m-, or p-)vinylbenzylepoxypropyl ether In the case of a body, a compound having an acid group such as (meth)acrylic acid and a radical polymerizable double bond may be added. The weight average molecular weight of the (A-4) acrylic resin of the present invention is not particularly limited, but is preferably a styrene-converted weight average molecular weight measured by GPC of from 2,000 to 200,000, preferably from 4,000 to 10,000, When the weight average molecular weight exceeds 200,000, the coating film may be formed because the viscosity is too high, and on the other hand, if it is less than 2,000, it is difficult to exhibit sufficient heat resistance. When the acrylic resin is used, the acid value is preferably from 3 to 500 mgKOH/g, more preferably from 50 to 400 mgKOH/g, and when the acid value is less than 30 mgKOH/g, it is difficult to apply to alkali development. When it exceeds 500 mgKOH/g, the viscosity becomes too high and it is difficult to form a coating film. In addition, among the above-mentioned acrylic resin components, the compound represented by the general formula (4) as a monomer component is a conventional compound, and examples thereof include, for example, JP-A-2004-300203 and JP-A-2004-300204. The compound described in the publication. (A-5): carboxyl group-containing epoxy acrylate resin-46- 200804974 (44) Epoxy acrylate resin, epoxy resin addition α,θ-unsaturated monocarboxylic acid or ester moiety having a carboxyl group The unsaturated monocarboxylic acid ester is synthesized by reacting a polybasic acid anhydride. The related reaction product does not substantially have an epoxy group in chemical structure, and is not limited to "acrylate", but epoxy resin is a raw material, and "acrylate" is a representative example, so it is customary to follow. .

成爲原料之環氧樹脂，可適用例如雙酚Α型環氧樹脂（例如油化雪路環氧公司製的「EPIKOTE82 8」、「EPIKOTE 1001」、「EPIKOTE 1 002」、「EPIKOTE 1 004」等）、可藉由雙酚A型環氧樹脂的醇性羥基與環氧氯丙烷的反應而得到之環氧樹脂（例如日本化藥公司製「NER- 1 302」（環氧當量3 23、軟化點76°C ))、雙酚F型樹脂（例如油化雪路環氧公司製之「EPIKOTE 807」、「EP4001」、「EP4002」、「EP4004」、可藉由雙酚 F 型環氧樹脂之醇性羥基與環氧氯丙烷的反應而得到環氧樹脂（例如日本化藥公司製「NER-7406」（環氧基當量3 50、軟化點66°C ))、雙酚S型環氧樹脂、聯苯環氧丙基醚（例如油化雪路環氧公司製的「YX-4000」、苯酚酚醛清漆型環氧樹脂（例如日本化藥公司製的「EPPN-201」、油化雪路環氧公司製的ΓΕΡ-152」、「ΕΡ-154」、Dow Chemical 公司製的「DEN-438」）、（o，m，p)甲酚酚醛清漆型環氧樹脂（例如曰本化藥公司製的「EOCN-102S」、「EOCN-1 020」、「EOCN-104S」、三環氧丙基三聚異氰酸酯（例如日產化學公司製的「TEPIC」）、三苯酚甲烷型環氧樹脂 -47- 200804974 (45) (例如日本化藥公司製的「EPPN-501」、「EPN-502」、For the epoxy resin to be used as a raw material, for example, a bisphenol quinone type epoxy resin (for example, "EPIKOTE 82 8", "EPIKOTE 1001", "EPIKOTE 1 002", "EPIKOTE 1 004", etc., manufactured by Oiled Snow Road Epoxy Co., Ltd., may be used. An epoxy resin obtained by a reaction of an alcoholic hydroxyl group of a bisphenol A type epoxy resin with epichlorohydrin (for example, "NER- 1 302" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 3 23, softening) Point 76 ° C)), bisphenol F type resin (for example, "EPIKOTE 807", "EP4001", "EP4002", "EP4004" made by Oily Snow Road Epoxy Co., Ltd., can be made of bisphenol F type epoxy resin An epoxy resin is obtained by reacting an alcoholic hydroxyl group with epichlorohydrin (for example, "NER-7406" (epoxy equivalent 3 50, softening point 66 ° C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy Resin, biphenyl epoxy propyl ether (for example, "YX-4000" manufactured by Oiled Snow Road Epoxy Co., Ltd., phenol novolak type epoxy resin (for example, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., oily snow ΓΕΡ-152", "ΕΡ-154" manufactured by Luke Epoxy Co., Ltd., "DEN-438" manufactured by Dow Chemical Co., Ltd.), (o, m p) Cresol novolac type epoxy resin (for example, "EOCN-102S", "EOCN-1 020", "EOCN-104S", and trisepoxypropyl trimer isocyanate (such as Nissan Chemical Co., Ltd.) "TEPIC" manufactured by the company, and trisphenol methane epoxy resin -47- 200804974 (45) (for example, "EPPN-501" and "EPN-502" manufactured by Nippon Kayaku Co., Ltd.

「EPPN-5 03」' 芴環氧樹脂（例如新日鐵化學公司製的硬環氧樹脂「ESF-300」）、脂環式環氧樹脂（DAICEL化學工業公司製的「C e 11 ο X i d e 2 0 2 1 P」、「C e 11 ο X i d e Ε Η P E」、藉由二環戊二烯與苯酚反應而使苯酚樹脂環氧丙基化的二環戊二烯型環氧樹脂（例如日本化藥公司製的「XD-1000」、大日本油墨公司製的「ΕΧΑ-7200」、日本化藥公司製的「NC-3000」、「NC-7300」、及下述結構式所表示的環氧樹脂（參考特許第2878486號公報）等。"EPPN-5 03"' Epoxy resin (for example, Epoxy Resin "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.) and alicyclic epoxy resin (C e 11 ο X manufactured by DAICEL Chemical Industry Co., Ltd.) Ide 2 0 2 1 P", "C e 11 ο X ide Ε Η PE", a dicyclopentadiene type epoxy resin obtained by reacting dicyclopentadiene with phenol to epoxidize a phenol resin ( For example, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., "ΕΧΑ-7200" manufactured by Dainippon Ink Co., Ltd., "NC-3000" manufactured by Nippon Kayaku Co., Ltd., "NC-7300", and the following structural formula Epoxy resin (refer to Japanese Patent No. 2878486) and the like.

此等可單獨使用1種，或可倂用2種以上。作爲環氧樹脂的其例子可列舉共聚型環氧樹脂，共聚型環氧樹脂’可列舉使例如（甲基）丙烯酸環氧丙酯、（甲基）丙嫌醯基甲基環己烷氧化物、乙烯環氧環己烯氧化物等（以下稱爲「共聚型環氧樹脂的第i成份」），與此等以外的含1官能乙烯性不飽和基之化合物（以下稱爲「共聚型環氧樹脂的第2成份」），例如（甲基）丙烯酸甲酯、（甲基）丙嫌酸乙酯、（甲基）丙烯酸丁酯、丙烯酸2_羥基乙酯、（甲基）丙烯酸酯2 -羥基丙酯、（甲基）丙烯酸酯、苯 -48- 200804974 (46) 乙烯、（甲基）丙烯酸苯氧基乙酯、（甲基）丙烯酸苄酯、α-甲基苯乙烯、單（甲基）丙烯酸甘油酯、下述一般式（8)所表示的化合物所選出的1種或2種以上經反應後所得到的共聚物。 m2]These may be used alone or in combination of two or more. Examples of the epoxy resin include a copolymer epoxy resin, and examples of the copolymer epoxy resin include, for example, (meth)acrylic acid propyl acrylate, (meth) propyl decyl methyl cyclohexane oxide. Ethylene epoxy cyclohexene oxide (hereinafter referred to as "the i-th component of the copolymer epoxy resin"), and a compound containing a monofunctional ethylenically unsaturated group other than these (hereinafter referred to as "copolymer ring") The second component of the oxyresin") is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl acrylate, (meth) acrylate 2 -hydroxypropyl ester, (meth) acrylate, benzene-48- 200804974 (46) ethylene, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, α-methyl styrene, single ( One or two or more kinds of copolymers obtained by reacting a methyl methacrylate or a compound represented by the following general formula (8). M2]

r61o I I CH2=C—C 一 O-e C2H4〇^：r62 (8>R61o I I CH2=C—C—O-e C2H4〇^:r62 (8>

式（8)中，R61表示氫原子或乙基，R62表示氫原子或碳數1〜6的垸基，r爲2〜10的整數。In the formula (8), R61 represents a hydrogen atom or an ethyl group, and R62 represents a hydrogen atom or a fluorenyl group having 1 to 6 carbon atoms, and r is an integer of 2 to 10.

一般式（8 )的化合物，可列舉例如二乙醇單（甲基）丙烯酸酯、三乙二醇單（甲基）丙烯酸酯、四乙二醇單（甲基）丙烯酸酯等之聚乙二醇單（甲基）丙烯酸酯；甲氧基二乙二醇單（甲基）丙烯酸酯、甲氧基三乙二醇單（甲基）丙烯酸酯、甲氧基四乙二醇單（甲基）丙烯酸酯等之烷氧基聚乙二醇 (甲基）丙烯酸酯等。上述共聚型環氧樹脂的分子量約1〇〇〇〜2〇〇〇〇〇爲佳’此外，上述共聚型環氧樹脂的第1成份的使用量，係相對於上述共聚型環氧樹脂的第2成份而言，較佳爲10 重量％以上，特別佳爲20重量％以上，較佳爲7〇重量％以下，特別佳爲5 0重量％以下。如此的共聚型環氧樹脂，具體而言列舉日本油脂公司製「CP-15」、「CP-30」、「CP-50| 、「CP-20SA 丨、 -49- 200804974 (47) 「CP-510SA」、「CP-5 OS」、「CP-50M」、「CP-20MA」等。原料環氧樹脂的分子量，以GPC測量的聚苯乙烯換算的重量平均分子量通常爲200〜20萬，較佳爲300〜The compound of the general formula (8) may, for example, be a polyethylene glycol such as diethanol mono(meth)acrylate, triethylene glycol mono(meth)acrylate or tetraethylene glycol mono(meth)acrylate. Mono (meth) acrylate; methoxy diethylene glycol mono (meth) acrylate, methoxy triethylene glycol mono (meth) acrylate, methoxytetraethylene glycol mono (methyl) An alkoxy polyethylene glycol (meth) acrylate such as acrylate. The copolymerization type epoxy resin preferably has a molecular weight of about 1 Torr to 2 Å. Further, the amount of the first component of the copolymerization type epoxy resin is the same as that of the copolymerized epoxy resin. The composition of 2 is preferably 10% by weight or more, particularly preferably 20% by weight or more, preferably 7% by weight or less, particularly preferably 50% by weight or less. Specifically, the copolymerized epoxy resin is "CP-15", "CP-30", "CP-50|, "CP-20SA", -49-200804974 (47) "CP-" manufactured by Nippon Oil & Fats Co., Ltd. 510SA", "CP-5 OS", "CP-50M", "CP-20MA", etc. The molecular weight of the raw material epoxy resin, the weight average molecular weight calculated by GPC measurement of polystyrene is usually 200 to 200,000, preferably 300 to

1 00000的範圍。重量平均分子量低於上述範圍則會有許多被膜形成性產生問題的情況，相反的超過上述範圍之樹脂’會有α，θ-不飽和單羧酸的加成反應時易引起凝膠化而製造變難之虞。 αΘ -不飽和單羧酸，可列舉衣康酸、巴豆酸、桂皮酸、丙烯酸、甲基丙烯酸等，較佳爲丙烯酸及甲基丙烯酸’特別是丙烯酸因爲具有豐富反應性而較佳。酯部份具有α，Θ -不飽和單羧酸酯，可列舉丙烯酸-2-琥珀醯基氧乙酯、丙烯酸_2-馬來醯基氧乙酯、丙烯酸-2-酞醯基氧乙酯、丙烯酸-2_六氫酞醯基氧乙酯、甲基丙烯酸-2-琥珀醯基氧乙酯、甲基丙烯酸-2-馬來醯基氧乙酯、甲基丙烯酸-2 ·酞醯基氧乙酯、甲基丙烯酸-2-六氫酞醯基氧乙酯、巴豆酸-2-琥珀醯基氧乙酯等。較佳爲丙烯酸-2 _ 馬來醯基氧乙酯、丙烯酸-2-酞醯基氧乙酯，特別佳爲丙烯酸-2-馬來醯基氧乙酯，此等可單獨使用1種或可倂用2 種以上。 /3-不飽和單羧酸或其酯與環氧樹脂的加成反應，可使用習知的方法，例如藉由在酯化催化劑存在下，以 50〜150 °C的溫度使其反應而實施。酯化催化劑可使用三乙胺、二甲胺、苄基二甲胺、苄基二乙胺等之3級胺；四 -50- 200804974 (48) 甲基銨氯化物、四乙基銨氯化物、十二烷基三甲基銨氯化物等之4級銨鹽等。The range of 1 00000. When the weight average molecular weight is less than the above range, there are many problems in film formability. On the contrary, the resin exceeding the above range may cause gelation when an addition reaction of α, θ-unsaturated monocarboxylic acid is caused. It’s hard to change. The αΘ-unsaturated monocarboxylic acid may, for example, beaconic acid, crotonic acid, cinnamic acid, acrylic acid or methacrylic acid, and preferably acrylic acid and methacrylic acid, particularly acrylic acid, are preferred because of their rich reactivity. The ester moiety has an α, Θ-unsaturated monocarboxylic acid ester, and examples thereof include 2-bromodecyloxyethyl acrylate, 2-bromomethyloxyethyl acrylate, and 2-mercaptooxyethyl acrylate. , 2-hexahydrofurfuryloxyethyl acrylate, 2-bromodecyloxyethyl methacrylate, 2-maleyl oxyethyl methacrylate, methacrylic acid-2 fluorenyl Oxyethyl ester, 2-hexahydroindenyloxyethyl methacrylate, crotonic acid-2-succinyloxyethyl ester, and the like. Preferred is acrylic acid-2 _ maleic oxyethyl ester, 2-mercaptooxyethyl acrylate, particularly preferably 2-methyl fluorenyl oxyethyl acrylate, which may be used alone or in one type. Use 2 or more types. The addition reaction of the /3-unsaturated monocarboxylic acid or its ester with an epoxy resin can be carried out by a conventional method, for example, by reacting it at a temperature of 50 to 150 ° C in the presence of an esterification catalyst. . As the esterification catalyst, a tertiary amine such as triethylamine, dimethylamine, benzyldimethylamine or benzyldiethylamine can be used; tetra-50-200804974 (48) methylammonium chloride, tetraethylammonium chloride a grade 4 ammonium salt such as dodecyltrimethylammonium chloride or the like.

α，/3 -不飽和單羧酸或其酯的使用量，相對於原料環氧樹脂的環氧基1當量而言，0.5〜1.2當量的範圍爲佳，較佳爲0.7〜1.1當量的範圍。不飽和單羧酸或其酯的使用量少則不飽和基的導入量不足，之後與多元酸酐的反應亦變不足，此外，殘留多量的環氧基亦並不有利，另一方面，該使用量太多則不飽和單竣酸或其酯以反應物殘留，認爲任一種狀況其硬化特性皆有變差的傾向。於不飽和單羧酸或其酯外加環氧樹脂上，再被加成的多元酸酐，可列舉馬來酸酐、琥珀酸酐、衣康酸酐、酞酸酐、四氫酞酸酐、六氫酞酸酐、均苯四甲酸酐、偏苯三酸酐、二苯甲酮四羧酸酐、甲基六氫酞酸酐、端伸甲基四氫酞酸酐、氯菌酸酐、甲基四氫酞酸酐、聯苯四羧酸二酐等。較佳爲馬來酸酐、琥珀酸酐、衣康酸酐、酞酸酐、四氫酞酸酐、六氫酞酸酐、均苯四甲酸酐、偏苯三酸酐、聯苯四羧酸二酐，特別佳的化合物爲四氫酞酸酐及聯苯四羧酸二酐，此等可單獨使用1種或可倂用2種以上。關於多元酸酐的加成反應，亦可使用習知的方法，可藉由在與α，0-不飽和羧酸或其酯的加成反應同樣的條件下持續反應而實施。多元酸酐的加成量，所生成的環氧基丙烯酸酯樹脂的酸價成爲10〜150mg-KOH/g的範圍之量較佳，更佳爲20 〜140mg-KOH/g的範圍。認爲樹脂的酸價太少則會有鹼 -51 - 200804974 (49) 顯影變不足，此外，樹脂的酸價太大則會有硬化性能變差的傾向。其他，具有羧基之環氧基丙烯酸樹脂，可列舉例如特開平6-49 1 74號公報記載的含萘樹脂·，特開200349716、特開 2003-165830、特開 2003-325331、特開 2001-354735 號公報所記載的含芴樹脂；特開 2005- 1 26674、特開 2005 -5 5 8 1 4、特開2004-295 084號公報所記載的樹脂。 % 此外，亦可使用市售的含羧基之環氧基丙烯酸酯樹脂，市售品可列舉例如 DIACEL公司製「ACA-200M」等。黏合劑樹脂，例如可使用特開2005- 1 54708號公報等所記載的丙烯系的黏合劑。The amount of the α,3-3-unsaturated monocarboxylic acid or its ester to be used is preferably in the range of 0.5 to 1.2 equivalents, preferably 0.7 to 1.1 equivalents, per equivalent of the epoxy group of the raw material epoxy resin. . When the amount of the unsaturated monocarboxylic acid or its ester used is small, the amount of introduction of the unsaturated group is insufficient, and then the reaction with the polybasic acid anhydride is also insufficient, and it is not advantageous to retain a large amount of the epoxy group. If the amount is too large, the unsaturated monodecanoic acid or its ester remains as a reactant, and it is considered that the hardening characteristics tend to deteriorate in any of the cases. The polybasic acid anhydride to be added to the unsaturated monocarboxylic acid or its ester plus an epoxy resin may, for example, be maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride. Pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, methyl hexahydrophthalic anhydride, terminal methyltetrahydrophthalic anhydride, chloric anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic dianhydride, etc. . Preferred are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, biphenyltetracarboxylic dianhydride, and particularly preferred compound is tetrahydrogen. The phthalic anhydride and the biphenyltetracarboxylic dianhydride may be used alone or in combination of two or more. The addition reaction of the polybasic acid anhydride can be carried out by a conventional method, and the reaction can be carried out under the same conditions as the addition reaction of the α,0-unsaturated carboxylic acid or its ester. The amount of addition of the polybasic acid anhydride is preferably in the range of 10 to 150 mg-KOH/g, and more preferably in the range of 20 to 140 mg-KOH/g. It is considered that the acid value of the resin is too small to have a base. -51 - 200804974 (49) The development becomes insufficient, and if the acid value of the resin is too large, the curing property tends to be deteriorated. Other examples of the epoxy group-containing acryl resin having a carboxyl group include a naphthalene resin described in JP-A-6-49 1749, JP-A-200349716, JP-A-2003-165830, JP-A-2003-325331, JP-A-2001- The resin described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2005-295 084. In addition, a commercially available carboxyl group-containing epoxy acrylate resin may be used, and a commercially available product such as "ACA-200M" manufactured by DIACEL Co., Ltd. may be used. For the adhesive resin, for example, a propylene-based adhesive described in JP-A-2005-15448.

本發明之（A)黏合劑樹脂，上述的各種黏合劑樹脂中，可單獨使用1種或可倂用2種以上。上述的各種黏合劑樹脂，特別是藉由倂用後述的（E)分散劑等，基板上的非影像部無殘留未溶解物，與基板的密著性優異，達成可形成高濃度的顏色畫素之效果，故較佳。本發明的硬化性組成物中，（A)黏合劑樹脂的含有比例，在總固形份中通常〇·1重量％以上，較佳爲1重量％以上，此外，通常8 0重量％以下，較佳爲6 0重量°/◦以下。黏合劑樹脂的含量少於此範圍，則會有膜變脆、與基板的密著性降低之情況，相反的多於此範圍，則會有顯影液滲透至露光部的滲透性變高、畫素的表面平滑性或感度變差之情況。 -52- 200804974 (50) [1-5](B)單體本發明的硬化性組成物，含有單體較佳，單體只要是可聚合的低分子化合物即可，並沒有特別的限制，但較佳爲具有至少1個乙烯性雙鍵之可加成聚合的化合物（以下，有稱爲「乙烯性化合物」的情況）。In the above-mentioned various binder resins, the (A) binder resin may be used alone or in combination of two or more. In the above-mentioned various binder resins, in particular, by using the (E) dispersant described later, the non-image portion on the substrate has no residual undissolved matter, and the adhesion to the substrate is excellent, and a high-density color painting can be achieved. The effect is good, so it is better. In the curable composition of the present invention, the content ratio of the (A) binder resin is usually 〇·1% by weight or more, preferably 1% by weight or more, and usually 80% by weight or less, based on the total solid content. Good for 60 weight ° / ◦ below. When the content of the binder resin is less than this range, the film becomes brittle and the adhesion to the substrate is lowered. On the contrary, if the content is more than this range, the penetration of the developer into the exposed portion becomes high, and the drawing becomes high. The surface smoothness or sensitivity of the element is deteriorated. -52-200804974 (50) (B) Monomer The curable composition of the present invention preferably contains a monomer, and the monomer is not particularly limited as long as it is a polymerizable low molecular compound. However, it is preferably an addition polymerizable compound having at least one ethylenic double bond (hereinafter referred to as "ethylenic compound").

乙烯性化合物，係本發明的硬化性組成物受到活性光線的照射時，藉由後述的光聚合起始系的作用而加成聚合而硬化之具有乙烯性雙鍵之化合物，再者，本發明中的單體之意，亦即爲相對於高分子物的槪念，狹義的單體以外，亦可含有二聚物、三聚物、低聚物。乙烯性化合物，可列舉例如（甲基）丙烯酸等之不飽和羧酸、單羥基化合物與不飽和羧酸之酯，脂肪族聚羥基化合物與不飽和羧酸之酯，芳香族聚羥基化合物與不飽和羧酸之酯，藉由不飽和羧酸與多元羧酸及上述的脂肪族聚羥基化合物、芳香族聚羥基化合物等之多元羥基化合物之酯化反應而得到的酯，具有使聚異氰酸酯化合物與含有（甲基）丙烯醯基之羥基化合物進行反應之尿烷骨架之乙烯性化合物等。脂肪族聚羥基化合物與不飽和羧酸之酯，可列舉乙二醇二（甲基）丙烯酸酯、三乙二醇二（甲基）丙烯酸酯、三羥甲基丙烷三（甲基）丙烯酸酯、三羥甲基乙烷三（甲基）丙烯酸酯、季戊四醇二（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、季戊四醇四（甲基）丙烯酸酯、二季戊四醇四（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、二季戊四 -53- 200804974 (51) 醇六（甲基）丙烯酸酯、甘油（甲基）丙烯酸酯等之（甲基）丙烯酸酯。此外，亦可列舉此等丙烯酸酯的（甲基）丙烯酸部份，被衣康酸部份取代之衣康酸酯，被巴豆酸部份取代之巴豆酸酯，或被馬來酸部份取代之馬來酸酯等。When the curable composition of the present invention is irradiated with active light, the curable composition of the present invention is a compound having an ethylenic double bond which is polymerized and hardened by the action of a photopolymerization initiation system to be described later. Further, the present invention The meaning of the monomer in the medium is the complication of the polymer, and the dimer, the trimer, and the oligomer may be contained in addition to the narrowly defined monomer. Examples of the ethylenic compound include an unsaturated carboxylic acid such as (meth)acrylic acid, an ester of a monohydroxy compound and an unsaturated carboxylic acid, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an aromatic polyhydroxy compound. An ester of a saturated carboxylic acid obtained by esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid, a polyvalent hydroxy compound such as the above aliphatic polyhydroxy compound or an aromatic polyhydroxy compound, and a polyisocyanate compound An ethylenic compound or the like having a urethane skeleton in which a hydroxy compound of a (meth) acrylonitrile group is reacted. Examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and trimethylolpropane tri(meth)acrylate. , trimethylolethane tri(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylic acid Ester, dipentaerythritol penta (meth) acrylate, dipentaquat tetra-53-200804974 (51) Alcohol hexa(meth) acrylate, glycerol (meth) acrylate or the like (meth) acrylate. In addition, the (meth)acrylic acid moiety of the acrylate, the itaconate partially substituted by itaconic acid, the crotonate partially substituted by crotonic acid, or partially substituted with maleic acid may also be mentioned. Maleic acid ester and the like.

此外，芳香族聚羥基化合物與不飽和羧酸之酯，可列舉氫醌二（甲基）丙烯酸酯、間苯二酚二（甲基）丙烯酸酯、焦掊酚三（甲基）丙烯酸酯等。此外，藉由不飽和羧酸與多元羧酸及多元羥基化合物之酯化反應而得到的酯，並不一定要爲單一物，亦可爲混合物，代表例可列舉（甲基）丙烯酸、酞酸、及乙二醇的縮合物；（甲基）丙烯酸、馬來酸、及二乙二醇的縮合物；（甲基）丙烯酸、對苯二甲酸、及季戊四醇的縮合物；（甲基）丙烯酸、己二酸、丁二醇、及甘油的縮合物等。具有使聚異氰酸酯化合物與含有（甲基）丙烯醯基之羥基化合物進行反應之尿院骨架之乙儲性化合物，可列舉六伸甲基二異氰酸酯、三甲基六伸甲基二異氰酸酯等之脂肪族二異氰酸酯；環己院二異氰酸酯、異氟爾酮二異氰酸酯等之脂環式二異氰酸酯；伸甲苯二異氰酸酯、二苯基甲烷二異氰酸酯等之芳香族二異氰酸酯，與（甲基）丙烯酸2 -羥基乙酯、3-羥基[1，1，1-三（甲基）丙烯醯基氧甲基]丙烷等之含有（甲基）丙烯醯基之羥基化合物的反應物。其他本發明所使用的乙烯性化合物之例，可列舉乙烯雙（甲基）丙烯醯胺等之（甲基）丙烯醯胺類；酞酸二烯丙酯等之烯丙酯類；二乙烯基酞酸酯等之含有乙烯之化合物 -54 - 200804974 (52) 等。Further, examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include hydroquinone di(meth)acrylate, resorcinol di(meth)acrylate, pyrogallol tri(meth)acrylate, and the like. . Further, the ester obtained by esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, and may be a mixture, and representative examples thereof include (meth)acrylic acid and decanoic acid. And condensates of ethylene glycol; condensates of (meth)acrylic acid, maleic acid, and diethylene glycol; condensates of (meth)acrylic acid, terephthalic acid, and pentaerythritol; (meth)acrylic acid a condensate of adipic acid, butylene glycol, and glycerin. The ethyl storable compound having a urethane skeleton which reacts a polyisocyanate compound with a hydroxy compound containing a (meth) acryl oxime group, and examples thereof include fats such as hexamethylene diisocyanate and trimethyl hexamethylene diisocyanate. a diisocyanate; an alicyclic diisocyanate such as cycloheximide diisocyanate or isophorone diisocyanate; an aromatic diisocyanate such as toluene diisocyanate or diphenylmethane diisocyanate; and (meth)acrylic acid 2 - A reactant of a hydroxy compound containing a (meth) acrylonitrile group such as hydroxyethyl ester or 3-hydroxy[1,1,1-tris(meth)acrylenyloxymethyl]propane. Other examples of the ethylenic compound used in the present invention include (meth)acrylamides such as ethylenebis(meth)acrylamide; allyl esters such as diallyl phthalate; divinyl Ethylene-containing compound such as phthalate ester-54 - 200804974 (52) and the like.

此外，乙烯性化合物亦可爲具有酸價之單體，具有酸價之單體，例如脂肪族聚羥基化合物與不飽各羧酸之酯，使脂肪族聚羥基化合物的未反應的羥基與非芳香族羧酸酐進行反應而成的具有酸基之多官能單體爲佳，特別佳爲於此酯中，脂肪族聚羥基化合物爲季戊四醇及/或二季戊四醇者。此等單體可單獨使用1種，但因爲在製造上很難得到單一的化合物，故亦可混合2種以上使用。此外，必要時可倂用不具有酸基之多官能單體與具有酸基之多官能單體作爲單體。具有酸値之多官能單體的較佳酸價爲0.1〜4 Omg · KOH/g，特別佳爲 5〜30mg · KOH/g。多官能單體的酸價太低則會有顯影溶解性降低的傾向，太高則會有製造或操作困難的情況，此外會有光聚合性能降低、畫素的表面平滑性等的硬化性變差的情況。所以，倂用2種以上之不同酸基的多官能單體時，或倂用不具有酸基之多官能單體時，總體的多官能單體的酸基調整於上述範圍內較佳。於本發明，更佳的具有酸基之多官能單體，以東亞合成公司製的以「TO 1 3 82」販售之二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇五丙烯酸酯的琥珀酸酯作爲主成份的混合物，此多官能單體可與其他的多官能單體組合使用。於本發明的硬化性組成物，此等單體的含有比例，總固形份中，通常爲0重量％以上，較佳爲5重量％以上， -55- 200804974 (53) 更佳爲10重量％以上，此外通常爲80重量％以下，較佳爲70重量％以下，更佳爲50重量％以下，特別佳爲40重量％以下。此外，相對於後述的色材的比率，通常爲0重量％以上，較佳爲5重量％以上，更佳爲10重量％以上，特別佳爲20重量％以上，此外，通常爲200重量％以下，較佳爲100重量％以下，更佳爲8〇重量％以下。 [1-6](C)溶劑In addition, the ethylenic compound may also be an acid having a value of a monomer having an acid value, such as an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and an unreacted hydroxyl group of the aliphatic polyhydroxy compound. A polyfunctional monomer having an acid group obtained by reacting an aromatic carboxylic acid anhydride is preferred, and particularly preferably, in the ester, the aliphatic polyhydroxy compound is pentaerythritol and/or dipentaerythritol. These monomers may be used singly. However, since it is difficult to obtain a single compound in the production, two or more kinds may be used in combination. Further, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used as a monomer as necessary. The preferred acid value of the polyfunctional monomer having an acid hydrazine is 0.1 to 4 mg / KOH / g, particularly preferably 5 to 30 mg · KOH / g. When the acid value of the polyfunctional monomer is too low, the development solubility tends to be lowered. If it is too high, the production or handling may be difficult, and the photopolymerization performance may be lowered, and the surface smoothness of the pixel may be changed. Poor situation. Therefore, when a polyfunctional monomer having two or more different acid groups is used, or when a polyfunctional monomer having no acid group is used, the acid group of the entire polyfunctional monomer is preferably adjusted within the above range. In the present invention, a more preferred polyfunctional monomer having an acid group is dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentaacrylate sold by Toago Chemical Co., Ltd., which is sold under "TO 1 3 82". Succinate is used as a mixture of main components which can be used in combination with other polyfunctional monomers. In the curable composition of the present invention, the content ratio of the monomers is usually 0% by weight or more, preferably 5% by weight or more, and -55 to 200804974 (53) more preferably 10% by weight. The above is usually 80% by weight or less, preferably 70% by weight or less, more preferably 50% by weight or less, and particularly preferably 40% by weight or less. Further, the ratio of the color material to be described later is usually 0% by weight or more, preferably 5% by weight or more, more preferably 10% by weight or more, particularly preferably 20% by weight or more, and usually 200% by weight or less. It is preferably 100% by weight or less, more preferably 8% by weight or less. [1-6] (C) Solvent

本發明的硬化性組成物，溶劑爲必須成份，溶劑具有溶解或分散上述各成份而調節黏度之機能。該相關的溶劑，只要可溶解或分散構成硬化性組成物的各成份者即可，選擇沸點爲1 〇〇〜2 0 0 T：的範圍者較佳’更佳爲具有1 2 0〜1 7 0 °C的沸點者。如此的溶劑，可列舉例如乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單丙基醚、乙二醇單丁基醚、丙二醇單甲基醚、丙二醇-t_丁基醚、二乙二醇單乙基醚、二乙二醇單乙基醚、甲氧基甲基戊醇、丙二醇單乙基醚、二丙二醇單乙基醚、二丙二醇單甲基醚、3-甲基-3-甲氧基丁醇、三丙二醇甲基醚等二醇單烷基醚類；如乙二醇二甲基醚、乙二醇二乙基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇二丙基醚、二乙二醇二丁基醚之二醇二烷基醚類；如乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙二醇單丙基醚乙酸酯、甲氧基丁基乙酸酯、3 -甲氧基丁基乙酸 -56- 200804974 (54) 酯、甲氧基戊基乙酸酯、二乙二醇單乙基醚乙酸酯、二丙二醇單甲基醚乙酸酯、3-甲基-3-甲氧基丁基乙酸酯之二醇烷基醚乙酸酯類；如戊基醚、丙基醚、二乙基醚、二丙基醚、二異丙基醚、丁基醚、二胺基醚、丁基異丁基醚、二己基醚之醚類；In the curable composition of the present invention, the solvent is an essential component, and the solvent has a function of dissolving or dispersing the above components to adjust the viscosity. The solvent to be used may be any one which can dissolve or disperse the components constituting the curable composition, and preferably has a boiling point of 1 〇〇 to 2 0 0 T: preferably more preferably 1 2 0 to 1 7 The boiling point of 0 °C. Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol-t-butyl Ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether, methoxymethylpentanol, propylene glycol monoethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3 a diol monoalkyl ether such as methyl-3-methoxybutanol or tripropylene glycol methyl ether; such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether glycol dialkyl ether; such as ethylene glycol monomethyl ether acetate, B Glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, 3-methoxy Butyl acetic acid-56- 200804974 (54) ester, methoxypentyl acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methyl-3 - methoxybutyl acetate Ether acetates; such as pentyl ether, propyl ether, diethyl ether, dipropyl ether, diisopropyl ether, butyl ether, diamine ether, butyl isobutyl ether, dihexyl ether Ethers;

如丙酮、甲基乙基酮、甲基戊基酮、甲基異丙酮、甲基異戊基酮、二異丙基酮、二異丁基酮、甲基異丁酮、環己酮、乙基戊基酮、甲基丁基酮、甲基己基酮、甲基壬基酮之酮類；如乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇、二乙二醇、二丙二醇、甘油之1元或多元醇類；如η -戊院、η -辛院、二異丁烯、η -己院、己烯、異戊二烯、二戊烯、十二烷之脂肪族烴類；環己烷、甲基環己烷、甲基環己烯、雙環己烷之脂環式烴類；如苯、甲苯、二甲苯、枯燃之芳香族烴類；如戊基甲酸酯、乙基甲酸酯、乙酸乙酯、乙酸丁酯、乙酸丙酯、乙酸戊酯、甲基異丁酸酯、乙二醇乙酸酯、乙基丙酸酯、丙基丙酸酯、丁酸丁酯、丁酸異丁酯、異丁酸甲酯、乙基辛酸酯、丁基硬脂酸酯、乙基苯甲酸酯、3 -乙氧基丙酸甲酯、3 -乙氧基丙酸乙酯、3 -甲氧基丙酸甲酯、 3 -甲氧基丙酸乙酯、3 -甲氧基丙酸丙酯、3 -甲氧基丙酸丁酯、Τ -丁內酯之鏈狀或環狀酯類； -57- 200804974 (55) 如3 -甲氧基丙酸、3 -乙氧基丙酸之烷氧基羧酸類；如丁基氯化物、戊基氯化物之鹵化烴類；如甲氧基甲基戊酮之醚酮類；如乙腈、苯甲腈之腈類。Such as acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropanone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, B Ketones of methyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl ketone ketone; such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol Alcohol, dipropylene glycol, glycerol 1 yuan or polyols; such as η - Wuyuan, η-Xinyuan, diisobutylene, η-hexa, hexene, isoprene, dipentene, dodecane fat Hydrocarbons; alicyclic hydrocarbons of cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexane; such as benzene, toluene, xylene, or burned aromatic hydrocarbons; Acid ester, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate , butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, 3 - Ethyl ethoxy propionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, chain or cyclic ester of Τ-butyrolactone; 57- 200804974 (55) Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and pentyl chloride; such as methoxymethyl An ether ketone of pentanone; a nitrile such as acetonitrile or benzonitrile.

上述該市售的溶劑，可列舉礦物油、帕魯索#2、阿布可#18溶劑、阿布可納、索卡爾溶劑No. 1及No.2、索爾貝手#150、雪路TS28溶劑、卡必醇、乙基卡必醇、丁基卡必醇、甲基溶纖劑、乙基溶纖劑、乙基溶纖劑乙酸酯' 甲基溶纖劑乙酸酯、二甘醇二甲醚（digly me)(皆爲商品名）等。此等的溶劑可單獨使用1種或可倂用2種以上。上述溶劑中，由塗佈性、表面張力等之平衡佳，組成物中的構成成份的溶解度比較高的觀點而言，二醇烷基醚乙酸酯類爲佳。此外，二醇烷基醚乙酸酯類，可單獨使用，但亦可倂用其他的溶劑，所倂用的溶劑特別佳爲二醇單烷基醚類，其中以組成物中的構成成份的溶解性而言，特別佳爲丙二醇單甲基醚。再者，二醇單烷基醚類因爲極性高，添加量過多’而會光阻顏料易凝聚、硬化性組成物的黏度提高等之保存安定性降低的傾向，故（C)溶劑中的二醇單烷基醚爲5 %〜3 0 %，較佳爲5 %〜2 0 %。此外’倂用具有1 5 (TC以上沸點之溶劑亦佳，藉由倂用如此的溶劑，雖然硬化性組成物不易乾，但具有很難引起因爲急速乾燥所造的顏料分散物的相互關係（如後述）的破壞。高沸點溶劑的含量，相對於（C)溶劑以3%〜50%爲 -58- 200804974 (56) 佳、更仕爲5〜40%，特別佳爲5〜30%。再者，沸點1 5 0 °C以上的溶劑，可爲乙二醇院基醚乙酸酯類，此外亦可爲二醇烷基醚類，此時不另外含有沸點 1 5 0 °C以上的溶劑亦可。The commercially available solvent may, for example, be mineral oil, Paruso #2, Abuco #18 solvent, Abucoona, Sokar solvent No. 1 and No. 2, Solby hand #150, Snow Road TS28 solvent. , carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate 'methyl cellosolve acetate, diethylene glycol Dimly me (all are trade names) and the like. These solvents may be used alone or in combination of two or more. Among the above solvents, a glycolic ether acetate is preferred because the balance between coatability and surface tension is good, and the solubility of constituent components in the composition is relatively high. Further, the glycol alkyl ether acetates may be used singly, but other solvents may be used, and the solvent to be used is particularly preferably a glycol monoalkyl ether in which the constituents in the composition are dissolved. In particular, propylene glycol monomethyl ether is particularly preferred. Further, since the diol monoalkyl ether has a high polarity and an excessive amount of addition, the photo-resistance pigment tends to aggregate, and the viscosity of the curable composition is improved, and the storage stability tends to be lowered. Therefore, (C) The alcohol monoalkyl ether is from 5% to 30%, preferably from 5% to 2%. In addition, it is also preferable to use a solvent having a boiling point of TC or higher. Since such a solvent is used, although the curable composition is not easily dried, it has a relationship that is difficult to cause a pigment dispersion due to rapid drying ( The content of the high-boiling solvent is preferably 5% to 50% with respect to the (C) solvent of -58 to 200804974 (56), more preferably 5 to 40%, particularly preferably 5 to 30%. Further, the solvent having a boiling point of 150 ° C or higher may be an ethylene glycol-based ether acetate or a glycol alkyl ether, and in this case, a solvent having a boiling point of 150 ° C or more is not contained. Also.

於本發明的硬化性組成物，（C)溶劑的含有比例並沒有特別的限制，但其上限通常爲9 9重量％，溶劑超過99 重量％時，除去溶劑之各成份的濃度變太小，會有不適合形成塗佈膜之虞，另一方面，溶劑含有比例的下限値，若考慮適合塗佈的黏性等，通常爲7 5重量％，較佳爲8 0重量％，更佳爲8 2重量％。 [1-7](D)顏料本發明的硬化性組成物，以（D)顏料爲必須成份，例如形成彩色濾光片的畫素等時，可使用紅色顏料、藍色顏料、綠色顏料、黃色顏料、紫色顏料、橙色顏料、棕色顏料等之各種顏色的顏料。此外’其化學結構可列舉偶氮系、酞靑系、喹吖酮系、苯並咪嗤酮系、異吲哚滿酮系、二異噁嗪系 '陰丹士林系、茈系等之有機顏料，亦可利用其他的各種無機顏料。以下，以顏料編號列示出可使用的顏料的具體例子’以下所列舉的「C I.」表示 index(顏色索引）。紅色顏料可列舉顏料紅1、2、3、4、5、6、7、8、 9、K、“、15、“、17、21、22、23、31、32、37、 38 、 41 、 47 、 48 、 48 : 1 、 48 : 2 、 48 : 3 、 48 : 4 、 49 、 49 : 1、49 : 2、50 : 1、52 : 1、52 : 2、53、53 :1、53 : -59- 200804974 (57) 2 、 53 : 3 、 57 、 57 : 1 、 57 : 2 、 58 : 4 、 60 、 63 、 63 ： 1 、 6 3 · 2、6 4、6 4 : 1、6 8、69、81、81 ： 1、81 ： 2、81 : 3、81 ： 4、8 3、88、90 ： 1、101、1 01 : 1、104、108、 108： 1、109、112、113、114、122、123、144、146、 147、 149、 151、 166、 168、 169、 170、 172、 173、 174、 175、 176、 177、 178、 179、 181、 184、 185、 187、 188、 190 、 193 、 194 、 200 、 202 、 206 、 207 、 208 、 209 、 210 、In the curable composition of the present invention, the content ratio of the solvent (C) is not particularly limited, but the upper limit is usually 99% by weight, and when the solvent is more than 99% by weight, the concentration of each component excluding the solvent becomes too small. There may be a coating which is not suitable for forming a coating film. On the other hand, the lower limit 溶剂 of the solvent content ratio is usually 75 wt%, preferably 80 wt%, more preferably 8 when considering the viscosity suitable for coating. 2% by weight. [1-7] (D) Pigment The curable composition of the present invention may have a red pigment, a blue pigment, a green pigment, or the like when the (D) pigment is an essential component, for example, a pixel for forming a color filter. Pigments of various colors such as yellow pigment, purple pigment, orange pigment, brown pigment, and the like. Further, the chemical structure thereof may, for example, be an azo system, an anthraquinone group, a quinophthalone group, a benzoquinone group, an isoindolinone system, a dioxoxazine system, an indanthrene system, or a guanidine system. Organic pigments can also be used in various other inorganic pigments. Hereinafter, specific examples of the pigments that can be used are shown by the pigment number column. "C I." exemplified below indicates an index (color index). The red pigment may be exemplified by pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, K, ", 15, ", 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48 : 1 , 48 : 2 , 48 : 3 , 48 : 4 , 49 , 49 : 1, 49 : 2 , 50 : 1, 52 : 1, 52 : 2 , 53 , 53 : 1, 53 : -59- 200804974 (57) 2 , 53 : 3 , 57 , 57 : 1 , 57 : 2 , 58 : 4 , 60 , 63 , 63 : 1 , 6 3 · 2 , 6 4 , 6 4 : 1, 6 8 , 69, 81, 81 : 1, 81 : 2, 81 : 3, 81 : 4, 8 3, 88, 90 : 1, 101, 1 01 : 1, 104, 108, 108: 1, 109, 112, 113 , 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188 , 190, 193, 194, 200, 202, 206, 207, 208, 209, 210,

214、 216、 220、 221、 224、 230、 231' 232、 233、 235、 236、 237、 238、 239、 242、 243、 245、 247、 249、 250、 251 、 253 > 254 、 255 、 256 > 257 、 258 、 259 、 260 、 262 、 263 、 264 、 265 、 266 、 267 、 268 ' 269 、 270 、 271 、 272 、 273、274、275、276此等中較佳爲 C.I.顏料紅48:1、 122 、 168 、 177 、 202 、 206 、 207 、 209 、 224 、 242 、 254 ，更佳爲 C.I.顏料紅 177、209、224、254。藍色顏料可列舉顏料藍1、1 : 2、9、14、15、1 5 : 1、 15: 2、 15: 3、 15: 4、 15: 6、 16、 17、 19、 25、 27 、 28 、 29 、 33 、 35 、 36 、 56 、 56 : 1 、 60 、 61 、 61 : 1 、 62、 63、 66、 67、 68、 71、 72、 73' 74、 75、 76、 78、 79 此等中較佳爲C · I.顏料藍]5、1 5 : 1、1 5 : 2、15 : 3、 15: 4、15: 6，更佳爲 C.I·顏料藍 15: 6。綠色顏料可列舉顏料綠1、2、4、7、8、10、13、 14、15、17、18、19、26、36、45、48、50、51、54、 5 5。此等中較佳爲C · I ·顏料綠7、3 6。黃色顏料可列舉顏料黃1、1 : 1、2、3、4、5、6、 -60- 200804974 (58)214, 216, 220, 221, 224, 230, 231' 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253 > 254, 255, 256 > 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268 '269, 270, 271, 272, 273, 274, 275, 276 are preferably CI Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably CI Pigment Red 177, 209, 224, 254. Blue pigments can be exemplified by pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73' 74, 75, 76, 78, 79 Preferably, C · I. Pigment Blue] 5, 1 5 : 1, 1 5 : 2, 15 : 3, 15: 4, 15: 6, more preferably CI·Pigment Blue 15: 6. The green pigments may be exemplified by pigment greens 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Preferred among these are C · I · Pigment Green 7, 3 6 . Yellow pigments can be listed as pigment yellow 1, 1: 1, 2, 3, 4, 5, 6, and -60-200804974 (58)

9、 10、1 2、13、 14、 16、 17、 24 > 3 1、32 、34、 3 5 、 35 ： 1 、 36 、 36 ： 1 、 37 、 37 ：1 、40、 41、42 、43、 4 8 、 53 ^ 55 ' 6 1、6 2 、62 ：1 ' 6 3' 65、 73、7 4 、75、 8 1 83、 8 7 ^ 93、9 4 、95 、97、 100 、10 1 、104、 1 OS- 1 0 8 、 109 、1 1 0 >111> 116、 117、 119 、120 、126、 127 > 127 ： 1 ' 128、 129、1： 33、 134、 136、 _ 138 、139、 142、 147 、 148 、150 > 151、 153 > 154、 155 ' 157 、158、 159、 160 161 、162 、163、 164、 165、 1 66 、167 、168、 169、 170 Λ 172 、173 、17 4、 175、 176、 180 、18 1 、1 82、 183、 1 84 、 185 、188 、189、 190 、191 、19 1 : 1 、192 ' 193、 194 、 195 、196 、197、 198、 199 ^ 2 00 ' 202 、2 03、 2 04、 205 、 206 、207 、20 8 Itt t等中較佳爲C . I.顏料黃8 3、 117、 129 138 、1 5 0 、154、 155 、180 、 1 8 5，更佳爲 c · I ·顏 ί料黃 83' 138、 139、1 50、 180。紫色顏料可列舉顏料紫 1 ' 1 : 1 、2、2 : 2、3 、3 ： 1 ' 3:3' 5— 5 ：卜1 4、1 5 、16 、1 9、 23、25 、27、 .29 V 3 1、 32、 37、3 9 、42 、44、 4 7 、49、 50 ° Ifc 等中較佳爲 C.I. 顏料紫19、23，更佳爲 C.I.顏料紫 23 〇橙色顏料可列舉顏料橙 1 ' 2、5、 13 ' 1 6 ，、：1 7、 •19 、 2 0、 21、 22、23 、2 4 、34、 36 、38 > 39、4 3 、4 6、 48 \ 4 9、 61、 62、64 、65 、67、 68 、6 9、 70、7 1 、72、 73 、 7 4 、 • 75、 ΊΊ、78 、79 。此等中較佳爲 C . I.顏料橙 38 \ 71 〇此外，無機顏料可列舉硫酸鋇、硫酸鉛、氧化鈦、黃 •61 - 200804974 (59) 色鉛、氧化鐵紅、氧化鉻等。上述的各種顏料可倂用複數種，例如爲了調整色度，顏料係可倂用綠色顏料與黃色顏料，或倂用藍色顏料與紫色顏料再者，此等的顏料係分散處理成爲平均粒徑爲1 μ m 以下，較佳爲〇·5μπι以下，更佳爲0.3μιη以下後使用。9, 10, 1, 2, 13, 14, 16, 17, 24 > 3 1, 32, 34, 3 5, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42 43, 4 8 , 53 ^ 55 ' 6 1 , 6 2 , 62 : 1 ' 6 3' 65, 73, 7 4 , 75 , 8 1 83 , 8 7 ^ 93 , 9 4 , 95 , 97 , 100 , 10 1, 104, 1 OS- 1 0 8 , 109 , 1 1 0 > 111 > 116, 117, 119, 120, 126, 127 > 127 : 1 ' 128, 129, 1: 33, 134, 136, _ 138, 139, 142, 147, 148, 150 > 151, 153 > 154, 155 ' 157 , 158 , 159 , 160 161 , 162 , 163 , 164 , 165 , 1 66 , 167 , 168 , 169 , 170 Λ 172, 173, 17 4, 175, 176, 180, 18 1 , 1 82, 183, 1 84 , 185 , 188 , 189 , 190 , 191 , 19 1 : 1 , 192 ' 193 , 194 , 195 , 196 , 197 , 198, 199 ^ 2 00 '202, 2 03, 2 04, 205, 206, 207, 20 8 Itt t, etc. are preferably C. I. Pigment Yellow 8 3, 117, 129 138, 1 50, 154 , 155 , 180 , 1 8 5 , more preferably c · I · Yan 料 yellow 83 ' 138, 139, 1 50, 180The purple pigment can be exemplified by pigment purple 1 ' 1 : 1 , 2 , 2 : 2 , 3 , 3 : 1 ' 3:3' 5 - 5 : 1 4 , 1 5 , 16 , 1 9 , 23 , 25 , 27 , .29 V 3 1, 32, 37, 3 9 , 42 , 44 , 4 7 , 49 , 50 ° Ifc etc. It is preferably CI pigment violet 19, 23, more preferably CI pigment violet 23 〇 orange pigment can be listed as pigment Orange 1 ' 2, 5, 13 ' 1 6 , , : 1 7 , • 19 , 2 0 , 21 , 22 , 23 , 2 4 , 34 , 36 , 38 > 39 , 4 3 , 4 6 , 48 \ 4 9, 61, 62, 64, 65, 67, 68, 6 9, 70, 7 1 , 72, 73, 7 4 , • 75, ΊΊ, 78, 79. Preferred among these are C. I. Pigment orange 38 \ 71 〇 In addition, examples of inorganic pigments include barium sulfate, lead sulfate, titanium oxide, and yellow. 61 - 200804974 (59) color lead, iron oxide red, chromium oxide, and the like. The above various pigments may be used in a plurality of kinds, for example, in order to adjust the chromaticity, the pigment may be a green pigment or a yellow pigment, or a blue pigment and a violet pigment may be used, and the pigments are dispersed to form an average particle diameter. It is 1 μm or less, preferably 〇·5 μm or less, more preferably 0.3 μm or less.

使用本發明的硬化性組成物形成彩色濾、光片的樹脂黑色矩陣時，可使用黑色顏料。此外可單獨使用黑色顏料，亦可混合紅色、綠色、藍色等的顏料後使用，此等色材可從無機或有機的顏料中適當選擇。無機顏料、有機顏料係分散成爲平均粒徑爲1 μηι以下，較佳爲0·5 μιη以下後使用較佳。可單獨使用的黑色顏料，可列舉碳黑、乙炔碳黑、燈黑、骨碳、石墨、鐵黑、欽墨寺’此等中由透光率、影像特性的觀點而言，以碳黑、鈦黑爲佳。碳黑之例，各自可列舉例如三菱化學公司製的商品之 ΜΑ7、ΜΑ8 、MA11、MA100、MA100R、MA220、MA230、MA600、#5、#10、#20、 #25、#30、#32、#33、#40、#44、#45、#47、#50、#52、#55、#650 、#750、#850、#950、#960、#970、#980、#990、#1000、#2200、# 2300、#2350、#2400、#2600、#3050、#3150、#3250、#3600、#37 50、#3950、#4000、#4010、OIL7B、OIL9B、OIL11B、OIL30B、OIL31B 等，Degussa 公司製的商品之 Printex3、PrintexSOP、PrintexSO、Printex30 OP、Printex40、Printex45、Printex55、Printex60、Printex75、PrintexSO、 -62- (60) 200804974When a resin black matrix of a color filter or a light sheet is formed using the curable composition of the present invention, a black pigment can be used. Further, a black pigment may be used alone or a pigment such as red, green or blue may be mixed, and these color materials may be appropriately selected from inorganic or organic pigments. The inorganic pigment or the organic pigment is preferably dispersed in an average particle diameter of 1 μη or less, preferably 0·5 μm or less. The black pigment which can be used alone, for example, carbon black, acetylene black, lamp black, bone carbon, graphite, iron black, and Chinmo Temple, in terms of light transmittance and image characteristics, carbon black, Titanium black is preferred. Examples of the carbon black include, for example, ΜΑ7, ΜΑ8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, which are manufactured by Mitsubishi Chemical Corporation. #33,#40,#44,#45,#47,#50,#52,#55,#650,#750,#850,#950,#960,#970,#980,#990,#1000 , #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #37 50, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B Etc., Degussa's products Printex3, PrintexSOP, PrintexSO, Printex30 OP, Printex40, Printex45, Printex55, Printex60, Printex75, PrintexSO, -62- (60) 200804974

Printex85、Printex90、Printex A、Print ex L、Printex G、Printex P、P rintex U、Printex V、PrintexG、SpecialBlack550、SpecialBlack 350、Sp ecialBlack250、SpecialBlacklOO、SpecialBlack6、SpecialBlack5、SpecialB lack4、Color Black FW1、Color Black FW2、Color Black FW2V、Colo r Black FW18、Color Black FW18、Color Black FW200、Color Black S160、Color Black S170 等，CABOT公司製的商品之 Monarchl20、Printex85, Printex90, Printex A, Print ex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack 350, Sp ecialBlack250, SpecialBlacklOO, SpecialBlack6, SpecialBlack5, SpecialB lack4, Color Black FW1, Color Black FW2 , Color Black FW2V, Colo r Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170, etc., Monarchl20 of CABOT products,

Monarch280、Monarcli460、MonarcliSOO、Monarch880、Monarch900、Monarch280, Monarcli 460, MonarcliSOO, Monarch880, Monarch900,

MonarchlOOO、MonarchllOO、Monarchl300、Monarchl400、Monarch4 630、REGAL99、REGAL99R、REGAL415、REGAL415R、REGAL250、R EGAL250R、REGAL330、REGAL400R、REGAL55R0、REGAL660R、BL ACK PEARLS480、PEARLS 130、VULCAN XC72R、ELFTEX—8 等， Columbian Carbon 公司製的商品之 RAVEN11、RAVEN14、RAVEN15、R AVEN16、RAVEN22RAVEN30、RAVEN35、RAVEN40、RAVEN410、R AVEN420、RAVEN450、RAVEN500、RAVEN780、RAVEN850、RAVE N890H、RAVEN1000、RAVEN1020、RAVEN1040、RAVEN1060U、RA VEN1080U、RAVEN1170、RAVEN1190U、RAVEN1250、RAVEN1500 、RAVEN2000、RAVEN2500U、RAVEN3500、RAVEN5000、RAVEN52 50、RAVEN5750、RAVEN7000。再者，具有高的光學濃度及高的表面電阻率之樹脂黑色矩陣的製造，使用被樹脂被覆的碳黒爲特別佳。再者，被樹脂被覆的碳黑，例如可藉由用特開平9-2657 1號公報、特開平9-7 1 73 3號公報、特開平9-95625號公報、特開平 9-238863、或特開平 11-60989號公報所記載的方法，處理習知的碳黑而得到。此外，鈦黑的製作方法，可列舉使二氧化鈦與金屬鈦的混合物在還原氣體環境下加熱還原之方法（特開昭49-5 432號公報）；將四氯化鈦藉由高溫水解所得到的超微細二氧化鈦，在含氫之還原氣體環境中還原之方法（特開昭 -63- 200804974 (61) 57-205322號公報）；將二氧化鈦或氫氧化鈦在氨存在下高溫還原之方法（特開昭 60-65069號公報、特開昭 6卜 201610號公報）；使二氧化鈦或氫氧化鈦上附著釩化合物’在氨存在下高溫還原之方法（特開昭61_20161〇號公報）等；並不限定於此等方法。鈦黑的市售品之例，可列舉三菱Materials公司製的鈦黑i〇s、12S、13R、13M、 1 3M-C 等。MonarchlOOO, MonarchllOO, Monarchl300, Monarchl400, Monarch4 630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, R EGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BL ACK PEARLS480, PEARLS 130, VULCAN XC72R, ELFTEX-8, etc., Columbian Carbon RAVEN11, RAVEN14, RAVEN15, R AVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, R AVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVE N890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RA VEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN52 50, RAVEN5750, RAVEN7000. Further, in the production of a resin black matrix having a high optical density and a high surface resistivity, it is particularly preferable to use a carbon ruthenium coated with a resin. In addition, the carbon black to be coated with the resin can be, for example, Japanese Laid-Open Patent Publication No. Hei 9-2657, No. Hei 9-7 1 73 3, Japanese Patent Laid-Open No. Hei 9-95625, No. Hei 9-238863, or The method described in JP-A-H09-60989 is obtained by treating a conventional carbon black. In addition, a method of producing titanium black may be a method of heating and reducing a mixture of titanium dioxide and titanium metal in a reducing gas atmosphere (JP-A-49-5 432); and titanium tetrachloride is obtained by high-temperature hydrolysis. Method for reducing ultrafine titanium dioxide in a hydrogen-containing reducing gas atmosphere (JP-A-63-200804974 (61) 57-205322); a method of reducing titanium dioxide or titanium hydroxide in the presence of ammonia at a high temperature (Special opening) Japanese Patent Publication No. Sho 60-65069, JP-A-2006-201610, and a method of reducing a high-temperature reduction of a vanadium compound to titanium dioxide or titanium hydroxide in the presence of ammonia (Japanese Unexamined Patent Publication No. Hei No. 61-20161 No.) These methods. Examples of commercially available products of titanium black include titanium black i s, 12S, 13R, 13M, and 1 3M-C manufactured by Mitsubishi Materials.

其他的黑色顏料之例，可混合紅色、綠色、藍色的三色的顏料後作爲黑色顏料使用，用於調製黑色顏料之可混合使用的色材，可列舉維多利亞純藍（42595)、阿拉明 (41 000)、Cathilon brilliant flavin(鹼性 13)、若丹明 6GCP(45 1 60)、若丹明 B(45 1 70)、藏紅 OK70 : 1 00(50240)、愛麗奧海嬰藍（42080)、No.l20/Lionol 黃 (21 090) 、 Lionol 黃 GRO(21 090) 、 Shimurafast 黃 8GF(21105)、聯苯胺黃 4T-564D(2 1 095)、Shimurafast 紅 40 1 5( 1 23 5 5)、Lionol 紅 7B440 1 (1 5 850)、Fastgen 藍 TGR-L(741 60)、Lionol 藍 SM(261 50)、Lionol 藍 ES(顏料藍 15 : 6)、Lionogen 紅 GD(顏料紅 168)、Lionol 綠 2YS(顏料綠3 6)等。再者，上述括弧內的數字表示彩色索引 (C.I·)。此外，再關於其他可混合使用的顏料，以C.I·編號袠示，可列舉例如 C.I.黃色顏料 20、24、86、93、109、 110、 117、 125、 137、 138、 147、 148、 153、 154、 166、 C.I·橘色顏料 36、43、51、55、59、61、C.I.紅色顏料 -64- 200804974 (62) 9、97 > 122、123、149、168、177、180、192、215、 216 、 217 、 220、 223 、 224 、 226 、 227 、 228 、 240 、 C.I. 紫色顏料 19、23、29、30、37、40、50、C.I·藍色顏料 15、15: 1、15: 4、22、60、64、C.I.綠色顏料 7、C.I.黑色顏料23、25、26等。Other examples of black pigments can be mixed with red, green, and blue pigments and used as black pigments. They can be used to prepare black pigments that can be mixed and used, including Victoria Pure Blue (42595), Alamin. (41 000), Cathilon brilliant flavin (alkaline 13), Rhodamine 6GCP (45 1 60), Rhodamine B (45 1 70), saffron OK70: 1 00 (50240), Alice Sea Blue ( 42080), No.l20/Lionol Yellow (21 090), Lionol Yellow GRO (21 090), Shimurafast Yellow 8GF (21105), Benzidine Yellow 4T-564D (2 1 095), Shimurafast Red 40 1 5 ( 1 23 5 5), Lionol Red 7B440 1 (1 5 850), Fastgen Blue TGR-L (741 60), Lionol Blue SM (261 50), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168) , Lionol Green 2YS (Pigment Green 3 6), etc. Furthermore, the numbers in the above brackets indicate the color index (C.I.). Further, regarding other pigments which can be used in combination, as indicated by CI numbers, for example, CI yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, CI·Orange pigments 36, 43, 51, 55, 59, 61, CI red pigment-64- 200804974 (62) 9, 97 > 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, CI violet pigments 19, 23, 29, 30, 37, 40, 50, CI·blue pigments 15, 15: 1, 15: 4, 22, 60, 64, CI green pigment 7, CI black pigment 23, 25, 26, and the like.

於本發明的硬化性組成物，此等（D)顏料的含有比例，總固形份中，通常爲1重量％以上，較佳爲5重量％以上，此外，通常爲80重量％以下，較佳爲70重量％以下。 (D)顏料的比例太少，則會有相對於色濃度而言膜厚變太厚，對於液晶盒化時的間隙控制等產生壞的影響之虞，另一方面，相反的（D)顏料的比例過多，則會有無法得到充分的影像形成性。再者，對每個後述的彩色濾光片的各色的畫素，將用於形成此的硬化生組成物中的色材量調整至最適當的範圍較佳。例如，一般形成被設置於彩色濾光片之紅色、綠色及藍色畫素時，紅色硬化性組成物較佳可列舉總固形份中含有15〜50重量％，更佳爲20〜45重量％的色材者，綠色硬化性組成物較佳可列舉總固形份中含有1 5〜60重量 %，更佳爲20〜50重量％的色材者，綠色硬化性組成物較佳可列舉總固形份中含有5〜3 5重量％，更佳爲1 〇〜3 0 重量％的色材者。此外，樹脂黑色矩陣時，黑色硬化性組成物較佳可列舉總固形份中含有20〜80重量％，更佳爲30〜70重量％ -65- 200804974 (63) 的色材者。 [1-8](E)分散劑本發明的硬化性組成物，再含有（E)分散劑爲佳。（E) 分散劑的種類，只要無損於本發明的效果即可，並沒有特別的限制，但較佳爲含有由（E-1):含有氮原子之接枝共聚物、（E-2) ·•含有氮原子之丙烯酸系嵌段共聚物、（E-3 ):尿烷樹脂分散劑所選出的1種以上的分散劑。In the curable composition of the present invention, the content of the pigment (D) is usually 1% by weight or more, preferably 5% by weight or more, and usually 80% by weight or less, and more preferably 80% by weight or less. It is 70% by weight or less. (D) When the ratio of the pigment is too small, the film thickness becomes too thick with respect to the color density, and the effect of the gap control during the liquid crystal cell is adversely affected. On the other hand, the opposite (D) pigment If the ratio is too large, sufficient image formation cannot be obtained. Further, it is preferable to adjust the amount of the color material used for forming the hardened green composition to the optimum range for each color of the color filter to be described later. For example, when the red, green, and blue pixels provided in the color filter are generally formed, the red curable composition preferably contains 15 to 50% by weight, more preferably 20 to 45% by weight, based on the total solid content. For the color material, the green curable composition preferably contains from 15 to 60% by weight, more preferably from 20 to 50% by weight, based on the total solid content, and the green curable composition preferably has a total solid form. The portion contains 5 to 35 wt%, more preferably 1 to 30 wt% of the color material. Further, in the case of the resin black matrix, the black curable composition may preferably be a color material containing 20 to 80% by weight, more preferably 30 to 70% by weight to 65 to 200804974 (63), of the total solid content. [1-8] (E) Dispersant The curable composition of the present invention preferably further contains (E) a dispersant. (E) The kind of the dispersing agent is not particularly limited as long as the effect of the present invention is not impaired, but preferably contains (E-1): a graft copolymer containing a nitrogen atom, (E-2) • One or more dispersants selected from the group consisting of acrylic block copolymers containing nitrogen atoms and (E-3): urethane resin dispersants.

(E-1):含有氮原子之接枝共聚物、及（E-2):含有氮原子之丙烯酸系嵌段共聚物，此等所含有的氮原子對顏料表面具有親和性，推測藉由提高氮原子以外的部份對媒介物的親和性，有助於整體的分散安定性的提升。分散劑的性能，極受到相對於其固體表面之吸附舉動的左右，關於分子的結構與吸附舉動的關係，已知使用同樣的裝置時，吸附舉動的優異順序爲無規共聚物 < 接技共聚物〈嵌段共聚物。（例如 Jones and Richards，“Polymers at Surfaces and Interfaces” p281) 〇詳細的機制並不清楚，但推想如下述。亦即’通常的無規共聚物時，構成共聚物的單體在聚合物形成時，以立體及/或電氣，安定地被配置於共聚物中之準確率變高。單體被安定地配置的部份（分子），因爲立體及/或電氣方面安定，故吸附於顏料時，反而會有成爲障礙的情況。相對於此，分子配列被控制在接枝共聚物或嵌段共聚物之樹脂，可將分散劑之妨礙吸附的部份，配置在遠離顏料與分散劑的吸附部位的位置。亦即，顏料與 -66 - 200804974 (64) 分散劑之吸附部上可配置最適合的部份，需要溶劑親和性的部份上配置適合其之部份。特別是對於含有結晶尺寸小的顏料之色材的分散，推想此分子配置係影響優良的分散性者。 (E-1):含有氮原子之接枝共聚物含有氮原子之接枝共聚物，由可極有效率的分散（D) 顏料的觀點而言爲佳，此理由尙不清楚，但推想因爲對顏(E-1): a graft copolymer containing a nitrogen atom, and (E-2): an acrylic block copolymer containing a nitrogen atom, and the nitrogen atoms contained therein have affinity for the surface of the pigment, presumably by Increasing the affinity of the part other than the nitrogen atom to the medium contributes to the overall dispersion stability. The performance of the dispersant is extremely affected by the adsorption behavior relative to the solid surface. Regarding the relationship between the structure of the molecule and the adsorption behavior, it is known that when the same device is used, the excellent order of adsorption behavior is a random copolymer < Copolymer <block copolymer. (eg Jones and Richards, “Polymers at Surfaces and Interfaces” p281) 〇 The detailed mechanism is not clear, but it is assumed as follows. That is, in the case of a normal random copolymer, the monomer constituting the copolymer has a high accuracy in stereoscopically and/or electrically and stably disposed in the copolymer when the polymer is formed. Since the monomer (molecule) in which the monomer is stably disposed is stable in stereo and/or electrical, it may become an obstacle when adsorbed to the pigment. On the other hand, the molecular arrangement is controlled by the resin of the graft copolymer or the block copolymer, and the portion of the dispersant which hinders adsorption can be disposed at a position away from the adsorption site of the pigment and the dispersant. That is, the most suitable portion of the adsorption portion of the pigment and the -66 - 200804974 (64) dispersant can be disposed on the portion requiring solvent affinity. In particular, for the dispersion of a color material containing a pigment having a small crystal size, it is assumed that this molecular arrangement affects an excellent dispersibility. (E-1): a graft copolymer containing a nitrogen atom and a graft copolymer containing a nitrogen atom, which is preferably from the viewpoint of extremely efficient dispersion of the (D) pigment, which is unclear, but is conceivable because Face

料與分散劑的吸附成爲障礙的部份（分子），具有可積極地排斥配置至顏料的吸附部周邊的構造。含有氮原子之接枝共聚物，較佳爲具有主鏈上含有氮原子之重複單元者，其中較佳爲具有式（I)所表示的重複單元或/及式（II)所表示的重複單元。 [化 13]The adsorption (molecular) of the material and the dispersant becomes an obstacle, and has a structure that can positively repel the periphery of the adsorption portion disposed to the pigment. The graft copolymer containing a nitrogen atom is preferably a repeating unit having a nitrogen atom in the main chain, and preferably has a repeating unit represented by the formula (I) or a repeating unit represented by the formula (II) . [Chem. 13]

式中，R51表示碳數1〜5的伸烷基，A表示氫原子或下述式（III)〜（V)之任一者。式（I)中，R51表示伸甲基、伸乙基、伸丙基等之直鏈狀或支鏈狀的碳數1〜5的伸烷基，較佳爲碳數2〜3，更佳爲伸乙基。A表示氫原子或下述式（III)〜（V)之任一者，但較佳爲式（III)。 -67- 200804974 (65)In the formula, R51 represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any one of the following formulae (III) to (V). In the formula (I), R51 represents a linear or branched alkyl group having 1 to 5 carbon atoms, preferably a carbon number of 2 to 3, more preferably a methyl group, an ethyl group or a propyl group. For the extension of ethyl. A represents a hydrogen atom or any one of the following formulae (III) to (V), but is preferably a formula (III). -67- 200804974 (65)

[化 14] A相同式（Π)中，R51、A與式（1)之R [化 15]In the same formula (Π), R51, A and R of the formula (1) [Chem. 15]

式（III)中，Wi表示碳數2〜10的直鏈狀伸烷基，其中又以伸丁基、伸戊基、伸己基等 7的伸烷基爲佳；P表示1〜2 0的整數，較佳整數。 [化 16]In the formula (III), Wi represents a linear alkyl group having a carbon number of 2 to 10, and preferably an alkyl group having 7 groups such as a butyl group, a pentyl group and a hexyl group; P represents 1 to 2 0; Integer, preferably an integer. [Chemistry 16]

式（IV)中，Yl表示2價的連結基，其中伸丙基等之碳數1〜4的伸烷基，或伸乙氧: 等之碳數1〜4的伸烷氧基爲佳；W2袠示] 基、伸丁基等之直鏈狀或支鏈狀的碳數2〜1 其中又以伸乙基、伸丙基等之碳數2〜3的 -68- 或支鏈狀的之碳數4〜爲5〜10的以伸乙基、、伸丙氧基乙基、伸丙的伸烷基，烷基爲佳； 200804974 (66) Y2表示氫原子或-CO-R52(R52表示乙基、丙基、丁基、戊基、己基等之碳數1〜10的烷基，其中又以乙基、丙基、丁基、戊基等之碳數2〜5的烷基爲佳。）；q表示1〜20 的整數，較佳爲5〜1 0的整數。 [化 17]In the formula (IV), Y1 represents a divalent linking group, wherein an alkylene group having a carbon number of 1 to 4 such as a propyl group or an alkylene group having a carbon number of 1 to 4; W2 shows a linear or branched carbon number of 2 to 1 such as a base or a butyl group, and a -68- or branched chain having a carbon number of 2 to 3 such as an extended ethyl group or a propyl group. The carbon number 4 to 5 to 10 is an ethyl group extending to an ethyl group, a propenyloxyethyl group, or a stretching alkyl group, and an alkyl group is preferred; 200804974 (66) Y2 represents a hydrogen atom or -CO-R52 (R52) An alkyl group having 1 to 10 carbon atoms such as an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, and an alkyl group having 2 to 5 carbon atoms such as an ethyl group, a propyl group, a butyl group or a pentyl group. Preferably, q represents an integer of 1 to 20, preferably an integer of 5 to 10. [Chem. 17]

式（V)中，W3表示碳數1〜50的烷基或具有1〜5個羥基之碳數1〜50的羥基烷基，其中又以硬脂醯基等之碳數10〜20的烷基、單羥基硬脂醯基等之具有1〜2個羥基之碳數10〜20的羥基烷基爲佳。In the formula (V), W3 represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms and having 1 to 50 carbon atoms, and an alkane having a carbon number of 10 to 20, such as a stearin group. A hydroxyalkyl group having 10 to 20 carbon atoms having 1 to 2 hydroxyl groups, such as a monohydroxystearyl group or the like, is preferred.

本發明的接枝共聚物中之式（I)或式（II)所表示的重複單元的含有率，含有率高者爲佳，通常50莫耳％以上，較佳爲70莫耳％以上。亦可爲同時含有式⑴所表示的重複單元、與式（II)所表示的重複單元兩者，其含有比率並沒特別的限制，但含有較多的式（I)的重複單元者較佳，式（I)或式（II)所表示的重複單元的合計數爲i分子中通常爲1〜100，較佳爲10〜70，更佳爲20〜50。此外’亦可含有式⑴及式（II)以外的重複單元，其他的重複單元，可列舉例如伸烷基、伸烷氧基等，本發明的接枝共聚物，較佳爲其末端爲與上述的R 1相同意義）者。再者，只要爲本發明的接枝共聚物即可，主鏈可爲直 -69- 200804974 (67) 鏈狀或支鏈狀。本發明的接枝共聚物的胺價，通常爲5〜lOOmgKOH/ g，較佳爲1〇〜7〇mgKOH/g’更佳爲15〜40mgKOH/g以下。胺價太低則會有分散安定性降低、黏度不安定的情況，相反的太高則會有殘渣增加、形成液晶面板後的電氣特性降低的情況。In the graft copolymer of the present invention, the content of the repeating unit represented by the formula (I) or the formula (II) is preferably a high content, and is usually 50 mol% or more, preferably 70 mol% or more. It is also possible to contain both the repeating unit represented by the formula (1) and the repeating unit represented by the formula (II), and the content ratio thereof is not particularly limited, but it is preferred to contain a plurality of repeating units of the formula (I). The total number of repeating units represented by the formula (I) or the formula (II) is usually from 1 to 100, preferably from 10 to 70, more preferably from 20 to 50, in the i molecule. Further, 'the repeating unit other than the formula (1) and the formula (II) may be contained, and other repeating units may, for example, be an alkylene group or an alkyleneoxy group. The graft copolymer of the present invention preferably has a terminal end and The above R 1 has the same meaning). Further, as long as it is the graft copolymer of the present invention, the main chain may be straight-69-200804974 (67) chain or branched. The graft copolymer of the present invention has an amine value of usually 5 to 100 mgKOH/g, preferably 1 to 7 mg/KOH', more preferably 15 to 40 mgKOH/g. If the amine price is too low, the dispersion stability may be lowered and the viscosity may be unstable. On the contrary, if the amount is too high, the residue may increase and the electrical characteristics after forming the liquid crystal panel may be lowered.

上述分散劑以GPC測量的聚苯乙烯換算的重量平均分子量以3000〜100000，5000〜50000爲特別佳。重量平均分子量低於3000，則會有無法防止色材的凝聚、高黏度化及凝膠化的情況，超過1 〇〇〇〇〇則會有本身變成高黏度，又溶解於機溶劑的溶解性不足的情況。上述分散劑的合成方法，可採用習知的方法，例如可使用特公昭62-30057號公報所記載的方法。本發明中，亦可適當使用具有與上述者相同結構之市售的接枝共聚物。 (E-2):丙烯酸系嵌段共聚物丙烯酸系嵌段共聚物，由可極有效率的分散（D)顏料之觀點而言爲佳，其理由並不清楚，但推想乃因爲藉由控制分子配列，而減少在分散劑吸附於顏料時成爲障礙的結構。丙烯酸系嵌段共聚物，較佳爲側鏈上由具有4級銨鹽基及/或胺基之A嵌段、與不具有4級銨鹽基及/或胺基之 B嵌段所成之A-B嵌段共聚物及/或B-A_B嵌段共聚合物。 -70- 200804974 (68) 構成丙烯酸系嵌段共聚物的嵌段共聚合物之A嵌段’具有4級錢鹽基及/或胺基。The above-mentioned dispersant is particularly preferably a polystyrene-equivalent weight average molecular weight measured by GPC of from 3,000 to 100,000 to 5,000 to 50,000. When the weight average molecular weight is less than 3,000, the aggregation of the color material, the high viscosity, and the gelation cannot be prevented. When the weight average molecular weight is more than 1 Torr, the solubility becomes high viscosity and solubility in the organic solvent. Insufficient situation. A method of synthesizing the above dispersant can be carried out by a conventional method. For example, the method described in JP-A-62-30057 can be used. In the present invention, a commercially available graft copolymer having the same structure as the above may be suitably used. (E-2): Acrylic block copolymer acrylic block copolymer is preferable from the viewpoint of extremely efficient dispersion of (D) pigment, and the reason is not clear, but it is assumed that it is controlled by The molecules are arranged to reduce the structure which becomes a barrier when the dispersant is adsorbed to the pigment. The acrylic block copolymer preferably has a side block having an A block having a quaternary ammonium salt group and/or an amine group, and a B block having no quaternary ammonium salt group and/or an amine group. AB block copolymer and / or B-A_B block copolymer. -70-200804974 (68) The A block of the block copolymer constituting the acrylic block copolymer has a 4-grade salt group and/or an amine group.

4級銨鹽基，較佳係具有-N + R31R32R33 · Z—(惟， R31、R3 2及R3 3各自獨立地表示氫原子、或可被取代的環狀或鏈狀的烴基，或R31、R32及R33中的2個以上亦可互相鍵結後形成環。）所表示的4級銨鹽基。此4級銨鹽基可直接鍵結於主鏈，但亦可透過2價的連結基鏈結於主鏈。 -N + R31R32R33 · Z—中，R31、R32 及 R33 中的 2 個以上互相鍵結後所形成的環結構，可列舉例如5〜7員環的含氮雜環環單環或此等的2個縮合而成的縮合環。該含氮雜環較佳爲不具有芳香性者，若爲飽和環更佳，具體而言，可列舉例如下述者。 [化 18]a quaternary ammonium salt group, preferably having -N + R31R32R33 · Z- (except that R31, R3 2 and R3 3 each independently represent a hydrogen atom or a cyclic or chain hydrocarbon group which may be substituted, or R31, Two or more of R32 and R33 may be bonded to each other to form a ring of a 4- to 4-ammonium salt represented by the ring. The quaternary ammonium salt group may be directly bonded to the main chain, but may also be bonded to the main chain through a divalent linking group. -N + R31R32R33 · In the Z-, a ring structure formed by bonding two or more of R31, R32 and R33 to each other, for example, a nitrogen-containing heterocyclic ring monocyclic ring of 5 to 7 member rings or the like a condensation ring formed by condensation. The nitrogen-containing hetero ring is preferably one having no aromaticity, and more preferably a saturated ring, and specific examples thereof include the following. [Chem. 18]

上述中，R表示R31、R32及R33中的任一者之基。此等的環狀結構亦可再具有取代基。 -N + R31R32R33中之R31、R32及R33，更佳爲各自獨立地表示可具有取代基之碳數1〜3的烷基、或可具有取代基之苯基、或可具有取代基之苄基。 -71 - 200804974 (69) 具有4級銨鹽基之A嵌段，較佳爲含有一般式（VI)所表示的部份結構。 [化 19] R34In the above, R represents a group of any of R31, R32 and R33. These cyclic structures may further have a substituent. R31, R32 and R33 in -N + R31R32R33, more preferably each independently represents an alkyl group having 1 to 3 carbon atoms which may have a substituent, or a phenyl group which may have a substituent, or a benzyl group which may have a substituent . -71 - 200804974 (69) The A block having a 4-stage ammonium salt group preferably contains a partial structure represented by the general formula (VI). [Chem. 19] R34

上述一般式（VI)中，R31、R32及R33各自獨立地表示氫原子、或可被取代的環狀或鏈狀的羥基，或者R31、R32 及R33中的2個以上亦可互相鍵結後形成環狀結構；R34 表示氫原子或甲基；X1表示2價的連結基，Z—表示陰離子對。In the above general formula (VI), R31, R32 and R33 each independently represent a hydrogen atom or a cyclic or chain-like hydroxyl group which may be substituted, or two or more of R31, R32 and R33 may be bonded to each other. A cyclic structure is formed; R34 represents a hydrogen atom or a methyl group; X1 represents a divalent linking group, and Z- represents an anionic pair.

一般式（VI)中，R31、R3 2及R33的烴基，係各自獨立地爲具有碳數1〜1 〇的烷基、碳數6〜20的芳香族基之取代基爲佳，具體而言，可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、苄基、苯基等，其中又以甲基、乙基、丙基、苄基較佳。一般式（VI)中，2價的連結基X1，可列舉例如碳數1 〜10的伸烷基、伸芳基、-CONH-R35-、-COO-R36-(惟， R3 5及R3 6各自獨立地表示直接結合鍵、碳數1〜10的伸烷基、或碳數1〜10的酯基（-R37-0-R38- : R37及R38各自獨_LL地爲伸院基）。）等，較佳爲- COO-R36-。 -72- 200804974 (70) 此外，陰離子對之Z—，可列舉Cl—、Br-、：[-、cn〇4 、bf4—、ch3coct、pf6-等。 A嵌段較佳爲具有胺基者，胺基較佳爲_NRMR42(惟， R41及R4 2各自獨立地表示可具有取代基之環狀或鏈狀的烷基、可具有取代基之烯丙基、或可具有取代基之芳烷基。）所表示，而且更佳爲下述式所表示的胺基。 [化 20] • j^r 尽43 R4KN、R42 惟，R41及R42與上述的R41及R42同意義，表示碳數1以上的伸烷基，R44表示氫原子或甲基。）其中，R41及R42較佳爲甲基，R43較佳爲伸甲基、伸乙基，R44較佳爲氫原子。如此的化合物可列舉下述式所In the general formula (VI), the hydrocarbon groups of R31, R3 2 and R33 are preferably each independently a substituent having an alkyl group having 1 to 1 carbon atom and an aromatic group having 6 to 20 carbon atoms, specifically Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a benzyl group, a phenyl group and the like. Among them, a methyl group, an ethyl group, a propyl group and a benzyl group are preferred. In the general formula (VI), the divalent linking group X1 may, for example, be an alkylene group having 1 to 10 carbon atoms, an extended aryl group, -CONH-R35-, or -COO-R36- (only, R3 5 and R3 6). Each of them independently represents a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ester group having 1 to 10 carbon atoms (-R37-0-R38-: R37 and R38 are each a sole group). And so on, preferably -COO-R36-. Further, the anion pair Z- may, for example, be Cl—, Br-, :[-, cn〇4, bf4—, ch3coct, pf6-, or the like. The A block is preferably an amine group, and the amine group is preferably _NRMR42 (however, R41 and R4 2 each independently represent a cyclic or chain alkyl group which may have a substituent, and an allylic group which may have a substituent The group represented by the formula or the aralkyl group which may have a substituent, and more preferably an amine group represented by the following formula. • j^r is as far as 43 R4KN and R42. R41 and R42 have the same meanings as R41 and R42 above, and represent an alkylene group having 1 or more carbon atoms, and R44 represents a hydrogen atom or a methyl group. Wherein R41 and R42 are preferably a methyl group, R43 is preferably a methyl group and an ethyl group, and R44 is preferably a hydrogen atom. Such a compound can be exemplified by the following formula

表示的取代基。 [化 21]The substituents indicated. [Chem. 21]

如上述的特定的含有4級銨鹽基及/或胺基之部份結構，1個的A嵌段中可含有2種以上，此時，2種以上之 -73- 200804974 (71)In the above-mentioned specific partial structure containing a quaternary ammonium salt group and/or an amine group, two or more A blocks may be contained, and in this case, two or more kinds are -73-200804974 (71)

含有4級銨鹽基及/或胺基之部份結構，該A嵌段中可以無規共聚物或嵌段共聚物的任一種型態含有。此外’該不含有4級銨鹽基及/或胺基之部份結構，A嵌段中亦可含有，該部份結構之例，可列舉後述的源自（甲基）丙烯酸酯系單體之部份結構等。該相關的不含有4級銨鹽基及/或胺基之部份結構之在A嵌段中的含量，較佳爲〇〜50重量％，更佳爲0〜2 0重量％，但該相關的不含有4級銨鹽基及/或胺基之部份結構不含於A嵌段中爲最佳。另一方面，構成分散劑的嵌段共聚物之B嵌段，可列舉例如使苯乙烯、α -甲基苯乙烯等之苯乙烯系單體；（甲基）丙烯酸甲酯、（甲基）丙烯酸乙酯、（甲基）丙烯酸丙酯、 (甲基）丙烯酸異丙酯、（甲基）丙烯酸丁酯、（甲基）丙烯酸辛酯、（甲基）丙烯酸2-乙基己酯、（甲基）丙烯酸環氧丙酯、（甲基）丙烯酸苄酯、（甲基）丙烯酸羥基乙酯、乙基丙烯酸環氧丙酯等之（甲基）丙烯酸酯系單體；（甲基）丙烯酸氯化物等之（甲基）丙烯酸氯系單體；乙酸乙烯酯系單體；烯丙基環氧丙基醚、巴豆酸環氧丙基醚等之環氧丙基醚系單體等之共聚物進行共聚之聚合物結構。 Β嵌段特別佳爲下述一般式（VII)所表示之源自（甲基）丙烯酸酯系單體之部份結構。 -74- 01)200804974 (72)I；化 22] 39A partial structure containing a 4-stage ammonium salt group and/or an amine group, and the A block may be contained in any one of a random copolymer or a block copolymer. In addition, the partial structure which does not contain a 4-stage ammonium salt group and/or an amine group may be contained in the A block, and examples of the structure of this part include the (meth)acrylate type monomer which will be described later. Part of the structure and so on. The content of the related partial structure containing no 4- to ammonium salt group and/or amine group in the A block is preferably 〇 50% by weight, more preferably 0 to 20% by weight, but the correlation is related. It is preferred that a part of the structure which does not contain a 4-stage ammonium salt group and/or an amine group is not contained in the A block. On the other hand, examples of the B block of the block copolymer constituting the dispersant include styrene monomers such as styrene and α-methylstyrene; methyl (meth)acrylate and (methyl) groups. Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( a (meth) acrylate monomer such as glycidyl methacrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate or glycidyl ethacrylate; (meth)acrylic acid Copolymerization of a (meth)acrylic acid chloride monomer such as chloride; a vinyl acetate monomer; a glycidyl ether monomer such as allyl epoxypropyl ether or crotonic acid glycidyl ether; The polymer structure in which the material is copolymerized. The hydrazine block is particularly preferably a partial structure derived from a (meth) acrylate monomer represented by the following general formula (VII). -74- 01)200804974 (72)I;ization 22] 39

R COOR4R COOR4

(一般式（VII)中，R3 9表示氫原子或甲基，R4G表示可具有取代基之環狀或鏈狀的烷基、可具有取代基之烯丙基，或可具有取代基之芳烷基。）(In the general formula (VII), R3 9 represents a hydrogen atom or a methyl group, and R4G represents a cyclic or chain-like alkyl group which may have a substituent, an allyl group which may have a substituent, or an aralkyl group which may have a substituent base.)

上述源自（甲基）丙烯酸酯系單體之部份結構，1個B 嵌段中可含有2種以上，當然該B嵌段，可再含有此等以外的部份結構，2種以上的源自單體之部份結構，存在於不含有4級銨鹽基之B嵌段中時，各部份結構可以無規共聚或嵌段共聚的任一種型態被含於B嵌段中，B嵌段中含有上述源自（甲基）丙烯酸酯系單體之部份結構以外的部份結構時，該（甲基）丙烯酸酯系單體以外的部份結構之B嵌段中的含量，較佳爲〇〜99重量％，更佳爲〇〜85重量 %。本發明所使用的丙烯酸系分散劑，係由如此的A嵌段與B嵌段所成之A-B嵌段或B_A-B嵌段共聚型高分子化合物，如此的嵌段共聚物，例如用以下所列舉的活性聚合法調製。活性聚合法有陰離子活性聚合法、陽離子活性聚合法、自由基活性聚合法；陰離子活性聚合法，係聚合活性種爲陰離子’例如下述流程圖所表示。 -75- 200804974 (73) [化 23] (陰離子活性聚合法) 單體①:The partial structure derived from the (meth) acrylate monomer may include two or more kinds of one B block. Of course, the B block may further contain a partial structure other than these, and two or more types thereof may be used. When a part of the structure derived from the monomer is present in the B block which does not contain the quaternary ammonium salt group, each of the partial structures may be contained in the B block in any of a random copolymerization or a block copolymerization. When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content of the B block in the partial structure other than the (meth) acrylate monomer Preferably, it is 〇~99% by weight, more preferably 〇~85% by weight. The acrylic dispersant used in the present invention is an AB block or a B_A-B block copolymer type polymer compound formed from such an A block and a B block, and such a block copolymer is, for example, the following The living polymerization method is exemplified. The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method; and an anionic living polymerization method in which the polymerization active species is an anion', as shown in the following scheme. -75- 200804974 (73) [Anionic Living Polymerization Method] Monomer 1:

H2C==|H 單體②:H2C==|H monomer 2:

:CH 時:CH

+ 有機金屬(M)化合物+ organometallic (M) compounds

單體炎一 -► CHg—CK:Monomer inflammation -► CHg-CK:

單體<2L —f-►Monomer <2L —f-►

ΗΗ

4¾ 一 GH: I •CHS?—GH_ .Ar： η十1 .i2. m+1 自由基活性聚合法係聚合活性種爲自由基，例如下述流程圖所表示。 -76- 200804974 (74) (自由基活性聚合法潲醯法) [化 24]43⁄4 a GH: I • CHS?—GH_.Ar: η 十1 .i2. m+1 The radical active polymerization method is a radical, as shown in the following scheme. -76- 200804974 (74) (Free radical living polymerization method) [Chem. 24]

-77- 200804974 (75) [化 25] (自由基活性聚合法:ATRP法) 單體①: h2c=ch COORa ©： HaC==CH C00Rb 時-77- 200804974 (75) [Free radical living polymerization method: ATRP method] Monomer 1: h2c=ch COORa ©: HaC==CH C00Rb

+ 有機金屬(Me)化合物+ Organometallic (Me) compounds

Me:過渡金屬Me: transition metal

單體 JwfCH2—CH——: COOH\ CH2— COOR11Monomer JwfCH2—CH——: COOH\ CH2—COOR11

CH2—CH-- 〇〇〇mm CH2一'CHHutnMaCH2—CH-- 〇〇〇mm CH2-'CHHutnMa

合成如此的丙烯酸系嵌段共聚物時，可採用特開昭 60-89452 號公報、特開平 9-62002 號公報、 P.Lutz,P.Masson et al.Polym.Bull.12,79(198 4) > B.C.For the synthesis of such an acrylic block copolymer, JP-A-60-89452, JP-A-9-62002, P. Lutz, P. Masson et al. Polym. Bull. 12, 79 (198 4) can be used. ) > BC

Anderson,G.D.Andrews et al，M a cr o m o 1 e cu 1 e s，1 4，1 6 0 1 (198 1) 、 K.H at ada，K.Ute，et al.，Polym.J· 17,977( 1 985)、 K.Hatada，K.Ute，et al ·，Polym · J · 1 8，1 03 7 ( 1 9 8 6)、右手浩一、畑田耕一、高分子加工、36、366(1987)、東村敏延、沢本光男、高分子論文集、46、1 89(1989)、 M.Kuroki，T.Aida，J.Am.Chem.Sic，1 09,473 7(1 987)、相田卓三、井上祥平、有機合成化學、43,3 00(1 985)、 D.Y.Sogoh，W.R.Hertler et al，Macromolecules，20,1473 -78- 200804974 (76) (1987)、K.Matyaszewski et al，Chem.Rev.2001，101，2921- 2990等所記載的習知的方法。本發明該相關的A-B嵌段共聚物及B-A-B嵌段共聚物之lg中的胺價，通常爲1〜300mgKOH/g左右，但此較佳範圍，A嵌段具有4級銨鹽基的情況與不具有情況不相同。、Anderson, GD Andrews et al, Ma cr omo 1 e cu 1 es, 1 4,1 6 0 1 (198 1) , KH at ada, K.Ute, et al., Polym.J· 17,977 (1 985) , K.Hatada, K.Ute, et al ·, Polym · J · 1 8,1 03 7 (1 9 8 6), Right Hand Hao Yi, Putian Gengyi, Polymer Processing, 36, 366 (1987), Dongcun Minyan , Sakamoto Hiroshi, Polymer Proceedings, 46, 1 89 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 1 09, 473 7 (1 987), Ada Shozo, Inoue Cheung Ping, Organic Synthetic Chemistry , 43, 3 00 (1 985), DYSogoh, WR Hertler et al, Macromolecules, 20, 1473-78-200804974 (76) (1987), K. Matyaszewski et al, Chem. Rev. 2001, 101, 2921- A conventional method described in 2990 et al. The amine valence in the lg of the related AB block copolymer and the BAB block copolymer of the present invention is usually about 1 to 300 mgKOH/g, but in the preferred range, the A block has a 4-stage ammonium salt group and There is no difference in the situation. ,

本發明該相關的A-B嵌段共聚物及B_A-B嵌段共聚物之A嵌段具有4級銨鹽基時，該共聚物lg中的4級銨鹽基的量，較佳爲〇·1〜10mm〇1，若在此範圍外，會有無法兼具優良的耐熱性與分散性的情況，如此的嵌段共聚物中，會含有製造過程中所產生的胺基的情況，此胺價通常每 lg共聚物爲 1〜100mgKOH/g左右，較佳爲 1〜 50mgKOH/g，更佳爲 1〜30mgKOH/g。此外，A嵌段中不含有4級銨鹽基時，該共聚物的胺價通常每 lg爲 50〜3 00mgKOH/g左右，較佳爲 50〜 200mgKOH/g，再者胺價係藉由酸中和滴定胺基，使其與酸價對應而以KOH的mg數表示之値。此外，此嵌段共聚物的酸價，依是否有爲該酸價的基礎之酸性基及種類而不同，但一般而言較低者爲佳’通常爲100mgKOH/g以下，此分子量以以GPC測量的聚苯乙烯換算的重量平均分子量（Mw)通常爲1 000以上1〇〇,〇〇〇以下的範圍，會有嵌段共聚物的分子量太小則分散安定性降低，太大則顯影性、解析性降低的傾向。本發明中，可用具有與上述者相同結構之市售的丙烯 -79· 200804974 (77) 酸系嵌段共聚物。 (E-3):尿烷樹脂分散劑尿烷樹脂分散劑，特別佳爲藉由使聚異氰酸酯化合物、與同一分子內具有1個或2個羥基之化合物、與同一分子內具有活性氫及3級胺基之化合物進行反應而得到的尿烷樹脂。When the A block of the related AB block copolymer and the B_A-B block copolymer of the present invention has a 4-stage ammonium salt group, the amount of the 4-stage ammonium salt group in the copolymer lg is preferably 〇·1. 〜10mm〇1, if it is outside this range, it may not have excellent heat resistance and dispersibility. In such a block copolymer, the amine group produced during the production process may be contained. It is usually about 1 to 100 mgKOH/g per lg of copolymer, preferably 1 to 50 mgKOH/g, more preferably 1 to 30 mgKOH/g. Further, when the A block does not contain a quaternary ammonium salt group, the amine valence of the copolymer is usually from about 50 to 300 mg KOH/g per lg, preferably from 50 to 200 mg KOH/g, and the amine valency is by acid. The amine group is neutralized and titrated to correspond to the acid value and expressed in mg of KOH. Further, the acid value of the block copolymer differs depending on whether or not there is an acidic group and a kind based on the acid value, but generally the lower one is preferably 'normally 100 mgKOH/g or less, and the molecular weight is GPC. The measured polystyrene-equivalent weight average molecular weight (Mw) is usually 1 000 or more and 1 〇〇. In the range below 〇〇〇, the molecular weight of the block copolymer is too small, the dispersion stability is lowered, and the development property is too large. The tendency to reduce the resolution. In the present invention, a commercially available propylene-79·200804974 (77) acid block copolymer having the same structure as the above may be used. (E-3): urethane resin dispersant urethane resin dispersant, particularly preferably by using a polyisocyanate compound, a compound having one or two hydroxyl groups in the same molecule, and having active hydrogen in the same molecule and A urethane resin obtained by reacting a compound of the amino group.

上述聚異氰酸酯化合物之例，可列舉例對伸苯二異氰酸酯、2,4-伸甲苯二異氰酸酯、2,6-伸甲苯二異氰酸酯、 4，4’-二苯基甲烷二異氰酸酯、萘-1，5-二異氰酸酯、聯甲苯胺二異氰酸酯等芳香族二異氰酸酯；六伸甲基二異氰酸酯、賴胺酸甲基酯二異氰酸酯、2,4,4·三甲基六伸甲基二異氰酸酯、二聚酸二異氰酸酯等之脂肪族二異氰酸酯；異佛爾酮二異氰酸酯、4，4’-伸甲基雙（環己基異氰酸酯）、ω， ω’-二異氰酸酯二甲基環己烷等之脂環族二異氰酸酯；具有伸二甲苯二異氰酸酯、α,α,α’，α’-四甲基伸二甲苯二異氰酸酯等之芳香環之脂肪族二異氰酸酯·，賴胺酸酯三異氰酸酯、1，6，1卜十一烷三異氰酸酯、1，8-二異氰酸酯-4-異氰酸酯甲基辛院、1，3,6-六伸甲基三異氰酸酯、雙環丁烷三異氰酸酯、參（異氰酸酯苯基甲烷）、參（異氰酸酯苯基）硫化磷酸酯等之三異氰酸酯；及此等的3聚物、水加成物、以及此等的多元醇加成物等。聚異氰酸酯較佳爲有機二異氰酸酯的三聚物，最佳爲伸甲苯基二異氰酸酯的三聚物與異佛爾酮二異氰酸酯的三聚物，此等可單獨使用或可倂用複數種。 -80- 200804974 (78) 異氰酸酯的三聚物的製造方法，可列舉使該聚異氰酸酯類，用適當的三聚化催化劑，例如第3級胺類、膦類、烷氧化物類、金屬氧化物、羧酸鹽類等進行異氰酸酯基的部份三聚化，藉由催化毒物的添加而使三聚化停止後，溶劑萃取未反應的聚異氰酸酯，藉由薄膜蒸餾去除後得到目的之含三聚異氰酸酯之聚異氰酸酯之方法。Examples of the above polyisocyanate compound include phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene-1. An aromatic diisocyanate such as 5-diisocyanate or tolidine diisocyanate; hexamethylene diisocyanate, lysine methyl diisocyanate, 2,4,4·trimethylhexamethylene diisocyanate, dimerization Aliphatic diisocyanate such as acid diisocyanate; alicyclic group such as isophorone diisocyanate, 4,4'-methyl bis(cyclohexyl isocyanate), ω, ω'-diisocyanate dimethylcyclohexane Diisocyanate; aliphatic diisocyanate having an aromatic ring of xylene diisocyanate, α,α,α',α'-tetramethylxylene diisocyanate, lysine triisocyanate, 1,6,1 Undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyl xinyuan, 1,3,6-hexamethylene monoisocyanate, dicyclobutane triisocyanate, ginseng (isocyanate phenylmethane), ginseng Isocyanate phenyl) sulfur Phosphate, etc. triisocyanate; 3 and oligomers of these, water adducts, and polyhydric alcohols such adducts. The polyisocyanate is preferably a terpolymer of an organic diisocyanate, preferably a trimer of a tolyl diisocyanate and a terpolymer of isophorone diisocyanate, which may be used singly or in combination. -80-200804974 (78) A method for producing a trimer of an isocyanate may be an appropriate trimerization catalyst such as a third-order amine, a phosphine, an alkoxide or a metal oxide. And the partial trimerization of the isocyanate group by a carboxylate or the like, and after the trimerization is stopped by the addition of the catalytic poison, the solvent extracts the unreacted polyisocyanate, and is removed by thin film distillation to obtain the desired trimerization. Method of polyisocyanate of isocyanate.

上述同一分子內具有1個或2個羥基之化合物，可列舉聚醚二醇、聚酯二醇、聚碳酸酯二醇、聚烯烴二醇等，或此等的化合物的末端羥基係被碳數1〜25的烷基進行烷氧基化者，或此等的2種類以上的混合物。聚醚乙二醇’可列舉聚醚二醇、聚醚酯二醇 '或此等 2種類以上的混合物。聚醚二醇，係可藉由使環氧化物進行單獨或使其共聚所得到者，例如聚乙二醇、聚丙二醇、聚乙烯-丙烯二醇、聚氧化四甲二醇、聚氧化六甲二醇、聚氧化八甲二醇、或此等的2種以上的混合物。聚醚酯二醇，可列舉使含醚基之二醇或其他的二醇之混合物，與二羧酸或此等的酐進行反應，或藉由使聚酯二醇與環氧化物進行反應而得到者，例如聚（聚氧化四伸甲基）己二酸酯等。聚醚二醇之最佳者爲聚乙二醇、聚丙二醇、聚氧化四甲二醇、或此等的化合物的一方末端羥基，用碳數1〜2 5 的烷基經烷氧化的化合物聚酯二醇’可列舉例如號拍酸、戊二酸、己二酸、癸二酸、富馬酸、馬來酸、酞酸等之二羧酸類或此等的酐，與例如乙二醇、二乙二醇、三乙二醇、丙二醇、二丙二 -81 - 200804974 (79)Examples of the compound having one or two hydroxyl groups in the same molecule include polyether diol, polyester diol, polycarbonate diol, polyolefin diol, etc., or the terminal hydroxyl group of these compounds is carbon number. The alkyl group of 1 to 25 is alkoxylated, or a mixture of two or more types thereof. The polyether glycol ' can be exemplified by a polyether diol or a polyether ester diol' or a mixture of two or more kinds thereof. The polyether diol can be obtained by separately or copolymerizing an epoxide such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyethylene hexahydrate. An alcohol, polyoxy octa octa diol, or a mixture of two or more of these. The polyether ester diol may, for example, be a mixture of an ether group-containing diol or another diol, reacted with a dicarboxylic acid or an anhydride thereof, or by reacting a polyester diol with an epoxide. The winner is, for example, poly(polyoxytetramethyl) adipate or the like. The most preferred polyether diol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or one terminal hydroxyl group of such a compound, which is agglomerated with a compound having an alkoxylation of an alkyl group having 1 to 25 carbon atoms. Examples of the ester diols include dicarboxylic acids such as acenamic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, and citric acid, and the like, and such as, for example, ethylene glycol. Diethylene glycol, triethylene glycol, propylene glycol, dipropylene-81 - 200804974 (79)

醇、三丙二醇、1，2-丁二醇、13-丁二醇、丨，4-丁二醇、 2,3· 丁二醇、3_甲基-U•戊二醇、新戊二醇、2-甲基-丙二醇、2-甲基-2-丙基-l，3-丙二醇、2-丁基-2-乙基-1，3-丙二醇、1，5·戊二醇、！，6_己二醇、2-甲基-2,和戊二醇、 2,2,4-三甲基-j，3_戊二醇、八乙基-1ϊ3•己二醇、2,5•二甲基-2,5-己二醇、1，8_八甲二醇、2_甲基_1，8_八甲二醇、 1，9-壬二醇等之脂肪族二醇；雙羥基甲基環己烷等之脂環族二醇；二甲苯二醇、雙羥基乙氧基苯等之芳香族二醇； Ν-甲基二乙二醇胺等之Ν_烷基二烷醇胺等之二醇類，進行聚縮合後所得到者’例如聚乙烯己二酸酯、聚丁烯己酸酯、聚六甲烯己二酸酯、聚乙烯/丙烯己二酸酯等，或者使用上述二醇類或碳數1〜25的1價醇作爲起始劑使用後所得到的聚內酯二醇或聚內酯單醇，例如聚己內酯二醇、聚甲基戊內酯、或此等的2種以上的混合物。聚酯二醇最佳者係以聚己內酯二醇或碳數1〜25的醇作爲起始劑之聚己內酯，更具體而言，係使單醇與ε ·己內酯進行開環加成聚合後所得到的化合物。聚碳酸酯二醇，可列舉聚（1，6-己烯）碳酸酯、聚（3-甲基-1，5-戊烯）碳酸酯等。此外，聚烯烴二醇，可列舉聚丁二烯二醇、氫化型聚丁二烯二醇、氫化型聚異戊二烯二醇等。此等同一分子內具有1個或2個羥基之化合物中，特別佳爲聚醚二醇與聚酯二醇，再者，同一分子內具有1個或 2個羥基之化合物的數平均分子量通常爲 3 00〜 -82- 200804974 (80) 10,000，較佳爲 500 〜6，0 00，更佳爲 1，000〜4,000。上述之同一分子內具有活性氫及3級胺基之化合物中，活性氫，亦即直接鍵結於氧原子、氮原子、或硫原子之氫，可列舉羥基、胺基、硫醇基等之官能基中的氫原子。其中胺基，特別是1級的胺基的氫原子爲佳，此外，Alcohol, tripropylene glycol, 1,2-butanediol, 13-butanediol, hydrazine, 4-butanediol, 2,3·butanediol, 3-methyl-U•pentanediol, neopentyl glycol , 2-methyl-propanediol, 2-methyl-2-propyl-l,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5·pentanediol,! , 6-hexanediol, 2-methyl-2, and pentanediol, 2,2,4-trimethyl-j,3-pentylene glycol, octaethyl-1ϊ3•hexanediol, 2,5 • an aliphatic diol such as dimethyl-2,5-hexanediol, 1,8-octadiol, 2-methyl-1,8-octadiol or 1,9-nonanediol; An alicyclic diol such as bishydroxymethylcyclohexane; an aromatic diol such as xylene diol or bishydroxyethoxy benzene; Ν-alkyl dioxane such as Ν-methyl diethylene glycol amine a glycol such as an alcohol amine, which is obtained by polycondensation, such as polyethylene adipate, polybutylene hexanoate, polyhexamethylene adipate, polyethylene/propylene adipate, or the like, or A polylactone diol or a polylactone monool obtained by using the above diol or a monovalent alcohol having 1 to 25 carbon atoms as a starter, for example, polycaprolactone diol, polymethyl valerolactone Or a mixture of two or more of these. The polyester diol is preferably a polycaprolactone having a polycaprolactone diol or an alcohol having 1 to 25 carbon atoms as a starter, and more specifically, a monool and ε·caprolactone are opened. The compound obtained after cycloaddition polymerization. Examples of the polycarbonate diol include poly(1,6-hexene) carbonate and poly(3-methyl-1,5-pentene) carbonate. Further, examples of the polyolefin diol include polybutadiene diol, hydrogenated polybutadiene diol, and hydrogenated polyisoprene diol. Among these compounds having one or two hydroxyl groups in the same molecule, particularly preferred are polyether diols and polyester diols, and the number average molecular weight of a compound having one or two hydroxyl groups in the same molecule is usually 3 00 to -82- 200804974 (80) 10,000, preferably 500 to 6,0 00, more preferably 1,000 to 4,000. In the above-mentioned compound having an active hydrogen and a tertiary amino group in the same molecule, active hydrogen, that is, hydrogen directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, may be exemplified by a hydroxyl group, an amine group, a thiol group or the like. a hydrogen atom in a functional group. The hydrogen atom of the amine group, particularly the amine group of the first stage, is preferred, and

3級胺基係具有甲基、乙基、異丙基、η-丁基等之碳數1 〜4的烷基之二烷基胺基、或該二烷基胺基連結後形成雜環結構之基。更具體而言，可列舉咪唑環、***環，但其中又以二甲基胺基及咪唑環因爲具有優異的安定性故較佳。若列舉出如此的同一分子內具有活性氫及3級胺基之化合物，可列舉Ν，Ν-二甲基-1，3·丙二胺、Ν，Ν-二乙基-1，3-丙二胺、Ν，Ν-二丙基-1，3-丙二胺、Ν，Ν-二丁基-1，3-丙二胺、Ν5Ν-二甲基乙二胺、Ν，Ν-二乙基乙二胺、Ν，Ν-二丙基乙二胺、Ν，Ν-二丁基乙二胺、ν，Ν-二甲基-1,4-丁二胺、Ν，Ν -二乙基-1，4 -丁二胺、Ν，Ν·二丙基-1，4-丁二胺、 Ν，Ν-二甲基-1，4-丁二胺等。此外，3級胺基爲含氮之雜環者，可列舉吡唑環、咪唑環、***環、四唑環、吲哚環、咔唑環、吲唑、苯並咪唑環、苯並***環、苯並噁唑環、苯並噻唑環、苯並噻二哩環等之含氮雜環5員環；吡啶環、噠嗪環、嘧啶環、三嗪環、喹啉、吖啶環、異喹啉環等之含氮原子雜6員環。具有此等咪唑環與1級胺基之化合物，若列出具體的例子，可列舉1 - (3 -胺基丙基）咪哩、組胺酸、2 ·胺基咪哩、 -83- 200804974 (81)The tertiary amine group is a dialkylamino group having an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an isopropyl group or a η-butyl group, or a dialkylamine group is bonded to form a heterocyclic structure. The basis. More specifically, an imidazole ring or a triazole ring is exemplified, but among them, a dimethylamino group and an imidazole ring are preferred because of their excellent stability. Examples of such a compound having an active hydrogen and a tertiary amino group in the same molecule include hydrazine, hydrazine-dimethyl-1,3·propylenediamine, hydrazine, hydrazine-diethyl-1,3-propene. Diamine, hydrazine, hydrazine-dipropyl-1,3-propanediamine, hydrazine, hydrazine-dibutyl-1,3-propanediamine, Ν5Ν-dimethylethylenediamine, hydrazine, hydrazine-diethyl Ethylenediamine, hydrazine, hydrazine-dipropylethylenediamine, hydrazine, hydrazine-dibutylethylenediamine, ν, Ν-dimethyl-1,4-butanediamine, hydrazine, hydrazine-diethyl -1,4-butanediamine, hydrazine, hydrazine dipropyl-1,4-butanediamine, hydrazine, hydrazine-dimethyl-1,4-butanediamine, and the like. Further, the tertiary amine group is a nitrogen-containing heterocyclic ring, and examples thereof include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an anthracene ring, an indazole ring, a carbazole, a benzimidazole ring, and a benzotriene. Nitrogen-containing heterocyclic 5-membered ring of azole ring, benzoxazole ring, benzothiazole ring, benzothiadiazine ring, etc.; pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline, acridine ring a 6-membered ring containing a nitrogen atom such as an isoquinoline ring. A compound having such an imidazole ring and a primary amine group, and specific examples are exemplified by 1-(3-aminopropyl)imidazole, histidine, 2-aminopyridinium, -83-200804974 (81)

1-(2-胺基乙基）咪唑等。此外，具有此等***環與〗級胺基之化合物，若列出具體的例子，可列舉3-胺基-1，2,4-三唑、5-(2-胺基-5-氯苯基）-3-苯基-1H-1，2,4-***、4-胺基-4H-1，2,4-***-3,5-二醇、3-胺基-5-苯基-1H-***-1，3,4-二醇、5-胺基-1，4-二苯基-1，2,3***、3-胺基-1-苄基-1H-2,4-***等。此等又以n，N-二甲基-1，3-丙二胺、N，N-二乙基-1，3-丙二胺、1-(3-胺基苯基）咪唑、3-胺基-1，2,4-*** 等。此等的尿烷樹脂分散劑原料的較佳使用比率，相對於聚異氰酸酯化合物1〇〇重量份，同一分子內具有1個或2 個羥基之化合物，通常10〜200重量份，較佳爲20〜190 重量份，更佳爲3 0〜18〇重量份；同一分子內具有活性氫及3級胺基之化合物，通常〇 . 2〜2 5重量份，較佳爲〇 . 3 〜24重量份。此外，尿烷樹脂分散劑的製造，依照尿烷樹脂製造的習知方法進行，製造時的溶劑，通常使用丙酮、甲基乙基酮、甲基異丁基酮、環戊酮、環己酮、異佛爾酮等之酮類；乙酸乙酯、乙酸丁酯、乙酸溶纖劑等之酯類；苯、甲苯、二甲苯、己烷等之烴類；二丙酮醇、異丙醇、第二丁醇、第三丁醇等的一部份的醇類；二氯甲烷、氯仿等鹵化烴類；四氫呋喃、二乙基醚等之醚類；二甲基甲醯胺、N-甲基吡咯烷酮、二甲基亞楓等之非質子性極性溶劑等。此外，製造時的催化劑，使用通常尿烷化反應催化劑，例如可列舉二丁基錫二月桂酸鹽、二辛基錫二月桂酸鹽、二丁 -84- 200804974 (82) 基錫二辛酸鹽、辛酸亞錫等錫系；乙醯丙酮合鐵、氯化鐵等之鐵系等之鐵系；三乙胺、三乙二胺等之3級胺系等。1-(2-Aminoethyl)imidazole and the like. Further, as the compound having such a triazole ring and an amine group, if specific examples are given, 3-amino-1,2,4-triazole and 5-(2-amino-5-chloride are mentioned. Phenyl)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5- Phenyl-1H-triazole-1,3,4-diol, 5-amino-1,4-diphenyl-1,2,3 triazole, 3-amino-1-benzyl-1H- 2,4-triazole and the like. These are again n,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminophenyl)imidazole, 3- Amino-1,2,4-triazole and the like. A preferred use ratio of the urethane resin dispersant raw material is a compound having one or two hydroxyl groups in the same molecule, usually 10 to 200 parts by weight, preferably 20% by weight based on 1 part by weight of the polyisocyanate compound. 190 parts by weight, more preferably 30 to 18 parts by weight; a compound having active hydrogen and a tertiary amino group in the same molecule, usually 2 to 2 parts by weight, preferably 〇. 3 to 24 parts by weight . Further, the production of the urethane resin dispersant is carried out in accordance with a conventional method for producing a urethane resin, and a solvent for production is usually acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone or cyclohexanone. a ketone such as isophorone; an ester of ethyl acetate, butyl acetate or cellosolve acetate; a hydrocarbon such as benzene, toluene, xylene or hexane; diacetone alcohol, isopropanol, a part of an alcohol such as dibutyl alcohol or a third butanol; a halogenated hydrocarbon such as dichloromethane or chloroform; an ether such as tetrahydrofuran or diethyl ether; dimethylformamide or N-methylpyrrolidone; An aprotic polar solvent such as dimethyl sulfoxide. Further, the catalyst used in the production is usually a urethane reaction catalyst, and examples thereof include dibutyltin dilaurate, dioctyltin dilaurate, dibutyl-84-200804974 (82)-based tin dioctanoate, and octanoic acid. Tin-based tin or the like; an iron-based system such as iron acetonitrile, iron chloride, or the like; a tertiary amine such as triethylamine or triethylenediamine.

此外’同一分子內具有活性氫及3級胺基之化合物的導入量’控制在以反應後的分散樹脂的胺價而言爲i〜 100mgKOH/g的範圍內爲佳，較佳爲5〜80mgKOH/g的範圍’更佳爲1〇〜60mgKOH/g的範圍。胺價在上述範圍以下則會有分散能力降低的傾向，此外，超過上述範圍則顯影性易降低。再者，以上的反應在分散樹脂中殘留異氰酸酯基時’再藉由醇或胺化合物去掉異氰酸酯基，則分散樹脂的經時安定性提高而較佳。再者，此等尿烷樹脂分散劑以GP C所測量的聚苯乙烯換算的重量平均分子量通常1，〇〇〇〜200, 〇〇〇，較佳爲 2,000〜1 00,0 00，更佳爲 3,000〜5 0,000的範圍。分子量低於1，〇〇〇以下則分散性及分散安定性變差，200,000以上則溶解性降低、分散性變差，而且反應的控制變困難。 (E-4)其他的分散劑本發明的硬化性組成物所使用的分散劑，除了上述的各種分散劑以外，可含有其他的分散劑。其他的分散劑，可列舉例如聚乙烯亞胺系分散劑、聚氧乙烯烷基醚系分散劑、聚氧乙烯二酯系分散劑、山梨糖醇酐脂肪族酯系分散劑、脂肪族改性聚酯系分散劑等。如此的分散劑的具體例子，可列舉商品名 EFKA( EFKA 公司製）、Dispei*byk(BYK-Chemie 公司製）、 DISPARLON(楠本化成公司製）、SOLSPERSE(ZENNECA 公 -85- 200804974 (83) 司製）、KP(信越化學工業公司製）、p〇lyfl〇W(共榮社化學公司製）、阿濟斯（味之素公司製）等。此等高分子分散劑可單獨使用1種，或可倂用2種以上。Further, the 'introduction amount of the compound having an active hydrogen and a tertiary amino group in the same molecule' is preferably in the range of i to 100 mgKOH/g, preferably 5 to 80 mgKOH, in terms of the amine value of the dispersion resin after the reaction. The range of /g is more preferably in the range of 1 〇 to 60 mg KOH/g. When the amine value is less than the above range, the dispersibility is lowered, and when it exceeds the above range, the visibility is liable to lower. Further, when the above reaction causes the isocyanate group to remain in the dispersion resin, the isocyanate group is removed by the alcohol or the amine compound, and the stability of the dispersion resin is improved. Further, the weight average molecular weight of the urethane resin dispersant measured by GP C in terms of polystyrene is usually 1, 〇〇〇 200, 〇〇〇, preferably 2,000 〜 1 00, 0 00, more preferably It is in the range of 3,000 to 5,000. When the molecular weight is less than 1, the dispersibility and the dispersion stability are deteriorated below 〇〇〇, and the solubility is lowered more than 200,000, the dispersibility is deteriorated, and the control of the reaction becomes difficult. (E-4) Other Dispersing Agent The dispersing agent used in the curable composition of the present invention may contain other dispersing agents in addition to the above various dispersing agents. Examples of the other dispersant include a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, a polyoxyethylene diester dispersant, a sorbitan fatty ester dispersant, and an aliphatic modification. A polyester-based dispersant or the like. Specific examples of such a dispersing agent include EFKA (manufactured by EFKA Co., Ltd.), Dispei*byk (manufactured by BYK-Chemie Co., Ltd.), DISPARLON (manufactured by Nanmoto Chemical Co., Ltd.), and SOLSPERS (ZENNECA-85-200804974 (83) , KP (manufactured by Shin-Etsu Chemical Co., Ltd.), p〇lyfl〇W (manufactured by Kyoeisha Chemical Co., Ltd.), Azis (manufactured by Ajinomoto Co., Ltd.), and the like. These polymer dispersants may be used alone or in combination of two or more.

本發明的硬化性組成物中，（E)分散劑的含有比例，相對於（D)顏料通常爲9 5重量％以下，較佳爲6 5重量％以下，更佳爲50重量％以下，此外，通常5重量％以上，較佳爲7重量％以上，特別佳爲1 〇重量％以上。分散劑的含有比例太少，則因爲吸附至色材的吸附不足，無法防止凝聚，會有高黏度化及凝膠化的情況，故分散安定性變差，可能發生再凝聚或增黏等的問題；相反的太多，因爲相對的顏料的比例減少，故著色力變差，相對於色濃度而言膜厚變厚，使用於彩色濾光片時，會發生液晶盒化步驟的盒間隙控制不良。認爲上述的塗佈適性評估方法（I)中之附著物的發生，而且狹縫及旋轉式塗佈法（si it and spin coating)或擠壓式塗佈法（die coating)中之凝聚異物的發生，特別是與分散劑之附著至顏料表面的附著部的結構有關。作爲本發明的（E)分散劑特別佳者爲，吸附至顏料的吸附部的氮原子不具有離子性者，亦即3級胺、2級胺、 1級胺、環狀胺、或亞胺基等未4級化的氮原子較佳，這恐怕不論分散劑的種類’對於上述（E-l)、（E-2)、（E-3)任一者的分散劑亦相同。詳細的機制並不清楚，認爲可能是殘留於氮原子的共價電子對與該機制有關。上述的各分散劑的構造，一般而 -86- 200804974 (84) 言具有anchor部份（吸附於顏料的吸附部）、與tail部份 (管理分散性的部份），爲吸附部上含有不具有離子性的氮原子之分散劑時，認爲相對於該氮原子所具有的電子對而言，溶劑分子、或溶劑中的水分子製造氫鍵，進入分散劑分子所具的複數的tail間，因此，與吸附部中具有4級胺基等、其他的基之分散劑比較下，變成tail間範圍擴大的構造。In the curable composition of the present invention, the content of the (E) dispersant is usually 95% by weight or less, preferably 65% by weight or less, more preferably 50% by weight or less, based on the (D) pigment. It is usually 5% by weight or more, preferably 7% by weight or more, particularly preferably 1% by weight or more. When the content of the dispersant is too small, the adsorption to the color material is insufficient, and aggregation cannot be prevented, and high viscosity and gelation may occur. Therefore, the dispersion stability may be deteriorated, and re-agglomeration or thickening may occur. The problem is too much, because the ratio of the relative pigment is reduced, so the coloring power is deteriorated, and the film thickness is thickened with respect to the color density, and when used for a color filter, the cell gap control of the liquid crystal cellization step occurs. bad. The occurrence of the deposit in the coating suitability evaluation method (I) described above, and the agglomerated foreign matter in the slit and spin coating or die coating is considered. This occurs, in particular, with the structure of the attachment portion of the dispersant attached to the surface of the pigment. Particularly preferred as the (E) dispersant of the present invention is that the nitrogen atom adsorbed to the adsorption portion of the pigment does not have ionicity, that is, a tertiary amine, a secondary amine, a tertiary amine, a cyclic amine, or an imine. The nitrogen atom which is not 4-staged is preferable, and the type of the dispersant is the same as the dispersant of any of the above (El), (E-2), and (E-3). The detailed mechanism is not clear, and it is believed that the covalent electron pair remaining in the nitrogen atom is related to this mechanism. The structure of each of the above-mentioned dispersants generally has an anchor portion (adsorption portion adsorbed to the pigment) and a tail portion (portion for managing dispersibility), and the adsorption portion contains no In the case of a dispersing agent having an ionic nitrogen atom, it is considered that a solvent molecule or a water molecule in a solvent produces a hydrogen bond with respect to an electron pair of the nitrogen atom, and enters a plurality of tails of the dispersant molecule. Therefore, in comparison with a dispersing agent having a group of other amine groups such as a 4-stage amine group in the adsorption portion, the structure between the tails is expanded.

「再溶解性優良」之意，係指硬化性組成物一度固化，再度浸漬於溶劑時馬上溶入溶劑，但吸附在顏料的分散劑的tail間的距離大時，溶劑分子易進入到此空間，例如水製作氫鍵時，認爲以溶劑分子的一部份與水分子或氮原子的電子對製造鍵結之方式，更容易進入到分散劑的 tail間，可輕易且微細地分散。再者，本發明的硬化性組成物，在後述的該硬化性組成物調製時的分散處理步驟中，在含有上述（E)分散劑同時，藉由使其含有上述的（A)黏合劑樹脂的一部份，可一起擔任分散劑的作用。 [1-9]光聚合起始劑本發明的硬化性組成物，可再含有光聚合起始劑，光聚合起始劑，通常以光聚合起始劑、及必要時所添加的增感色素、聚合加速劑等之加成劑之混合物使用；爲具有直接吸收光’或被光增感後引起分解反應或去氫反應，而產生聚合活性自由基之機能之成份。構成光聚合起始系之光聚合起始劑，可列舉例如特開 -87- 200804974 (85)"Improved re-solubility" means that the curable composition is once cured, and is dissolved in the solvent immediately after being immersed in the solvent again. However, when the distance between the tails of the dispersant adsorbed by the pigment is large, the solvent molecules easily enter the space. For example, when water is hydrogen-bonded, it is considered that a part of the solvent molecule and the electron pair of the water molecule or the nitrogen atom are bonded to each other, and it is easier to enter the tail of the dispersant, and can be easily and finely dispersed. Further, in the step of dispersing the curable composition prepared in the present invention, the curable composition of the present invention contains the above (A) dispersant and contains the above (A) binder resin. Part of it can act as a dispersant together. [1-9] Photopolymerization initiator The curable composition of the present invention may further contain a photopolymerization initiator, a photopolymerization initiator, usually a photopolymerization initiator, and a sensitizing dye added as necessary. A mixture of an additive such as a polymerization accelerator or the like; a component having a function of directly absorbing light or causing a decomposition reaction or a dehydrogenation reaction after photo-sensitization to generate a polymerization active radical. The photopolymerization initiator which constitutes the photopolymerization initiation system is exemplified by, for example, JP-A-87-200804974 (85)

昭59-152396號、特開昭61-151197號公報等所記載的二茂鈦衍生物類；特開平1 0-300922號、特開平1U 74224 號、特開2000-56 1 1 8號公報等所記載的六芳基雙咪唑衍生物類；特開平1 0-3 95 03號公報等所記載的鹵甲基化噁二唑衍生物類、鹵甲基-s-三嗪衍生物類、N -苯基甘胺酸等之N -芳基·α-胺基酸類、N -芳基-α-胺基酸鹽類-芳基-α -胺基酸酯類等之自由基活性劑、α -胺基烷基苯醒衍生物類；特開2000-80068號公報等所記載的肟酯系衍生物類等。具體而言，例如二茂鈦衍生物類可列舉二環戊二燒基鈦二氯化物、二環戊二烯基鈦聯苯、二環戊二烯基鈦雙 (2,3,4,5,6-五氟苯-1-基）、二環戊二烯基鈦雙（2,3,5,6-四氟苯-1-基）、二環戊二烯基鈦雙（2,4,6-三氟苯-1-基）、二環戊二烯基鈦雙（2,6-二氟苯-1-基）、二環戊二烯基鈦雙（2,4_ 二氟苯-1-基）、二（甲基環戊二烯基）鈦雙（2,3,4,5,6-五氟苯-1-基）、二（甲基環戊二烯基）鈦雙（2,6-二氟苯-1-基）、二環戊二烯基鈦[2,6-二-氟- 3-(吡咯-1-基）-苯-1-基]等。此外，咪唑衍生物類可列舉2-(2’·氯苯基）-4,5-二苯基咪唑2聚物、2-(2’-氯苯基）-4,5-雙（3’ _甲氧基苯基）咪哩 2聚物、2-(2’-氟苯基）-4,5-二苯基咪唑2聚物、2-(2，·甲氧基苯基）-4,5-二苯基咪唑2聚物、（4’-甲氧基苯基）-4,5. 二苯基咪唑2聚物等。此外，鹵甲基化噁二唑衍生物類，可列擧2 _三氯甲基-5-(2，-苯並呋喃基）-1，3,4-噁二唑、2-三氯甲基-5-[/3. -88- 200804974 (86) (2，-苯並呋喃基）乙烯]-1，3，4 -噁二唑、2 _三氯甲基-5 - [ /3 -(2，·（6，，-苯並呋喃基）乙烯）]-l，3,4-噁二唑、 2-三氯甲基 _5· 呋喃基-1，3 5 4 _噁二唑等。此外，鹵甲基化三嗪衍生物，可列舉2-(4-甲氧基苯基）-4,6-雙（三氯甲基）-s-三嗪、2-(4-甲氧基萘基）-4,6·雙 (三氯甲基）-s-三嗪、2-(4-乙氧基萘基）-4,6-雙（三氯甲基）· ^三嗪、2-(4-乙氧基羰基萘基）-4,6·雙（三氯甲基三曉The ferrocene derivatives described in JP-A-59-151197, JP-A-61-151197, and the like, and the publications of JP-A No. 10-300922, JP-A No. 1U 74224, and JP-A-2000-56 1 18 The hexaarylbisimidazole derivatives described in the above-mentioned publications, the halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N described in JP-A-10-03-93 03 a radical active agent such as N-aryl·α-amino acid such as phenylglycine or N-aryl-α-amino acid salt-aryl-α-amino acid ester, α An aminoalkyl benzene oxime derivative; an oxime ester derivative described in JP-A-2000-80068 or the like. Specifically, examples of the titanocene derivative include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium biphenyl, and dicyclopentadienyl titanium bis (2, 3, 4, 5). ,6-pentafluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl-1-yl), dicyclopentadienyl titanium bis (2,4 ,6-trifluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,6-difluorophenyl-1-yl), dicyclopentadienyl titanium bis(2,4-difluorobenzene- 1-yl), bis(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl-1-yl), bis(methylcyclopentadienyl)titanium ( 2,6-difluorophenyl-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3-(pyrrol-1-yl)-phenyl-1-yl] and the like. Further, examples of the imidazole derivative include 2-(2'-chlorophenyl)-4,5-diphenylimidazole 2 polymer and 2-(2'-chlorophenyl)-4,5-bis (3'. _Methoxyphenyl)imidate 2, 2-(2'-fluorophenyl)-4,5-diphenylimidazole 2, 2-(2,-methoxyphenyl)-4 , 5-diphenylimidazole 2 polymer, (4'-methoxyphenyl)-4, 5. diphenylimidazole 2 polymer, and the like. Further, as the halomethylated oxadiazole derivative, 2 - trichloromethyl-5-(2,-benzofuranyl)-1,3,4-oxadiazole or 2-trichloromethane can be cited. Base-5-[/3. -88- 200804974 (86) (2,-benzofuranyl)ethylene]-1,3,4-oxadiazole, 2 _trichloromethyl-5 - [ /3 - (2,·(6,,-benzofuranyl)ethene)]-l,3,4-oxadiazole, 2-trichloromethyl_5·furanyl-1,3 5 4 oxazolyl, etc. . Further, the halomethylated triazine derivative may, for example, be 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine or 2-(4-methoxy group. Naphthyl)-4,6·bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)·^ triazine, 2 -(4-ethoxycarbonylnaphthyl)-4,6·bis(trichloromethyltris)

等。此外，α -胺基烷基苯酮衍生物類，可列舉2-甲基· 44-(甲基硫）苯基]-2-嗎啉代丙烷-1-酮、2-苄基-2-二甲基胺基—1-(4-嗎啉代苯基）_ 丁酮-1、2-苄基-2-二甲基胺基-1-(4·嗎啉代苯基）· 丁烷-1-酮、4-二甲基胺基乙基苯甲酸 _、4-二甲基胺基異戊基苯甲酸酯、4_二乙基胺基苯乙酮、4-二甲基胺基苯丙酮、2-乙基己基- l，4-二甲基胺基苯甲酸酯、2,5-雙（4-二乙基胺基苄叉）環己酮、7-二乙基胺 ί-3-(4-二乙基胺基苯甲醯基）香豆素、4_(二乙基胺基）芳基丙烯醯芳烴等。此外’肟酯系衍生物，可列舉1，2-辛二酮、1-[4-(苯基硫）苯基]、2-(〇_苯甲醯基肟）、乙酮（ethan〇ne)、乙基-6·(2_甲基苯甲醯基咔唑-3-基]、1_(0_乙醯基肟）等。另外’亦可列舉苯偶因甲基醚、苯偶因苯基醚、苯偶因異丁基醚、苯偶因丙基醚等之苯偶因烷基醚類；2 -甲基悤醌、2-乙基蒽醌、2-卜丁基蒽醌、氯蒽醌等之蒽醌衍 -89 - 200804974 (87)Wait. Further, the α-aminoalkylphenone derivatives include 2-methyl·44-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-benzyl-2- Dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-2-dimethylamino-1-(4.morpholinophenyl)-butane 1-ketone, 4-dimethylaminoethylbenzoic acid _, 4-dimethylaminoisoamyl benzoate, 4-diethylamino acetophenone, 4-dimethylamine Phenylpropiophenone, 2-ethylhexyl-l,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 7-diethylamine Ί-3-(4-Diethylaminobenzimidyl)coumarin, 4-(diethylamino)arylpropene oxime or the like. Further, 'the oxime ester derivative may, for example, be 1,2-octanedione, 1-[4-(phenylsulfanyl)phenyl], 2-(indolyl-benzhydrylhydrazine), or ethyl ketone (ethan〇ne) ), ethyl-6·(2-methylbenzimidazol-3-yl), 1_(0-ethylindenyl), etc. Further, benzoin methyl ether and benzoin can also be cited. a benzoin alkyl ether such as phenyl ether, benzoin isobutyl ether or benzoin propyl ether; 2-methyl hydrazine, 2-ethyl hydrazine, 2-dibutyl hydrazine, chloranil醌等之蒽醌衍-89 - 200804974 (87)

生物類；二苯甲酮、米希勒酮、2 -甲基二苯甲酮、3 -甲基二苯甲酮、4-甲基二苯甲酮、2-氯二苯甲酮、4-溴二苯甲酮、2 -羧基二苯甲酮等之二苯甲酮衍生物類；2,2 -二甲氧基-2-苯基苯乙酮、2，2-二乙氧基苯乙酮、1-羥基環己基苯基酮、α-羥基-2-甲基苯基丙酮、1-羥基-1-甲基乙基- (P· 異丙基苯基）酮、1-羥基-ΐ-(ρ-十二烷基苯基）酮、2-甲基-(4’-甲基硫苯基）-2-嗎啉代-1-丙酮、1，1，1-三氯甲基-(Ρ-丁基苯基）酮等之苯乙酮衍生物類；噻噸酮、2-乙基噻噸酮、2-異丙基噻噸酮、2-氯噻噸酮、2,4-二甲基噻噸酮、 2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等之噻噸酮衍生物類；P-二甲基胺基苯甲酸乙酯、P-二乙基胺基苯甲酸酯等之苯甲酸酯衍生物類；9-苯基吖啶、9-(p甲氧基苯基）吖啶等之吖啶衍生物類；9,1 0-二甲基苯並吩嗪等之吩嗪衍生物類；苯並蒽酮等之蒽酮衍生物類等。必要時可使用的聚合加速劑’可列舉例如N，N-二甲基胺基苯甲酸乙酯等之Ν,Ν-二烷基胺基苯甲酸烷基酯類；2 -氫硫基苯並噻唑、2 -氫硫基苯並噁唑、2 -氫硫基苯並咪唑等之具有雜環之氫硫基化合物；或脂肪族多官能氫硫基化合物等之氫硫基化合物類等。此等的光聚合起始劑及聚合加速劑，可各自單獨使用 1種，或可倂用2種以上。本發明的硬化性組成物中，此等的光聚合起始系的含有比例，總固形分中通常爲〇·1重量％以上，較佳爲0 5 重量％以上，此外，通常爲4 0重量％以下，較佳爲3 〇重 -90- 200804974 (88) 量％以下。此含有比例顯著降低則會有成爲造成對曝光光線的感度降低的原因的情況，相反的太高則會有未曝光部份對顯影液的溶解性降低、誘發顯影不良的情況。Biological; benzophenone, michelone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4- Benzophenone derivatives such as bromobenzophenone and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxybenzene Ketone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylacetone, 1-hydroxy-1-methylethyl-(P·isopropylphenyl)one, 1-hydroxy-oxime -(ρ-dodecylphenyl)one, 2-methyl-(4'-methylthiophenyl)-2-morpholino-1-propanone, 1,1,1-trichloromethyl- Acetophenone derivatives such as (Ρ-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4- a thioxanthone derivative such as dimethylthioxanthone, 2,4-diethylthioxanthone or 2,4-diisopropylthioxanthone; ethyl P-dimethylaminobenzoate; a benzoate derivative such as P-diethylaminobenzoate; an acridine derivative such as 9-phenyl acridine or 9-(p methoxyphenyl) acridine; a phenazine derivative such as 1 0-dimethylbenzophenazine; Derivatives and the like. The polymerization accelerator which can be used as necessary 'for example, N,N-dimethylaminobenzoic acid ethyl ester or the like, anthracene-dialkylaminobenzoic acid alkyl ester; 2-hydrothiobenzobenzene a hydrogenthio group compound having a heterocyclic ring such as thiazole, 2-hydrothiobenzoxazole or 2-hydrothiobenzimidazole; or a hydrogenthio group compound such as an aliphatic polyfunctional thiol compound. These photopolymerization initiators and polymerization accelerators may be used alone or in combination of two or more. In the curable composition of the present invention, the content ratio of the photopolymerization initiation system is usually 〇·1% by weight or more, preferably 5% by weight or more, and usually 40% by weight. % or less, preferably 3 〇 -90- 200804974 (88) % or less. When the content ratio is remarkably lowered, the sensitivity to the exposure light may be lowered. On the contrary, if the content is too high, the solubility of the unexposed portion to the developer may be lowered to cause poor development.

此外，必要時爲了提高感應感度之目的，可使用增感色素，依影像曝光光源的波長使用適當的增感色素，但可列舉例如特開平4-22 1 95 8號、特開平4-2 1 9756號公報等所記載的咕噸系色素；特開平3 - 2 3 9 7 0 3號、特開平5 -2 8 93 3 5號公報等所記載的具有雜環的香豆系色素；特開平3-23 9703號、特開平5-2 8 93 3 5號公報等所記載的3-香豆素酮系色素；特開平- 6-19240號公報等所記載的甲撐吡咯系色素；特開昭47-2528號、特開昭54- 1 55292號、特開昭 45-373 77號、特開昭 48-84 1 83號、特開昭 52- 1 1 268 1號、特開昭5 8- 1 5 5 03號、特開昭60-8 8005號、特開昭59-56403號、特開平2-69號、特開昭57- 1 68088 號、特開平5- 1 0776 1號、特開平5-21 0240號、特開平4- 2 8 88 1 8號各公報等所記載的具有二烷基胺基苯骨架之色素等。此等增感色素中較佳者爲含有胺基增感色素，更佳爲同一分子內具有胺基及苯基之化合物，特別佳者例如 4,4’·二甲基胺基二苯甲酮、4，4’-二乙基胺基二苯甲酮、2-胺基二苯甲酮、4_胺基二苯甲酮、4，4’-二胺基二苯甲酮、 3，3’-二胺基二苯甲酮、3，4-二胺基二苯甲酮等之二苯甲酮系化合物；2-(p-二甲基胺基苯基）苯並噁唑、2-(p-二乙基胺基苯基）苯並噁唑、2-(p-二甲基胺基苯基）苯並[4,5]苯並 200804974 (89)Further, if necessary, a sensitizing dye may be used for the purpose of improving the sensitivity of the sensing, and an appropriate sensitizing dye may be used depending on the wavelength of the image-exposure light source, but for example, JP-A-4-22 1 95 8 , JP-A 4-2 1 a xanthene-based dye having a heterocyclic ring as described in JP-A No. 3,275, and the like; a 3-coumarin-based dye described in Japanese Unexamined Patent Publication No. Hei No. Hei. No. Hei. No. 47-2528, Special Open No. 54- 1 55292, Special Open No. 45-373 No. 77, Special Open No. 48-84 No. 1 83, Special Open No. 52- 1 1 268 No. 1, Special Open No. 5 8 - 1 5 5 03, Special Open 60-8 8005, Special Open 59-56403, Special Open 2-69, Special Open 57- 1 68088, Special Kaiping 5-1 0776 1 A dye having a dialkylamino benzene skeleton described in each of the publications of Japanese Patent Laid-Open No. Hei. No. Hei. Preferred among these sensitizing dyes are amine-containing sensitizing dyes, more preferably compounds having an amine group and a phenyl group in the same molecule, and particularly preferably, for example, 4,4'-dimethylaminobenzophenone. , 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3 a benzophenone compound such as '-diaminobenzophenone or 3,4-diaminobenzophenone; 2-(p-dimethylaminophenyl)benzoxazole, 2- (p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5]benzo-200804974 (89)

噁唑、2-(ρ·二甲基胺基苯基）苯並[6,7]苯並噁唑、2,5-雙 (p-二乙基胺基苯基）-1，3,4-噁唑、2-(p-二甲基胺基苯基）苯並噻唑、2-(p-二乙基胺基苯基）苯並噻唑、2-(p-二甲基胺基苯基）苯並咪唑、2-(p-二乙基胺基苯基）苯並咪唑、 2,5-雙（p-二乙基胺基苯基）-1，3,4-噻二唑、（p-二甲基胺基苯基）吡啶、（P-二乙基胺基苯基）吡啶、（P-二甲基胺基苯基）喹啉、（P-二乙基胺基苯基）喹啉、（P-二甲基胺基苯基）嘧啶、（p-二乙基胺基苯基）嘧啶等之含有p-二烷基胺基苯基之化合物等。此等中最佳者爲4,4’-二烷基胺基二苯甲酮，增感色素亦爲可單獨使用1種或可倂用2種以上。本發明的硬化性組成物中，此等的增感色素的含有比例，總固形分中通常〇重量％以上，較佳爲0.2重量％以上，更佳爲0.5重量％以上，此外，通常20重量％以下，較佳爲1 5重量％以下，更佳爲1 〇重量％以下的範圍。 [1-10]界面活性劑本發明的硬化性組成物，亦可再含有界面活性劑，界面活性劑可使用陰離子性、陽離子性、非離子性、兩性界面活性劑等，但由電壓保持率或對有機溶劑的相溶性等諸特性產生壞影響的可能性低的觀點而言，使用非離子性界面活性劑較佳。陰離子性界面活性劑，可列舉例如花王公司製的「艾瑪魯1 〇」等之烷基硫酸酯鹽系界面活性劑、花王公司製的「PELEX B-L」等之烷基萘磺酸鹽系界面活性劑、花王公司製的「荷爾魯 L-18」、「荷爾魯L-100」等之特殊 -92- 200804974 (90) 高分子系界面活性劑等。此等中’以特殊高分子系界面活性劑較佳，更佳爲特殊聚羧酸型高分子系界面活性劑。陽離子界面活性劑，可列舉例如花王公司製的「ACETAMIN 24」等之烷基胺鹽系界面活性劑、花王公司製的「克他命24P」、「克他命8 6W」等之第4級銨鹽系界面活性劑等。此等中，以第4級銨鹽系界面活性劑較佳，更佳爲硬脂醯基三甲基銨鹽系界面活性劑。Oxazole, 2-(ρ·dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4 -oxazole, 2-(p-dimethylaminophenyl)benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl) Benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-thiadiazole, ( P-Dimethylaminophenyl)pyridine, (P-diethylaminophenyl)pyridine, (P-dimethylaminophenyl)quinoline, (P-diethylaminophenyl) a compound containing a p-dialkylaminophenyl group such as quinoline, (P-dimethylaminophenyl)pyrimidine or (p-diethylaminophenyl)pyrimidine. The best one of these is 4,4'-dialkylaminobenzophenone, and the sensitizing dye may be used alone or in combination of two or more. In the curable composition of the present invention, the content of the sensitizing dyes is usually 5% by weight or more, preferably 0.2% by weight or more, more preferably 0.5% by weight or more, based on the total solid content, and usually 20% by weight. % or less is preferably 15% by weight or less, more preferably 1% by weight or less. [1-10] Interfacial Agent The curable composition of the present invention may further contain a surfactant, and an anionic, cationic, nonionic, amphoteric surfactant or the like may be used as the surfactant, but the voltage retention ratio is used. Further, it is preferable to use a nonionic surfactant in view of the low possibility that the characteristics such as the compatibility of the organic solvent have a bad influence. Examples of the anionic surfactants include alkylsulfate-based surfactants such as "Amaru 1" manufactured by Kao Corporation, and alkyl naphthalenesulfonate-based interfaces such as "PELEX BL" manufactured by Kao Corporation. Special agent, such as "Hollu L-18" and "Hollu L-100" manufactured by Kao Corporation - 92- 200804974 (90) Polymer surfactant. Among these, a special polymer-based interface active agent is preferred, and a special polycarboxylic acid-type polymer-based surfactant is more preferred. Examples of the cation surfactant include alkylamine salt-based surfactants such as "ACETAMIN 24" manufactured by Kao Corporation, "Ketamine 24P" manufactured by Kao Corporation, and Grade 4 of "Ketamine 8 6W". An ammonium salt surfactant or the like. Among these, a fourth-order ammonium salt-based surfactant is preferred, and a stearyl-trimethylammonium salt-based surfactant is more preferred.

非離子性界面活性劑，可列舉例如東麗道康寧公司製「SH8400」：聚矽氧烷公司製之「KP341」等之聚矽氧烷系界面活性劑；住友3M公司製的「FC430」：大日本油墨化學工業公司製的「F470」；NEOS公司製的「DFX-18」等之氟系界面活性劑；花王公司製的「Emulgen 1 0 4 P」、「E m u 1 g e η A 6 0」等之聚氧乙嫌系界面活性劑等。此等中以聚矽氧烷系界面活性劑較佳，更佳爲具有聚二甲基矽氧烷上加成聚醚基或芳烷基的側鏈之結構，所謂的聚醚改性或芳烷基改性聚矽氧烷系界面活性劑。界面活性劑可倂用2種以上，較佳爲例如聚矽氧烷系界面活性劑/氟系界面活性、聚矽氧烷系界面活性劑/特殊高分子系界面活性劑、氟系界面活性劑/特殊高分子系界面活性劑的組合等，其中又以聚矽氧烷系界面活性劑/氟系界面活性劑的組合較佳。此聚矽氧烷系界面活性劑/氟系界面活性劑的組合，可列舉例如聚醚改性聚矽氧烷系界面活性劑/低聚型氟系界面活性劑的組合等，具體而言，可列舉例如GE東芝聚 -93- 200804974 (91) 矽氧烷公司製「TSF4460」/NEOS公司公司製「DFX-18」、BYK-Chemie 公司製「BYK-3 00」/SEIMI CHEMICAL公司製「S-3 93」、信越聚矽氧烷公司製「KP340」/大日本油墨化學工業公司製「F-478」、東麗聚矽氧烷公司製「SH7PA」/大金公司製「DS-401」、曰本UNICAR公司製「L-77」/住友 3 Μ公司製「F C 4 4 3 0」等的組合。Examples of the nonionic surfactants include "SH8400" manufactured by Toray Dow Corning Co., Ltd.: a polyoxyalkylene surfactant such as "KP341" manufactured by Polyoxane Co., Ltd.; and "FC430" manufactured by Sumitomo 3M Co., Ltd.: large "F470" manufactured by Nippon Ink Chemical Industry Co., Ltd.; fluorine-based surfactant such as "DFX-18" manufactured by NEOS Co., Ltd.; "Emulgen 1 0 4 P" and "E mu 1 ge η A 6 0" manufactured by Kao Corporation Such as polyoxyethylene is suspected to be a surfactant and the like. Among these, a polyoxyalkylene-based surfactant is preferred, and a structure having a side chain of a polyether group or an aralkyl group on a polydimethylsiloxane is preferably used. Alkyl modified polyoxyalkylene surfactant. The surfactant may be used in combination of two or more kinds, and is preferably, for example, a polyoxyalkylene-based surfactant/fluorine-based surfactant, a polyoxyalkylene-based surfactant, a special-polymer surfactant, or a fluorine-based surfactant. A combination of a special polymer-based surfactant, and the like, and a combination of a polyoxyalkylene-based surfactant/fluorine-based surfactant is preferred. The combination of the polyoxyalkylene-based surfactant/fluorine-based surfactant may, for example, be a combination of a polyether-modified polyoxyalkylene surfactant or an oligomeric fluorine-based surfactant. Specifically, For example, GE Toshiba Poly-93-200804974 (91) "TSF4460" manufactured by Ndoxane Co., Ltd. / "DFX-18" manufactured by NEOS Co., Ltd., "BYK-3 00" manufactured by BYK-Chemie Co., Ltd., and "S" manufactured by SEIMI CHEMICAL Co., Ltd. -3 93", "KP340" manufactured by Shin-Etsu Chemical Co., Ltd. / "F-478" manufactured by Dainippon Ink Chemical Industry Co., Ltd., "SH7PA" manufactured by Toray Polyoxane Co., Ltd., and "DS-401" manufactured by Daikin Co., Ltd.曰 UNI UNICAR company "L-77" / Sumitomo 3 Μ company "FC 4 4 3 0" and other combinations.

本發明的硬化性組成物中，此等界面活性劑的含有比例，總固形分中通常0.0 0 1重量％以上，較佳爲0.0 0 5重量％以上，更佳爲0 · 0 1重量％以上，特別佳爲〇 . 02重量％以上，此外，通常1 0重量％以下，較佳爲1重量％以下，更佳爲0.1重量％以下，特別佳爲〇.〇5重量％以下的範圍使用。 [1 · 1 1 ]其他成份本發明的硬化性組成物’除了上述各成份以外，可含有分散助劑、有機羧酸或/及有機羧酸酐、可塑劑、染料I防止熱聚合劑、保存安定劑、表面保護劑、密著提升劑、影像改良劑等。分政助劑被使用於提高上述（D)顏料的分散性、提高分散性安定性等，可列舉例如偶氮系、酞菁系、喹吖酮系、苯並咪唑酮系、喹酞酮系、異吲哚滿酮系、二噁嗪系、蒽醌系、陰丹士林系、茈系、peHn〇ne系、二酮吡咯並吡咯系 '二噁嗪顏料等之衍生物。此等顏料衍生物的取代基，可列舉磺酸基、磺胺基及 -94- 200804974 (92) 其4級Η女鹽、鄰本一甲醯B女甲基、二院基胺基院基、經基、羧基、醯胺基等，此等取代基可直接鍵結於顏料骨架’或透過烷基、芳基、雜環基等而鍵結。上述取代基中’以擴胺基及其4級胺鹽、擴酸基較佳，磺酸基爲最佳。此等取代基可複數取代於一個顏料的骨架，亦可爲取代數不同化合物的混合物。In the curable composition of the present invention, the content ratio of the surfactant is usually 0.001% by weight or more, preferably 0.025% by weight or more, and more preferably 0. 0% by weight or more. In particular, it is preferably 0.2% by weight or more, and usually 10% by weight or less, preferably 1% by weight or less, more preferably 0.1% by weight or less, and particularly preferably 5% by weight or less. [1 · 1 1 ] Other components The curable composition of the present invention may contain, in addition to the above components, a dispersing aid, an organic carboxylic acid or/and an organic carboxylic anhydride, a plasticizer, a dye I, a thermal polymerization inhibitor, and a preservation stability. Agent, surface protectant, adhesion enhancer, image improver, etc. The dispersing aid is used to improve the dispersibility of the above (D) pigment, and to improve the dispersibility stability, and examples thereof include an azo type, a phthalocyanine type, a quinophthalone type, a benzimidazolone type, and a quinophthalone type. Derivatives such as isoindolinone, dioxazine, anthraquinone, indanthrene, anthraquinone, peHn〇ne, diketopyrrolopyrrole-dioxazine pigment. The substituents of such pigment derivatives include a sulfonic acid group, a sulfonyl group, and -94-200804974 (92), a 4th-grade prostitute salt, a phthalic acid, a di-amylamino group, a second-complex amine group, These substituents may be bonded directly to the pigment skeleton or via an alkyl group, an aryl group, a heterocyclic group or the like via a group, a carboxyl group, a guanamine group or the like. Among the above substituents, 'an amine group and a quaternary amine salt thereof and an acid extension group are preferred, and a sulfonic acid group is preferred. These substituents may be substituted in plural to the skeleton of one pigment, or may be a mixture of different compounds.

顏料衍生物的具體例子，可列舉偶氮系顏料的磺酸衍生物、酞菁系顏料的磺酸衍生物、喹酞酮系顏料的磺酸衍生物、蒽醌系顏料的磺酸衍生物、喹吖酮系顏料的磺酸衍生物、二酮吡咯並吡咯系顏料的磺酸衍生物、二噁嗪系顏料的磺酸衍生物等。其中又以顏料黃1 3 8的磺酸衍生物、顏料黃139的磺酸衍生物、顏料紅254的磺酸衍生物、顏料紅25 5的磺酸衍生物、顏料紅264的磺酸衍生物、顏料紅272的磺酸衍生物、顏料紅209的磺酸衍生物、顏料橙 7 1的磺酸衍生物、顏料紫23的磺酸衍生物較佳，更佳爲顏料黃1 3 8的磺酸衍生物、顏料紅2 5 4的磺酸衍生物。本發明硬化性組成物中，此等的分散助劑的含有比例，相對於上述色材成份，通常爲〇· 1重量％以上，此外，通常爲30重量％以下，較佳爲20重量％以下’更佳爲10重量％以下，特別佳爲5重量％以下。添加量太少則無法發揮其效果，相反的添加量太多則分散性、分散安定性反而變差。本發明的硬化性組成物中，未含有磷酸丙燃酸酯含 -95 -Specific examples of the pigment derivative include a sulfonic acid derivative of an azo-based pigment, a sulfonic acid derivative of a phthalocyanine-based pigment, a sulfonic acid derivative of a quinacridone pigment, and a sulfonic acid derivative of an anthraquinone-based pigment. A sulfonic acid derivative of a quinophthalone pigment, a sulfonic acid derivative of a diketopyrrolopyrrole pigment, a sulfonic acid derivative of a dioxazine pigment, and the like. Among them, a sulfonic acid derivative of Pigment Yellow 138, a sulfonic acid derivative of Pigment Yellow 139, a sulfonic acid derivative of Pigment Red 254, a sulfonic acid derivative of Pigment Red 25 5 , and a sulfonic acid derivative of Pigment Red 264. a sulfonic acid derivative of Pigment Red 272, a sulfonic acid derivative of Pigment Red 209, a sulfonic acid derivative of Pigment Orange 71, a sulfonic acid derivative of Pigment Violet 23, and more preferably a sulfonate of Pigment Yellow 138. An acid derivative, a sulfonic acid derivative of Pigment Red 2 5 4 . In the curable composition of the present invention, the content of the dispersing aid is usually 〇·1% by weight or more based on the color material component, and is usually 30% by weight or less, preferably 20% by weight or less. It is more preferably 10% by weight or less, particularly preferably 5% by weight or less. When the amount of addition is too small, the effect cannot be exerted. On the contrary, if the amount of addition is too large, the dispersibility and dispersion stability are rather deteriorated. The curable composition of the present invention does not contain a phosphoric acid propionate containing -95 -

200804974 (93) 量，或相對於總固形份而言5重量％以下爲佳，磷酸酯部份主要作爲密著改良劑使用，但因爲極性高而會有阻顏料與分散劑的吸附的傾向，引起顏料的再凝聚，因此有硬化性樹脂組成物的黏度上升，安定性降低之虞，此凝聚會因爲組成物中所含有的水分而被加速。磷酸丙烯酸酯，可列舉例如特開2006-343648號公中所記載的化合物等。本發明的硬化性組成物，使用於後述的彩色濾光時，爲了一邊保持高黏合劑密著性，一邊更進一步的減樹脂組成物的未溶解物的殘留，可含有分子量1 000以的有機羧酸或/及有機羧酸酐，此等在含有尿烷樹脂分劑時作爲上述的（E)分散劑被含有較佳。此有機羧酸，具體而言可列舉脂肪族羧酸及芳香族酸。脂肪族羧酸可列舉甲酸、乙酸、丙酸、丁酸、戊酸三甲基乙酸、己酸、乙醇酸、（甲基）丙烯酸等之單羧酸草酸、丙二酸、珀琥酸、戊二酸、己二酸、庚二酸、環烷二羧酸、環己烯二羧酸、衣康酸、檸康酸、馬來酸、馬酸等之二羧酸；丙三羧酸、烏頭酸等之三羧酸等。外，芳香族羧酸可列舉苯甲酸、酞酸等直接鍵結於苯基羧基鍵結的羧酸、透過來自苯基的碳鍵鍵結於羧基之酸。此等中以分子量600以下者爲佳，特別是分子量〜500者較佳。具體而言，較佳爲馬來酸、丙二酸、琥大礙會再報片少下散羧己虽此之羧 50 珀 -96- 200804974 (94) 酸、衣康酸。200804974 (93) The amount is preferably 5% by weight or less based on the total solid content, and the phosphate ester portion is mainly used as a adhesion improving agent, but because of its high polarity, there is a tendency to hinder the adsorption of the pigment and the dispersing agent. When the re-agglomeration of the pigment is caused, the viscosity of the curable resin composition increases, and the stability is lowered. This aggregation is accelerated by the moisture contained in the composition. The phosphate acrylate is, for example, a compound described in JP-A-2006-343648. When the coloring filter of the present invention is used for the color filter described later, it is possible to further reduce the residual amount of the undissolved material of the resin composition while maintaining high adhesive adhesion, and may contain an organic substance having a molecular weight of 1,000. The carboxylic acid or/and the organic carboxylic anhydride are preferably contained as the above (E) dispersant when the urethane resin component is contained. Specific examples of the organic carboxylic acid include aliphatic carboxylic acids and aromatic acids. Examples of the aliphatic carboxylic acid include monocarboxylic acid oxalic acid, malonic acid, persuccinic acid, and glutaric acid such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid trimethylacetic acid, caproic acid, glycolic acid, or (meth)acrylic acid. Dicarboxylic acid such as acid, adipic acid, pimelic acid, cycloalkanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, maleic acid, and horse acid; glycerin tricarboxylic acid, aconitic acid Etc. tricarboxylic acid and the like. Further, examples of the aromatic carboxylic acid include a carboxylic acid which is directly bonded to a phenylcarboxy group such as benzoic acid or citric acid, and an acid which is bonded to a carboxyl group through a carbon bond derived from a phenyl group. Among them, those having a molecular weight of 600 or less are preferred, and those having a molecular weight of preferably 1,500 are preferred. Specifically, it is preferred that maleic acid, malonic acid, and sulphate will re-send the carboxylic acid, which is a small amount of carboxylic acid, and itaconic acid.

有機羧酸酐，可列舉脂肪族羧酸酐、芳香族羧酸酐，具體而言可列舉乙酸酐、三氯乙酸酐、三氟乙酸酐、四氫酞酸酐、琥珀酸酐、馬來酸酐、檸康酸酐、衣康酸酐、戊二酸酐、1，2_環己烯二羧酸酐、η-十八烷基琥珀酸酐、5_ 降冰片烯-2,3-二羧酸酐等之脂肪族羧酸酐。芳香族羧酸酐’可列舉酞酸酐、偏苯三酸酐、均苯四甲酸酐、萘二甲酸酐等。此等中又以分子量600以下者爲佳，特別是子量50 〜500者較佳’具體而言馬來酸酐、琥珀酸酐、檸康酸酐、衣康酸酐較佳。本發明的硬化性組成物中，此等的有機羧酸或/及有機羧酸酐的含量，總固形分中通常0·01重量％以上，較佳爲0.0 3重量％以上，更佳爲0.05重量％以上，此外，通常 1〇重量％以下，較佳爲5重量％以下，更佳爲3重量％以下。本發明的硬化性組成物，亦可含有染料，例如偶氮系染料、蒽醌系染料、酞菁系染料、苯醌亞胺系染料、嗤Β林系染料、硝基系染料、羰基系染料、甲基系染料等。偶氮系染料可列舉例如C.I·酸性黃11、C.I·酸性檀 7、C.I.酸性紅37、C.I·酸性紅180、C.I·酸性藍29、c j 直接紅28、C.I.直接紅83、C.I·直接黃12、C.I·直接檀 26、C.I.直接綠28、C.I·直接綠59、C.I·活性黃2、C.I.活性紅17、C.I.活性紅120、C.I·活性黑5、C.I.分散橙5、 -97- 200804974 (95) C.I.分散紅58、C.I.分散藍165、C.I_鹼性藍41、C·1.驗性紅18、C.I.媒介紅7、C.I·媒介黃5、C.I·媒介黑7等。蒽醌系染料可列舉例如C.I.Vat藍4、C.I·酸性藍 40、C.I·酸性綠25、C.I·活性藍19、C.I.活性監49、C.L 分散紅60、C.I·分散藍56、C.I.分散藍6〇等。Examples of the organic carboxylic acid anhydride include aliphatic carboxylic anhydrides and aromatic carboxylic anhydrides, and specific examples thereof include acetic anhydride, trichloroacetic anhydride, trifluoroacetic anhydride, tetrahydrophthalic anhydride, succinic anhydride, maleic anhydride, and citraconic anhydride. An aliphatic carboxylic anhydride such as itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic anhydride, η-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic anhydride or the like. Examples of the aromatic carboxylic acid anhydrides include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and naphthalic anhydride. Among them, those having a molecular weight of 600 or less are preferred, and those having a molecular weight of 50 to 500 are preferred. Specifically, maleic anhydride, succinic anhydride, citraconic anhydride, and itaconic anhydride are preferred. In the curable composition of the present invention, the content of the organic carboxylic acid or/and the organic carboxylic anhydride is usually 0. 01% by weight or more, preferably 0.03% by weight or more, more preferably 0.05% by weight based on the total solid content. % or more is usually 1% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less. The curable composition of the present invention may further contain a dye such as an azo dye, an anthraquinone dye, a phthalocyanine dye, a benzoquinone dye, a eucalyptus dye, a nitro dye, or a carbonyl dye. , methyl dyes, etc. Examples of the azo dye include CI·Acid Yellow 11, CI·Acid Tan 7, CI Acid Red 37, CI·Acid Red 180, CI·Acid Blue 29, cj Direct Red 28, CI Direct Red 83, CI·Direct Yellow 12. CI·Direct Tan 26, CI Direct Green 28, CI·Direct Green 59, CI·Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI·Reactive Black 5, CI Disperse Orange 5, -97- 200804974 (95) CI Disperse Red 58, CI Disperse Blue 165, C.I_Basic Blue 41, C·1. Confirmatory Red 18, CI Medium Red 7, CI·Media Yellow 5, CI·Medium Black 7, and the like. Examples of the lanthanoid dyes include CIVat Blue 4, CI·Acid Blue 40, CI·Acid Green 25, CI·Reactive Blue 19, CI Activity Monitoring 49, CL Disperse Red 60, CI·Disperse Blue 56, and CI Disperse Blue 6 Hey.

酞菁系染料可列舉例如C.I. Vat藍5等’苯酿亞胺系染料可列舉例如C.I.鹼性藍3、C.I·鹼性藍9等’嗟琳系染料可列舉例如C.I.溶劑黃33、C.I·酸性黃3、C.1·分散黃64等，硝基系染料可列舉例如C · I ·酸性黃1、C ·1.酸性橙3、C.I·分散黃42等。本發明的硬化性組成物，亦可含有可塑劑’此可M齊1 可列舉例如二辛基酞酸酯、雙十二烷基酞酸酯、三乙二醇二辛酸酯、二甲二醇酞酸酯、三甲酚磷酸酯、二辛基己二酸酯、二丁基癸二酸酯、三乙醯基甘油等。此等可塑劑的含有比例，總固形分中，以1 0重量％以下的範圍爲佳。此外，本發明的硬化性組成物，亦可含有防止熱聚合劑，此防止熱聚合劑可列舉例如氫醌、p-甲氧基苯酚、焦掊酚、鄰苯二酚、2,6-t-丁基-P-甲酚、0 -萘酚等。此等防止熱聚合劑的含有比例，總固形分中，以3重量％以下的範圍爲佳。 [2]硬化性組成物的調製方法接者’ δ兌明g周製本發明的硬化性組成物之方法。首先依各所定的量秤量（D)顏料、（c)溶劑、及任意成份之（E)分散劑’於分散處理步驟中，使（D)顏料分散後成 -98- 200804974 (96) 爲油墨狀液體，於此分散處理步驟，可使用塗料調節機、砂硏磨機、球磨機、輥碎機、石磨機、噴磨機、均質機等。因爲藉由進行此分散處理而使顏料微粒化，故提高硬化性組成物的塗佈特性，提高製品的彩色濾光片基板等的穿透率。Examples of the phthalocyanine-based dyes include, for example, CI Vat Blue 5, and the like. For example, CI Basic Blue 3, CI·Basic Blue 9 and the like can be mentioned, for example, CI Solvent Yellow 33, CI· Acid Yellow 3, C.1·Disperse Yellow 64, etc., and examples of the nitro dye include C · I · Acid Yellow 1, C · 1. Acid Orange 3, CI·Disperse Yellow 42 and the like. The curable composition of the present invention may further contain a plasticizer, which may be exemplified by, for example, dioctyl phthalate, dodecyl decanoate, triethylene glycol dicaprylate, dimethyl Alcohol phthalate, tricresol phosphate, dioctyl adipate, dibutyl sebacate, triethylene glyceryl, and the like. The content ratio of these plasticizers is preferably in the range of 10% by weight or less in the total solid content. Further, the curable composition of the present invention may further contain a thermal polymerization preventing agent, and examples of the thermal polymerization preventing agent include hydroquinone, p-methoxyphenol, pyrogallol, catechol, 2,6-t. - Butyl-P-cresol, 0-naphthol, and the like. The content of the thermal polymerization agent is preferably such that the total solid content is preferably 3% by weight or less. [2] Method for preparing curable composition The method of producing a curable composition of the present invention by δ δ. First, weigh (D) the pigment, (c) the solvent, and the optional component (E) dispersant in the dispersion treatment step, and disperse the (D) pigment to form -98-200804974 (96) as the ink. As the liquid, in the dispersion treatment step, a paint conditioner, a sand honing machine, a ball mill, a roller mill, a stone mill, a jet mill, a homogenizer, or the like can be used. Since the pigment is atomized by performing the dispersion treatment, the coating characteristics of the hardenable composition are improved, and the transmittance of the color filter substrate or the like of the product is improved.

分散處理顏料時，可適當倂用（A)黏合劑樹脂的一部份及分散助劑，此外，用砂硏磨機進行分散處理時，使用 0.1〜數mm徑的玻璃珠，或氧化銷珠較佳。分散處理時的溫度，被設定在通常〇 °C以上，較佳爲室溫以上，此外，通常l〇〇°C以下，較佳爲80°C以下的範圍內。再者，分散時間，因爲依油墨狀液體的組成、及砂硏磨機的裝置的大小等而其適當的時間有所不同，故需要適度調整。經由上述分散處理所得到的油墨狀液體中，再混合入必須成份之（A)黏合劑樹脂、（B)單體、及（C)溶劑，依情況混合任意成份之光聚合起始系、界面活性劑、及此等以外的成份，藉由使其成爲均勻的分散溶液而得到硬化性組成物。再者，於分散處理步驟及混合的各步驟中，因爲會有混入微細的垃圾，故將所得到的油墨狀液體藉由過濾器進行過濾處理較佳。 [3]硬化性組成物的應用本發明的硬化性組成物，通常爲所有的構成成份溶解或分散於溶劑中之狀態，將其供給至基板上，形成彩色濾光片或液晶顯示裝置的構成構件。以下’說明關於本發明的硬化性組成物應用於仪晶顯 -99 - 200804974 (97) 示裝置之應用例，應用於彩色濾光片的黑色矩陣或畫素，以及使用此等之液晶顯示裝置（面板）。 [3-1]彩色濾光片的畫素及黑色矩陣When dispersing the pigment, a part of the binder resin (A) and a dispersing aid may be suitably used. In addition, when the dispersion treatment is carried out by a sand honing machine, glass beads of 0.1 to several mm diameter or oxidized beads are used. Preferably. The temperature during the dispersion treatment is set to usually 〇 ° C or higher, preferably at room temperature or higher, and usually not more than 10 ° C, preferably 80 ° C or less. Further, since the dispersion time is different depending on the composition of the ink liquid and the size of the apparatus of the sand honing machine, it is necessary to appropriately adjust. The ink-like liquid obtained by the above dispersion treatment is further mixed with the (A) binder resin, the (B) monomer, and the (C) solvent, and the photopolymerization initiation system and interface of any component are mixed as the case may be. The active agent and components other than these are obtained as a uniform dispersion solution to obtain a curable composition. Further, in the dispersion treatment step and the mixing step, since fine waste is mixed, it is preferable to filter the obtained ink-like liquid by a filter. [3] Application of Curable Composition The curable composition of the present invention is usually in a state in which all constituent components are dissolved or dispersed in a solvent, and is supplied onto a substrate to form a color filter or a liquid crystal display device. member. The following is a description of an application example of the apparatus for applying the curable composition of the present invention to the apparatus shown in the apparatus, the black matrix or the pixel applied to the color filter, and the liquid crystal display device using the same. (panel). [3-1] Color Filters and Black Matrix

彩色濾光片的透明基板，只要是透明且適度的強度者即可，其材質並沒特別的限制，材質可列舉例如聚對苯二甲酸乙二醇酯等之聚酯系樹脂；聚丙烯、聚乙烯等之聚烯烴系樹脂；聚碳酸酯系樹脂；聚甲基丙烯酸甲酯等之丙烯酸系樹脂；聚颯系樹脂等之熱可塑性樹脂製薄板；環氧樹脂、不飽和聚酯樹脂等之熱硬化性樹脂薄板；或各種玻璃等。其中，由耐熱性的觀點而言，以玻璃、耐熱性樹脂爲佳。此等的透明基板，爲了黏著性等的表面物性的改良，必要時亦可進行電暈放電處理或臭氧處理等之表面處理、藉由矽烷偶合劑或尿烷系樹脂等之各種樹脂之薄膜形成處理等。透明基板的厚度通常爲〇.〇5mm以上，較佳爲 0.1mm以上，此外，通常爲10mm以下，較佳爲7mm以下的範圍。此外，藉由各種樹脂進行薄膜形成處理時，其膜厚通常爲Ο.ΟΙμπι以上，較佳爲0.05μηι以上，此外，通常爲10 μιη以下，較佳爲5 μιη以下的範圍。上述的透明基板上設置黑色矩陣，再藉由形成通常爲紅色、綠色、藍色的畫素影像，可製作彩色濾光片。黑色矩陣係利用遮光金屬薄膜、或本發明的硬化性組成物，形成於透明基板上。此遮光金屬薄膜，可使用金屬鉻、氧化鉻、氮化鉻等之鉻化合物鎳與鎢合金等，亦可爲使此等層合爲複數層狀 -100- 200804974 (98) 者。此等的遮光金屬薄膜，一般而言藉由濺鍍法被形成，藉由正型光阻而在膜狀形成所希望的圖型。The transparent substrate of the color filter may be any material that is transparent and moderate in strength, and the material thereof is not particularly limited, and examples of the material include polyester resins such as polyethylene terephthalate; and polypropylene; Polyolefin resin such as polyethylene; polycarbonate resin; acrylic resin such as polymethyl methacrylate; thermoplastic resin sheet such as polyfluorene resin; epoxy resin, unsaturated polyester resin, etc. A thermosetting resin sheet; or various glasses or the like. Among them, from the viewpoint of heat resistance, glass or a heat resistant resin is preferred. In order to improve the surface physical properties such as adhesion, the transparent substrate may be subjected to surface treatment such as corona discharge treatment or ozone treatment, and film formation of various resins such as a decane coupling agent or a urethane resin. Processing and so on. The thickness of the transparent substrate is usually 〇5 mm or more, preferably 0.1 mm or more, and is usually 10 mm or less, preferably 7 mm or less. Further, when the film formation treatment is carried out by various resins, the film thickness is usually Ο.ΟΙμπι or more, preferably 0.05 μm or more, and is usually 10 μm or less, preferably 5 μm or less. A black matrix is disposed on the transparent substrate, and a color filter is formed by forming a pixel image of generally red, green, and blue. The black matrix is formed on a transparent substrate by using a light-shielding metal film or a curable composition of the present invention. As the light-shielding metal film, a chromium compound such as metal chromium, chromium oxide or chromium nitride, a tungsten alloy or the like may be used, or such a layer may be laminated to a plurality of layers -100-200804974 (98). Such a light-shielding metal film is generally formed by a sputtering method, and a desired pattern is formed in a film shape by a positive photoresist.

對鉻使用混合硝酸鈽銨與過氯酸及/或硝酸所成的鈾刻液，對於其他的材料，使用依材料所選的飩刻液進行蝕刻，最後藉由用專用的剝離劑進行剝離正型光阻，可形成黑色矩陣。此時，首先，藉由蒸鍍或濺鍍法，於透明基板上形成此等金屬或金屬•金屬氧化物的薄膜，接著，於此薄膜上形成正型光阻用樹脂組成物的塗佈膜，接著，重複條列式、馬賽克、三角形等，使用具有圖型的光罩，使塗佈膜進行曝光、顯影，形成影像，然後，於此塗佈膜施以蝕刻處理後可形成黑色矩陣。利用本發明的硬化性組成物時，使用含有黑色的（D) 顏料之硬化性組成物，形成黑色矩陣，例如使用含有混合單獨或複數之碳黑、石墨、鐵黑、鈦黑等之黑色顏料，或者，從無機或有機的顏料適當選擇的紅色、綠色、藍色等的顏料後所得到的黑色顏料之硬化性組成物，與後述之形成紅色、綠色、藍色的畫素影像之方法相同作法，可形成黑色矩陣。上述硬化性組成物，作爲此等黑色、紅色、綠色、藍色中至少一種的畫像形成用塗佈液使用，關於黑色的硬化性組成物，關於紅色、綠色、藍色的硬化性組成物，透明基板上所形成的樹脂黑色矩陣形成面上，或使用鉻化合物以外的其他的遮光金屬材料所形成的金屬黑色矩陣形成面上，經由塗佈、加熱乾燥、影像曝光、顯影及熱硬化的各 -101 - 200804974 (99) 處理，各色的畫素影像被形成。設置黑色矩陣的透明基板上，塗佈含有紅色、綠色、藍色中一色的顏料之硬化性組成物且乾燥後，塗佈膜上重疊光罩，透過此光罩影像曝光、顯影，必要時藉由熱硬化或光硬化形成畫素影像，而製作著色層，關於紅色、綠色、藍色的三色的硬化性組成物，藉由各自進行此操作，可形成彩色濾光片影像。For chrome, use uranium engraving made of mixed ammonium cerium nitrate and perchloric acid and/or nitric acid. For other materials, etch with the etching solution selected by the material, and finally peel off with a special stripping agent. Type photoresist to form a black matrix. At this time, first, a film of such a metal or metal/metal oxide is formed on a transparent substrate by vapor deposition or sputtering, and then a coating film of a resin composition for a positive resist is formed on the film. Then, the strip pattern, the mosaic, the triangle, and the like are repeated, and the coating film is exposed and developed using a mask having a pattern to form an image, and then the coating film is subjected to an etching treatment to form a black matrix. When the curable composition of the present invention is used, a black matrix is formed using a curable composition containing a black (D) pigment, for example, a black pigment containing a mixture of carbon black, graphite, iron black, titanium black, or the like, alone or in combination. Or a curable composition of a black pigment obtained by selecting a pigment such as red, green or blue which is appropriately selected from an inorganic or organic pigment, and a method of forming a red, green, and blue pixel image to be described later. In practice, a black matrix can be formed. The curable composition is used as a coating liquid for forming an image of at least one of black, red, green, and blue, and the curable composition of red, green, and blue is a black curable composition. Each of the resin black matrix forming surface formed on the transparent substrate or a metal black matrix forming surface formed using a light shielding metal material other than a chromium compound, each of coating, heat drying, image exposure, development, and heat curing -101 - 200804974 (99) Processing, pixel images of each color are formed. On a transparent substrate provided with a black matrix, a curable composition containing a pigment of one of red, green, and blue is applied and dried, and a mask is placed on the coating film, and the image is exposed and developed through the mask, and if necessary, borrowed A color image is formed by thermosetting or photohardening to form a colored layer, and a color filter image can be formed by performing the operation on each of the red, green, and blue three-color hardenable compositions.

硬化性組成物供給至基板之供給方法，可列舉先前技術習知的方法，例如旋轉塗佈法、線棒塗佈法、流動式塗佈法、狹縫及旋轉式塗佈法、輥乳塗佈法、及擠壓式塗佈法較佳，亦即，如同上述，本發明的硬化性組成物，因爲配料機噴嘴的先端不易發生凝聚異物，故不會降低產率可提供具有平滑且優美的表面之塗佈膜。此外，此塗佈時的塗佈不均勻、或在之後的乾燥步驟中亦不會發生乾燥不均勻，經過曝光步驟、顯影步驟、熱處理步驟等，可形成具有極平滑的表面之層。藉由狹縫及旋轉式塗佈法、及擠壓式塗佈法之塗佈條件，可依硬化性組成物的組成、或所製作的彩色濾光片的種類而適當選擇，例如於兩方法中皆使噴嘴先端的唇部寬度爲 50〜50 Ομηι，使噴嘴先端與基板面的間隔爲 30〜 3 0 0 μ m較佳。若藉由擠壓式塗佈法，爲了調節塗佈膜的厚度，可調整唇部的進行速度、及從唇部的液狀的樹脂組成物的吐出量，若藉由狹縫及旋轉式塗佈法，主要爲藉由狹縫塗佈後 -102- 200804974 (100) 的旋轉塗佈的旋轉數及旋轉時間調整。塗佈膜的厚度太厚則圖型顯影變難，同時液晶盒化步驟之間隙的調整亦變難，另一方面，太薄則很難提高顏料濃度，而無法逹到所希望的顏色表現。塗佈膜的厚度，乾燥後的膜厚通常爲〇.2μιη以上，較佳爲〇·5μπι以上，更佳爲〇.8μιη以上，此外，通常爲 20μπι以下，較佳爲 ΙΟμιη以下，更佳爲5μηι以下的範圍。The method of supplying the curable composition to the substrate may be a conventionally known method such as a spin coating method, a wire bar coating method, a flow coating method, a slit and a rotary coating method, or a roll coating method. The cloth method and the extrusion coating method are preferably, that is, as described above, the hardenable composition of the present invention, since the tip end of the nozzle of the batching machine is less likely to agglomerate foreign matter, the yield can be provided without being reduced and elegant. Coating film on the surface. Further, the coating at the time of coating is not uniform, or drying unevenness does not occur in the subsequent drying step, and a layer having an extremely smooth surface can be formed by an exposure step, a development step, a heat treatment step, or the like. The coating conditions by the slit, the spin coating method, and the extrusion coating method can be appropriately selected depending on the composition of the curable composition or the type of the color filter to be produced, for example, in two methods. The width of the lip at the tip end of the nozzle is 50 to 50 Ομηι, so that the interval between the tip end of the nozzle and the substrate surface is preferably 30 to 300 μm. According to the extrusion coating method, in order to adjust the thickness of the coating film, the speed of the lip portion and the discharge amount of the liquid resin composition from the lip portion can be adjusted, and the coating can be performed by slit and rotary coating. The cloth method is mainly adjusted by the number of rotations and the rotation time of the spin coating of -102-200804974 (100) after slit coating. When the thickness of the coating film is too thick, the pattern development becomes difficult, and the adjustment of the gap of the liquid crystal cell step is also difficult. On the other hand, if it is too thin, it is difficult to increase the pigment concentration, and the desired color performance cannot be obtained. The thickness of the coating film is usually 〇.2 μm or more, more preferably 〇5 μm or more, more preferably 〇8 μm or more, and usually 20 μm or less, preferably ΙΟμηη or less, more preferably A range of 5 μηι or less.

本發明的硬化性組成物，使用擠壓式塗佈法時，其有效性顯著，於基板塗佈硬化性組成物後的塗佈膜的乾燥，較佳爲藉由使用熱板、IR烘箱、對流烘箱之乾燥法。通常是預備乾燥後再度加熱而使其乾燥，預備乾燥的條件，可依上述溶劑成份的種類、使用的乾燥機的性能等而適當的選擇’乾燥溫度及乾燥時間，依溶劑成份的種類、使用的乾燥機的性能等進行選擇，具體而言，乾燥溫度通常爲 4 0 °C以上，較佳爲5 0 °C以上，此外，通常爲8 0。(：以下，較佳爲7〇°C以下的範圍，乾燥時間通常爲15秒以上，較佳爲30秒以上，此外，通常爲5分鐘以下，較佳爲3分鐘以下的範圍。此外，再加熱乾燥的溫度條件，高於預備乾燥溫度的溫度較佳，具體而言，通常爲5〇 X：以上，較佳爲7 0 °C以上，此外，通常爲2 〇 0 °C以下，較佳爲1 6 0 °C 以下，特別佳爲130°C以下的範圍，又乾燥時間，雖然依加熱溫度而不同，但通常爲10秒以上，較佳爲15秒以上，此外’通常爲10分鐘以下，較佳爲5分鐘以下的範圍。乾燥溫度愈高，對透明基板的黏著性愈提高，但太高 -103- 200804974 (101) 則會有黏合劑樹脂產生分解，誘發熱聚合而產生顯影不良的情況，再者，此塗佈膜的乾燥步驟，可使用在溫度未提高下於減壓室內進行乾燥之減壓乾燥法。When the extrusion coating method of the curable composition of the present invention is used, the effectiveness is remarkable, and drying of the coating film after the substrate is coated with the curable composition is preferably performed by using a hot plate or an IR oven. Drying method of convection oven. Usually, it is prepared by drying and then heating and drying, and the conditions for drying are prepared. The drying temperature and drying time can be appropriately selected depending on the type of the solvent component and the performance of the dryer to be used, depending on the type of the solvent component. The performance of the dryer is selected, and specifically, the drying temperature is usually 40 ° C or higher, preferably 50 ° C or higher, and is usually 80. (The following is preferably in the range of 7 ° C or less, and the drying time is usually 15 seconds or longer, preferably 30 seconds or longer, and usually 5 minutes or shorter, preferably 3 minutes or shorter. The temperature of the heating and drying is preferably higher than the pre-drying temperature, and specifically, it is usually 5 〇 X: or more, preferably 70 ° C or more, and more preferably 2 〇 0 ° C or less. It is 1 60 ° C or less, particularly preferably 130 ° C or less, and the drying time varies depending on the heating temperature, but is usually 10 seconds or longer, preferably 15 seconds or longer, and 'usually 10 minutes or less. Preferably, the range is less than 5 minutes. The higher the drying temperature, the higher the adhesion to the transparent substrate, but the higher the density -103-200804974 (101), the decomposition of the binder resin causes thermal polymerization to cause poor development. In the case of the drying step of the coating film, a vacuum drying method in which drying is performed in a reduced pressure chamber without increasing the temperature can be used.

影像曝光，係於著色樹脂組成物的塗佈膜上，重疊負型的矩陣圖型，透過此光罩圖型，進行照射紫外線或可見光線的光源，此時，必要時爲了防止因爲氧所造成的光聚合性層的感度降低，亦可在光聚合性層上形成聚乙烯醇層等之氧遮斷層後進行曝光，上述的影像曝光所使用的光源，並沒有特別的限制，光源可列舉例如氙氣燈、鹵素燈、鎢燈、高壓水銀燈、超高壓水銀燈、金屬鹵化物燈、中壓水銀燈、低壓水銀燈、碳弧燈、螢光燈等之燈光源；氬離子雷射、YAG雷射、準分子雷射、氮雷射、氯鎘雷射、半導體雷射等之雷射光源等，照射特定波長的光後使用時，亦可利用光學濾光片。彩色濾光片，可對硬化生組成物的塗佈膜，藉由上述光源進行影像曝光後，藉由使用有機溶劑、或含有界面活性劑與鹼性化合物之水溶液進行顯影，於基板上形成影像後製成。此處，鹼性化合物可列舉氫氧化鈉、氫氧化鉀、氫氧化鋰、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、砂酸鈉、矽酸鉀、偏矽酸鈉、磷酸鈉、磷酸鉀、磷酸氫鈉、磷酸氫鉀、磷酸二氫鈉、磷酸二氫鉀、氫氧化銨等之無機鹼性化合物；單-·二-·或三-乙醇胺、單-·二-·或三-乙胺、單-·二-·或三-乙胺、單-·或一-異丙胺、η-丁胺、單· •104-Image exposure is performed on a coating film of a colored resin composition, and a negative matrix pattern is superimposed, and a light source that irradiates ultraviolet rays or visible rays is transmitted through the mask pattern, and at this time, if necessary, to prevent oxygen generation The sensitivity of the photopolymerizable layer is lowered, and an oxygen blocking layer such as a polyvinyl alcohol layer may be formed on the photopolymerizable layer and then exposed. The light source used for the above image exposure is not particularly limited. For example, the light source may be, for example, a light source. Xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc lamp, fluorescent lamp, etc.; argon ion laser, YAG laser, quasi Optical lasers such as molecular lasers, nitrogen lasers, cadmium-cadmium lasers, and semiconductor lasers can be used when irradiating light of a specific wavelength. a color filter for forming a film on a substrate by subjecting a coating film of the cured composition to image exposure by the above-mentioned light source, and developing using an organic solvent or an aqueous solution containing a surfactant and a basic compound Made afterwards. Here, examples of the basic compound include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium silicate, potassium citrate, sodium metasilicate, sodium phosphate, and the like. An inorganic basic compound such as potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate or ammonium hydroxide; mono-·di- or tri-ethanolamine, mono-·di-· or three -ethylamine, mono-di- or tri-ethylamine, mono- or mono-isopropylamine, η-butylamine, mono··104-

200804974 (102) •二-·或三-異丙醇胺、乙烯亞胺、乙烯二亞銨氫氧化物（TMAH)、膽鹼等之有機鹼性化合鹼性化合物，亦可爲2種以上的混合物。界面活性劑，可列舉例如聚氧乙烯烷基醚烯烷基芳基醚類、聚氧乙烯烷基酯類、山梨糖類、單甘油酯烷基酯類等之非離子性界面活性磺酸鹽類、烷基萘磺酸鹽類、烷基硫酸鹽類、類、磺基琥珀酸酯鹽類等之陰離子性界面活性菜鹼類、胺基酸類等之兩性界面活性劑。有機溶劑，可列舉例如異丙醇、苄醇、乙丁基溶纖劑、苯基溶纖劑、丙二醇、二丙酮醇劑可單獨或與水溶液合倂使用。顯影處理的條件並沒有特別的限制，但顯 10°c以上，其中又以l5°c以上爲佳，更佳爲此外，通常爲5〇°C以下，其中又以45°c以下爲40°C以下的範圍。顯影方法可使用浸漬顯影法、噴霧顯影法法、超苜波顯影法等之任一種方法。再者，本發明的彩色濾光片，除了上述外’亦可藉由下述方法製作，（1)將含有溶劑之酞菁系顏料、作爲黏合劑樹脂之聚醯亞胺系性組成物，塗佈於基板，可使用藉由餽刻法开多之方法製作；此外，（2)將含有酞菁系顏料之物作爲著色油墨使用，藉由印刷機於透明基板胺、四甲基物，此等的類、聚氧乙醇酐烷基酯劑；烷基苯烷基磺酸鹽劑；烷基甜基溶纖劑、等，有機溶影溫度通常 2 0 °C以上，爲佳，更佳、刷式顯影製作方法以、作爲顏料樹脂之硬化成畫素影像硬化性組成 :上直接形成 -105- 200804974 (103)200804974 (102) • Organic alkaline basic compound such as di- or tri-isopropanolamine, ethyleneimine, ethylene diammonium hydroxide (TMAH) or choline, or two or more kinds thereof mixture. Examples of the surfactant include nonionic interfacial active sulfonates such as polyoxyethylene alkyl ether olefin alkyl aryl ethers, polyoxyethylene alkyl esters, sorbose, and monoglyceride alkyl esters. An amphoteric surfactant such as an anionic interface active alkaloid or an amino acid such as an alkylnaphthalenesulfonate, an alkylsulfate or a sulfosuccinate. The organic solvent may, for example, be isopropyl alcohol, benzyl alcohol, ethyl butyl cellosolve, phenyl cellosolve, propylene glycol or diacetone alcohol, either alone or in combination with an aqueous solution. The conditions of the development treatment are not particularly limited, but are preferably 10 ° C or more, and more preferably 15 ° C or more, more preferably, usually 5 ° ° C or less, wherein 40 ° C or less is 40 °. C below the range. As the developing method, any one of a dipping development method, a spray development method, and an ultra-chopper development method can be used. Further, the color filter of the present invention can be produced by the following method except for the above, (1) a phthalocyanine-based pigment containing a solvent, and a polyimine-based composition as a binder resin. It can be applied to a substrate by a method of feeding a plurality of methods, and (2) a material containing a phthalocyanine-based pigment can be used as a coloring ink, and a transparent substrate amine or tetramethyl group can be used by a printing machine. Such a class, polyoxyethylene glycol anhydride alkyl ester; alkyl benzene alkyl sulfonate; alkyl sweet cellosolve, etc., organic dissolution temperature is usually above 20 ° C, preferably, better , brush development method, as a pigment resin hardened into a picture image hardening composition: directly formed -105- 200804974 (103)

畫素影像之方法；（3 )含有酞菁系顏料之硬化性組成物作爲電著液使用，將基板浸漬於此電鍍沈積液，在被形成所定圖型的ITO電極上，析出著色膜之方法；以及（4)將塗佈含有酞菁系顏料之硬化性組成物之薄膜，貼合於透明基板上後剝離，進行影像曝光、顯影而形成畫素影像之方法；（5)將含有酞菁系顏料之硬化性組成物作爲著色油墨使用，藉由噴墨印刷機形成畫素影像之方法等。彩色濾光片的製作方法，依本發明的硬化性組成物的組成，採用適合的方法。對顯影後的彩色濾光片，施以熱硬化處理，此時的熱硬化處理條件，溫度通常爲100 °C以上，較佳爲15(TC以上，此外，通常爲280°C以下，較佳爲250°C以下的範圍內進行選擇，時間爲5分鐘以上，60分鐘以下的範圍內進行選擇。經過此等一連串的步驟，一色的圖型化影像形成結束，依序重複此等步驟，使黑色、紅色、綠色、藍色圖型化，形成彩色濾光片，再者，4色的圖型化的順序，並不限定於上述的順序。而且，彩色濾光片，在此狀態下直接於影像上形成 ITO等的透明電極，被作爲彩色顯示器、液晶顯示裝置等的零件的一部份使用，惟爲了提高表面平滑性或持久性，必要時可於影像上設置聚醯胺、聚醯亞胺等之頂塗佈層，此外，——部份在平面配向型驅動方式（IP模組）等的用途中，亦有不形成透明電極的情況。此外，垂直配向型驅動方式（MVA模組）’亦有形成稜 -106- 200804974 (104) (rib)的情況，此外，亦有藉由微影術形成柱構造（光間隔物）取代珠散佈型間隔物的情況。 [3-2]液晶顯示裝置（面板）(3) A method of depositing a colored film by using a hardening composition containing a phthalocyanine-based pigment as an electro-hydraulic liquid, immersing the substrate in the plating deposition liquid, and forming a colored film on the ITO electrode to be formed into a predetermined pattern And (4) a method of applying a film of a curable composition containing a phthalocyanine-based pigment to a transparent substrate, peeling it off, and performing image exposure and development to form a pixel image; (5) containing a phthalocyanine A curable composition of a pigment is used as a colored ink, a method of forming a pixel image by an ink jet printer, or the like. The method for producing the color filter is a suitable method according to the composition of the curable composition of the present invention. The color filter after development is subjected to a heat hardening treatment, and the temperature of the heat curing treatment at this time is usually 100 ° C or higher, preferably 15 (TC or more, and usually 280 ° C or lower, preferably The selection is in the range of 250 ° C or less, and the time is selected in the range of 5 minutes or more and 60 minutes or less. After a series of steps, the formation of the one-color patterned image is completed, and the steps are sequentially repeated to make The black, red, green, and blue patterns are patterned to form a color filter. Further, the order of patterning of the four colors is not limited to the above order. Moreover, the color filter is directly in this state. A transparent electrode such as ITO is formed on the image, and is used as a part of a color display or a liquid crystal display device. However, in order to improve the surface smoothness or durability, it is possible to provide polyimide and polyfluorene on the image if necessary. In the case of a top coating layer such as an imide, a part of a planar alignment type driving method (IP module) or the like does not form a transparent electrode. In addition, a vertical alignment type driving method (MVA) The group also has the case of forming a rib-106-200804974 (104) (rib). In addition, there is also a case where a pillar structure (photo spacer) is formed by lithography to replace the bead-scatter spacer. [3-2 LCD display device (panel)

本發明該相關的液晶顯示裝置，例如可將上述[3 -1 ] 彩色濾光片（以下亦稱爲「彩色濾光片基板」）、與藉由薄膜晶體管（TFT)驅動之基板，藉由隔著液晶層對向的構造而構成。更具體而言，將塗佈配向膜材料及施以配向處理的彩色濾光片基板、與同樣的TFT驅動基板，藉由周邊密封材而貼合，藉由於其空隙中注入液晶材料，可成爲液晶顯示裝置。本發明相關的液晶顯示裝置，通常在上述本發明相關的彩色濾光片上形成配向膜，於此配向膜上散佈間隔物後’與對向基板貼合後形成液晶盒，於所形成的液晶盒內注入液晶，連線於對向電極而製成。配向膜以聚醯胺等的樹脂膜較適合，配向膜的形成，通常採用照相凹版印刷法及/或可撓性印刷法，配向膜的厚度被設定在1 〇nm ’藉由熱燒成進行配向膜的硬化處理後，藉由紫外線的照射或經由摩擦布處理進行表面處理，加工成可調整液晶的傾斜之表面狀態。間隔物，可使用符合與對向基板的間隙（gap)的大小者，通常2〜8μιη者較適合，彩色濾光片基板上，藉由微影術法形成透明樹脂膜的光間隔物（P S )，可活用此物取代間隔物。對向基板通常使用陣列基板，特別是TFT(薄膜晶體 -107- 200804974 (105) 管）基板較適合，此外，與對向基板貼合的間隙，依液晶面板的用途而不同’但通常爲2μπι以上8μπχ以下的範圍內進行選擇，與對向基板貼合後，液晶注入口以外的部份，藉由環氧樹脂等之密封材被封閉，密封材可藉由UV 照射及/或加熱而被硬化，液晶盒周邊被密封。In the liquid crystal display device of the present invention, for example, the above [3 - 1 ] color filter (hereinafter also referred to as "color filter substrate") and a substrate driven by a thin film transistor (TFT) can be used. It is configured by a structure in which the liquid crystal layer faces each other. More specifically, the alignment film material and the color filter substrate subjected to the alignment treatment and the same TFT drive substrate are bonded together by the peripheral sealing material, whereby the liquid crystal material can be injected into the voids. Liquid crystal display device. In the liquid crystal display device according to the present invention, an alignment film is formed on the color filter according to the present invention, and after the spacer is spread on the alignment film, a liquid crystal cell is formed after bonding to the opposite substrate, and the liquid crystal is formed. A liquid crystal is injected into the cell and wired to the counter electrode. The alignment film is preferably a resin film of polyamine or the like, and the formation of the alignment film is usually performed by gravure printing and/or flexographic printing, and the thickness of the alignment film is set at 1 〇 nm ' by thermal firing. After the hardening treatment of the alignment film, the surface treatment is performed by irradiation of ultraviolet rays or by rubbing cloth treatment, and processing is performed to adjust the surface state of the tilt of the liquid crystal. For the spacer, it is suitable to use a gap corresponding to the opposite substrate, usually 2 to 8 μm, and a photo spacer for forming a transparent resin film by a lithography method on a color filter substrate (PS) ), this substance can be used instead of the spacer. The alignment substrate is generally used as an array substrate, in particular, a TFT (Thin Crystal-107-200804974 (105) tube) substrate, and the gap to be bonded to the opposite substrate differs depending on the use of the liquid crystal panel, but is usually 2 μm. In the range of 8 μπχ or less, the portion other than the liquid crystal injection port is bonded to the counter substrate, and the sealing material is sealed by UV irradiation and/or heating. Hardened, the perimeter of the cell is sealed.

周邊被密封的液晶盒，切割成面板單位後，於真空室內減壓，將上述的液晶注入口浸漬於液晶後，藉由泄漏室內，而將液晶注入至液晶盒內，液晶盒內的減壓度，通常爲lxlO_2Pa以上，較佳爲lxl(T3Pa以上，此外，通常爲 lxl(T7Pa以下，較佳爲lxl(T6Pa以下的範圍。此外，減壓時加溫液晶盒較佳，加溫溫度通常3 0 °C以上，較佳爲 5(TC以上，此外，通常l〇〇°C以下，較佳爲90°C以下的範圍。減壓時的加溫保持通常1 〇分鐘以上，60分鐘以下的範圍，然後，浸漬於液晶中。注入液晶的液晶盒，藉由使UV硬化樹脂硬化後封閉液晶注入口，完成液晶顯示裝置。再者’液晶的種類並沒有特別的限制，可爲芳香族系、脂肪族系、多環狀化合物等自先前技術以來已知的液晶’可爲液向型液晶、熱致液晶等的任一種，熱致液晶已知有向列型液晶、層列型液晶、及膽固醇型液晶等，任一者皆可。【實施方式】以τ，藉由實施例更詳細說明本發明，但本發明並不限定於此等所解釋之內容。 108- 200804974 (106) [塗佈適性評估方法（1)] 將依後述的順序所得到的硬化性組成物，經由以下記載之（1)〜（4)的步驟評價時，將試驗片放置於執行器的手臂，使用自動重複進行將其先端放進取出充滿著色硬化性組成物的瓶中之操作的控制裝置。The liquid crystal cell sealed in the periphery is cut into panel units, and then decompressed in a vacuum chamber, and the liquid crystal injection port is immersed in the liquid crystal, and the liquid crystal is injected into the liquid crystal cell by leaking the chamber, and the liquid crystal cell is decompressed. Degree, usually lxlO_2Pa or more, preferably lxl (T3Pa or more, in addition, usually lxl (T7Pa or less, preferably lxl (T6Pa or less). In addition, it is preferable to warm the liquid crystal cell under reduced pressure, and the heating temperature is usually 30 ° C or more, preferably 5 (TC or more, and usually l〇〇 ° C or less, preferably 90 ° C or less. The heating at the time of pressure reduction is usually 1 minute or more, 60 minutes or less. The liquid crystal cell is injected into the liquid crystal cell, and the liquid crystal display device is completed by curing the UV curable resin and sealing the liquid crystal injection port. Further, the type of the liquid crystal is not particularly limited and may be aromatic. Liquid crystals known from the prior art, such as aliphatic, polycyclic compounds, and the like, may be any of liquid-oriented liquid crystals, thermotropic liquid crystals, etc., and thermotropic liquid crystals are known to have nematic liquid crystals and smectic liquid crystals. And cholesterol [Embodiment] The present invention will be described in more detail by way of τ, but the present invention is not limited to the contents explained herein. 108- 200804974 (106) [Coating suitability Evaluation method (1)] When the curable composition obtained in the order described later is evaluated by the procedures (1) to (4) described below, the test piece is placed on the arm of the actuator and automatically repeated. The apex is placed in a control device for taking out the operation of the bottle filled with the colored curable composition.

(1)在氣體環境溫度23°C，將長度lOOmmx寬度5mmx 厚度0.7mm的玻璃試驗片的縱方向的前端部份20mm，以 1 2.5 m m /秒的速度浸漬於硬化物組成物中，然後維持 4 秒； (2) 將該玻璃試驗片，以12.5mm/秒的速度從硬化性組成物取出，將該玻璃試驗片的前端往下保持垂直後，在氣體環境溫度23°C、濕度55%、風速0.5±0.2m/秒的條件下使其乾燥52秒； (3) 重複步驟（1)及（2)合計25 0次，該玻璃試驗片上形成源自硬化性組成物的附著物U); (4) 該玻璃試驗片的4稜線中，選擇該附著物量最多的稜線，測量該稜線上的附著物（「附著物（a)」）的重量。再者，附著物（a)的重量測量，亦可預先使用該硬化物組成物測量所形成的膜的比重備用’用3維雷射顯微鏡等測量附著物（a)的體積，由此等之積計算。 [硬化性組成物的含水量的測量] 關於依照後述的順序所得到的硬化性組成物’用卡 -109- 200804974 (107) 爾-費歇法測量，依下述條件進行水分量的測量。 •裝置：Dia Instruments公司製KF水分計CA-100 •注入重· 40〜50μί(1) The tip end portion of the glass test piece having a length of 100 mm x a width of 5 mm x and a thickness of 0.7 mm was immersed in a hardened composition at a rate of 1 2.5 mm / sec at a gas ambient temperature of 23 ° C, and then maintained. 4 seconds; (2) The glass test piece was taken out from the curable composition at a rate of 12.5 mm/sec, and the front end of the glass test piece was kept vertical, at a gas atmosphere temperature of 23 ° C and a humidity of 55%. And drying at a wind speed of 0.5±0.2 m/sec for 52 seconds; (3) repeating steps (1) and (2) for a total of 25 times, the adhesion of the curable composition is formed on the glass test piece U) (4) Among the four ridge lines of the glass test piece, the ridge line having the largest amount of attached matter was selected, and the weight of the attached matter ("attachment (a)") on the ridge line was measured. Further, the weight of the attached matter (a) may be measured by using the cured composition to measure the specific gravity of the formed film in advance, and the volume of the attached matter (a) is measured by a three-dimensional laser microscope or the like. Product calculation. [Measurement of the water content of the curable composition] The measurement of the moisture content was carried out under the following conditions by measuring the curable composition obtained in the order described later by the card-109-200804974 (107)-Fercher method. • Device: KF Moisture Meter CA-100 manufactured by Dia Instruments Inc. • Injecting weight · 40~50μί

•陽極 /陰極液：Aquamicron AS/CXU • End Sens. ： 0· 1 pg/sec [黏度測量方法]• Anode / Catholyte: Aquamicron AS/CXU • End Sens. : 0· 1 pg/sec [Viscometry]

關於依照後述的順序所得到的硬化性組成物，硬化性組成物剛調製後的黏度，與常壓下、351保存2週後的黏度，用以下的條件測量。 •裝置：東機產業公司製RE 8 0L型黏度計（E型黏度計） •試樣量：1.0 m 1 •旋轉數：20rpm [硬化性組成物的水分含量的調整] 關於依照後述的順序所得到的硬化性組成物，用上述 [硬化性組成物的含水量的測量]方法測量水分含量，硬化性組成物皆比本發明的水分含量的範圍（0 · 4重量％以上 2.0重量％以下）少。接著，於各組成物中滴下水，再度用上述方法確認水分含量’各組成物的最終的水分含量列示於表1。 (合成例1 :黏合劑樹脂a :相當於（A-3)黏合劑樹脂） -110- 200804974 (108) 於反應容器中裝入丙二醇單甲基醚乙酸酯 220.73 份、V-59(和光純藥公司製偶氮系聚合起始劑）8.5重量份，在氮氣的氣體環境下，昇溫至80°C，用2小時滴入丙二醇單甲基醚乙酸酯1 27.5重量份、甲基丙烯酸苄酯5 5 重量份、甲基丙烯酸45重量份，再進行6小時攪拌，得到聚合反應液。With respect to the curable composition obtained in the order described later, the viscosity immediately after preparation of the curable composition and the viscosity after storage for 2 weeks under normal pressure and 351 were measured under the following conditions. • Device: RE 8 0L viscometer (E-type viscometer) manufactured by Toki Sangyo Co., Ltd. • Sample size: 1.0 m 1 • Number of rotations: 20 rpm [Adjustment of moisture content of curable composition] About the order described later The obtained curable composition was measured for the moisture content by the above method [measurement of the water content of the curable composition], and the curable composition was in the range of the moisture content of the present invention (0. 4 wt% or more and 2.0 wt% or less). less. Next, water was dropped on each of the compositions, and the water content was confirmed again by the above method. The final moisture content of each of the compositions is shown in Table 1. (Synthesis Example 1: Adhesive Resin a: Corresponding to (A-3) Binder Resin) -110- 200804974 (108) 220.73 parts of propylene glycol monomethyl ether acetate, V-59 (and 8.5 parts by weight of an azo-based polymerization initiator prepared by Wako Pure Chemical Industries Co., Ltd., heated to 80 ° C under a nitrogen atmosphere, and dropped 1 27.5 parts by weight of propylene glycol monomethyl ether acetate in 2 hours, methacrylic acid 5 parts by weight of benzyl ester and 45 parts by weight of methacrylic acid were further stirred for 6 hours to obtain a polymerization reaction liquid.

接著，將甲基丙烯酸3,4-環氧環己酯20重量份、p-甲氧基苯酚0 · 2份、三乙胺〇. 4份，溶解於丙二醇單甲基醚乙酸酯3 0重量份後滴入於反應槽內，就這樣以1 1 〇 °C 反應9小時，得到濃度4〇重量％的聚合溶液，聚合物經由GPC所測量的聚乙烯換算的重量平均分子量（以下，相同）爲 8000，酸値爲 72mgKOH/g。 (合成例2 :黏合劑樹脂b :相當於（A-3)黏合劑樹脂）除了 V-59爲6重量份以外，與合成例1同樣的調製聚合物溶液，所得到的聚合物的重量平均分子量爲 20000，酸値爲 72mgKOH/g。 (合成例3 :黏合劑樹脂c :相當於（A_2)黏合劑樹脂）於500ml的分離燒瓶中裝入甲基丙烯酸苄酯55重量份、甲基丙烯酸45重量份、丙二醇單甲基醚乙酸酯150 份，燒瓶內充分用氮氣置換，然後添加2,2’-偶氮雙異丁腈6重量份，以8 0 °C攪拌5小時，得到聚合物溶液。被合成的聚合物的重量平均分子量爲 8000，酸値爲 -111 - 200804974 (109) 1 76mgKOH/g 〇 (合成例4 :黏合劑樹脂d :相當於（A- i )黏合劑樹脂）Next, 20 parts by weight of 3,4-epoxycyclohexyl methacrylate, 0.2 parts of p-methoxyphenol, and 4 parts of triethylamine are dissolved in propylene glycol monomethyl ether acetate 3 0 After the weight fraction was dropped into the reaction vessel, the reaction was carried out at 1 1 〇 ° C for 9 hours to obtain a polymerization solution having a concentration of 4 〇 by weight, and the weight average molecular weight of the polymer measured by GPC (hereinafter, the same ) is 8000, and the acidity is 72 mgKOH/g. (Synthesis Example 2: Adhesive Resin b: Corresponding to (A-3) Binder Resin) The polymer composition obtained in the same manner as in Synthesis Example 1 except that V-59 was 6 parts by weight, and the weight average of the obtained polymer was The molecular weight was 20,000 and the acid hydrate was 72 mgKOH/g. (Synthesis Example 3: Adhesive Resin c: Corresponding to (A_2) Binder Resin) 55 parts by weight of benzyl methacrylate, 45 parts by weight of methacrylic acid, and propylene glycol monomethyl ether acetate were placed in a 500 ml separation flask. 150 parts of the ester, the flask was sufficiently replaced with nitrogen, and then 6 parts by weight of 2,2'-azobisisobutyronitrile was added, and the mixture was stirred at 80 ° C for 5 hours to obtain a polymer solution. The polymer to be synthesized had a weight average molecular weight of 8,000, and the acid hydrate was -111 - 200804974 (109) 1 76 mgKOH/g 〇 (Synthesis Example 4: binder resin d: equivalent to (A-i) binder resin)

一邊進行氮氣置換一邊攪拌丙二醇單甲基醚乙酸酯 145份，昇溫至120 °C ’此時滴入苯乙烯20重量份、甲基丙烯酸環氧丙酯57份及具有三環癸烷骨架之單丙烯酸酯 (曰立化成公司製FA-513M)82重量份，再以120°C持續攪拌2小時。接著將反應容器內改變爲空氣置換，投入丙烯酸27 重量份、參二甲基胺甲基苯酚0.7重量份及氫醌0.1 2重量份，以1 20 °C持續反應6小時，然後，加入四氫酞酸酐 (THPA)52重量份、三乙胺0.7重量份，以120°C使其反應 3.5小時。如此所得到的聚合物的重量平均分子量 Mw約爲 8000 〇145 parts of propylene glycol monomethyl ether acetate was stirred while replacing with nitrogen, and the temperature was raised to 120 ° C. At this time, 20 parts by weight of styrene, 57 parts of glycidyl methacrylate, and a tricyclodecane skeleton were dropped. 82 parts by weight of monoacrylate (FA-513M, manufactured by Toray Chemical Co., Ltd.) was further stirred at 120 ° C for 2 hours. Then, the inside of the reaction vessel was changed to air displacement, and 27 parts by weight of acrylic acid, 0.7 parts by weight of dimethylaminomethylphenol and 0.12 parts by weight of hydroquinone were charged, and the reaction was continued at 10 ° C for 6 hours, and then tetrahydrogen was added. 52 parts by weight of phthalic anhydride (THPA) and 0.7 parts by weight of triethylamine were reacted at 120 ° C for 3.5 hours. The weight average molecular weight Mw of the polymer thus obtained is about 8000 〇

(合成例5 :黏合劑樹脂e :相當於（A-5)黏合劑樹脂）於反應容器內裝入日本化藥公司製XD 1 000(二環戊二燒•苯酚聚合物的聚環氧丙醚、重量平均分子量700、環氧當量252)300份、甲基丙烯酸101份、p-甲氧基苯酚 0.2份、三苯基膦5份、丙二醇單甲基醚乙酸酯255份，以l〇〇t：攪拌至酸價成爲3.0mgKOH/g爲止’酸價逹到目標爲止需要9小時（酸價2.5)，接著再添加四氫酞酸酐I45 份，以120°C使其反應4小時，得到酸價100mgKOH/g、 -112- 200804974 (110) 以GPC所測量的聚苯乙烯換算的重量平均分子量1 800的黏合劑樹脂。 (合成例6 :分散劑f: (E-1)相當於含有氮原子之接枝共聚物）(Synthesis Example 5: Adhesive Resin e: Corresponding to (A-5) Adhesive Resin) XD 1 000 (dicyclopentane pentoxide/phenol polymer polyepoxypropyl) manufactured by Nippon Kayaku Co., Ltd. was placed in a reaction container. Ether, weight average molecular weight 700, epoxy equivalent 252) 300 parts, 101 parts of methacrylic acid, 0.2 parts of p-methoxyphenol, 5 parts of triphenylphosphine, 255 parts of propylene glycol monomethyl ether acetate, 〇〇t: stirring until the acid value becomes 3.0 mgKOH/g, it takes 9 hours (acid value 2.5) until the acid value reaches the target, and then I45 parts of tetrahydrophthalic anhydride is further added, and the reaction is carried out at 120 ° C for 4 hours. A binder resin having a weight average molecular weight of 1,800 in terms of polystyrene measured by GPC was obtained at an acid value of 100 mgKOH/g, -112-200804974 (110). (Synthesis Example 6: Dispersant f: (E-1) corresponds to a graft copolymer containing a nitrogen atom)

將具有分子量約5000之聚乙烯亞胺50重量份’及 n = 5之聚己內酯40重量份，與丙二醇單甲基醚乙酸酯300 重量份混合，以1 5 0 °C 3小時’在氮氣的氣體環境下攪拌，如此合成的分散劑之以GPC所測量的重量平均分子量Mw約爲9000。 (合成例7 :分散劑g : (E-2)相當於含有氮原子之丙烯酸系嵌段共聚物）除了共聚物中的胺基（二甲胺基）未4級化以外，依據特開平1 -229014號公報的實施例1，合成具有3級胺基之丙烯酸系B_A-B嵌段共聚物，所得到的共聚物的重量平均分子量Mw爲9000，胺價爲121mgKOH/g，酸價爲 OmgKOH/g 〇 (合成例8 :分散劑h : (E-2)相當於含有氮原子之丙烯酸系嵌段共聚物）依據特開平1 -22901 4號公報的實施例1，合成具有4 錢鹽基（二甲基苄基銨鹽基）之丙烯酸系B-A — B嵌段共聚物’所得到的共聚物的重量平均分子量Mw爲9000，胺 -113- 200804974 (111) 價爲 lOmgKOH/g，酸價爲 0mgKOH/g。 [實施例1、2、4〜7、比較例1〜4及7〜9] [顏料分散液的調製]40 parts by weight of polyethyleneimine having a molecular weight of about 5,000 and 40 parts by weight of polycaprolactone having n = 5, mixed with 300 parts by weight of propylene glycol monomethyl ether acetate, at 150 ° C for 3 hours' The mixture was stirred under a nitrogen atmosphere, and the thus synthesized dispersant had a weight average molecular weight Mw of about 9000 as measured by GPC. (Synthesis Example 7: Dispersant g: (E-2) corresponds to an acrylic block copolymer containing a nitrogen atom) Except that the amine group (dimethylamino group) in the copolymer is not classified into four stages, In Example 1 of the publication No. 229,014, an acrylic B_A-B block copolymer having a tertiary amino group was synthesized, and the obtained copolymer had a weight average molecular weight Mw of 9000, an amine value of 121 mgKOH/g, and an acid value of OmgKOH. /g 〇 (Synthesis Example 8: Dispersant h: (E-2) corresponds to an acrylic block copolymer containing a nitrogen atom) According to Example 1 of JP-A No. Hei 1-22901, a salt having 4 money is synthesized. The copolymer obtained by the (acrylic BA-B block copolymer of (dimethylbenzylammonium salt)) has a weight average molecular weight Mw of 9000, and an amine-113-200804974 (111) price of 10 mgKOH/g, an acid value. It is 0 mgKOH/g. [Examples 1, 2, 4 to 7, Comparative Examples 1 to 4 and 7 to 9] [Preparation of Pigment Dispersion]

將作爲色材之7 · 3重量份的c . I.顏料綠3 6、3 . 1重量份的C.I.顏料黃150，作爲溶劑之60.0重量份的丙二醇單甲基醚乙酸酯’作爲分散劑之將表_丨所記載的分散劑以固形份換算爲1.3重量份，（表）中所記載的樹脂3·4重量份，平均粒徑〇.5mm的氧化鉻珠225重量份，塡充於不鏽鋼容器內，用塗料調節機分散6小時後，經由過濾器分離珠與分散液，調製綠顏料分散液。 [硬化性組成物的調製] 添加上述所得到的顏料分散液5 8.4重量份，作爲溶劑之丙二醇單甲基醚乙酸酯（PGMEA)35.0重量份，樹脂 3.5重量份，作爲單體之二季戊四醇六丙酸酯3.2重量份、作爲光聚合起始系2 -氫硫基苯並噻唑、p -二甲基胺基苯甲酸甲酯、及米希勒酮各〇. 7重量份，調製硬化性組成物。此外，關於比較例8及9，加入上述組成的各成份後，將磷酸丙烯酸酯（PΜ-21 :日本化藥公司製），以對總固形分爲1重量％的比例加入。 [實施例3、比較例5、6] -114- 200804974 (112) [顏料分散液的調製]7 parts by weight of c. I. Pigment Green 3 6 , 3.1 parts by weight of CI Pigment Yellow 150, and 60.0 parts by weight of propylene glycol monomethyl ether acetate as a solvent as a dispersing agent The dispersant described in Table 丨 is 1.3 parts by weight in terms of solid content, 3.4 parts by weight of the resin described in (Table), and 225 parts by weight of chrome oxide beads having an average particle diameter of 55 mm. After dispersing for 6 hours in a stainless steel container by a paint conditioner, the beads and the dispersion were separated by a filter to prepare a green pigment dispersion. [Preparation of Curable Composition] 8.4 parts by weight of the pigment dispersion liquid obtained above, 35.0 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) as a solvent, 3.5 parts by weight of a resin, and dipentaerythritol as a monomer were added. 3.2 parts by weight of hexapropionate, as a photopolymerization initiating unit of 2-hydrothiobenzothiazole, methyl p-dimethylaminobenzoate, and michlerone. 7 parts by weight, modulating hardenability Composition. Further, in Comparative Examples 8 and 9, the components of the above composition were added, and then phosphoric acid acrylate (PΜ-21: manufactured by Nippon Kayaku Co., Ltd.) was added in a ratio of 1% by weight to the total solid content. [Example 3, Comparative Example 5, 6] -114- 200804974 (112) [Preparation of pigment dispersion]

將彩色用碳黑（三菱化學公司製「MA-8」、平均粒徑 24μπι、DBP吸油量5 8ml/l 00g) 1 〇〇g，於2軸揑合機內與超純水500ml混練20分鐘，藉由過濾去除超純水，被過濾的碳黑再度添加超純水後混練，重複進行4次過濾，最後乾燥經過濾的碳黑後得到被洗淨的碳黑，於洗淨的碳黑 50重量份中，加入bykl61(BYK-Chemie公司製尿烷樹脂分散劑，胺價 39mgKOH/g)10重量份、及PGMEA，將固形份濃度調整爲30重量％，顏料分散液的總重量爲5〇g，將其藉由攪拌機充分攪拌而進行預混。接著，藉由塗料調節機在2 5〜4 5 °C的範圍進行6小時分散處理，使用〇 · 5 mm φ的氧化锆珠，加入與分散液相同重量，分散結束後（JIS Z8741中 20度鏡面光澤度 1 70)，藉由過濾器分散珠與分散液，調製顏料分散液。 [硬化性組成物的調製] 使用上述黑色顏料分散液，加入各成份使其成爲下述的摻合比例，藉由攪拌器使其攪拌、溶解，調製黑色光阻感光液。經調製的油墨：以固形份而言爲50g 黏合劑e :以固形份而言30g 單體（乙烯性化合物：二季四成醇六丙烯酸酯）：l〇g 分散劑（bykl6 1)含有溶液：以固形份而言5g 光聚合起始劑（Ciba Specialty chemicals公司製 -115- 200804974 (113) 「CGI2 42」，下述結構式所示的化合物。）：5g [化 26]Color black carbon (manufactured by Mitsubishi Chemical Corporation "MA-8", average particle size 24 μm, DBP oil absorption of 5 8 ml / l 00 g) 1 〇〇g, and mixed with ultra-pure water 500ml in a 2-axis kneader for 20 minutes, The ultrapure water is removed by filtration, the filtered carbon black is again added with ultrapure water, and then mixed, and the filtration is repeated four times. Finally, the filtered carbon black is dried to obtain the washed carbon black, and the washed carbon black is 50. To the parts by weight, 10 parts by weight of bykl61 (a urethane resin dispersant manufactured by BYK-Chemie Co., Ltd., an amine price of 39 mgKOH/g), and PGMEA were added, and the solid content concentration was adjusted to 30% by weight, and the total weight of the pigment dispersion liquid was 5 〇. g, premixed by thorough stirring by a mixer. Next, the coating conditioner was subjected to dispersion treatment for 6 hours in the range of 25 to 45 ° C, and zirconia beads of 〇·5 mm φ were used, and the same weight as the dispersion was added, and after the dispersion was completed (20 degrees in JIS Z8741) Specular gloss 1 70), the pigment dispersion was prepared by dispersing the beads and the dispersion by a filter. [Preparation of curable composition] Using the above black pigment dispersion liquid, each component was added to have the following blending ratio, and the mixture was stirred and dissolved by a stirrer to prepare a black photoresist photosensitive liquid. Prepared ink: 50 g binder in solid form e: 30 g monomer in solid form (ethylene compound: diquaternary alcohol hexaacrylate): l〇g dispersant (bykl6 1) contains solution: 5 g of a photopolymerization initiator (Ciba Specialty Chemicals, Ltd. - 115 - 200804974 (113) "CGI2 42", a compound represented by the following structural formula.): 5 g [Chem. 26]

有機溶劑（PGMEA) ·· 3 00g 界面活性劑（住友3M公司製「FC-43 0」，氟活性劑）：光阻液中的濃度成爲lOOppm之量。對所得到的硬化性組成物，用[硬化性組成物含量的調整]之項所記載的方法調整水分量後，用_ 佈適性評估方法（I)]進行評估。接著，使用i〇cm 型Lab塗工機藉由擠壓式塗佈法進行塗佈試驗，乾到的塗佈膜後，於1 0 c m X 1 0 c m的塗佈區域，觀察離片異物所造成的缺陷的狀況，再者，塗佈： O.lm/sec，塗佈間隙爲〇.imm，濕狀態的塗佈膜n 微米，結果列示於表-1。而且，依照上述的[黏度測量方法]，相對於硬成物的剛調製後的黏度，觀察保存2週後的黏度的結果列示於表-1。接著，使用保存2週後的硬化性組成物，用與系界面的水分匕述[塗寬的小燥所得因爲剝產度爲 !爲20 化性組變化，上述相 -116- 200804974 (114) 同的條件，使用小型Lab塗工機進行塗佈試驗。保存2週後的黏度上升低於0.5 cps，實施例1〜3及 5〜7的組成物，可毫無問題地塗佈，因爲凝聚異物所造成的缺陷很少，黏度上升同樣低於〇·5 cps，關於比較例 1、3、5及8的硬化性組成物，雖然進行塗佈，但與硬化性組成物剛調製後的塗佈試驗時，同樣在lOcmxl 0cm的塗佈區域中發生因爲多數的剝離片異物所造成的缺陷。Organic solvent (PGMEA) ·· 3 00g of surfactant ("FC-43 0" manufactured by Sumitomo 3M Co., Ltd., fluorine active agent): The concentration in the photoresist is 100 ppm. The moisture content of the obtained curable composition was adjusted by the method described in [Adjustment of the content of the curable composition], and then evaluated by the evaluation method (I). Next, the coating test was carried out by a squeeze coating method using an i〇cm type Lab coater, and after drying the applied film, the foreign matter was observed in a coating area of 10 cm×10 cm. The state of the defects caused was further coated with O.lm/sec, the coating gap was 〇.imm, and the coating film in the wet state was n μm. The results are shown in Table-1. Further, according to the above-mentioned [viscosity measurement method], the results of observing the viscosity after storage for 2 weeks with respect to the viscosity immediately after preparation of the hard product are shown in Table-1. Next, the curable composition after storage for 2 weeks was used, and the water content at the interface with the system was used. [The result of the drying of the coating was because the peeling degree was changed to 20, and the above-mentioned phase -116-200804974 (114) Under the same conditions, a coating test was performed using a small Lab coater. After 2 weeks of storage, the viscosity rise was less than 0.5 cps, and the compositions of Examples 1 to 3 and 5 to 7 could be applied without any problem, because the defects caused by agglomerated foreign matter were few, and the viscosity rise was also lower than that of 〇· 5 cps, the curable compositions of Comparative Examples 1, 3, 5, and 8 were coated, but in the coating test immediately after the preparation of the curable composition, the same occurred in the coating region of 10 cm x 10 cm. Most of the defects caused by peeling off foreign objects.

保存2週後的黏度上升爲0.5cps以下l.Ocps以下的範圍之實施例4，塗佈時發生些許的塗佈條紋，但所得到的塗佈區域中的缺陷數少。保存2週後的黏度上升爲lcps以上，比較例2、4及 6〜8係在保存中顏料分散體壞掉，因此硬化性組成物中顏料凝聚，從擠壓式塗佈法的配料機噴嘴供給硬化性組成物，顯著地變困難，所得到的塗佈膜亦發生許多塗佈不均勻0In Example 4, in which the viscosity after the storage for 2 weeks was 0.5 cps or less and 1.0 Ocps or less, a slight coating streak occurred during coating, but the number of defects in the obtained coated region was small. After 2 weeks of storage, the viscosity increased to lcps or more, and in Comparative Examples 2, 4, and 6 to 8 the pigment dispersion was broken during storage, so that the pigment in the curable composition was agglomerated, and the nozzle of the batching machine from the extrusion coating method was used. The supply of the curable composition is remarkably difficult, and the coating film obtained also has many coating unevenness.

-117· 200804974 (115)-117· 200804974 (115)

""黏度上昇_ ◎ ◎ ◎ 〇△ ◎ ◎ ◎ ◎ X ◎ X ◎ X X X ◎ 異物& ◎ ◎ ◎ ◎ 〇〇〇△ X ◎ X ◎ X ◎ X ◎ X 附著量 ◎ ◎ ◎ ◎ 〇〇〇 X ◎ X ◎ X ◎ X ◎ X PM-21 ο ο 0 ο ο 0 ο 0 ο ο o ο 0 ο 1—Η < < 分散劑 I^L m & m CO m 3級胺 3級胺 CO m 繼寸 3級胺 CO s CO s cn m m 籲繼寸 ΓΠ 3級胺驟 >1vtS 伽11 w q-t OJO s \ < t>J〇 U) r* i VO 1—* Λ J=! t+H C4-H S Ϊ8 1 ίί <R 8000 8000 1800 8000 8000 20000 8000 8000 8000 8000 8000 1800 1800 8000 8000 8000 種類 cd CD cd 〇 cd T3 <L> CD 〇〇3 ci 水分量 (wt%) 〇〇 oo 0 00 0 〇〇 in oo CD 〇〇〇 CO csi 〇4 m c5 r<i CO c5 CO CN* 0 CO 〇 1實施例1 CN1 n CO s Λ u VO Λ r- 1— 鎰 λλ <N 鎰 JJJ λλ 1比較例3 寸鎰 ΛΛ in 鎰 J_J VO 鎰 ΛΑ 卜鎰〇〇鎰 λλ os 鎰 JlJ ju SSUS 載ttTsli sfase: ©(s 画} 1 〜〇 I蛾—: ◎ (I 州緯 boaoT®®: χ o&0§_:◎(£ w f - ^ ^ 00^ - X TKI®U猶鬆_北觀蒎〆 #s sdoo.Iq^s&s 藝親·讓CSI.pge : v〇画01 〜9 讓5議：v〇 ϊ&ςΌ 1} s&ssm>i(ii籍CS!裝1,3¾ :〇画〒 5—i?〇 -118- 200804974 (116) 產業上的可利用性"" viscosity increase _ ◎ ◎ ◎ 〇 △ ◎ ◎ ◎ ◎ X ◎ X ◎ XXX ◎ foreign matter & ◎ ◎ ◎ ◎ 〇〇〇 △ X ◎ X ◎ X ◎ X ◎ X adhesion amount ◎ ◎ ◎ ◎ 〇〇〇X ◎ X ◎ X ◎ X ◎ X PM-21 ο ο 0 ο ο 0 ο 0 ο ο o ο 0 ο 1—Η << Dispersant I^L m & m CO m Grade 3 amine grade 3 Amine CO m followed by 3-grade amine CO s CO s cn mm 继 ΓΠ ΓΠ ΓΠ ΓΠ ΓΠ ΓΠ ΓΠ ΓΠ ΓΠ ΓΠ ΓΠ ΓΠ ΓΠ ΓΠ 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = ! t+H C4-H S Ϊ8 1 ίί <R 8000 8000 1800 8000 8000 20000 8000 8000 8000 8000 8000 1800 1800 8000 8000 8000 cd CD cd 〇cd T3 <L> CD 〇〇3 ci moisture (wt %) 〇〇oo 0 00 0 〇〇in oo CD 〇〇〇CO csi 〇4 m c5 r<i CO c5 CO CN* 0 CO 〇1 Example 1 CN1 n CO s Λ u VO Λ r- 1— 镒Λλ <N 镒JJJ λλ 1 Comparative Example 3 Inch 镒ΛΛ in 镒J_J VO 镒ΛΑ Bu 镒〇〇镒λλ os 镒JlJ ju SSUS ttTsli sfase: ©(s 画} 1 〇I Moth——: ◎ (I State waboT®®: χ o&0§_:◎(£ wf - ^ ^ 00^ - X TKI®U 依松_北观蒎〆#s sdoo.Iq^s&s 艺亲·让CSI.pge : v〇画01 ～9 Let 5: v〇ϊ&ςΌ 1 } s&ssm>i(ii CS! Installed 1,33⁄4: 〇画〒 5—i?〇-118- 200804974 (116) Industrial availability

依據本發明，可提供較少發生凝聚異物、具有優異的保存安定性之硬化性組成物，以及藉由使用如此的硬化性組成物，可提供較少發生因爲剝離片異物所造成的缺陷且高品質的彩色濾光片、及液晶顯示裝置。所以，在成爲畫素或黑色矩陣等的材料之各種硬化性組成物、彩色濾光片、及液晶顯示裝置的領域，產業上的可利用性極高。再者，本發明引用2006年3月1 0日申請的日本特許出願2006-066107號的說明書、專利申請範圍、圖面及摘要的全部內容，放入本發明中作爲本發明的說明書的揭示內容。【圖式簡單說明】 [圖1 ]表示附著物被形成之玻璃試驗片的照片。 [圖2]表示附著物被形成之玻璃試驗片的一稜線上的部份的放大照片。 [圖3]表示附著物被形成之玻璃試驗片的模式圖。【主要元件對照表】 1 :玻璃試驗片 2 :附著物 3 :硬化性組成物的塗膜 4 :稜線 -119-According to the present invention, it is possible to provide a hardenable composition which is less likely to cause agglomerated foreign matter, has excellent storage stability, and by using such a hardenable composition, it is possible to provide a defect which is less caused by foreign matter peeling off the sheet and is high. Quality color filters and liquid crystal display devices. Therefore, in the field of various curable compositions, color filters, and liquid crystal display devices which are materials such as pixels or black matrices, industrial availability is extremely high. In addition, the present invention is incorporated by reference to the entire contents of the specification, the patent application, the drawings and the abstract of the Japanese Patent Application No. 2006-066107, filed on Jan. . BRIEF DESCRIPTION OF THE DRAWINGS [Fig. 1] A photograph showing a glass test piece in which an attached matter is formed. Fig. 2 is an enlarged photograph showing a portion on a ridge line of a glass test piece in which an attached matter is formed. Fig. 3 is a schematic view showing a glass test piece in which an attached matter is formed. [Main component comparison table] 1 : Glass test piece 2 : Attachment 3 : Coating film of hardenable composition 4 : ridge line -119-

Claims

200804974 (1) 十、申請專利範圍200804974 (1) X. Application for patent scope

1· 一種硬化物組成物，係含有（A)黏合劑樹脂、（B)單體、（C)溶劑及（D)顏料之硬化性組成物，其特徵爲該硬化性組成物的水分含量爲0.4重量％以上2.0重量％以下，於下述（1)〜（4)的步驟所成的塗佈適性評估方法（I)中，被形成於玻璃試驗片的一稜線上的附著物（a)爲2 Mg以下，而且將該硬化性組成物在常壓下以3 5 °C保存2週時的黏度上升爲l.Ocps以下； [塗佈適性評估方法（I)] (1) 在氣體環境溫度23°C，將長度lOOmmx寬度5mmx 厚度0.7mm的玻璃試驗片的縱方向的前端部份20mm，以 12.5mm/秒的速度浸漬於硬化物組成物中，然後維持4秒之步驟 (2) 將該玻璃試驗片，以12.5mm/秒的速度從硬化性組成物取出，將該玻璃試驗片的前端往下保持垂直後，在氣體環境溫度23°C、濕度55%、風速0.5±0.2m/秒的條件下使其乾燥52秒之步驟 (3) 重複步驟（1)及（2)合計25 0次，該玻璃試驗片上形成源自硬化性組成物的附著物之步驟 (4) 該玻璃試驗片的4棱線中，選擇該附著物量最多的稜線之步驟（再者，被選擇的稜線上的附著物被稱爲「附著物（a)」）。 2 ·如申請專利範圍第1項之硬化性組成物，其係未含有磷酸丙烯酸酯，或該磷酸丙烯酸酯的含量在硬化性組 -120- 200804974 (2) 成物的總固形份中爲5重量％以下。 3.如申請專利範圍第1或2項之硬化性組成物，其係再含有（E)分散劑。 4 ·如申請專利範圍第3項之硬化性組成物，其係含有（E-1):含有氮原子之接枝共聚物、（E-2):含有氮原子之丙烯酸系嵌段共聚物、及（E-3):尿烷系分散劑所成群中選出的至少1種以上作爲（E)分散劑。A cured composition comprising (A) a binder resin, (B) a monomer, (C) a solvent, and (D) a curable composition of the pigment, wherein the curable composition has a moisture content of 0.4% by weight or more and 2.0% by weight or less, in the coating suitability evaluation method (I) obtained in the following steps (1) to (4), the deposit (a) formed on the ridge line of the glass test piece When it is 2 Mg or less, and the viscosity of the curable composition is kept at 35 ° C for 2 weeks under normal pressure, the viscosity is increased to 1.0 cp or less; [Applicability evaluation method (I)] (1) In a gaseous environment At a temperature of 23 ° C, a longitudinal end portion of a glass test piece having a length of 100 mm x a width of 5 mm x a thickness of 0.7 mm was immersed in the cured composition at a rate of 12.5 mm/sec, and then maintained for 4 seconds (2). The glass test piece was taken out from the curable composition at a rate of 12.5 mm/sec, and the front end of the glass test piece was kept vertical, and the gas atmosphere temperature was 23 ° C, the humidity was 55%, and the wind speed was 0.5 ± 0.2 m. Step of drying for 52 seconds under conditions of /second (3) Repeat steps (1) and (2) for a total of 25 times, the glass Step (4) of forming a deposit derived from the curable composition on the test piece (4) The step of selecting the ridge line having the largest amount of attached matter among the four ridge lines of the glass test piece (again, the attached matter on the selected ridge line is called It is "attachment (a)"). 2) The curable composition of claim 1 which does not contain phosphoric acid acrylate, or the content of the phosphoric acid acrylate is 5 in the total solid content of the curable group -120-200804974 (2) Below weight%. 3. The curable composition according to claim 1 or 2, which further comprises (E) a dispersing agent. 4. The curable composition according to item 3 of the patent application, which comprises (E-1): a graft copolymer containing a nitrogen atom, (E-2): an acrylic block copolymer containing a nitrogen atom, And (E-3): at least 1 or more selected from the group of urethane-type dispersing agents as (E) dispersing agent.

5·如申請專利範圍第3或4項之硬化性組成物，其係含有於吸附部上具有未離子化的氮原子之分散劑作爲（E) 分散劑。 6. 如申請專利範圍第1至5項中任一項之硬化性組成物，其係含有二醇烷基醚乙酸酯類作爲（C)溶劑。 7. 如申請專利範圍第6項之硬化性組成物，其係含有沸點150°C以上的溶劑作爲（C)溶劑。 8. 如申請專利範圍第1至7項中任一項之硬化性組成物，其係含有由（A-1)〜（A-5)所選出的至少1種作爲（A) 黏合劑樹脂； (A-1):對含環氧基之（甲基）丙烯酸酯、與其他的自由基聚合性單體之共聚物，於該共聚物所具有的環氧基的至少一部份上加成不飽和一元酸，再於藉由該加成反應所產生的羥基的至少一部份上加成多元酸後所得到的鹼可溶性樹脂 (A-2):含羧基之樹脂 (A-3):於該（A-2)樹脂的羧基部份上’加成含有環氧 -121 - 200804974 (3) 基之不飽和化合物之樹月旨 (A-4):丙烯酸系樹脂 (A-5):具有羧基之環氧基丙烯酸酯樹脂 9.如申請專利範圍第〗至8項中任一項之硬化性組成物，其係擠壓式塗佈法用。 1 〇. —種彩色濾光片，其特徵係使用申請專利範圍第 1至8項中任一項之硬化性組成物所形成。5. The curable composition according to claim 3 or 4, which comprises a dispersing agent having an unionized nitrogen atom on the adsorption portion as (E) a dispersing agent. 6. The curable composition according to any one of claims 1 to 5, which comprises a glycol alkyl ether acetate as the solvent (C). 7. The curable composition of claim 6 which contains a solvent having a boiling point of 150 ° C or more as the solvent (C). 8. The curable composition according to any one of claims 1 to 7, which contains at least one selected from (A-1) to (A-5) as (A) binder resin; (A-1): a copolymer of an epoxy group-containing (meth) acrylate and another radical polymerizable monomer, which is added to at least a part of an epoxy group of the copolymer An alkali-soluble resin (A-2) obtained by adding a polybasic acid to at least a portion of a hydroxyl group produced by the addition reaction, an unsaturated monobasic acid: a carboxyl group-containing resin (A-3): Adding an epoxy group containing an epoxy-121 - 200804974 (3) group to the carboxyl group of the (A-2) resin (A-4): Acrylic resin (A-5): The epoxy group acrylate resin having a carboxyl group. The hardenable composition according to any one of the above claims, which is an extrusion coating method. A color filter characterized in that it is formed using the curable composition of any one of claims 1 to 8.

圍範利專請申。用成使形係所徵物特成其組，性置化裝硬示之顯項晶| 液任種中一項 8 11至 11 第 -122- 200804974 七、（一）、本案指定代表圖為：第（3)圖 (二）、本代表圖之元件代表符號簡單說明： 1 :玻璃試驗片 2 :附著物 3:硬化性組成物的塗膜 4 :稜線Wei Fanli invited for the application. The object of the formation is made into a group, and the character is placed in the shape of the crystal. The liquid is one of the items 8 11 to 11 -122- 200804974 VII. (1) The representative representative of the case is: (3) Figure (2), the representative symbol of the representative figure is a simple description: 1 : Glass test piece 2: Attachment 3: Coating film of the hardening composition 4: ridge line

八、本案若有化學式時，請揭示最能顯示發明特徵的化學式：無8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: none

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