TW201213336A - Colored curable composition, fabricating method of color filter, color filter, solid state imaging device, and liquid crystal display apparatus - Google Patents
Colored curable composition, fabricating method of color filter, color filter, solid state imaging device, and liquid crystal display apparatus Download PDFInfo
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201213336 J/ 六、發明說明: 【發明所屬之技術領域】 本發明是有關於一種著色硬化性組成物、彩色濾光片 的製造方法、彩色濾光片、及具有該彩色濾光片之固體攝 影元件、液晶顯示裝置。 【先前技術】 作為製作液晶顯示裝置(LCD等)或固體攝影元件 (CCD、CMOS等)中所使用之彩色濾光片的方法,廣泛 已知有顏料分散法。 顏料分散法是使用使顏料分散於各種感光性組成物中 而成的著色感光性組成物,藉由光微影法而製作彩色濾光 片的方法。其藉由光微影法而進行圖案化,因此是適於位 置精度尚地製作大畫面、高精細之彩色濾光片的方法。於 藉由顏料分散法而製作彩色濾光片之情形時,藉由旋轉式 塗佈機或輥塗機等將感光性組成物塗佈於玻璃基板上而形 成塗膜,對s亥塗膜進行圖案曝光、顯影,藉此而形成著色 晝素,對每種顏色重複進行該操作,藉此而獲得彩色濾光 片0 作為使用顏料之著色感光性組成物,例如已知有日本 專利特開2謝_33616號公報中所記載之含有酞菁系顏料 之彩色濾光片用藍色著色組成物。 於設置使用顏料之彩色濾光片而製作液晶顯示裝置或 固體攝影元件等顯示元件之情形時,自提高對比度之方面 而吕,開始需求粒徑更微小之顏料。其原因在於:由於顏 4 201213336. J / /Z-Jpli 料所造成之光之散射、雙折射等,偏光軸會旋轉。若顏料 之微細化不充分,則由於顏料而造成光被散射、吸收,透 光率降低,對比度變低,另外圖案曝光時之硬化感光度降 低。 特別是於固體攝影元件用彩色濾光片中,近年來開始 期望更進一步之高精細化,因此存在如下之現狀:藉由先 刖所進行之顏料分散系,難以進一步提高解像度。亦即, 存在由於顏料之粗大粒子之影響而產生色斑等問題。因 此,顏料分散系並不適於如固體攝影元件這樣的要求畫素 尺寸為1.5 μιη〜3.0 μιη見方之微細圖案的用途中。 為了應對此種狀況,自先前便提出了使用染料代替顏 料之技術。然而,已知染料通常情況下與顏料相比而言耐 光性、耐熱性差,於彩色濾光片之性能方面成為問題。而 且,染料亦具有如下等問題:相對於感光性組成物之溶解 性低,於液狀製備物或塗佈膜之狀態下,經時穩定性低, 從而造成染料析出。 對於該些問題,提出了藉由併用包含二吡咯亞甲基系 化合物之染料與酞菁染料,可形成保存穩定性優異、耐光 性咼之彩色濾'光片的著色硬化性組成物(例如參照日本專 利特開2008-292970號公報)。 而且,亦已知有染料與顏料組合而成之著色硬化性組 成物(例如參照美國專利申請公開第2008/0171271號說明 書)。 如上所述’關於使用染料之著色硬化性組成物,雖然 201213336 J//zopu 所:i用之?料而獲得可形成财光性高之彩 古二’旦現狀疋為了彩色渡光片之更進一步之 冋精、,,田化或k高性能,期望該此效 【發明内容】 -欢果之更進步之&向。 圖索匕明疋鑒於上述而成者’其目的在於提供於 =形成中之顯影時間之依存性小,且可形成耐光性高的 者色硬化膜的著色硬化性組成物,達成該目的成為第i課 題0 而且’其目的在於提供耐紐優異之純據光片與該 彩色濾、光片的製造方法、及具有鄉色濾光片之固體攝影 元件、液晶顯示裝置,達成該目的成為第2課題。 用以達成所述課題之具體手段如下所述。 < 1〉一種者色硬化性組成物,其至少包含:(Α_ι ) 包含下述通式(I)所表示之化合物與金屬原子或金屬化合 物的錯合物、(A-2)酞菁系顏料、(B)分散劑、(c)選自 下述通式(MO-1)〜通式(MO-5)所表示之聚合性化合 物的至少1種化合物、(D)光聚合起始劑、及(E)有機 溶劑; 6 201213336 [化l]201213336 J/6. OBJECTS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a color hardening composition, a method of manufacturing a color filter, a color filter, and solid photography having the color filter Component, liquid crystal display device. [Prior Art] As a method of producing a color filter used in a liquid crystal display device (LCD or the like) or a solid-state imaging device (CCD, CMOS, etc.), a pigment dispersion method is widely known. The pigment dispersion method is a method of producing a color filter by photolithography using a colored photosensitive composition obtained by dispersing a pigment in various photosensitive compositions. Since it is patterned by the photolithography method, it is a method for producing a large-screen, high-definition color filter suitable for positional accuracy. When a color filter is produced by a pigment dispersion method, a photosensitive composition is applied onto a glass substrate by a spin coater or a roll coater to form a coating film, and the coating film is formed. The pattern is exposed and developed, whereby the coloring elements are formed, and the operation is repeated for each color, whereby the color filter 0 is obtained as a coloring photosensitive composition using a pigment, for example, Japanese Patent Laid-Open No. 2 is known. A blue coloring composition for a color filter containing a phthalocyanine-based pigment described in Japanese Laid-Open Patent Publication No. Hei No. 33-16. When a color filter using a pigment is used to produce a display element such as a liquid crystal display device or a solid-state imaging device, since the contrast is improved, a pigment having a smaller particle size is required. The reason for this is that the polarization axis rotates due to the scattering of light, birefringence, etc. caused by the color of the film 20121336. J / /Z-Jpli. When the pigment is insufficiently refined, light is scattered and absorbed by the pigment, the light transmittance is lowered, the contrast is lowered, and the hardening sensitivity at the time of pattern exposure is lowered. In particular, in color filters for solid-state imaging devices, in recent years, further improvement in refinement has been desired. Therefore, there is a situation in which it is difficult to further improve the resolution by the pigment dispersion system performed by the prior art. That is, there are problems such as generation of color spots due to the influence of coarse particles of the pigment. Therefore, the pigment dispersion system is not suitable for applications such as solid-state imaging elements which require a fine pattern having a pixel size of 1.5 μm to 3.0 μm square. In order to cope with this situation, a technique of using a dye instead of a pigment has been proposed from the past. However, it is known that a dye is generally poor in light resistance and heat resistance as compared with a pigment, and is a problem in terms of performance of a color filter. Further, the dye has problems such as low solubility with respect to the photosensitive composition, low stability with time in the state of the liquid preparation or the coating film, and precipitation of the dye. In order to solve these problems, it is proposed to form a color-curable composition of a color filter 'light sheet having excellent storage stability and light resistance by using a dye containing a dipyrromethene-based compound and a phthalocyanine dye in combination (for example, Japanese Patent Laid-Open Publication No. 2008-292970). Further, a color hardening composition in which a dye and a pigment are combined is also known (for example, refer to the specification of U.S. Patent Application Publication No. 2008/0171271). As described above, 'the color-hardening composition for dyes, although 201213336 J//zopu: i used it, it can be used to form a high-growth color. Further 冋 、,,, 田化 or k high performance, it is expected that this effect [invention] - the fruit of the more progressive & In view of the above-mentioned composition, the object of the present invention is to provide a color-curable composition which is small in the development time in the formation of the film, and which can form a color-curable film having high light resistance. i Question 0 and 'The purpose is to provide a pure light film excellent in Nike, a method for producing the color filter, a light film, a solid-state imaging device having a color filter, and a liquid crystal display device, and the object is the second Question. The specific means for achieving the problem are as follows. < 1> A color curable composition comprising at least (Α_ι) a complex comprising a compound represented by the following formula (I) and a metal atom or a metal compound, and (A-2) a phthalocyanine system a pigment, (B) a dispersing agent, (c) at least one compound selected from the group consisting of a polymerizable compound represented by the following formula (MO-1) to (MO-5), and (D) a photopolymerization initiator And (E) organic solvents; 6 201213336 [Chemical]
[於通式(I)中,R1〜R6個別獨立地表示氫原子或取 代基;R7表示氫原子、鹵素原子、烷基、芳基、或雜環基; 其中,R1與R6並不相互鍵結而形成環]; 7 201213336 j / /z^pif [化2] CHz-fT^-R RfT^CH2-C-CH2-fT^R (HO-1) CHz-fT-tR CH2-fT-^R 严2俳 R-f%GH2-C~CH2-Z-CH2—C-CH2fT^-R (MO-2)[In the formula (I), R1 to R6 each independently represent a hydrogen atom or a substituent; and R7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; wherein R1 and R6 are not bonded to each other; Junction to form a ring]; 7 201213336 j / /z^pif [Chemical 2] CHz-fT^-R RfT^CH2-C-CH2-fT^R (HO-1) CHz-fT-tR CH2-fT-^ R 严2俳Rf%GH2-C~CH2-Z-CH2—C-CH2fT^-R (MO-2)
CH2fT^-R CH2-(-T^R R-fT)frCH2^C-CH2 -〇-CH2—C-CH2-(-T-^-R ίΜ0_3>CH2fT^-R CH2-(-T^R R-fT)frCH2^C-CH2 -〇-CH2-C-CH2-(-T-^-R ίΜ0_3>
R~fT七 CH2 \:H2+T^RR~fT7 CH2 \:H2+T^R
CH2^R R~fTfnCH2-N CH2^R (HO-5) ch2|t^r 〇γΝγ〇 (MO-4) R~fT七CH2’N 丫问、〇12~(?·)^ [化3] ch3 I J R: C-0 — Η2〇β0ΐ — G-0— 1L » 1 -0-C-fCH,V-C-0H -0-C-NH-fCH,t-C-0H ώ , 6 ’CH2^RR~fTfnCH2-N CH2^R (HO-5) ch2|t^r 〇γΝγ〇(MO-4) R~fT七CH2'N 丫,〇12~(?·)^ [化3] Ch3 IJR: C-0 — Η2〇β0ΐ — G-0— 1L » 1 -0-C-fCH, VC-0H -0-C-NH-fCH, tC-0H ώ , 6 '
-OH T: -fCH2^- -OCHj~ , -OCH2CH2- , -OCH2CH2CH2- , -〇CH2CH2CH2CH2- 於通式(MO-1)〜通式(MO-5)中,n為0〜14之 整數,m 1〜ni4為1〜8之整數;同一分子内多個存在之R 及T可個別相同亦可不同; 8 201213336 )/ /zjpii 於通式(MO-1)〜通式(MO-5)所表示之聚合性化 合物之各個中’多個存在之R中的至少1個表示-〇C( = 〇)CH=CH2、或-0C( = 0)C(CH3) = CH2 ;於通式(MO-2) 中’ Z為-Ο-之情形時’ n為1以上或者R為_〇c( = 〇)CH = CH2以外之基。 <2>如<1>所述之著色硬化性組成物,其中,所 述(c)聚合性化合物是所述通式(M〇_2)所表示之化合 物,且該通式(MO-2)中所存在之至少一個R是如下所 示之任意基; [化4]-OH T: -fCH2^- -OCHj~ , -OCH2CH2-, -OCH2CH2CH2-, -〇CH2CH2CH2CH2- in the formula (MO-1) to formula (MO-5), n is an integer from 0 to 14, m 1 to ni4 are integers of 1 to 8; a plurality of R and T existing in the same molecule may be the same or different; 8 201213336 ) / /zjpii in the formula (MO-1) to (MO-5) At least one of the plurality of R present in each of the polymerizable compounds represented represents -〇C(= 〇)CH=CH2, or -0C(=0)C(CH3)=CH2; In the case of 'Z is -Ο- in 'MO-2) 'n is 1 or more or R is _〇c( = 〇)CH = CH2. The colored hardening composition according to the above-mentioned item (1), wherein the (c) polymerizable compound is a compound represented by the above formula (M〇_2), and the formula (MO) At least one R present in -2) is an arbitrary base as shown below; [Chemical 4]
-o-c4ph2]-g-oh Ο 〇 於上述基中’ ml及m2個別為1〜8之整數。 <3>如<1>或<2>所述之著色硬化性組成物,其 中,所述(D)光聚合起始劑是肟系化合物。 <4>如<1>〜<3>中任—項所述之著色硬化性 組成物,其中,所述(A_l)包含通式(1)所表示之化合 物與金屬原子或金屬化合物的錯合物是下述通式(ΙΜ) 所表示之化合物; 201213336 [化5]-o-c4ph2]-g-oh Ο ’ In the above base, 'ml and m2 are each an integer of 1 to 8. The colored curing composition according to <1> or <2>, wherein the (D) photopolymerization initiator is an anthraquinone compound. The colored hardening composition according to any one of the above-mentioned items, wherein the (A-1) comprises a compound represented by the formula (1) and a metal atom or a metal compound. The complex is a compound represented by the following formula (ΙΜ); 201213336 [Chemical 5]
[於通式(II-1)中,R1〜R6個別獨立地表示氫原子或 取代基;R7表示氩原子、鹵素原子、烷基、芳基、或雜環 基;Ma表示金屬原子或金屬化合物,X2表示中和Ma之 電荷所必須之基,X1表示可鍵結於Ma上之基;另外,X1 與X2亦可相互鍵結而形成5員、6員、或7員之環;其中, R1與R6並不相互鍵結而形成環]。 <5>如<1>〜<3>中任一項所述之著色硬化性 組成物,其中,所述(A-1)包含通式(I)所表示之化合 物與金屬原子或金屬化合物的錯合物是下述通式(Π-2) 所表示之化合物; 201213336 J / / L/ii.[In the formula (II-1), R1 to R6 each independently represent a hydrogen atom or a substituent; R7 represents an argon atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group; and Ma represents a metal atom or a metal compound. X2 denotes a base necessary for neutralizing the charge of Ma, and X1 denotes a group which can be bonded to Ma; in addition, X1 and X2 may be bonded to each other to form a ring of 5 members, 6 members, or 7 members; R1 and R6 are not bonded to each other to form a ring]. The colored hardening composition according to any one of the above-mentioned, wherein the (A-1) comprises a compound represented by the formula (I) and a metal atom or The complex of the metal compound is a compound represented by the following formula (Π-2); 201213336 J / / L/ii.
[於通式(II-2)中,R1〜R6及R8〜R13個別獨立地表 示氫原子或取代基;R7及R14個別獨立地表示氫原子、鹵 素原子、烷基、芳基、或雜環基;Ma表示金屬原子或金 屬化合物;其中,R1與R8或R13、及R6與R8或R13並不 個別相互鍵結而形成環]。 <6>如<1>〜<3>中任一項所述之著色硬化性 組成物,其中,所述(A-1)包含通式(I)所表示之化合 物與金屬原子或金屬化合物的錯合物是下述通式(III)所 表示之化合物; 11 201213336 J / /Δ〇ρ\[ [化η[In the formula (II-2), R1 to R6 and R8 to R13 each independently represent a hydrogen atom or a substituent; and R7 and R14 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic ring. a group; a metal atom or a metal compound; wherein R1 and R8 or R13, and R6 and R8 or R13 are not bonded to each other to form a ring]. The colored hardening composition according to any one of the above-mentioned items, wherein the (A-1) comprises a compound represented by the formula (I) and a metal atom or The complex of the metal compound is a compound represented by the following formula (III); 11 201213336 J / /Δ〇ρ\[ [化
[於通式(III)中,R2〜R5個別獨立地表示氫原子或 取代基;R7表示氫原子、鹵素原子、烷基、芳基、或雜環 ,;Ma表示金屬原子或金屬化合物,X3表示NR (R表示 氫原子、烷基、烯基、芳基、雜環基、醯基、烷基磺醯基、 芳基磺醯基)、氮原子、氧原子、或硫原子,X4表示NRa (Ra表示氫原子、烷基、烯基、芳基、雜環基、醢基、烷 基續酿基、或芳基磺醯基)、氧原子、或硫原子,γι表示 NRc (Rc表示氫原子、烷基、烯基、芳基、雜環基、醯基、 貌基磺醯基 '或芳基磺醯基;)、氮原子、或碳原子,Y2表 =氮原子或碳原子,R8及R9個別獨立地表示烷基、烯基、 芳基、雜環基、烷氧基、芳氧基、烷基胺基、芳基胺基、 或雜環胺基;R8與γΐ亦可相互鍵結而形成5員、6員、或 7員之環,R9與γ2亦可相互鍵結而形成5員、6員、或7 員之環;X5表示可與Ma鍵結之基,a表系0、1、或2]。 <7>如<1>〜<3>中任一項所述之著色硬化性 12 201213336 J / / 厶 組成物,其中,所述金屬原子或金屬化合物是Fe、Zn、Co、 v = 0、及Cu之任意者。 <8>如<ι>〜<3>中任一項戶斤述之著色硬化性 組成物,其中’所述通式(I)中之以及〆個別為苯基。 <9> 一種彩色濾光片的製造方法,其具有: 步驟(A),於支撐體上塗佈如<1:>〜<8>中任一項 所述之著色硬化性組成物而形成著色硬化性組成物層; 步驟(B) ’介隔遮罩對該步驟(A)中所形成之著色 硬化性組成物層進行曝光後,進行顯影而形成著色圖案。 <1〇>如<9>所述之彩色濾光片的製造方法,其 具有: 、 射紫3⑹’糾所述步驟(B)所形成之著色圖案照 步驟⑼,對在該步驟(c)中被照射了紫外線 色圖案進行加熱處理。 、十、一種彩色濾光片’其藉由如<9>或<10>所 攻之彩色濾光片的製造方法而製造。 色據—種固體攝影元件’其具有如<11:>所述之彩 色遽=一種液晶顯示裝置,其具有如<u>所述之彩 [發明的效果] 藉由本發明,可提供於圖案形成中之顯影時間之依存 、’且可形成财光性高的著色硬化_著色硬化性組成 13 201213336 物。 藉由本發明,可提供耐光性優異之彩色濾光片與該彩 色濾光片的製造方法、及具有該彩色濾光片之固體攝影元 件、液晶顯示裝置。 【實施方式】 《著色硬化性組成物》 首先’對本發明之著色硬化性組成物加以說明。 本發明之著色硬化性組成物是至少包括包含 下述通式⑴所表示之化合物與金屬原子或金屬化合物的 錯合物、(A-2)酞菁系顏料、(B)分散劑、(c)選自下述 通式(MCM)〜通式(m〇_5)所表示之聚合性化合物的 =1種化合物、(D)光聚合起始劑、及⑻有 的者色硬化性組成物。 & =,對(A_1)、(a_2)、(b)、(c)、(d)KE) 之各成分加以說明。 金屬所表示之化合物與金屬原子或 切tr之著色硬化性組成物含有⑷)包含下述通 合物與金屬原子或金屬化合物的錯合物 錯合物」)作為著色劑之-。特定錯 :物通常μ脫質子化之狀態下包含通式⑴所表示之化合 •二吡咯亞甲基系化合物_ 首先,對構成特定錯合物之通式⑴所表示之化合物 201213336 ^ · φ mm αλ. 加以說明。 [化8][In the formula (III), R2 to R5 each independently represent a hydrogen atom or a substituent; R7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic ring; and Ma represents a metal atom or a metal compound, X3 Represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, an arylsulfonyl group), a nitrogen atom, an oxygen atom, or a sulfur atom, and X4 represents NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur atom, and γι denotes NRc (Rc represents hydrogen Atom, alkyl, alkenyl, aryl, heterocyclic, fluorenyl, fluorenyl sulfonyl or arylsulfonyl;), nitrogen atom, or carbon atom, Y2 table = nitrogen atom or carbon atom, R8 And R9 each independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group, or a heterocyclic amine group; R8 and γΐ may also be bonded to each other; Forming a ring of 5 members, 6 members, or 7 members, R9 and γ2 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members; X5 indicates a base that can be bonded to Ma, a form 0, 1, 2]. The colored hardening 12 201213336 J / / 厶 composition according to any one of <1>, wherein the metal atom or metal compound is Fe, Zn, Co, v. = 0, and any of Cu. <8> The colored hardening composition according to any one of <1>, wherein the oxime in the above formula (I) is phenyl. <9> A method of producing a color filter, comprising: step (A), applying a color hardening composition according to any one of <1:> to <8> The colored curable composition layer is formed as a material; Step (B) 'The mask is exposed to the colored curable composition layer formed in the step (A), and then developed to form a colored pattern. The method for producing a color filter according to <9>, comprising: a coloring pattern formed by the step (B) of the photographic purple (3) step (B), and the step (9), in the step (c) is irradiated with an ultraviolet color pattern for heat treatment. And a color filter 'made by a method of producing a color filter as taught in <9> or <10>. A solid-state photographic element having a color 遽 as described in <11:>=a liquid crystal display device having a color as described in <u> [Effects of the Invention] Provided by the present invention Dependence on the development time in pattern formation, and can form a color hardening _ color hardening composition 13 201213336. According to the present invention, it is possible to provide a color filter excellent in light resistance, a method for producing the color filter, a solid-state imaging device having the color filter, and a liquid crystal display device. [Embodiment] "Coloring curable composition" First, the coloring composition of the present invention will be described. The color hardening composition of the present invention includes at least a complex comprising a compound represented by the following formula (1) and a metal atom or a metal compound, (A-2) a phthalocyanine-based pigment, (B) a dispersing agent, (c) a compound selected from the group consisting of a polymerizable compound represented by the following general formula (MCM) to (m〇_5), (D) a photopolymerization initiator, and (8) a color curable composition . & =, the components of (A_1), (a_2), (b), (c), (d) KE) will be described. The color-curable composition of the compound represented by the metal and the metal atom or the tantr contains (4) a complex compound containing the following compound and a metal atom or a metal compound as a colorant. Specific error: a compound containing a compound represented by the formula (1) and a dipyrromethene-based compound in a state in which the substance is usually deprotonated. First, a compound represented by the formula (1) constituting a specific complex compound 201213336 ^ · φ mm Λλ. Explain. [化8]
於上述通式(I)中,R1〜R6個別獨立地表示氫原子或 取代基。R7表示氫原子、鹵素原子、烷基、芳基、或雜環 基。其中,R1與R6並不相互鍵結而形成環。 衣 於通式(I)中,R1〜R6所表示之取代基可列舉如下所 示之1價基(以下有時將所列舉之一價基之群組總稱為「取 我基R 11。 —,ν ·軋屌卞、氧ν 原子)、絲(較佳為魏〗〜48之錢、分支鏈 之烧基,更佳的是碳數丨〜24之直鏈、分 = 炫基’例如:f基、乙基、丙基、異丙基、丁基次= f、=、己基、庚基、辛基、2_乙基己基、 十六烷基、環丙基、環戊基、環 1 燒基)、婦基(較佳為碳數2〜48之·,=,金剛 〜18之稀基,例如:乙烯A、=:基询是碳數2 使乙炸基歸丙基、3·丁婦小其、名In the above formula (I), R1 to R6 each independently represent a hydrogen atom or a substituent. R7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Wherein R1 and R6 are not bonded to each other to form a ring. In the general formula (I), the substituent represented by R1 to R6 may be exemplified by a monovalent group shown below (hereinafter, a group of one of the valence groups listed may be collectively referred to as "the base R 11". , ν · rolling 氧, oxygen ν atom), silk (preferably Wei 〗 〖48 money, branched chain burning base, more preferably carbon number 丨 ~ 24 linear, sub = 炫 base ' For example: f group, ethyl, propyl, isopropyl, butyl = f, =, hexyl, heptyl, octyl, 2-ethylhexyl, hexadecyl, cyclopropyl, cyclopentyl, ring 1 Burning base), base (preferably carbon number 2 to 48, =, diamond ~ 18 thin base, for example: ethylene A, =: basic query is carbon number 2 to make the B-based propyl, 3 · Ding Xiaoxiao, name
基(較佳為碳數6〜48之芳基,更佳的是碳數6〜^)之J 15 201213336 =二歹’ 口 .苯基、萘基)、雜環基(較佳為碳數N32之雜 %土’更佳的是碳數卜18之雜環基例如· 2_嗟吩基、 4_°比°定基、2·°夫喃基、2♦定基、1«基、2_苯并射基、 L t坐ί'苯并三唾·1-基)、石夕烧基(較佳為碳 一〜之矽烷基’更佳的是碳數3〜18之矽烷基,例如: :甲基魏基、三乙基魏基、三丁基魏基、第三丁基 二甲基魏基、第三己基二甲基魏基)、絲、氰基、硝 基烧氧基(車父佳為碳數卜48之烧氧基更佳的是碳數 1〜24之烷氧基’例如:甲氧基、乙氧基、1-丁氧基、2_ 丁氧基、異丙氧基、第三丁氧基、十二烧氧基;而且,若 為環烧氧基,則例如:環戊氧基、環己氧基)、芳氧基(較 佳為碳數6〜48之芳氧基,更佳的是碳數6〜24之芳氧基, 例如.苯氧基、1_萘氧基)、雜環氧基(較佳為碳數1〜32 =雜環氧基,更佳的是碳數丨〜18之雜環氧基,例如:^ 苯基四唑-5-氧基、2-四氫吼喃基氧基)、矽烷氧基(較佳 為碳數1〜32之矽烷氧基,更佳的是碳數丨〜18之矽烷氧 基’例如.二曱基矽院基氧基、第三丁基二甲基矽烧氧基、 二笨基甲基矽烷氧基)、醯氧基(較佳為碳數2〜48之醯氧 基,更佳的是碳數2〜24之醯氧基,例如:乙醯氧基、特 戊醯氧基、苯甲醯氧基、十二醯氧基)、烷氧基羰氧基(較 佳為碳數2〜48之烧氧基羰氧基,更佳的是碳數2〜24之 燒氧基綠氧基,例如:乙氧基幾氧基、第三丁氧基幾氧基; 而且’若為環烧氧基羰氧基,則例如:環己基氧基羰氧基)、 芳氧基羰氧基(較佳為碳數7〜32之芳氧基羰氧基,更佳 201213336 j/ /ζ^ριι ί ίίίΓ24之芳氧絲氧基,例如:苯氧基幾氧基)、 女土—基(較佳為碳數1〜48之胺甲醯基氧基,上〇 好K < (i碳數卜24之胺甲酿基氧基,例如:n,n_ 二甲基胺甲酿基氧基、N_丁基胺甲醯基氧基、Ν·苯基胺甲 酿基氧基、Ν_乙基·Ν·苯基胺m基氧基)、胺顧基氧基 (較佳為碳數1〜32之胺顧基氧基,更㈣是碳數1〜 24之胺續醯基氧基,例如:N,N二乙基胺雜基氧基、n_ 丙基胺~醯基氧基)、烧基續g錄基(較佳為碳數卜% 之烧基續醯氧基,更佳的是碳數1〜24之絲續醯氧基, 例如—甲基%醯氧基、十六院基續醯氧基、環己基績醯氧 基)、芳基雜基氧基(難為碳數6〜32之芳基續醯基氧 ^佳的是碳數6〜24之芳基續酿基氧基,例如:苯基 %醯氧基)、醯基(較佳為碳數丨〜48之醯基’更佳的是碳 數1〜24之醯基’例如:甲醯基、乙酿基、特戊酿基、苯 甲酿基、十四醯基、環己醯基)、烧氧基Μ基(較佳為碳數 2〜48之錄基縣,更佳岐碳數2〜24之錄基幾基, 例如:甲氧基幾基、乙氧基縣、十八院氧基減、環己 ,氧基羰基、2,6-二-第三丁基_4_曱基環己基氧基縣)、 芳氧基幾基(較佳為碳數7〜32之芳氧基裁基,更佳的是 碳數7〜24之芳氧基幾基,例如:苯氧基叛基)、胺甲醯基 (較佳為碳數1〜48之胺甲醯基,更佳的是碳數丨〜24之 胺曱醯基’例如:胺曱酿基、N,N_二乙基胺曱醯基、队乙 基-N-辛基胺曱醯基、N,N_二丁基胺曱酿基、N_丙基胺甲醯 基、N-苯基胺曱酿基、N_曱基_N_苯基胺甲醯基、取-二 17 201213336 I I μ/Αχ 環己基胺甲醯基)、胺基(較佳為碳數32以下之胺基,更 佳的是碳數24以下之胺基,例如:胺基、曱基胺基、N,N_ 二丁基胺基、十四烷基胺基、2-乙基己基胺基、環已基胺 基)、苯胺基(較佳為碳數6〜32之苯胺基,更佳的是6〜 24之苯胺基,例如:苯胺基、N_曱基苯胺基)、雜環胺基 (較佳為碳數1〜32之雜環胺基’更佳的是1〜18之雜環 胺基,例如:4-吡啶基胺基)、羧醯胺基(較佳為碳數2〜 48之羧醯胺基,更佳的是2〜24之羧醯胺基,例如:乙醯 胺基、苯曱醯胺基、十四醯胺基、特戊醯基醯胺基、環己 醯胺基)、脲基(較佳為碳數1〜32之脲基,更佳的是碳數 1〜24之脲基,例如:脲基、Ν,Ν·二曱基脲基、N_苯基脲 基)、醯亞胺基(較佳為碳數36以下之醯亞胺基,更佳的 是碳數24以下之醢亞胺基,例如:N-玻珀酿亞胺基、N-鄰苯二甲醯亞胺基)、烷氧基羰基胺基(較佳為碳數2〜48 之烷氧基羰基胺基,更佳的是碳數2〜24之烷氧基羰基胺 基,例如:甲氧基羰基胺基、乙氧基羰基胺基、第三丁氧 羰基胺基、十八烷氧基羰基胺基、環己基氧基羰基胺基)、 芳氧基羰基胺基(較佳為碳數7〜32之芳氧基羰基胺基, 更佳的是碳數7〜24之芳氧基羰基胺基,例如:苯氧基羰 基胺基)、磺醯胺基(較佳為碳數1〜48之續醯胺基,更佳 的是碳數1〜24之磺醯胺基,例如:曱基磺醯胺基、丁基 磺醯胺基、苯基磺醯胺基、十六烷基磺醯胺基、環己基 項醯胺基)、胺續醯胺基(較佳為碳數1〜48之胺續醯 胺基,更佳的是碳數1〜24之胺磺醯胺基,例如:ν,Ν- 18 201213336 二丙基胺項醯胺基、N-乙基_N_十二烧基胺顧胺基)、偶 氮基(較佳為碳數1〜32之偶錄,更佳的是碳數卜24 之偶氮基,例h .笨基偶氮基、3_。比嗤基偶氮基)、烧硫基 (較佳為碳數1〜48之烷硫基,更佳的是碳數丨〜24之烷 硫基,例如:曱硫基、乙硫基、辛硫基、環己基硫基)、芳 硫基(較佳為碳數6〜48之芳硫基,更佳的是碳數6〜24 之芳硫基,例如:苯硫基)、雜環硫基(較佳為碳數丨〜32 之雜環硫基,更佳的是碳數1〜18之雜環硫基,例如:2_ 本并嗔嗤基硫基、2-°比°定基硫基、苯基四β坐基硫基)、烧 基亞磺醯基(較佳為碳數1〜32之烷基亞磺醯基,更佳的 是碳數1〜24之烷基亞磺醯基’例如:十二烷基亞磺醯 基)、务基亞橫酿基(較佳為碳數6〜32之芳基亞確酿基, 更佳的是碳數6〜24之芳基亞磺醯基,例如:苯基亞磺醯 基)、烧基續醯基(較佳為礙數1〜48之烧基確醢基,更佳 的是碳數1〜24之烷基磺醯基’例如:甲基確醯基、乙基 磺醯基、丙基磺醯基、丁基磺醯基、異丙基磺醯基、2_乙 基己基磺醯基、十六烷基磺醯基、辛基磺醯基、環己基磺 酿基)、芳基確醯基(較佳為碳數6〜48之芳基續酿基,更 佳的是碳數6〜24之芳基磺醯基,例如:苯基磺醯基、1-萘基續醯基)、胺績緣基(較佳為碳數32以下之胺績醯基, 更佳的是碳數24以卞之胺磺醯基’例如:胺磺醯基、Ν,Ν-二丙基胺磺醯基、Ν-匕基-Ν_十二烷基胺磺醯基、Ν-乙基-Ν-笨基胺磺醯基、Ν-環已基胺磺醯基)、磺基、膦醯基(較 佳為碳數1〜32之膦醯基’更佳的是碳數1〜24之膦醯基, 201213336 膦醯基、辛氧基膦醯基、苯基膦_)、膦醯 數卜32之氧胺基,更佳較碳數1〜 胺基)。-土,例如.二乙氧基膦醯胺基、二辛氧基膦醯 =上述之1價基是可被進—步取代之基之情形時亦 Γ上取=基ί任意基而進一步取代。另外,於具有2個 土之情形時,該些取代基可相同亦可不同。 於通式(I)中, ” 一亦可個卿立地相互_而形成5員、6員、或7員 二另二,作為所形成之環,存在有飽和環或不飽和環。 2.5Α 6員、或7員之飽和環或不飽和環,例如可 列舉。比略環、°夫俩”塞吩環吻坐環、μ環、三峻環、 ,嗤%、嗔唾環“比„各0定環、略咬環、環戊稀環、環己稀 環、細,樹列舉苯環、 、另外,於所形成之5員、6員、及7員之環是可進〆 步被取代之基之情形時,亦可被所述取代基R之任意基而 取代,於被2個以上取代基取代之情形時,該些取代基圩 相同亦可不同。 _ -金屬原子或金屬化合物_ 其次,對構成特定錯合物之金屬原子或金屬化合物妒 以說明。 作為此處所使用之金屬或金屬化合物,若為可形成鍺 合物之金屬原子或金屬化合物則可為任意種,包括2價食 201213336 屬原子、2價金屬氧化物、2價金屬氫氧化物、或2價金屬 氣化物。例如,除了 Zn、Mg、Si、Sn、Rh、Pt、Pd、Mo、 Mn、Pb、Cu、Ni、Co、Fe 等以外,亦包含 A1C1、Ina、a group (preferably an aryl group having 6 to 48 carbon atoms, more preferably a carbon number of 6 to 2) J 15 201213336 = dioxin, a phenyl group, a naphthyl group, a heterocyclic group (preferably a carbon number) N32 heterozygous soil is more preferably a heterocyclic group of carbon number 18, such as 2_nonyl, 4_° ratio, 2, °, and 2, benzene, 2, benzene, 2, benzene And the base group, L t sit ί 'benzo tris-l-l-yl), and the base group (preferably carbon mono- to decyl group) is more preferably a C 3 to 18 alkyl group, for example: Methylweiki, triethylweiyl, tributylweil, tert-butyldimethylpropyl, trihexyldimethylpropanyl), silk, cyano, nitro alkoxy More preferably, the alkoxy group of the carbon number 48 is an alkoxy group having a carbon number of 1 to 24, for example, a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, an isopropoxy group, a third butoxy group, a decyloxy group; and, if it is a cycloalkyloxy group, for example, a cyclopentyloxy group, a cyclohexyloxy group, an aryloxy group (preferably an aromatic oxygen having a carbon number of 6 to 48) More preferably, the aryloxy group having a carbon number of 6 to 24, for example, a phenoxy group, a 1-naphthyloxy group, or a heterocyclic oxy group (preferably a carbon number of 1) 32 = heterocyclic oxy group, more preferably a heterocyclic oxy group having a carbon number of 丨 18 or 18, for example: phenyltetrazolium-5-oxy, 2-tetrahydrofuranyloxy), decyloxy ( It is preferably a decyloxy group having a carbon number of from 1 to 32, more preferably a decyloxy group having a carbon number of 丨 18 or 18, for example, a fluorenyloxy group, a butyl dimethyl oxime alkoxy group, Diphenylmethyl alkoxy), anthracenyloxy (preferably a decyloxy group having a carbon number of from 2 to 48, more preferably a decyloxy group having a carbon number of from 2 to 24, for example, an ethoxy group, a pentylene group a decyloxy group, a benzhydryloxy group, a dodecyloxy group, an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having a carbon number of 2 to 48, more preferably a carbon number of 2 to 24) An alkoxy greenoxy group, for example: an ethoxyoxyoxy group, a third butoxyoxy group; and 'if a cycloalkyloxycarbonyloxy group, for example, a cyclohexyloxycarbonyloxy group, An oxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 201213336 j/ /ζ^ριι ί ί 24 an aryloxymethyloxy group, for example, a phenoxy oxy group), Female soil-based (preferably aminomethylamino group having a carbon number of 1 to 48, and a good K < (i-carbon number 24 of the amine-brenyloxy group, for example: n, n-dimethylamine-mercaptooxy, N-butylamine-mercaptooxy, oxime-phenylamine-methoxyloxy , Ν 乙基 乙基 乙基 苯基 苯基 苯基 苯基 苯基 胺 胺 胺 胺 胺 胺 胺 胺 胺 胺 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( Alkoxy group, for example, N,N diethylaminoheterooxy group, n-propylamine-fluorenyloxy group, calcinyl group (preferably carbon number More preferably, it is a fluorenyloxy group having a carbon number of from 1 to 24, for example, a methyl group, a decyloxy group, a hexanyl group, a fluorenyl group, a cyclyl group, and an aryl group. The aryl group which is difficult to have a carbon number of 6 to 32 is preferably an aryl group having a carbon number of 6 to 24, for example, a phenyl group of a methoxy group, and a fluorenyl group (preferably a carbon number 丨). 48 48 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' An alkoxy group (preferably a carbon number of 2 to 48 in the base of the record, more preferably a carbon number of 2 to 24, such as: methoxy group, ethoxy Ke County, 18th Institute oxyl reduction, cyclohexyl, oxycarbonyl, 2,6-di-t-butyl-4-indolylcyclohexyloxy county), aryloxy group (preferably carbon number) 7 to 32 of an aryloxy group, more preferably an aryloxy group having 7 to 24 carbon atoms, for example, a phenoxy group, an amine methyl group (preferably an amine having 1 to 48 carbon atoms) Mercapto, more preferably an amine fluorenyl group having a carbon number of 2424, for example: amine aryl, N,N-diethylamino fluorenyl, aceto-N-octylamine fluorenyl , N, N-dibutylamine oxime, N_propylamine carbhydryl, N-phenylamine oxime, N_mercapto_N_phenylamine formazan, take-two 17 201213336 II μ /Αχ cyclohexylamine methyl hydrazide), an amine group (preferably an amine group having a carbon number of 32 or less, more preferably an amine group having a carbon number of 24 or less, for example, an amine group, a mercaptoamine group, N, N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, cyclohexylamino group), anilino group (preferably an anilino group having a carbon number of 6 to 32, more preferably 6~) An anilino group of 24, for example, an anilino group, an N-mercaptoanilide group, or a heterocyclic amino group (preferably a heterocyclic amino group having a carbon number of 1 to 32) is more preferably 1 a heterocyclic amino group of 18, for example, a 4-pyridylamino group, a carboguanamine group (preferably a carboxamide group having a carbon number of 2 to 48, more preferably a carboxamide group of 2 to 24, for example : acetamino group, benzoguanamine group, tetradecylamino group, pentyl decylamino group, cyclohexylamino group), urea group (preferably a urea group having a carbon number of 1 to 32, more preferably Is a ureido group having a carbon number of 1 to 24, for example, a urea group, an anthracene, a fluorenyldithiourea group, an N-phenylureido group, or a quinone imine group (preferably a quinone imine having a carbon number of 36 or less) More preferably, the quinone imine group having a carbon number of 24 or less, for example, N-Boprene-based imine group, N-phthalimido group, or alkoxycarbonylamino group (preferably carbon) Alkoxycarbonylamino group of 2 to 48, more preferably an alkoxycarbonylamino group having 2 to 24 carbon atoms, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a third butoxycarbonyl group Amino, octadecyloxycarbonylamino, cyclohexyloxycarbonylamino), aryloxycarbonylamino (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably a carbon number) An aryloxycarbonylamino group of 7 to 24, for example, a phenoxycarbonylamino group, Amidino group (preferably a hydrazine group having a carbon number of 1 to 48, more preferably a sulfoniumamino group having a carbon number of 1 to 24, for example, a mercaptosulfonylamino group, a butylsulfonylamino group, a benzene group a sulfonamide, a hexadecylsulfonylamino group, a cyclohexylamine amide group, an amine hydrazide group (preferably an amine having a carbon number of 1 to 48, more preferably a carbon number) Aminosulfonylamino group of 1 to 24, for example: ν, Ν- 18 201213336 dipropylamine-non-amine amide group, N-ethyl-N-dodecanylamine amide group, azo group (preferably) It is an even number of carbon numbers of 1 to 32, more preferably an azo group of carbon number 24, for example, a phenyl group, 3_. More than a mercapto azo group, a sulfur-burning group (preferably an alkylthio group having a carbon number of 1 to 48, more preferably an alkylthio group having a carbon number of 2424, for example, anthracenylthio group, ethylthio group, octyl group) a thio group, a cyclohexylthio group, an arylthio group (preferably an arylthio group having 6 to 48 carbon atoms, more preferably an arylthio group having a carbon number of 6 to 24, for example, a phenylthio group) or a heterocyclic sulfur a base (preferably a heterocyclic thio group having a carbon number of 3232 to 32, more preferably a heterocyclic thio group having a carbon number of 1 to 18, for example, 2_ indenylthio group, 2-° ratio of alkylthio group , phenyltetra-β-ylthio), alkylsulfinyl (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably an alkylsulfinyl group having 1 to 24 carbon atoms) 'Example: dodecylsulfinyl), ketone kiln (preferably an aryl aryl group having a carbon number of 6 to 32, more preferably an aryl sulfene having a carbon number of 6 to 24) A mercapto group, for example, a phenylsulfinyl group, a decyl group (preferably a sulfhydryl group having a hindrance of 1 to 48, more preferably an alkylsulfonyl group having a carbon number of 1 to 24) For example: methyl thiol, ethyl sulfonyl, propyl sulfonyl, butyl sulfonyl, isopropyl sulfonyl, 2 - B More preferably, the hexylsulfonyl group, the hexylsulfonyl group, the octylsulfonyl group, the cyclohexylsulfonyl group, the aryl group (preferably the aryl group having a carbon number of 6 to 48), more preferably An arylsulfonyl group having 6 to 24 carbon atoms, for example, a phenylsulfonyl group, a 1-naphthyl fluorenyl group, and an amine base group (preferably an amine having a carbon number of 32 or less, more Preferred is an amine sulfonyl group having a carbon number of 24, for example: amidoxime, anthracene, fluorenyl-dipropylamine sulfonyl, fluorenyl-fluorenyl-hydrazine-dodecylamine sulfonyl, hydrazine -ethyl-hydrazine-stupylamine sulfonyl, fluorenyl-cyclohexylsulfonyl), sulfo, phosphinyl (preferably a phosphinyl group having a carbon number of 1 to 32) more preferably a carbon number 1 to 24 phosphinyl group, 201213336 phosphinyl group, octyloxyphosphonium group, phenylphosphine _), phosphine oxime 32 oxyamino group, more preferably carbon number 1 to amine group). - soil, for example, diethoxyphosphonium amide, dioctyloxyphosphine 醯 = the above-mentioned monovalent group is a group which can be further substituted, and is further substituted by a radical . Further, in the case of having two soils, the substituents may be the same or different. In the general formula (I), one may form a five-member, six-member, or seven-member two, and as a ring formed, a saturated ring or an unsaturated ring may exist. 2.5Α 6 The saturated or unsaturated ring of the member or the 7 member can be exemplified, for example, the ring, the couple, the ring, the ring, the ring, the triple ring, the 嗤%, the 嗔 环 ring 0 ring, slightly bite ring, cyclopentate ring, ring rare ring, fine, tree benzene ring, and, in addition, the formation of the 5 members, 6 members, and 7 members of the ring can be replaced by In the case of a group, it may be substituted by any substituent of the substituent R, and when it is substituted by two or more substituents, the substituents may be the same or different. _ - Metal atom or metal compound _ Next, a description will be given of a metal atom or a metal compound constituting a specific complex. The metal or metal compound used herein may be any metal atom or metal compound which can form a chelating compound, and includes a valent atom of 201213336, a divalent metal oxide, a divalent metal hydroxide, Or a divalent metal vapor. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, etc., A1C1, Ina,
FeCl、TiCl2、SnCl2 ' SiCl2、GeCl2 等金屬氣化物,Ti〇、 V〇等金屬氧化物,Si(OH)2等金屬氫氧化物。 該些中,自錯合物之穩定性、分光特性、耐熱、耐光 性、及製造適合性等觀點考慮,較佳為Fe、Zn、Mg、Si、 Pt、Pd、Mo、Μη、Cu、Ni、Co、TiO、或 VO,更佳的是 Fe、Zn、Mg、Si、Pt、Pd、Cu、Ni、Co、或 VO,最佳的 是 Fe、Zn、Cu、Co、或 VO (V=〇)。 以下表示包含通式(I)所表示之化合物與金屬原子或 金屬化合物的錯合物中較佳之態樣。 亦即,可列舉於通式(I)中,R1及R6個別獨立地表 示氫原子、烷基、烯基、芳基、雜環基、矽烷基、羥基、 氰基、烷氧基、芳氧基、雜環氧基、醯基、烷氧基羰基、 胺曱醯基、胺基、苯胺基、雜環胺基、羧醯胺基、脲基、 醯亞胺基、烷氧基羰基胺基、芳氧基羰基胺基、磺醯胺基、 偶氮基、烷硫基、芳硫基、雜環硫基、烷基磺醯基、芳基 磺醯基、或膦醯胺基,R2及R5個別獨立地表示氫原子、 鹵素原子、烷基、烯基、芳基、雜環基、羥基、氰基、硝 基、烷氧基、芳氧基、雜環氧基、醯基、烷氧基羰基、芳 氧基羰基、胺甲醯基、醯亞胺基、烷氧基羰基胺基、磺醯 胺基、偶氮基、烷硫基、芳硫基、雜環硫基、烷基磺醯基、 芳基確醯基、或胺磺醯基,R3及R4個別獨立地表示氫原 21 201213336 -> / /Zjpif 子、素原子、烷基、烯基、芳基、雜環基、矽烷基、羥 基、氰基、烷氧基、芳氧基、雜環氧基、醯基、烷氧基羰 基、胺曱醯基、苯胺基、羧醯胺基、脲基、醯亞胺基、烷 氧基羰基胺基、續醯胺基、偶氮基、烧硫基、芳硫基、雜 環硫基、烷基磺醯基、芳基磺醯基、胺磺醯基、或膦醯胺 基’ R7表示氫原子、鹵素原子、烷基、芳基、或雜環基, 金屬原子或金屬化合物表示Zn、Mg、Si、Pt、Pd、Mo、 Mn、Cu、Ni、Co、TiO、或 VO 之態樣。 以下表示包含通式(I)所表示之化合物與金屬原子或 金屬化合物的錯合物中更佳之態樣。Metal oxides such as FeCl, TiCl2, SnCl2'SiCl2, GeCl2, metal oxides such as Ti〇 and V〇, and metal hydroxides such as Si(OH)2. Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Μη, Cu, Ni are preferable from the viewpoints of stability, spectral characteristics, heat resistance, light resistance, and manufacturing suitability of the self-aligning compound. , Co, TiO, or VO, more preferably Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or VO, most preferably Fe, Zn, Cu, Co, or VO (V= 〇). The preferred aspect of the complex comprising a compound represented by the formula (I) and a metal atom or a metal compound is shown below. That is, in the general formula (I), R1 and R6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a decyl group, a hydroxyl group, a cyano group, an alkoxy group, or an aryloxy group. , heterocyclic oxy, fluorenyl, alkoxycarbonyl, aminyl, amine, anilino, heterocyclic amine, carboxy oxime, ureido, quinone, alkoxycarbonyl , aryloxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, or phosphonium amine, R2 and R5 independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a cyano group, a nitro group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a decyl group or an alkoxy group. Carbocarbonyl, aryloxycarbonyl, amine carbaryl, oximine, alkoxycarbonylamino, sulfonylamino, azo, alkylthio, arylthio, heterocyclic thio, alkyl sulfonate An anthracenyl group, an aryl group or an amine sulfonyl group, and R3 and R4 each independently represent a hydrogen atom 21 201213336 -> / /Zjpif, a peptide, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, Decyl group, hydroxyl group , cyano, alkoxy, aryloxy, heterocyclooxy, decyl, alkoxycarbonyl, aminyl, anilino, carboxamide, ureido, quinone, alkoxycarbonyl Amine, hydrazine, azo, thiol, arylthio, heterocyclic thio, alkylsulfonyl, arylsulfonyl, sulfonyl, or phosphonium amino group 'R7 a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, a metal atom or a metal compound means a state of Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or VO . The following shows a more preferable aspect of the complex comprising a compound represented by the formula (I) and a metal atom or a metal compound.
亦即,可列舉於通式(I)中,R1及R6個別獨立地表 示氫原子、烷基、烯基、芳基、雜環基、氰基、醯基、烷 氧基羰基、胺甲醯基、胺基、雜環胺基、羧醯胺基、腺基、 醢亞胺基、烧氧基羰基胺基、芳氧基羰基胺基、續醯胺基、 偶氮基、烧基績酿基、芳基確gt基、或膦醯胺基,R2及 R5個別獨立地表示烷基、烯基、芳基、雜環基、氰基、硝 基、醯基、烷氧基羰基、芳氧基羰基、胺曱醯基、醯亞胺 基、烧基橫酿基、芳基續酿基、或胺續醯基,R3及R4個 別獨立地表示氫原子、烷基、烯基、芳基、雜環基、氰基、 醯基、烧氧基羰基、胺曱醯基、叛醯胺基、腺基、醯亞胺 基、烷氧基羰基胺基、磺醯胺基、烷硫基、芳硫基、雜環 硫基、烧基續醯基、芳基橫醯基、或胺續醯基,R7表示氫 原子、鹵素原子、烷基、芳基、或雜環基,金屬原子或金 屬化合物表示 Zn、Mg、Si、Pt、Pd、Cu、Ni、Co、或 VO 22 201213336, 之態樣。 以下表示於包含通式(I)所表示之化合物與金屬原子 或金屬化合物的錯合物中特佳之態樣。 亦即,可列舉於通式(I)中,R1及R6個別獨立地表 示氫原子、烧基、芳基、雜環基、胺基、雜環胺基、缓醯 胺基、脲基、酿亞胺基、烧氧基幾基胺基、續醯胺基、偶 氮基、烧基績醯基、芳基續醯基、或膦醯胺基,R2及R5 個別獨立地表示烷基、芳基、雜環基、氰基、醯基、烷氧 基羰基、胺甲醯基、烧基磺醯基、或芳基績醯基,R3及 R4個別獨立地表示氫原子、烷基、芳基、或雜環基,R7 表示氫原子、烷基、芳基、或雜環基,金屬原子或金屬化 合物表示Zn、Cu、Co、或VO之態樣。 特別是自堅牢性優異之方面考慮,較佳為於通式(D 中’ R3及R4個別為苯基。認為其理由是:(丨)由於R3及 R4個別為苯基,因此該化合物之分光長波長化,與所併用 之敵菁系顏料之分光之重疊(550 nm附近)變大,變得容 易能量移動,(2)由於立體體積大的取代基之存在,該化 合物自身之堅牢性變高。 而且,自溶劑溶解性優異之方面考慮,較佳為於通式 (I)中,R2及/或R5為2,6_二-第三丁基_4_曱基環己基氧 基羰基。 -通式(II-1)所表示之化合物· 作為本發明中之特定錯合物,下述通式(II-1)所表 示之化合物是較佳例之一。 23 201213336 ό ΐ /z^pif [化9]That is, in the general formula (I), R1 and R6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a decyl group, an alkoxycarbonyl group or an amine formamidine. Base, amine group, heterocyclic amine group, carboxylammonium group, gland group, quinone imine group, alkoxycarbonylamino group, aryloxycarbonylamino group, hydrazine group, azo group, base a aryl group or an arylphosphonium group, and R2 and R5 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, a decyl group, an alkoxycarbonyl group, or an aryloxy group. a carbonyl group, an amine fluorenyl group, an oxime imine group, a decyl aryl group, an aryl aryl group, or an amine fluorenyl group, and R 3 and R 4 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, Heterocyclic group, cyano group, fluorenyl group, alkoxycarbonyl group, amine sulfhydryl group, retinoyl group, gland group, quinone imine group, alkoxycarbonylamino group, sulfonylamino group, alkylthio group, aromatic a thio group, a heterocyclic thio group, a decyl group, an aryl fluorenyl group, or an amine fluorenyl group, and R7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, a metal atom or a metal compound Indicates Zn, Mg Si, Pt, Pd, Cu, Ni, Co, or VO 22 201213336, of aspects. The following is a particularly preferred aspect of the complex comprising a compound represented by the formula (I) and a metal atom or a metal compound. That is, in the general formula (I), R1 and R6 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amine group, a heterocyclic amine group, a sulfhydryl group, a urea group, and a An imido group, an alkoxyamino group, a hydrazine group, an azo group, an alkyl group, an aryl group, or a phosphinium group, and R 2 and R 5 each independently represent an alkyl group or an aromatic group. a group, a heterocyclic group, a cyano group, a decyl group, an alkoxycarbonyl group, an amine carbaryl group, a decyl sulfonyl group, or an aryl fluorenyl group, and R 3 and R 4 each independently represent a hydrogen atom, an alkyl group, or an aryl group. Or a heterocyclic group, R7 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and a metal atom or a metal compound represents a state of Zn, Cu, Co, or VO. In particular, from the viewpoint of excellent fastness, it is preferably in the formula (D in the case where R3 and R4 are each a phenyl group. The reason is considered to be: (丨) Since R3 and R4 are each a phenyl group, the compound is split. The longer wavelength, the overlap with the splitting of the ***e pigment used in combination (around 550 nm), and the easy movement of energy, and (2) the fastness of the compound itself due to the presence of a bulky bulky substituent. Further, from the viewpoint of excellent solvent solubility, it is preferred that in the formula (I), R 2 and/or R 5 are 2,6-di-t-butyl-4-indolylcyclohexyloxycarbonyl group. - a compound represented by the formula (II-1). As a specific complex in the present invention, a compound represented by the following formula (II-1) is one of preferable examples. 23 201213336 ό ΐ /z ^pif [化9]
於上述通式(II-1)中,R1〜R6個別獨立地表示氫原 子或取代基。R7表示氫原子、鹵素原子、烷基、芳基、或 雜環基。Ma表示金屬原子或金屬化合物,X2表示中和Ma 之電荷所必須之基,X1表示可鍵結於Ma上之基。另外, X1與X2亦可相互鍵結而形成5員、6員、或7員之環。其 中,R1與R6並不相互鍵結而形成環。 通式(II-1)中之R1〜R6與通式(I)中之R1〜R6同 義,較佳之態樣亦相同。 通式(II-1)中之Ma表示金屬原子或金屬化合物,與 前述之構成特定錯合物之金屬原子或金屬化合物同義,其 較佳之範圍亦相同。 通式(II-1)中之R7與通式(I)中之R7同義,較佳 之態樣亦相同。 通式(II-1)中之X1只要為可鍵結於Ma上之基則可 為任意種,進而可列舉源自水、醇類(例如曱醇、乙醇、 丙醇)等,以及「金屬螯合物」[1]阪口武一 •上野景平著 24 201213336 Λ. 年南江堂)、「金屬f合物」[2] 整合物」、[3](⑽年)等中所記載之化合物的基。 通式(II-1)中之X2表示中和Ma之電荷所必須之基, "T列舉鹵素原子、赵基、敌酸基、碌酸基、績酸基等。 /通式(11_ 1)中之X1與X2亦可相互鍵結而與Ma共同 =成5員、6員、或7員之環。所形成之5員、6員、及7 員之環可為飽和環亦可為不飽和環。而且,5員、6員、及 7員之環亦可僅以碳原子及氫原子構成,亦可為具有至少1 個選自氮原子 '氧原子、及硫原子之原子的雜環。 *通式(II-2)所表示之化合物- 作為本發明中之特定錯合物,下述通式(II-2)所表 示之化合物是較佳例之一。 [化 10]In the above formula (II-1), R1 to R6 each independently represent a hydrogen atom or a substituent. R7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound, X2 represents a group necessary for neutralizing the charge of Ma, and X1 represents a group which can be bonded to Ma. In addition, X1 and X2 may also be bonded to each other to form a ring of 5 members, 6 members, or 7 members. Among them, R1 and R6 are not bonded to each other to form a ring. R1 to R6 in the formula (II-1) are the same as R1 to R6 in the formula (I), and preferred embodiments are also the same. In the formula (II-1), Ma represents a metal atom or a metal compound, and is synonymous with the above-mentioned metal atom or metal compound constituting a specific complex, and the preferred range thereof is also the same. R7 in the formula (II-1) is synonymous with R7 in the formula (I), and preferred embodiments are also the same. X1 in the general formula (II-1) may be any one as long as it can be bonded to Ma, and may be derived from water, alcohols (for example, decyl alcohol, ethanol, propanol), and the like. Chelate"[1]Sakaguchi Takeo, Ueno Jingping, 24 201213336 Λ. Year Nanjiangtang), "Metal F Compound" [2] Integrator, [3] ((10) Years, etc.) base. X2 in the formula (II-1) represents a group necessary for neutralizing the charge of Ma, and "T" exemplifies a halogen atom, a thiol group, an acid group, an acid group, a acid group, and the like. X1 and X2 in the general formula (11_1) may also be bonded to each other and together with Ma = a ring of 5 members, 6 members, or 7 members. The ring of the 5 members, 6 members, and 7 members formed may be a saturated ring or an unsaturated ring. Further, the ring of 5 members, 6 members, and 7 members may be composed only of a carbon atom and a hydrogen atom, or may be a hetero ring having at least one atom selected from the group consisting of a nitrogen atom and an oxygen atom. * Compound represented by the formula (II-2) - As a specific complex in the present invention, a compound represented by the following formula (II-2) is one of preferable examples. [化10]
於上述通式(II-2)中,R1〜R6、及R8〜R13個別獨立 地表示氫原子或取代基。R7及R14個別獨立地表示氫原 子、鹵素原子、烷基、芳基、或雜環基。Ma表示金屬原 25 201213336 子或金屬化合物。其中,R1與R8或R13、及R6與R8或Rl3 並不個別相互鍵結而形成環。 通式(II-2)中之R1〜R6與通式(I)中之ri〜r6 $ 義,較佳之態樣亦相同。 通式(II-2)中之R8〜R13所表示之取代基與通式q) 所表示之化合物之R1〜R6所表示之取代基同義,其較佳之 態樣亦相同。於通式(II-2)所表示之化合物之R8〜R13 所表示之取代基是可進一步被取代之基之情形時,可被前 述之取代基R之任意基取代,於被2個以上取代基取代之 情形時,該些取代基可相同亦可不同。 通式(II-2)中之R7與通式(I)中之R7同義,較佳 之態樣亦相同。 通式(II-2)中之R14表示氫原子、鹵素原子、烷基、 芳基、或雜環基,R14之較佳之範圍與所述R7之較佳之範 圍相同。於R14為可進一步被取代之基之情形時,可被前 述之取代基R之任意基取代,於被2個以上取代基取代之 情形時,該些取代基可相同亦可不同。 通式(II-2)中之Ma表示金屬或金屬化合物,與前述 之構成特定錯合物之金屬原子或金屬化合物同義,其較佳 之範圍亦相同。 通式(II-2)中之 R^R9、r^r10、r1^r12、r12 與R13亦可個別獨立地相互鍵結而形成5員/6員、或7 員之飽和環或不飽和環。作為所形成之飽和環或不飽和 環’與通式(I)中之由R1與R2、反2與R3、R4與R5、及 26 201213336 R5與R6所形成之飽和環或不飽和環同義,較佳例亦相同。 •通式(III)所表示之化合物_ 作為本發明中之特定錯合物,下述通式(III)所表示 之化合物是較佳例之一。 [化 11] ψ R7 R4In the above formula (II-2), R1 to R6 and R8 to R13 each independently represent a hydrogen atom or a substituent. R7 and R14 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal former 25 201213336 sub or metal compound. Wherein R1 and R8 or R13, and R6 and R8 or Rl3 are not individually bonded to each other to form a ring. R1 to R6 in the formula (II-2) and ri~r6 in the formula (I) are preferably the same. The substituent represented by R8 to R13 in the formula (II-2) is synonymous with the substituent represented by R1 to R6 of the compound represented by the formula (q), and the preferred embodiment is also the same. When the substituent represented by R8 to R13 of the compound represented by the formula (II-2) is a group which may be further substituted, it may be substituted by any of the substituents R described above, and may be substituted by two or more. In the case of a base substitution, the substituents may be the same or different. R7 in the formula (II-2) is synonymous with R7 in the formula (I), and preferred embodiments are also the same. R14 in the formula (II-2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, and a preferred range of R14 is the same as the preferred range of the above R7. In the case where R14 is a group which may be further substituted, it may be substituted by any of the substituents R described above, and when substituted by two or more substituents, the substituents may be the same or different. In the formula (II-2), Ma represents a metal or a metal compound, and is synonymous with the above-mentioned metal atom or metal compound constituting a specific complex, and the preferred range thereof is also the same. R^R9, r^r10, r1^r12, r12 and R13 in the formula (II-2) may be independently bonded to each other to form a 5- or 6-membered or 7-membered saturated or unsaturated ring. . The saturated ring or unsaturated ring formed as a synonym with the saturated ring or unsaturated ring formed by R1 and R2, the reverse 2 and R3, R4 and R5, and 26 201213336 R5 and R6 in the formula (I), The preferred examples are also the same. • Compound represented by the formula (III) _ As a specific complex of the present invention, a compound represented by the following formula (III) is one of preferable examples. [化11] ψ R7 R4
'於上述通式(III)中,R2〜R5個別獨立地表示氫原子 或取代基。R7表示氫原子、鹵素原子 '烧基、芳基、或雜 環基。Ma表示金屬原子或金屬化合物,X3表示NR (R表 示氫原子、烷基、烯基、芳基、雜環基、醯基、烷基磺醯 基、芳基磺醯基)、氮原子、氧原子、或硫原子,X4表示 NRa(Ra表示氫原子、烧基、烯基、芳基、雜環基醯基、 烷基磺醯基、或芳基磺醯基)、氧原子、或硫原子,γ1表 不NRC (rc表示氫原子、烷基、烯基、芳基、雜環基、醯 基2、烷基磺醯基、或芳基磺醯基)、氮原子、或碳原子, Y2表示氮原子或碳原子,R8及R9個別獨立地表示烷基、 烯基、芳基、雜環基、烷氧基、芳氧基 '烧基胺基、芳棊 27 201213336 ^ / /ζ^ριι f基、或雜環胺基。尺8與γ1亦可相互鍵結而形成5員、6 戎/g7員》之環,&9與¥2亦可相互鍵結而形成5員、6員、 5 之環。χ5表示可與Ma鍵結之基,a表示〇、丨、或 2 〇 通式(III)中之R2與R3、及R4與R5亦可個別獨立 i 1互鍵結而形成5員、6員、《7員之飽和環、或不飽 和環2作,所形成之飽和環或不飽和環,與通式(I)中之 由R與R、及尺4與尺5所形成之飽和環或不飽和環同義, 較佳例亦相同。 6通式(III)中之R2〜R5、及R7與通式(1)中之Rl 〜R、及R7同義,較佳之態樣亦相同。 通式(III)中之Ma表示金屬或金屬化合物,與前述 之構成特定錯合物之金屬原子或金屬化合物同義,其較佳 之範圍亦相同。 於通式(III)中,尺8及R9個別獨立地表示烷基(較 f為碳數1〜36之直鏈、分支鏈、或環狀之烷基,更佳的 是1〜12之直鏈、分支鏈、或環狀之烷基,例如:曱基、 乙基、丙基、異丙基、丁基、異丁基、第三丁基、己基、 2-乙基己基、十二烷基、環丙基、環戊基、環己基、丨金 剛烷基)、烯基(較佳為碳數2〜24之烯基,更佳的是2〜 12之烯基,例如:乙烯基、烯丙基、3-丁烯-1-基)、芳基 (較佳為碳數6〜36之芳基,更佳的是6〜18之芳基,例 如·本基、萘基)、雜環基(較佳為碳數1〜24之雜環基, 更佳的是1〜12之雜環基,例如:2-噻吩基、4-吡啶基、 28 201213336 2-0夫喃基、2-n密唆基、l-α比π定基、2-苯并嘆η坐基、1_咪^坐基、 1-吡唑基、苯并***-1-基)、烷氧基(較佳為碳數丨〜36 之烷氧基’更佳的是1〜18之烷氧基,例如:曱氧基、乙 氧基、丙基氧基、丁氧基、己氧基、2-乙基己氧基、十二 烧基氧基、環己氧基)、芳氧基(較佳為碳數6〜24之芳氧 基,更佳的是1〜18之芳氧基,例如:苯氧基、萘氧基)、 烷基胺基(較佳為碳數1〜36之烷基胺基,更佳的是 18之烷基胺基,例如:甲基胺基、乙基胺基、丙基胺基、 丁基胺基、己基胺基、2-乙基己基胺基、異丙基胺基、第 二丁基胺基、第三辛基胺基、環己基胺基、N,N_:乙基胺 基、N,N-二丙基胺基、n,N-二丁基胺基、N-曱基-N-乙基胺 基)、务基私基(較佳為碳數6〜36之芳基胺基,更佳的是 1 〜18之芳基胺基,例如:苯基胺基、萘基胺基、N,N-二 苯基胺基、N-乙基-N·苯基胺基)、或雜環胺基(較佳為碳 數1〜24之雜環胺基,更佳的是丨〜;^之雜環胺基,例如: 2_胺基吡咯基、3_胺基吡唑基、2_胺基吡啶基、3·胺基吡啶 基)。 於通式(III)中,R8及R9所表示之烷基、烯基、芳 基„雜環基、烷氧基、芳氧基、烧基胺基、芳基胺基、或 =環胺基是可進-步被取代之基之情形時,可被所述取代 土 R之任意基所取代,於被2個以上取代基取代之情 時,該些取代基可相同亦可不同。 於通式(III)中,X3表示NR、氮原子、氧原子 硫原子,X4表示NRa、氧原子、或硫原子,R與Ra個別 29 201213336 獨立地表示氫原子、烷基(較佳為碳數〗〜36之直鏈、分 支鏈、或環狀之烧基,更佳的是1〜12之直鏈、分支鏈、 或環狀之烧基,例如:曱基、乙基、丙基、異丙基、丁基、 異丁基、第三丁基、己基、2-乙基己基、十二烷基、環丙 基、環戊基、環己基、1-金剛烷基)、烯基(較佳為碳數2 〜24之烯基,更佳的是2〜12之烯基,例如:乙烯基、烯 丙基、3-丁烯-1-基)、芳基(較佳為碳數6〜36之芳基, 更佳的是6〜18之芳基,例却:苯基、萘基)、雜環基(較 佳為碳數1〜24之雜環基,更佳的是丨〜12之雜環基,例 如塞吩基、比啶基、2_吱喃基、2-嘴啶基、1-吼啶基、 2-笨并噻唑基、丨_咪唑基、丨_吡唑基、苯并***_1基)、醯 基(較佳為碳數1〜24之醯基,更佳的是2〜18之醯基, 例如·乙醯基、特戊醯基、2-乙基己基、苯曱醯基、環己 醯基)/烷基磺醯基(較佳為碳數丨〜24之烷基磺醯基,更 佳的疋1〜18之烷基磺醯基,例如:曱基磺醯基、乙磺醯 基、異丙基磺醯基、環己基磺醯基)、芳基磺醯基(較佳為 ,數6〜24之芳基續醯基’更佳的是6〜18之芳基確醯基, 例如·笨基磺醯基、萘基磺醯基)。 所述R與Ra之絲、烯基、芳基、雜環基、酿基、 ,基磺醯基、芳基磺醯基亦可進一步被所述取代基r之任 意基所取代,於被多個取代基取代之情形時,該些取代基 可相同亦可不同。 土 於通式(m)巾,γΐ表示NRc、氮原子、或碳原子, 表示氮原子或碳原子,Rc與所述X3中之r同義。 30 201213336 J / 於通式(III)中,圮斑 碳原子共同形成S員产r/,、亦可相互鍵結,R8、Y1及 二氧五環烷、四氣噢私、?如%戊烷、吡咯啶、四氫呋喃、 呋喃、苯并嘆吩〕:員产^各、Π夫喃、嗟吩、,朵、笨并 琳、四氫t南、二外1例如環己燒、錢、旅嗓、嗎 终噠唤,、苯、錢、 六亞曱基亞胺)。 ,7員環(例如:環庚烷、 於通式(III)中,p9 & 碳原子共同形成5員、6 M ^ ^可相f鍵結,R8、Yl及 6員、及7員之5貝之環。所形成之5員、 成之#中的解所述之由R8與Υΐ及碳原子所形 成之%中的1個鍵變化為雙鍵之環。 s二通:式I1?中,汉8與γ1、及妒與γ2鍵結而形成之 貝 員之環是可進一步被取代之環之情形時, 可被所述取代基R的㈣所說明之基取代,於被2個以上 取代基取代之情形時,該些取代基可相同亦可不同。 於通式(III)中,X5表示可與Ma鍵結之基,可列舉 與所述通式(II-1)中之χΐ相同之基。 a表示0、1 '或2。 將通式(III)所表示之化合物之較佳之態樣表示如下。 亦即,R2〜R5、R7、及Ma個別為包含通式(〗)所表 示之化合物與金屬原子或金屬化合物的錯合物之較佳態 樣’ X3為NR (R為氫原子、烧基)、氮原子、或氧原子, X4為NRa (Ra為氫原子、烷基、雜環基)、或氧原子,γΐ 為NRc (Rc為氫原子、或炫基)、氮原子、或碳原子,γ2 31 201213336 為氮原子、或碳原子,χ5為經由氧原子而鍵結之基,r8 及R9個別獨立地表示貌基、芳基、雜環基' 規氧基、或烷 基胺基,或者圮與γ】相互鍵結而形成5員或6員環,R9 與Υ2相互鍵結而形成5員、6員環,a表示0或!之態樣。 將通式(III)所表示之化合物之更佳態樣表示如下。 亦即,112〜115、117、以3個別為包含通式(1)所表示 之化合物與金屬原子或金屬化合物的錯合物的較佳態樣, X3及X4為氧原子,γΐ為NH,Y2為氮原子,X5為經由氧 原子而鍵結之基,R8及R9個別獨立地表示烷基、芳基、 雜裱基、烷氧基、或烷基胺基,或者R8與γι相互鍵結而 形成5員或6員環’R9與γ2相互鍵結而形成5員、6員環, a表示〇或1之態樣。 以下,表示本發明中之特定錯合物之具體例,但本 明並不限定於該些具體例。 [化 12] 32 201213336 /ZjpifIn the above formula (III), R2 to R5 each independently represent a hydrogen atom or a substituent. R7 represents a hydrogen atom, a halogen atom 'alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound, and X3 represents NR (R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, an arylsulfonyl group), a nitrogen atom, and an oxygen. An atom or a sulfur atom, X4 represents NRa (Ra represents a hydrogen atom, a pyridyl group, an alkenyl group, an aryl group, a heterocyclic fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or a sulfur atom. , γ1 represents NRC (rc represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a fluorenyl group, an alkylsulfonyl group, or an arylsulfonyl group), a nitrogen atom, or a carbon atom, Y2 Represents a nitrogen atom or a carbon atom, and R8 and R9 each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkyl group, and an aryl group 27 201213336 ^ / /ζ^ριι Or a heterocyclic amine group. The ruler 8 and the γ1 may also be bonded to each other to form a ring of 5 members, 6 戎/g7 members, and & 9 and ¥2 may also be bonded to each other to form a ring of 5 members, 6 members, and 5 members. Χ5 denotes a group which can be bonded to Ma, a denotes 〇, 丨, or 2 R R2 and R3 in the formula (III), and R4 and R5 may be independently bonded to each other to form 5 members and 6 members. , "saturated ring of 7 members, or unsaturated ring 2, formed by a saturated or unsaturated ring, and a saturated ring formed by R and R, and 4 and 5 in the formula (I) or The unsaturated ring is synonymous, and the preferred embodiment is also the same. 6 R2 to R5 and R7 in the formula (III) are synonymous with R1 to R and R7 in the formula (1), and preferred embodiments are also the same. In the formula (III), Ma represents a metal or a metal compound, and is synonymous with the above-mentioned metal atom or metal compound constituting a specific complex, and the preferred range thereof is also the same. In the formula (III), the dentine 8 and R9 each independently represent an alkyl group (f is a linear, branched, or cyclic alkyl group having a carbon number of 1 to 36, more preferably 1 to 12 straight). a chain, a branched chain, or a cyclic alkyl group, for example, anthracenyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecane a group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a ruthenium alkyl group, an alkenyl group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably an alkenyl group of 2 to 12, for example, a vinyl group, Allyl, 3-buten-1-yl), aryl (preferably an aryl group having 6 to 36 carbon atoms, more preferably an aryl group of 6 to 18, such as a benzyl group or a naphthyl group), a ring group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably a heterocyclic group of 1 to 12, for example, 2-thienyl, 4-pyridyl, 28 201213336 2-0-folyl, 2 -n-denyl group, l-α ratio π-group, 2-benzo-n-n-nylene, 1-m-sodium, 1-pyrazolyl, benzotriazol-1-yl), alkoxy Preferably, the alkoxy group having a carbon number of 3636 is more preferably an alkoxy group of 1 to 18, such as a decyloxy group, an ethoxy group, a propyloxy group, or a butoxy group. , hexyloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy), aryloxy (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 1 to 18) An aryloxy group, for example, a phenoxy group, a naphthyloxy group, an alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably an alkylamino group of 18, for example, a methyl group) Amino, ethylamino, propylamino, butylamino, hexylamino, 2-ethylhexylamino, isopropylamino, second butylamino, third octylamino, Cyclohexylamine, N,N_:ethylamino, N,N-dipropylamino, n,N-dibutylamino, N-fluorenyl-N-ethylamino), a group (preferably an arylamine group having 6 to 36 carbon atoms, more preferably an arylamine group of 1 to 18, for example, a phenylamino group, a naphthylamino group, an N,N-diphenylamino group , N-ethyl-N-phenylamino), or a heterocyclic amine group (preferably a heterocyclic amino group having 1 to 24 carbon atoms, more preferably a heterocyclic amino group of hydrazine~; ^, for example: 2_Aminopyrrolyl, 3-aminopyrazolyl, 2-aminopyridyl, 3·aminopyridyl). In the formula (III), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a = cyclic amino group represented by R8 and R9. When it is a group which can be further substituted, it may be substituted by any substituent of the substituted soil R, and when substituted by two or more substituents, the substituents may be the same or different. In the formula (III), X3 represents NR, a nitrogen atom, an oxygen atom sulfur atom, X4 represents NRa, an oxygen atom, or a sulfur atom, and R and Ra are individually 29 201213336 independently represent a hydrogen atom, an alkyl group (preferably a carbon number) a straight chain, a branched chain, or a cyclic alkyl group of ~36, more preferably a linear chain, a branched chain, or a cyclic alkyl group of 1 to 12, for example, a thiol group, an ethyl group, a propyl group, or an isopropyl group. Base, butyl, isobutyl, tert-butyl, hexyl, 2-ethylhexyl, dodecyl, cyclopropyl, cyclopentyl, cyclohexyl, 1-adamantyl), alkenyl (preferably) It is an alkenyl group having 2 to 24 carbon atoms, more preferably an alkenyl group of 2 to 12, for example, a vinyl group, an allyl group, a 3-buten-1-yl group, or an aryl group (preferably a carbon number of 6~) 36 aryl, more preferably 6~18 The aryl group, for example, a phenyl group, a naphthyl group, a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably a heterocyclic group of 丨~12, such as a thiophene group or a pyridyl group) Base, 2_indolyl, 2-hydrazinyl, 1-acridinyl, 2-phenylthiazolyl, oxime-imidazolyl, oxime-pyrazolyl, benzotriazol-1-yl), fluorenyl ( It is preferably a fluorenyl group having 1 to 24 carbon atoms, more preferably a fluorenyl group having 2 to 18, such as an ethyl fluorenyl group, a pentylene group, a 2-ethylhexyl group, a benzoinyl group or a cyclohexyl group. /alkylsulfonyl (preferably an alkylsulfonyl group having a carbon number of 丨24, more preferably an alkylsulfonyl group of 疋1 to 18, such as a mercaptosulfonyl group, an ethylsulfonyl group, or a different A propylsulfonyl group, a cyclohexylsulfonyl group, an arylsulfonyl group (preferably, an aryl group having a number of from 6 to 24) is more preferably an aryl group of 6 to 18, for example Stupyl sulfonyl, naphthylsulfonyl). The R and Ra filaments, alkenyl, aryl, heterocyclic, aryl, sulfenyl, arylsulfonyl can be further Where the substituent of the substituent r is substituted, when substituted by a plurality of substituents, the substituents may be the same or not In the general formula (m), γΐ represents NRc, a nitrogen atom, or a carbon atom, and represents a nitrogen atom or a carbon atom, and Rc is synonymous with r in the X3. 30 201213336 J / In the general formula (III), Freckle carbon atoms form S-members to produce r/, and can also bond with each other, R8, Y1 and dioxane, four gas, such as % pentane, pyrrolidine, tetrahydrofuran, furan, benzopyrene吩]: members of the production of each, ^ Fu Fu, 嗟 、,, Duo, Lin and Lin, tetrahydro t South, two outside 1 such as the ring burned, money, travel, finally call, benzene, money, Hexamethyleneimine)., 7-membered ring (eg, cycloheptane, in formula (III), p9 & carbon atoms together form 5 members, 6 M ^ ^ phase f-bond, R8, Yl And 6 members, and 5 members of the 5 ring. One of the % of the bonds formed by R8 and hydrazine and carbon atoms described in the solution of the five members formed in the #, is a ring of double bonds. s two-way: in the case of the formula I1?, when the ring of the beijing formed by the bonding of the ninth and the gamma 1, and the yttrium and the gamma 2 is a ring which can be further substituted, it can be explained by (4) of the substituent R. The substituent may be the same or different when substituted by two or more substituents. In the formula (III), X5 represents a group which may be bonded to Ma, and examples thereof are the same as those in the above formula (II-1). a means 0, 1 ' or 2. Preferred aspects of the compound represented by the formula (III) are shown below. That is, R2 to R5, R7, and Ma are each a preferred aspect of a complex comprising a compound represented by the formula (') and a metal atom or a metal compound, and X3 is NR (R is a hydrogen atom, a halogen group). ), a nitrogen atom, or an oxygen atom, X4 is NRa (Ra is a hydrogen atom, an alkyl group, a heterocyclic group), or an oxygen atom, and γΐ is NRc (Rc is a hydrogen atom or a thio group), a nitrogen atom, or a carbon atom. , γ2 31 201213336 is a nitrogen atom or a carbon atom, χ5 is a group bonded via an oxygen atom, and r8 and R9 each independently represent a vinyl group, an aryl group, a heterocyclic group, an oxy group, or an alkylamino group. Or 圮 and γ] are bonded to each other to form a 5-member or 6-member ring, and R9 and Υ2 are bonded to each other to form a 5-member, 6-member ring, and a represents 0 or! The situation. A more preferred aspect of the compound represented by the formula (III) is shown below. That is, 112 to 115, 117, and 3 are preferably a combination of a compound represented by the formula (1) and a metal atom or a metal compound, X3 and X4 are oxygen atoms, and γΐ is NH. Y2 is a nitrogen atom, X5 is a group bonded via an oxygen atom, and R8 and R9 each independently represent an alkyl group, an aryl group, a heterofluorenyl group, an alkoxy group, or an alkylamine group, or R8 and γι are bonded to each other. The formation of a 5-member or 6-member ring 'R9 and γ2 are mutually bonded to form a 5-member, 6-member ring, and a represents a 〇 or 1 aspect. Specific examples of the specific complex compounds in the present invention are shown below, but the present invention is not limited to these specific examples. [化 12] 32 201213336 /Zjpif
化合物 編號 綱薄響 Nik . * 'fp 1¾ ~9Hk -rt m Μ -HvIHs: 侧¢)¾¾ mm V.=0 Ιϊ-5: -N.晒胸 \·· •广·、 .· * ·*'.;» / Γ\ 1-» .·· -COO'r^hrCH^ -CHa: -d Ζή :iar6 ^HCOCHs wo -GOO-iT^CHa e&t) —-GH3.; -B Cu :Ia-7 -NH.eQCHj mm V—TV. 侧 mm -CH? -pw3 Zri -NHCOCH2OOH2COOH ψφ ^OOr^-CH, 4¾ ~QH?: ^ch3 Zn* .滅 ^HGQGHidCHoCOOH -x\*· »·.r-·..-.·*.,, *,· . .......... mm rCOO-C^CH3 -^H-3: --9¾ Zn: 獅嫌拥祕0胡 mm Wft) —ό与輔㈣ —H Zn Ia-1;1 HMHCOCHi〇CH2COOH ψψ> -mim -C^3 Zft 13-121 ^HCd^CHi0GH2C00H ^OOhQ^C.M3 -¾瞒 ^r-H 0u 33 201213336 3//Zipif [化 13]The compound number is thinner Nik. * 'fp 13⁄4 ~9Hk -rt m Μ -HvIHs: side ¢)3⁄43⁄4 mm V.=0 Ιϊ-5: -N. Sun chest\·· • 广·······* '.;» / Γ\ 1-» ..· -COO'r^hrCH^ -CHa: -d Ζή :iar6 ^HCOCHs wo -GOO-iT^CHa e&t) —-GH3.; -B Cu : Ia-7 -NH.eQCHj mm V-TV. Side mm -CH? -pw3 Zri -NHCOCH2OOH2COOH ψφ ^OOr^-CH, 43⁄4 ~QH?: ^ch3 Zn* .灭^HGQGHidCHoCOOH -x\*· »·. R-·..-.·*.,, *,· . ............. mm rCOO-C^CH3 -^H-3: --93⁄4 Zn: Lions secretly secret 0 Hu mm Wft) - ό and auxiliary (4) - H Zn Ia-1; 1 HMHCOCHi 〇 CH2COOH ψψ > -mim -C^3 Zft 13-121 ^HCd^CHi0GH2C00H ^OOhQ^C.M3 -3⁄4瞒^rH 0u 33 201213336 3/ /Zipif [化13]
化合物 編號 R^RSrR^rR13 F^=F^=F?-R12 F^=r4=r10=r1' R^R14 Ma Fa-13 —nh2 C^He(t) rCOO-(^)-CH3 cCHg(t) -C4Hg(t) "CH3 Zn !a,14 —nh2 CJHs(t) Λ(ΐ) -C4He(t) —H Zn la-15 *-nh2 C4H9(t) COO-<^)"CH3 -〇 -Ή Zn la-16 —nhcoch3 C/}g(t) ooo-^)~ch3 c&) ch3 -CH2S-0HCOOH -ch3 Cu la-17 -^h2 C^H9(t> coo-^)·01^ 〇 —H Zn la-18 —NH2 C>[9(t) •CO〇H^}cH3 ώθ(〇 -〇 -H Cu la-19 —nh2 coo-<^)ch3 <) —H V=0 la-20 —NHj OXH^€H3 Λα) 〇 -gh3 Zr* la-21 —NHCOCH3 -coch^>oh3 ώίω 〇 -ch3 Zn la-22 -NHCOCH2OCH2COOH OOGH^>"CH3 άώ) 〇 -H Zn 34Compound No. R^RSrR^rR13 F^=F^=F?-R12 F^=r4=r10=r1' R^R14 Ma Fa-13 —nh2 C^He(t) rCOO-(^)-CH3 cCHg( t) -C4Hg(t) "CH3 Zn !a,14 —nh2 CJHs(t) Λ(ΐ) -C4He(t) —H Zn la-15 *-nh2 C4H9(t) COO-<^)" ;CH3 -〇-Ή Zn la-16 —nhcoch3 C/}g(t) ooo-^)~ch3 c&) ch3 -CH2S-0HCOOH -ch3 Cu la-17 -^h2 C^H9(t> coo- ^)·01^ 〇—H Zn la-18 —NH 2 C>[9(t) •CO〇H^}cH3 ώθ(〇-〇-H Cu la-19 —nh2 coo-<^)ch3 < ) —HV=0 la-20 —NHj OXH^€H3 Λα) 〇-gh3 Zr* la-21 —NHCOCH3 -coch^>oh3 ώίω 〇-ch3 Zn la-22 -NHCOCH2OCH2COOH OOGH^>"CH3 άώ ) 〇-H Zn 34
201213336 J I I201213336 J I I
[化 14][Chem. 14]
化合物 編號 R^R^R'R1'. r7=r14 Ma la-23 -N HCOCH 2〇Q,H2C〇〇H W) ^qo-<Vch3 ciim -ch3 Zn la-24 '^COCH20C^C.〇6h W(t) GOO-pK)H3 -ch3 Cu Ja-25 -N HC0CH20CH2C00H CM) <Χ>〇Η^ΗΖ QHgit) —gh3 Zn la-26 coCH2ochi:2coori Wt) <XX3-T^CH3 Η·ρ *13。 ~-ch3 Zn fa-27 COOH -NHCp-^ 〇άψ ~COQHpK>l3 QHgP): -CH3 —H Cu 与-28 COOH Wt) ^oo-/^gh3 i5Hg(t) -ch3 -CH3 Zn la-29 ^i503H W) •c〇P-^}*ch3 -ch3 -CH3 Cu Ia-30 -NHCO~^), -GGO-^^CH3 c2h5 —〇Η2-0Η〇4Η9 -CHg, Cu Ia—31 -coo-cVch3 -〇 -CH3. Zn 35 201213336 - ---χ- [化 15]Compound No. R^R^R'R1'. r7=r14 Ma la-23 -N HCOCH 2〇Q,H2C〇〇HW) ^qo-<Vch3 ciim -ch3 Zn la-24 '^COCH20C^C.〇 6h W(t) GOO-pK)H3 -ch3 Cu Ja-25 -N HC0CH20CH2C00H CM) <Χ>〇Η^ΗΖ QHgit) —gh3 Zn la-26 coCH2ochi:2coori Wt) <XX3-T^CH3 Η · ρ *13. ~-ch3 Zn fa-27 COOH -NHCp-^ 〇άψ ~COQHpK>l3 QHgP): -CH3 —H Cu and -28 COOH Wt) ^oo-/^gh3 i5Hg(t) -ch3 -CH3 Zn la-29 ^i503H W) •c〇P-^}*ch3 -ch3 -CH3 Cu Ia-30 -NHCO~^), -GGO-^^CH3 c2h5 —〇Η2-0Η〇4Η9 -CHg, Cu Ia—31 -coo -cVch3 -〇-CH3. Zn 35 201213336 - ---χ- [化15]
化合物 編號 R’sR^R^R’3 ^=^=1^=^2 r3=^=r'°=r'' r7=r14 Ma la-32 JrCH3 C>|9(t) -coo-^)~ch3 QH9(t) O -ch3 Zn la-33 —nhso2ch3 QHs(t) ^oo-CVgh, —CH3 -ch3 Zn la-34 -CH70-Q^(y〇2 W) •coo-^)~ch3 W) -ch3 -ch3 Zn la-35 -ch2o-^-och3 QHs(t) •<XX)-/~VcH3 QHs(t) <} —οη3 Zn la-36 QH3 —N-SO2CH3 QH9(t) <y〇〇-{ycH3 QHs(i) -ch3 Zn la-37 ch2cooh —Λ-δ〇2〇Η3 〇Ηβ(1) coo-^k;h3 cft(t) -〇 -ch3 Zn Ia-38 —Cl QHs(t) -COO-T^CHs W) CH3 Cu la-39 «-s-ch2cooh W(t) -<X»-<3-GH3 W) —CH3 Cu Ia-40 ch3 —8-0HCOOH QHs(t) -CCO-Q-CH3 QHg(t) -ch3 -ch3 Cu 36 201213336 ----[一 [化 16]Compound number R'sR^R^R'3 ^=^=1^=^2 r3=^=r'°=r'' r7=r14 Ma la-32 JrCH3 C>|9(t) -coo-^ )~ch3 QH9(t) O -ch3 Zn la-33 —nhso2ch3 QHs(t) ^oo-CVgh, —CH3 —ch3 Zn la-34 -CH70-Q^(y〇2 W) •coo-^)~ Ch3 W) -ch3 -ch3 Zn la-35 -ch2o-^-och3 QHs(t) •<XX)-/~VcH3 QHs(t) <}_οη3 Zn la-36 QH3 —N-SO2CH3 QH9( t) <y〇〇-{ycH3 QHs(i) -ch3 Zn la-37 ch2cooh —Λ-δ〇2〇Η3 〇Ηβ(1) coo-^k;h3 cft(t) -〇-ch3 Zn Ia -38 —Cl QHs(t) -COO-T^CHs W) CH3 Cu la-39 «-s-ch2cooh W(t) -<X»-<3-GH3 W) —CH3 Cu Ia-40 ch3 —8-0HCOOH QHs(t) -CCO-Q-CH3 QHg(t) -ch3 -ch3 Cu 36 201213336 ----[一[化16]
化合物 編號 R’=R^=R,3 R?=fi5=R0=R!2 R?=R^RW r7=r14 Ma la-41 ch3, —S-^HCOOH «t) 娜^)~ch3 cS(t) —^h3 -CH3 y=〇 fe-42 —eb2CH3 QHgit) -COO-Q-CHs c2S(t) -ch3 —ch3 v=o Iar43 ,—β02〇Η3 -CX50-Q-CH3 cvi(t) Ό -ch3 Cu br44 f3 CHa W(t) ~coo-^^~ch3 -0 -ch3 Cu la-45 -coo-Qk^Hs C&9(t) -CH3 —H Cu Ia~46 —CH3 C/|9(t) -coo-〇^h3 cS(t) —CH3 -CHj Zn Ia~47 -ch3 W) -coo-/^ch3 cm) -CH3 -ch3 Gu V48 -CH3 W) ~〇Ρ〇-ζ^Η3 eS(t) -ch3 -ch3 Ni 轉 -W-T^CH? w) -ch3 -gh3 Zn 37 201213336 37723pifCompound number R'=R^=R,3 R?=fi5=R0=R!2 R?=R^RW r7=r14 Ma la-41 ch3, —S-^HCOOH «t) Na^)~ch3 cS (t) —^h3 -CH3 y=〇fe-42 —eb2CH3 QHgit) -COO-Q-CHs c2S(t) -ch3 —ch3 v=o Iar43 ,—β02〇Η3 -CX50-Q-CH3 cvi(t Ό -ch3 Cu br44 f3 CHa W(t) ~coo-^^~ch3 -0 -ch3 Cu la-45 -coo-Qk^Hs C&9(t) -CH3 —H Cu Ia~46 —CH3 C /|9(t) -coo-〇^h3 cS(t) -CH3 -CHj Zn Ia~47 -ch3 W) -coo-/^^33) -CH3 -ch3 Gu V48 -CH3 W) ~〇Ρ〇 -ζ^Η3 eS(t) -ch3 -ch3 Ni to -WT^CH? w) -ch3 -gh3 Zn 37 201213336 37723pif
Hb 17]Hb 17]
化合物 編號 rLr^B^r13 ^=1^=^=^2 r7=r'4 Ma la-50 -C4_ QH9(t) <X50-〇-CH3 -CH3 -ch3 Pd la-51 —CH2CH2COOH QHg(t) 000-<^)·€Η3 -ch3 -ch3 Zn la-52 —ch2ch2cooh C^Hgit) -COO-Q^Hj QHgit) ~o -ch3 Zn la-53 —·CH3 CJHgit) -ax)-(\cH3 -CH3 Zn b-54 -ch3 -CXX3-()-CH3 ^Fwt) -^Qhcooh -ch3 Zn la-55 -ch3 -COO-<VcH3 QH^t) -Qkcooh -ch3 Cu la-56 -ch3. c^t) -<xo-Q-ch3 Wt) ^Q-cooh 0 Zn la-57 0 C^Hgit) -cx)〇-<\ch3 -ch3 —H Zn la-58 0 W) <XX5-〇-CH3 QH9(t) -ch3 -CH3 Zn la-59 W) -C00-<\CH3 -CH2〇-〇-〇〇2 —ch3 Zn 38 201213336 j//zjpu [化 18]Compound No. rLr^B^r13^=1^=^=^2 r7=r'4 Ma la-50 -C4_ QH9(t) <X50-〇-CH3 -CH3 -ch3 Pd la-51 —CH2CH2COOH QHg( t) 000-<^)·€Η3 -ch3 -ch3 Zn la-52 —ch2ch2cooh C^Hgit) -COO-Q^Hj QHgit) ~o -ch3 Zn la-53 —·CH3 CJHgit) -ax)- (\cH3 -CH3 Zn b-54 -ch3 -CXX3-()-CH3 ^Fwt) -^Qhcooh -ch3 Zn la-55 -ch3 -COO-<VcH3 QH^t) -Qkcooh -ch3 Cu la-56 -ch3. c^t) -<xo-Q-ch3 Wt) ^Q-cooh 0 Zn la-57 0 C^Hgit) -cx)〇-<\ch3 -ch3 —H Zn la-58 0 W <XX5-〇-CH3 QH9(t) -ch3 -CH3 Zn la-59 W) -C00-<\CH3 -CH2〇-〇-〇〇2 —ch3 Zn 38 201213336 j//zjpu [Chemistry 18 ]
化合物 編號 R1=R^=R13 ff=R^=R9=R12 ^rW^R*· r7=r14 Ma ΙΜ0 -hQ^cooh CfiHis HD〇6w2-<iHC^17 -ΟΗπΗττΡ-^^-ρρ^ -CH3 Zns la-61 NHCOCH^CH^CQbH -^00CH2-CHC4H9 -CH3 Zn la-62 ~Q 戰(t) -COOH^-CH: cS(t) -CH2CH^rO"^^"〇C|H3 -ch3 Zn la-63 -CH3 c^Hgit) ^OO-hQkjH: cS(t) -CH2CH2"〇"^~^~〇CH3 -ch3 Cu Ιβ-«7 -wh2 —CM —GH3 —H Zn Ia-ββ —NHCOCH3 —CN —CH3 —qH3 Zn la-69 -ch3 —CN -CH3 -CH3 Zn la-70 —CH3 —CN —0 -gh3 Zn 39 201213336 [化 19]Compound number R1=R^=R13 ff=R^=R9=R12 ^rW^R*· r7=r14 Ma ΙΜ0 -hQ^cooh CfiHis HD〇6w2-<iHC^17 -ΟΗπΗττΡ-^^-ρρ^ - CH3 Zns la-61 NHCOCH^CH^CQbH -^00CH2-CHC4H9 -CH3 Zn la-62 ~Q Battle(t) -COOH^-CH: cS(t) -CH2CH^rO"^^"〇C|H3 -ch3 Zn la-63 -CH3 c^Hgit) ^OO-hQkjH: cS(t) -CH2CH2"〇"^~^~〇CH3 -ch3 Cu Ιβ-«7 -wh2 —CM —GH3 —H Zn Ia -ββ -NHCOCH3 -CN -CH3 -qH3 Zn la-69 -ch3 -CN -CH3 -CH3 Zn la-70 -CH3 -CN -0 -gh3 Zn 39 201213336 [Chem. 19]
化合物 編號 R'rR^^R13 R^R^R^R12 |^=^=^0=^1 r7=r'4 Ma la-71 Cl3H27 —CN -CH3 〇 Cu la-72 —nh2 —QN 一0F3 -〇 Cu b_73 —nhcoch2och2cooh —CN -cf3 -Q Cu Ia»74 ^ηοο^ηο-<〇^Γ^ο2 —CN -cf3 -CH3 Zn la-75 hQhCO-N(CH2CH2OCH3)2 —CN -C3H7(iso) -ch3 Zn la-76 -^>-CO-N(Ol2CH?OCH3)2 ««CN 0 —CH3 Zh la-77 -Q>-CO"N(CH2CH?OCH3)i -»CN -CF3 -ch3 Zn Ia-78 —NHCOCH2OCH2COOH —CN -Q»-CO-N(CH2CH2〇CH3b -ch3 Zn la-79 COO-<^CH3 0¾) CH3 Zn la-80 C/[8(t) ^oo-/^ch3 0¾) -C4_ —H Zn la-81 —c13h27 C^HsU) <:oo-(3-ch3 C%t) ~Q —H Zn la-82 —nhcoch2och2cooh —COOC2H5 S02N(CH2CH30G2Hg)2 —H Co la-83 "Q ch2cooh S〇2-isl-CH2COOH QiHsO) όοο-(^>·οη3 0¾) 一CH3 —H Zn 40 201213336 [化 20]Compound No. R'rR^^R13 R^R^R^R12 |^=^=^0=^1 r7=r'4 Ma la-71 Cl3H27 —CN —CH3 〇Cu la-72 —nh2 —QN —0F3 -〇Cu b_73 —nhcoch2och2cooh —CN —cf3 —Q Cu Ia»74 ^ηοο^ηο-<〇^Γ^ο2 —CN —cf3 —CH3 Zn la-75 hQhCO-N(CH2CH2OCH3)2 —CN —C3H7( Iso) -ch3 Zn la-76 -^>-CO-N(Ol2CH?OCH3)2 ««CN 0 —CH3 Zh la-77 -Q>-CO"N(CH2CH?OCH3)i -»CN -CF3 -ch3 Zn Ia-78 —NHCOCH2OCH2COOH —CN —Q»-CO-N(CH2CH2〇CH3b -ch3 Zn la-79 COO-<^CH3 03⁄4) CH3 Zn la-80 C/[8(t) ^oo- /^ch3 03⁄4) -C4_ —H Zn la-81 —c13h27 C^HsU) <:oo-(3-ch3 C%t) ~Q —H Zn la-82 —nhcoch2och2cooh —COOC2H5 S02N(CH2CH30G2Hg)2 — H Co la-83 "Q ch2cooh S〇2-isl-CH2COOH QiHsO) όοο-(^>·οη3 03⁄4) A CH3 —H Zn 40 201213336 [Chem. 20]
化合物 编號 r>,.—γλ ·*τ\.*-Γλ Ff=F^=F?=R,:i Ff=Ff=R,0=R,v r7=r'4 Ma la-A -nhcoch3 c^(t) ^C0〇"^CH3 -CHj Zn QHa(t) ch2cooh 41 201213336 J//23plf [化 21] I la-1Compound number r>,.—γλ ·*τ\.*-Γλ Ff=F^=F?=R,:i Ff=Ff=R,0=R,v r7=r'4 Ma la-A - Nhcoch3 c^(t) ^C0〇"^CH3 -CHj Zn QHa(t) ch2cooh 41 201213336 J//23plf [化21] I la-1
42 201213336 [化 22]42 201213336 [Chem. 22]
43 201213336 [化 23]43 201213336 [Chem. 23]
H3 I l a-6H3 I l a-6
(t)C4H9CO-NH(t) C4H9CO-NH
-CH2COOH PH3 NHCOC4_ NHCOC4H9(t) (t)G4H9CX)-NH /Ni HC^r^U'-CH2COOH PH3 NHCOC4_ NHCOC4H9(t) (t)G4H9CX)-NH /Ni HC^r^U'
CN •oh2cooh 44 201213336 [化 24] ΙΙδ-7 gh3—^ V~O00CN •oh2cooh 44 201213336 [Chem. 24] ΙΙδ-7 gh3—^ V~O00
%-CO〇Hf_V-CH3%-CO〇Hf_V-CH3
HOOGtHapCHzCb-NH NH-GOGH2OCH2GOQH f 9 CHrC、CH人 CH3 lla«8HOOGtHapCHzCb-NH NH-GOGH2OCH2GOQH f 9 CHrC, CH person CH3 lla«8
GHS, GHjGHS, GHj
€00-< V-gh3 G4H9(t) ooc 晒) ^NH2 / \ H3〇PCf .d; O b〇CH3 H〇人CH3 45 201213336 [化 25]€00-< V-gh3 G4H9(t) ooc sun) ^NH2 / \ H3〇PCf .d; O b〇CH3 H〇人CH3 45 201213336 [Chem. 25]
I \ eriQI \ eriQ
46 201213336 n rii^n [化· 26] I la-13 ila-a46 201213336 n rii^n [化·26] I la-13 ila-a
I la-15I la-15
4747
CH3 Q4H9(t)CH3 Q4H9(t)
C4H9(t) CHfW Χ:Η3 201213336 i//2ipif [化 27] I la-16 /C4H9(t) GH3 )oc c4_) HOOCCH2CH2-CH2 I la-17C4H9(t) CHfW Χ:Η3 201213336 i//2ipif [Chem. 27] I la-16 /C4H9(t) GH3 )oc c4_) HOOCCH2CH2-CH2 I la-17
C4H9(t) C4H9(t)C4H9(t) C4H9(t)
I la-18I la-18
Q^OC HOOCCH2CH2-CH2Q^OC HOOCCH2CH2-CH2
C2H500G-C 48 201213336 [化* 28]C2H500G-C 48 201213336 [化* 28]
HaH炔HaH alkyne
49 201213336 j/ /zjpif C4H9(t)49 201213336 j/ /zjpif C4H9(t)
C4Hg(t)C4Hg(t)
CH3CH3
CH3 ch3 〇OC 〜A^chCH3 ch3 〇OC ~A^ch
C· / 、NH2 C· zri 0··Η2 \〇-COCH3 卜2C· / , NH2 C· zri 0··Η2 \〇-COCH3
C4H9(t) C00-<>-CH3C4H9(t) C00-<>-CH3
'。4哺 N’H N\ ./N、NH C4H9(t)'. 4 feeding N’H N\ ./N, NH C4H9(t)
O-COCHsO-COCHs
1-4 ch3 ch3 C4H9(t) v COO- Λ> mJ, 〇4H9(t) ..Zn、 N -ch3 ch2och2cooh CH,1-4 ch3 ch3 C4H9(t) v COO- Λ> mJ, 〇4H9(t) ..Zn, N -ch3 ch2och2cooh CH,
C4H9(t)C4H9(t)
C4H9(t) Hrvi :Zn: N )=〇"' xo-d CH3 、CH2OCH2〇〇〇H 50 201213336 [化 30]C4H9(t) Hrvi : Zn: N )=〇"' xo-d CH3 , CH2OCH2〇〇〇H 50 201213336 [Chem. 30]
,s(t) -\^ y~CH3 cJC(t),s(t) -\^ y~CH3 cJC(t)
C4_ dW) 1-7C4_ dW) 1-7
_t) 0½ 〇〇C^ ^_t) 01⁄2 〇〇C^ ^
C4H9(t) G00~^^H3H3 c>yt)C4H9(t) G00~^^H3H3 c>yt)
51 201213336 37723pif 〇4H9(t)51 201213336 37723pif 〇4H9(t)
CH3 OOG·^ ^GHCH3 OOG·^ ^GH
C4H9(t) ,Fe:dH3C4H9(t), Fe:dH3
GOO 丨-< C4H9(t)GOO 丨-< C4H9(t)
-ch3 〇4H9(t) CH3-ch3 〇4H9(t) CH3
HOHO
C4H9(t) e4H9(t)C4H9(t) e4H9(t)
ch3 -11Ch3 -11
C4H9(t)C4H9(t)
ch3 C4H9(t)Ch3 C4H9(t)
CH3—C—CH=0-CH3 C4H9(t)CH3—C—CH=0-CH3 C4H9(t)
ch3 C4H9(t) 52 201213336 [化 32] 1-13 CH3Ch3 C4H9(t) 52 201213336 [化32] 1-13 CH3
〇4Hg(t) QtH9(t) οοα〇4Hg(t) QtH9(t) οοα
-COO-COO
CH3 _ _ O'* \〇 H-(CH3 _ _ O'* \〇 H-(
1-14 CH1-14 CH
C4H9(t) ⑽ 3OOG^A^CHwAy^Qoo—Q^_ ‘,Νχ·則 'c=o;* CH3C4H9(t) (10) 3OOG^A^CHwAy^Qoo—Q^_ ‘,Νχ·则 'c=o;* CH3
1-15 GH31-15 GH3
P編 CH3 00C~人〆CHP series CH3 00C~人〆CH
C·) .、Zrr>=r- · O CH 〇4H9(t) Mi3 vΟΟό-^Λ-ΟΗ,N 'CH3C·) ., Zrr>=r- · O CH 〇4H9(t) Mi3 vΟΟό-^Λ-ΟΗ,N 'CH3
1-16 CH,1-16 CH,
C4H9(t) CH3 Gh3 ooc^A^ch^A^cooC4H9(t) CH3 Gh3 ooc^A^ch^A^coo
C4H9(t)C4H9(t)
CH5 c4H9(t) N’H' :Jv! ^4Hg(t) (ί=〇Γ Ut*% bCsHs 53 201213336 [化 33] 1-17CH5 c4H9(t) N’H' : Jv! ^4Hg(t) (ί=〇Γ Ut*% bCsHs 53 201213336 [化 33] 1-17
C4H9(t) 〇μC4H9(t) 〇μ
〇4H9(t) N^H Ν^Ζη:*·'Ν= N b=〇·〇4H9(t) N^H Ν^Ζη:*·'Ν= N b=〇·
.、 II O-C C4H9{t)., II O-C C4H9{t)
gh3 C4H9(t) nhc4h9 1-18 CH3Gh3 C4H9(t) nhc4h9 1-18 CH3
,C4H9(t) ch3 ch3,C4H9(t) ch3 ch3
* u /f\ / . 4.--·Ν· ^Hg(t) NH Zn- N \ .·· N. if〇〇, 、s-c G4H9(t)* u /f\ / . 4.--·Ν· ^Hg(t) NH Zn- N \ .·· N. if〇〇, s-c G4H9(t)
CH, C4H9(t) CH3 nhc4h9 1-19 ch3- 〇4H9(t)CH, C4H9(t) CH3 nhc4h9 1-19 ch3- 〇4H9(t)
CH3 ch3 OOC、CH^^A^COO C4H9(t)CH3 ch3 OOC, CH^^A^COO C4H9(t)
OO
G4H9(t)G4H9(t)
ch3 〇4Hg(t)Ch3 〇4Hg(t)
ch3- \〇-cf bn3 ΌΗCh3- \〇-cf bn3 ΌΗ
C4H9(t)C4H9(t)
CH3 ch3OQC^y w-CHwV-COO 〇4H9(t)CH3 ch3OQC^y w-CHwV-COO 〇4H9(t)
OO
ZrfZrf
\〇-cf N C4H9(t)\〇-cf N C4H9(t)
CH3 C4H9(t) CHNHS02CH3 CH3_C、OH ch3 54 201213336 J / /ζοριι [化 34] 1-21CH3 C4H9(t) CHNHS02CH3 CH3_C, OH ch3 54 201213336 J / /ζοριι [化 34] 1-21
嘱t) A x〇0-/^)-CH3 ;Zrf N W) ‘ bHNHS02GH3 CH3 1-22 CHa嘱t) A x〇0-/^)-CH3 ;Zrf N W) ‘ bHNHS02GH3 CH3 1-22 CHa
ZnZn
,_t) 〇〇C‘ 人 /CH,_t) 〇〇C‘人 /CH
C4H9(t)〇〇〇~^y-cH2 CH, 1-23:C4H9(t)〇〇〇~^y-cH2 CH, 1-23:
T NC、^V^CHwV^e〇OH -CHj C4_)T NC, ^V^CHwV^e〇OH -CHj C4_)
N、 .Ns v - 、Zn·〆 \l QH9(t)N, .Ns v - , Zn·〆 \l QH9(t)
ch3-《mCh3-“m
NHSO^H3 1-24NHSO^H3 1-24
bHNHS〇2CH3 0H C4H9(t)bHNHS〇2CH3 0H C4H9(t)
Hj 〇4晒 55 1. 201213336 [化 35] 1-25 〇4H9(t)Hj 〇4 drying 55 1. 201213336 [化35] 1-25 〇4H9(t)
C4H9(t)C4H9(t)
OOCOOC
Zn* ch3 gh3Zn* ch3 gh3
G4H9(t) )~\ COO -·*( 7CH3N cjCit) n 'chnhso2ch3 gh3 1-26G4H9(t) )~\ COO -·*( 7CH3N cjCit) n 'chnhso2ch3 gh3 1-26
CHNHSOaCl· 6h3 CH3 C4W) COO-/^^CH3 Zn, N 。此⑴ σ \)-cf bHNHSO^CHa 1-27 CH3CHNHSOaCl· 6h3 CH3 C4W) COO-/^^CH3 Zn, N . This (1) σ \)-cf bHNHSO^CHa 1-27 CH3
p4H9(t) CH? OOC 〜 :4哺p4H9(t) CH? OOC ~ :4 feeding
GNGN
CN ch3 oh2CN ch3 oh2
bHNHS〇2CH3 CHS 1-28 CH3bHNHS〇2CH3 CHS 1-28 CH3
P4H9(t) CH3 OOC 〜A^ghP4H9(t) CH3 OOC ~A^gh
C4H9(t) ν7η ^Zn;C4H9(t) ν7η ^Zn;
N ,<r 丨 \〇-d H3 6h2 bHNH5〇2CH3 6h3 56 201213336 377Z3pif [化 36] 1-29N , <r 丨 \〇-d H3 6h2 bHNH5〇2CH3 6h3 56 201213336 377Z3pif [化36] 1-29
關9份 CH^Close 9 copies CH^
CHCH
mm GR3 6h2 eRNHS02GH2 CH3 (¾關)Mm GR3 6h2 eRNHS02GH2 CH3 (3⁄4 off)
CHa 0H3 GHj 賴 卿- iN、,N=^_ 卿CHa 0H3 GHj Lai Qing - iN,, N=^_ Qing
CHS:CHS:
•、'丨〆 N— nh2 04喃 鳴“.’ 'n__^H2 C^t) ^hAJ^c〇〇- 57 201213336 37723pif [化 37] 1-32•, '丨〆 N— nh2 04 “ “.’ 'n__^H2 C^t) ^hAJ^c〇〇- 57 201213336 37723pif [化 37] 1-32
1-331-33
C4H9(t) n"H2 〇4H9(t) N^2 OOC C4H9(t) nh2 nh2C4H9(t) n"H2 〇4H9(t) N^2 OOC C4H9(t) nh2 nh2
CHiCHi
C4H9(t) coo-/~Vch3叫如9⑴NH2 cooC4H9(t) coo-/~Vch3 is called 9(1)NH2 coo
:4H9(t) 1-34:4H9(t) 1-34
CH3 ch3 CHCH3 ch3 CH
C4H9(t)C4H9(t)
:4_ NH2、nhcoch3v CH3CQ-NH Zn、 … • / /NHG0CH3 〇4_):4_ NH2, nhcoch3v CH3CQ-NH Zn, ... • / /NHG0CH3 〇4_)
丫、COO ch3 ch3丫, COO ch3 ch3
C4H9(t) 58 201213336 [化 38] 1-350¾C4H9(t) 58 201213336 [化38] 1-3503⁄4
CHr ΘΗ^ NH2 GH3CQ-NHCHr ΘΗ^ NH2 GH3CQ-NH
NN
QOC C4H9(t)QOC C4H9(t)
G4H9(t)G4H9(t)
NHCOCH3C4H9(t)NHCOCH3C4H9(t)
OOC-^V<^CH-^^COO CH3 ch3OOC-^V<^CH-^^COO CH3 ch3
C4H9(t)C4H9(t)
mm CH3 CH3Mm CH3 CH3
ms NH, GH3CO-NH 〇ύ A嗎 ‘ ’oocMs NH, GH3CO-NH 〇ύ A? ‘ ’ooc
NN
G4H9(t)G4H9(t)
NHCOC^Hs^sW _OCH3 _ C4Hg(t): CH^ ^ '€〇〇— ~ζ~^~〇Η2 CH3 dHj C4Hg(t) 59 201213336 37723pif [化 39]NHCOC^Hs^sW _OCH3 _ C4Hg(t): CH^ ^ '€〇〇— ~ζ~^~〇Η2 CH3 dHj C4Hg(t) 59 201213336 37723pif [化39]
X1··* R3 u R4 背 coo-(~\-ch3 IX\ M C^Hgtt)X1··* R3 u R4 back coo-(~\-ch3 IX\ M C^Hgtt)
V 化合物 編號 R1 R3 R4 R9 X' U-1 -ch3 —COOC2H5 _CH3 -ch3 —CH3 h2o Π-2 -ch3 -COOC2Hs —ch3 -CHg -CHNHS02CH3 CH? h2o fl-3 -ch3 -cooc2hs -ch3 —CH3 NHS02CH3 h2o Π-4 nhso2ch3 —COOCH3 -ch3 -ch3 h2o Π-5 nhso2ch3 —COOC2H5 —CH3 —ch2och2cooH H?0 Π-6 nhso2ch3 -COOC2H5 -ch3 -0 —CH3 h2〇 [化 40]V Compound number R1 R3 R4 R9 X' U-1 -ch3 —COOC2H5 _CH3 -ch3 —CH3 h2o Π-2 -ch3 -COOC2Hs —ch3 -CHg -CHNHS02CH3 CH? h2o fl-3 -ch3 -cooc2hs -ch3 —CH3 NHS02CH3 H2o Π-4 nhso2ch3 —COOCH3 -ch3 -ch3 h2o Π-5 nhso2ch3 —COOC2H5 —CH3 —ch2och2cooH H?0 Π-6 nhso2ch3 -COOC2H5 -ch3 -0 —CH3 h2〇[40]
化合物 编珑 R1 R8 R9 R' X' Π-7 -ch3 -COC5C2H5 〇 —CH3 h2o D-8 ~Q -COOC2H5 〇 〇 —CH3 h2o Π-9 ~ο nhso2ch3 —CM —CH3 —ch3 —CHa h3o Π-10 nhso2ch3 —CN —ch3 —ch3 nhso2ch3 h2o Π-11 nhso3ch3 —CN ~o o -ch3 H20 60 201213336 [化 41]Compound 珑R1 R8 R9 R' X' Π-7 -ch3 -COC5C2H5 〇—CH3 h2o D-8 ~Q -COOC2H5 〇〇—CH3 h2o Π-9 ~ο nhso2ch3 —CM —CH3 —ch3 —CHa h3o Π- 10 nhso2ch3 —CN —ch3 —ch3 nhso2ch3 h2o Π-11 nhso3ch3 —CN ~oo -ch3 H20 60 201213336 [化41]
化合物 編珑 R1 R* R5 R4 R7 R9 X1 IJ-A ~ch3 -COOCjHs -ch3 —CH3: —ζ} ch2cooh —CH3 HjO 61 201213336 [化 42]Compounds 珑 R1 R* R5 R4 R7 R9 X1 IJ-A ~ch3 -COOCjHs -ch3 —CH3: —ζ} ch2cooh —CH3 HjO 61 201213336 [Chem. 42]
化合物 編號 R9 化合物 编號 ΙΠ-1 -ch3 -ch3 ID-2 C2H6 —CHC4H9 -ch3 Uh3 -C4H9(t) -ch3 m-4 ?zh5 -CHC4Hg (p2H5 •"CHC4H9 III-5 -c4_ -c4h9 ⑴ 1Π-β -ch3 1Π-7 s-c4H9 —chch3 -ch3 m-a —CH2〇CH3 —CH3 ΙΠ-9 -CH-O-Q-OCHs -ch3 ΠΜ0 —CH3 Π卜11 -ch-s-ch2cooc2h5 0H3 -ch3 π卜12 ch3 —0=CH2 -ch3 ΠΜ3 9H3 —C-COOCH, 0H3 -ch3 ΠΙ-14 一co-ch-coch3 ch3 -ch3 ΠΗ5 —ch2och2cooc2h5 -ch3 ΠΜ6 —ch2nhso2ch3 —ch3. ΠΙ-17 "CHNHS02CH3 0H3 -ch3 ΠΙ-18 —chnhso2ch3 ύ2Η5 -ch3 ΠΗ19 —chnhso2ch3 c4h9 -ch3 Π卜20 —chnhso2ch3: ch3 ch3 -ch3. ΠΙ-21 -chnhso2-c4h9 ch3 -ch3 m-22 -CHNHS02-^Q)-CH3 CH3 —ch3 ΠΙ-23 —CHNHSO,一^》 CH3 I H3C02SHN -ch3 Di-24 P2H5 -CHNHSd2-N CH3 'C2H5 ~〇H3. 62 201213336 J//2Jpif [化 43]Compound No. R9 Compound No. ΙΠ-1 -ch3 -ch3 ID-2 C2H6 —CHC4H9 -ch3 Uh3 -C4H9(t) -ch3 m-4 ?zh5 -CHC4Hg (p2H5 •"CHC4H9 III-5 -c4_ -c4h9 (1) 1Π-β -ch3 1Π-7 s-c4H9 —chch3 -ch3 ma —CH2〇CH3 —CH3 ΙΠ-9 —CH—OQ-OCHs —ch3 ΠΜ0 —CH3 Π 11 11 —ch-s-ch2cooc2h5 0H3 —ch3 π 12 ch3 —0=CH2 —ch3 ΠΜ3 9H3 —C—COOCH, 0H3 —ch3 ΠΙ-14 a co-ch-coch3 ch3 -ch3 ΠΗ5 —ch2och2cooc2h5 —ch3 ΠΜ6 —ch2nhso2ch3 —ch3. ΠΙ-17 "CHNHS02CH3 0H3 -ch3 ΠΙ-18 —chnhso2ch3 ύ2Η5 -ch3 ΠΗ19 —chnhso2ch3 c4h9 -ch3 Π卜20 —chnhso2ch3: ch3 ch3 -ch3. ΠΙ-21 -chnhso2-c4h9 ch3 -ch3 m-22 -CHNHS02-^Q)-CH3 CH3 —ch3 ΠΙ -23 —CHNHSO,一^” CH3 I H3C02SHN -ch3 Di-24 P2H5 -CHNHSd2-N CH3 'C2H5 ~〇H3. 62 201213336 J//2Jpif [化43]
化合物 编號 Re Re 化合物 編號 R? (f UF25 —CHs Ili-26 -ch^ch2cooc2hs_ -ch3 Ιϊί-27 CHa —CH3 IHr28 CHg -6h-shQ- —CH3 :Π 卜 29 -CH2NHS02qH3, -CH^HSOjCHg ΙΪΙ-30 -ch2-chnhso2ch? 6H3 -CH2-CHNHS03CH3 0H3 -CH2NHSp2CHi 修 -CHC4H3 IU-32 -ch2-chnhso2ch3 ch3 ΙίΙ-33 -CH3 Hl-34 -ch2-chnhso2ch3 CHs, 63 201213336 [化 44]Compound No. Re Re Compound No. R? (f UF25 - CHs Ili-26 -ch^ch2cooc2hs_ -ch3 Ιϊί-27 CHa -CH3 IHr28 CHg -6h-shQ- -CH3 :Π卜29 -CH2NHS02qH3, -CH^HSOjCHg ΙΪΙ -30 -ch2-chnhso2ch? 6H3 -CH2-CHNHS03CH3 0H3 -CH2NHSp2CHi repair-CHC4H3 IU-32 -ch2-chnhso2ch3 ch3 ΙίΙ-33 -CH3 Hl-34 -ch2-chnhso2ch3 CHs, 63 201213336 [化44]
化合物 編號 R8· R9 化合物 編珑 R9 f? 01-35 一CH3 ΠΙ-36 ~〇 nhso2gh3 一 ch3 II 卜37 〇 nhs〇2ch3 -CH3 10^38 "^ihsoj-Q -ch3 ΠΙ-09 —CH3 ΠΙ-40 ~〇 dCH3 —CH3 ΙΠ-41 -ch3 ΠΙ-42 ~Q ch3 so2nch3 -ch3 0卜43 -Q-SCH3 -CH3 ΠΜ4 -·^^-S〇2CH3 -ch3 64 201213336 [化 45]Compound No. R8· R9 Compound Codification R9 f? 01-35 One CH3 ΠΙ-36 ~〇nhso2gh3 One ch3 II Bu 37 〇nhs〇2ch3 -CH3 10^38 "^ihsoj-Q -ch3 ΠΙ-09 —CH3 ΠΙ -40 ~〇dCH3 -CH3 ΙΠ-41 -ch3 ΠΙ-42 ~Q ch3 so2nch3 -ch3 0卜43 -Q-SCH3 -CH3 ΠΜ4 -·^^-S〇2CH3 -ch3 64 201213336 [化45]
化合物 編號: R8 R® 化合物 編號 R9 UR5 —ch3. —ch3 HM6 92Ηδ ~CHC4H9 C2H5 —CHC4h% UF47 -c4h3 ⑴: U1H18 -0 ΙΠτ49 -CH2NHS〇2CH3, BI-50 —CH3NHS02〇H3 —CH2NHS02CH3 IU-51 —CHNhS〇2CH3 0H3 ^-ch3 Bi-62 -CHNHS02CH3 —CHNHSb2CH3 0H3 m-53 -CHNHSC^iCH^ 64Hg -CH3 ΠΙ-54 ~Q NHS〇2CHb -ch3 -q NHS^CH3 NHSQ2CH3 01-56 SOiNHCOCf^. ™ch3 [化 46] CHjCompound number: R8 R® Compound number R9 UR5 —ch3. —ch3 HM6 92Ηδ ~CHC4H9 C2H5 —CHC4h% UF47 -c4h3 (1): U1H18 -0 ΙΠτ49 -CH2NHS〇2CH3, BI-50 —CH3NHS02〇H3 —CH2NHS02CH3 IU-51 — CHNhS〇2CH3 0H3 ^-ch3 Bi-62 -CHNHS02CH3 —CHNHSb2CH3 0H3 m-53 -CHNHSC^iCH^ 64Hg -CH3 ΠΙ-54 ~Q NHS〇2CHb -ch3 -q NHS^CH3 NHSQ2CH3 01-56 SOiNHCOCf^. TMch3 [Chem. 46] CHj
p麟 TOC ) R8 A K ! XR9P Lin TOC ) R8 A K ! XR9
〇Sb& c^m〇Sb& c^m
X3H 化合物 編號 R8 化合物 編號 R8: JD-57 -<>CH3 -ch3 11F58 -〇^H3 c% chT CHi IU-59 ~Q OCH^jOH -ch3 CXX)OH3 ™CH3 〇Ch3 7=\ 触1 0晰 —ch3 NHS02PH3 Ϊ0-63; ~Q —ch3 ㈣ ☆ 65 201213336 J / /zjpif [化 47]X3H Compound No. R8 Compound No. R8: JD-57 -<>CH3 -ch3 11F58 -〇^H3 c% chT CHi IU-59 ~Q OCH^jOH -ch3 CXX)OH3 TMCH3 〇Ch3 7=\ Touch 1 0明—ch3 NHS02PH3 Ϊ0-63; ~Q —ch3 (4) ☆ 65 201213336 J / /zjpif [化47]
C^Hgd) ch3-/ \-ooc C,Hg(t) 化合物 編珑 R3 R4 R5 R6 R9 [Π-65 一CHa -CHa —COOC2H5 -CH3 -ch3 Hi-66 —ch3 -CH3 —C00C2Hs —CHNHS〇2CH3 0Ha —CHNHS02CH3 0H3 iil-67 ~ch3 —ch3. -COOC2H5 NHS〇2CH3 <X NHSOsCHs m-68 O —CHg. —COOC2H5 —CHa -ch3 111-69 -o ~o —COOCaHg —CHa -c.h3 IH-70 -ch3 ~o C· -C00-/^)-CH3 —ch3 —CH2NHS02-^^-CH3 [化 48]C^Hgd) ch3-/ \-ooc C,Hg(t) Compound 珑R3 R4 R5 R6 R9 [Π-65 A CHa -CHa —COOC2H5 -CH3 -ch3 Hi-66 —ch3 -CH3 —C00C2Hs —CHNHS〇 2CH3 0Ha —CHNHS02CH3 0H3 iil-67 ~ch3 —ch3. —COOC2H5 NHS〇2CH3 <X NHSOsCHs m-68 O —CHg. —COOC2H5 —CHa —ch3 111-69 —o ~o —COOCaHg —CHa —c.h3 IH-70 -ch3 ~o C· -C00-/^)-CH3 —ch3 —CH2NHS02-^^-CH3 [化48]
化合物 編號 R3 R4 R5 R8 R* BI-71 CHa —co-nch3 —CH3 -CH2NHSP2^^^-CH3 ΠΙ-72 -〇 C3H?(i8〇) -CO-iilC3H7(Iso) —ch3 —CH2NHS〇2-^^-CM3 HI-73 ~o -〇 —ch3 —CH2NHS〇2-^=^-CH3 DI-74 0 -0 CHa —conh^^^-ch3 —ch3 ~CH2NHSP2™^^-CH3 QI-75 ~o CH3 ya™, -°0Ν-〇 -ch3 -CH2NHS02-^^"CH3 66 201213336 [化 49]Compound No. R3 R4 R5 R8 R* BI-71 CHa —co-nch3 —CH3 —CH2NHSP2^^^-CH3 ΠΙ-72 -〇C3H?(i8〇) -CO-iilC3H7(Iso) —ch3 —CH2NHS〇2- ^^-CM3 HI-73 ~o -〇—ch3 —CH2NHS〇2-^=^-CH3 DI-74 0 -0 CHa —conh^^^-ch3 —ch3 ~CH2NHSP2TM^^-CH3 QI-75 ~ o CH3 yaTM, -°0Ν-〇-ch3 -CH2NHS02-^^"CH3 66 201213336 [化49]
化合物 編號 R3 R4 Ff R9 ΗΗ7β -gh3 —ch3 —CH3 «Η7 -ch3 —chnhso2ch3. ch3 —ch3 ΠΗ78 ~~CH3 —0H3 —qHNHS02CH3 CHj —chnhso2ch3 έΗ3 ΗΙ-79 —ch3 -CH3 —chnhso2ch, 6h3 —CHNHS02CH3 ch3: Dh80 -ch3 -0 -ch3 -ch3 ΗΗ8ί -ch3 ~o -ch3 —chnhso2ch3 ch3 ΠΙ-82 -CH3 0 —CHNHS02eH3 ch3 -CHNHS02CH3 ch3 67 201213336 37723pif [化 50]Compound number R3 R4 Ff R9 ΗΗ7β -gh3 —ch3 —CH3 «Η7 -ch3 —chnhso2ch3. ch3 —ch3 ΠΗ78 ~~CH3 —0H3 —qHNHS02CH3 CHj —chnhso2ch3 έΗ3 ΗΙ-79 —ch3 —CH3 —chnhso2ch, 6h3 —CHNHS02CH3 ch3: Dh80 -ch3 -0 -ch3 -ch3 ΗΗ8ί -ch3 ~o -ch3 —chnhso2ch3 ch3 ΠΙ-82 -CH3 0 —CHNHS02eH3 ch3 -CHNHS02CH3 ch3 67 201213336 37723pif [化50]
化合物 编號 R3 R8 R9 UF-83 一 ch3 O -CHNHSO2CH3 0H3 —chnhso2ch3 0H3 ΠΙ-84 —ch3 ~o —CHNHS〇2pH3 nhso2ch3 m-85 -ch3 0 -CiH9(t) nhso2ch3 m-86 o -ch3 -ch3 —ch3 m-Bi -o -ch3 —ch2nhso2ch3 -ch2nhso2ch3 ΠΗ的 -o 〇 ~CH3 -ch3 ΙΠ-89 -~ch^ NHSO2CH3 —ch3 -CH3 68 201213336 [化 51]Compound number R3 R8 R9 UF-83 a ch3 O -CHNHSO2CH3 0H3 —chnhso2ch3 0H3 ΠΙ-84 —ch3 ~o —CHNHS〇2pH3 nhso2ch3 m-85 -ch3 0 -CiH9(t) nhso2ch3 m-86 o -ch3 -ch3 —ch3 m-Bi -o -ch3 —ch2nhso2ch3 -ch2nhso2ch3 --o 〇~CH3 -ch3 ΙΠ-89 -~ch^ NHSO2CH3 —ch3 -CH3 68 201213336 [化51]
化合物 編號 Rf* if R9 12-90 -ch3 -CH3 —ch3 DH91 -ph3 -ch3 ^Ch3 —CHNHS〇2QH3 C4H9 m-92 —CH3 —ch3 —chnhso2ch3 c4h9 -hCHNHSO^H3 C4H9 ΠΗ93 〇 —cr3 —CH3 Dh$4 〇 -C4He(t) -C4H90) 10-95 ~o ^O —chnhso2ch3 C4H9 -C4H9(t) ΠΗ9β -〇 ~o NHS〇2CsH17 .-rOHj m-97 ~o rgHS〇2GH3 ~Q rjHS〇2CH3 —ch3 ~PH3 69 201213336 [化 52] R3 μ R4Compound number Rf* if R9 12-90 -ch3 -CH3 —ch3 DH91 -ph3 -ch3 ^Ch3 —CHNHS〇2QH3 C4H9 m-92 —CH3 —ch3 —chnhso2ch3 c4h9 —hCHNHSO^H3 C4H9 ΠΗ93 〇—cr3 —CH3 Dh$4 〇-C4He(t) -C4H90) 10-95 ~o ^O —chnhso2ch3 C4H9 -C4H9(t) ΠΗ9β -〇~o NHS〇2CsH17 .-rOHj m-97 ~o rgHS〇2GH3 ~Q rjHS〇2CH3 —ch3 ~PH3 69 201213336 [化52] R3 μ R4
化合物 編號 R3 R4 R9 ΙΠ-9Β p ch3 ch3 ^CHs —CH3 12-99 —CH3 —CH3 m-ioo ~O~°qH3 —(3~PCH3 -ch3 —CH3 ΠΗ101 ~Q ~Q 一 ch3 一 ch3 m-102 CH3 —0HC2H5 ch3 -CHC2H5 —chnhso2ch3 c4h9 —chnhso2ch3 04H9 hh〇3 -0 "Q NHS02C3Hi7 ^Q NHS02CsH17 70 201213336 [化 53]Compound No. R3 R4 R9 ΙΠ-9Β p ch3 ch3 ^CHs —CH3 12-99 —CH3 —CH3 m-ioo ~O~°qH3 —(3~PCH3 -ch3 —CH3 ΠΗ101 ~Q ~Q a ch3 a ch3 m- 102 CH3 —0HC2H5 ch3 -CHC2H5 —chnhso2ch3 c4h9 —chnhso2ch3 04H9 hh〇3 -0 "Q NHS02C3Hi7 ^Q NHS02CsH17 70 201213336 [Chem. 53]
化合物 編號 R7 R8 ΠΙ-Α -/j| CHzCQOH -c4_ —〇4Η9(ί) [化 54]Compound No. R7 R8 ΠΙ-Α -/j| CHzCQOH -c4_ —〇4Η9(ί) [Chem. 54]
化合物 編號 R, R5 R7 R8 R9 1Π-Β -CHj -ch3 -goog2h5 oi2cooh 一 ch3 一 ch3 71 201213336 37723pif [化 55]Compound No. R, R5 R7 R8 R9 1Π-Β -CHj -ch3 -goog2h5 oi2cooh a ch3 a ch3 71 201213336 37723pif [化55]
化合物 編號 R3 R4 R7 R9 I1I-C —CH3 -ch3 CH2COON —CH3 -ch3.Compound No. R3 R4 R7 R9 I1I-C —CH3 -ch3 CH2COON —CH3 -ch3.
[化 56][化56]
c4_ -^3~ch3 化合物編號 R8 R9 W-A σ 72 201213336 37723pif [化 57]C4_ -^3~ch3 Compound number R8 R9 W-A σ 72 201213336 37723pif [化57]
OH: 化合物 編號 r3 R4 Rs P7 Rs R9 «1-65-2 HjC 丫 CH3 Κ3〇γ.ρΗ3 -cooc2h5 —H -ch3 -CH3 ,70,2 he:丫 cri3 H3CyCH3 -coo-Q-ch3 一 H "CH3i -ch2nhs〇2^^^-ch3 HhB-2 HaCyCHa ftc 丫 C“3 -GOOC2H5 CHaCOOH -ch3 -ch3 [化 58]OH: Compound No. r3 R4 Rs P7 Rs R9 «1-65-2 HjC 丫CH3 Κ3〇γ.ρΗ3 -cooc2h5 —H -ch3 -CH3 ,70,2 he:丫cri3 H3CyCH3 -coo-Q-ch3 One H " ;CH3i -ch2nhs〇2^^^-ch3 HhB-2 HaCyCHa ftc 丫C"3 -GOOC2H5 CHaCOOH -ch3 -ch3 [化58]
化合物 編號 R3 R4 r7 III-90-2 H3C CH3 T H3G^CH3 —H -ch3 -ch3 in-C-2 H3C^CH3 h3c 丫 ch3 ~ψ CH2〇QQH 、 —ch3. -ch3; 自膜厚之觀點考慮,較佳為本發明中之特定錯合物之 莫耳吸光係數儘可能高。而且,自色純度提高之觀點考慮, 73 201213336 最大吸收波長Xmax較佳為520 nm〜580 nm,更佳的是530 nm〜570 nm。另外,最大吸收波長、及莫耳吸光係數可利 用分光光度計UV-2400PC(島津製作所公司製造)而測定。 自溶解性之觀點考慮,較佳為本發明中之特定錯合物 之熔點並不過高。 本發明中之特定錯合物可藉由美國專利第4,774,339 號、美國專利第5,433,896號、日本專利特開2〇〇1’_2W61 號、曰本專利特開2002-155052號、曰本專利第3614586 號、澳大利亞化學雜誌(AustJChem),1965,u, 1835-1845、J.H.B〇ger 等人,雜原子化學(Heter〇at〇mCompound No. R3 R4 r7 III-90-2 H3C CH3 T H3G^CH3 —H -ch3 -ch3 in-C-2 H3C^CH3 h3c 丫ch3 ~ψ CH2〇QQH , —ch3. -ch3; From the viewpoint of film thickness It is preferable that the Mohr absorption coefficient of the specific complex compound in the present invention is as high as possible. Moreover, from the viewpoint of improvement in color purity, 73 201213336 The maximum absorption wavelength Xmax is preferably 520 nm to 580 nm, more preferably 530 nm to 570 nm. Further, the maximum absorption wavelength and the molar absorption coefficient can be measured by using a spectrophotometer UV-2400PC (manufactured by Shimadzu Corporation). From the standpoint of solubility, it is preferred that the melting point of the specific complex in the present invention is not too high. The specific complexes in the present invention can be obtained by U.S. Patent No. 4,774,339, U.S. Patent No. 5,433,896, Japanese Patent Laid-Open Publication No. Hei No. Hei. No. 2002-155052, and Japanese Patent Laid-Open No. 2002-155052. No., Australian Chemical Journal (AustJChem), 1965, u, 1835-1845, JHB〇ger et al., Heteroatomatology (Heter〇at〇m
Chemistry) ’ V〇U,N〇 5 ’ 389 ( 199〇)等中所記載之方法 而合成。 關於本發明中之特定錯合物之合成方法,具體而言可 適用日本專利特開2008-292970號之段落[〇131]〜[〇157] 中所記載之方法。 本發明之感光性著色硬化性組成物可單獨使用i種特 定錯合物,亦可併用2種以上。 、^發明之特定錯合物於著色硬化性組成物中之含量因 为子里及莫耳吸光係數而異,相對於著色硬化性組成物之 所有固形物成分而言,較佳為10 wt%〜70量%,更佳的是 i〇wt% 〜5Gwt%,最佳的是 15wt%〜3〇wt%。 [(A-2)酞菁系顏料] 作為本發明中所使用之酞菁系顏料,若為具有酞菁骨 /員料則並無特別限制。而且,作為酜菁系顏料中所 74 201213336 構成酞菁骨架之金屬即可’並無特 鋅、紹作i中心^使用鎮、欽、鐵、姑、錦、鋼、 15、月^之敝菁系顏料,具體可列舉C.1.顏料藍 1、ΓΜ Γ員抖藍15 · 1、C·1.顏料藍15 : 2、C.L顏料藍15 : ••顏料藍15:4、CI顏料藍15:5 (:1顏料藍15:6、 • j料藍16、C.I.顏料藍17 :卜c丄顏料藍75、c ι顏 "C.1.顏料綠7、C.I.顏料綠36、C.I.顏料綠37、1化 t菁、,基触菁、銘酞菁氧化物、鋅㈣。其中:自 ::丨生與著色力之方面而言,較佳為CJ顏料Μ 15 J員料藍15:6、顏料藍15:1、CI顏料藍15:2,特上 C.I·顏料藍15:6較佳。 疋 本發明之欧菁系顏料於著色硬化性組成物中之 對。於著色硬化性組成物之所有固形物成分而言較佳為里 wt/〇〜70 wt°/〇,更佳的是2〇 wt%〜6〇 wt%,最佳 wt%〜5〇wt%。 疋 35 而且’作為特定錯合物與駄菁系顏料之含有比,較佳 ,酞菁系顏料:特定錯合物=1〇〇 : 5〜1〇〇 : 1〇〇,更佳的 疋100. 15〜100: 75 ’進一步更佳的是1〇〇: 25〜1〇〇: 5〇。 [(B)分散劑] 本發明之著色硬化性組成物含有(B)分散劑。 (B)分散劑使用公知之顏料分散劑或界面活性劑。 作為刀政劑,使用多種化合物,例如可列舉醜菁衍生 物(市售品EFKA-745 (咖公司製造、s〇lsperse 5〇〇〇 75 201213336 (日本Lubrizol股份有限公司製造);有機聚碎氧燒聚合物 KP341 (信越化學工業股份有限公司製造)、(曱基)丙二酸 系(共)聚合物Polyflow Νο.75、Νο.90、Ν〇·95 (以上由共榮 社化學股份有限公司製造)、wool (袼商股份有限公/司製 造)等陽離子系界面活性劑;聚氧乙烯月桂基鱗、聚氧乙 烯硬脂基醚、聚氧乙烯油基醚、聚氧乙烯辛基苯基醚、聚 氧乙烯壬基苯基醚、聚乙二醇二月桂酸酯、聚乙二醇二硬 脂酸酯、山梨糖醇酐脂肪酸酯等非離子系界面活性劑; W004、W005、W017 (以上由裕商股份有限公司製造)等 陰離子系界面活性劑;EFKA-46、EFKA-47、EFKA_47EA、 EFKA聚合物1〇〇、EFKA聚合物400、EFKA聚合物401、 EFKA聚合物450 (以上由森下產業股份有限公司製造) 等高分子分散劑;Solsperse 3000、5000、9000、12000、 13240、13940、17000、24000、26000、28000 等各種 Solsperse 分散劑(曰本Lubrizol股份有限公司製造);Adeka Pluronic L31、F38、L42、L44、L61、L64、F68、L72、P95、F77、 P84、F87、P94、L1(U、P103、F108、L12卜 P-123 (以上 由ADEKA股份有限公司製造)、及isonet S-20 (三洋化成 股份有限公司製造)。 本發明之(B)分散劑於著色硬化性組成物中之含量 相對於顏料而言較佳為1 wt%〜80 wt%,更佳的是5 wt% 〜70 wt% ’最佳的是10 wt%〜60 wt%。 [(C)聚合性化合物] 本發明之著色硬化性組成物含有(C)選自下述通式 76 201213336 37723pif (MO-1)〜通式(MO-5)所表示之聚合性化合物之至少 1種化合物。 [化 59] 〒㈠猶民Chemistry) synthesized by the method described in 'V〇U, N〇 5' 389 (199 〇). With regard to the synthesis method of the specific complex in the present invention, the method described in paragraphs [〇131] to [〇157] of JP-A-2008-292970 can be specifically applied. The photosensitive coloring-curable composition of the present invention may be used alone or in combination of two or more. The content of the specific complex compound of the invention in the coloring curable composition varies depending on the ray absorption coefficient and the molar absorption coefficient, and is preferably 10 wt% with respect to all the solid content components of the colored curable composition. 70% by weight, more preferably i〇wt% 〜5Gwt%, most preferably 15wt%~3〇wt%. [(A-2) phthalocyanine-based pigment] The phthalocyanine-based pigment used in the present invention is not particularly limited as long as it has a phthalocyanine bone/member. In addition, as a phthalocyanine pigment, 74 201213336 constitutes a phthalocyanine skeleton metal. 'There is no special zinc, Shao Zuo i center ^ Use town, Qin, iron, aunt, Jin, steel, 15, month ^ 敝 敝For the pigment, specifically, C.1. Pigment Blue 1, Γ 抖 抖 Blue 15 · 1, C·1. Pigment Blue 15: 2, CL Pigment Blue 15: • • Pigment Blue 15: 4, CI Pigment Blue 15 :5 (:1 Pigment Blue 15:6, • j Material Blue 16, CI Pigment Blue 17: Bu C丄 Pigment Blue 75, c 颜颜"C.1. Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37, 1 chemistry, phthalocyanine, phthalocyanine oxide, zinc (4). Among them: from: in terms of twinning and coloring, preferably CJ pigment Μ 15 J staff material blue 15:6 , Pigment Blue 15:1, CI Pigment Blue 15:2, and especially CI·Pigment Blue 15:6. 疋The phthalocyanine pigment of the present invention is in the coloring curable composition. Preferably, all solid components are wt/〇~70 wt°/〇, more preferably 2〇wt%~6〇wt%, optimal wt%~5〇wt%. 疋35 and 'as The specific ratio of the specific complex to the phthalocyanine pigment is preferably, the phthalocyanine Material: Specific complex = 1 〇〇: 5~1 〇〇: 1 〇〇, better 疋 100. 15~100: 75 ' Further better is 1 〇〇: 25~1 〇〇: 5〇 [(B) Dispersing Agent] The colored curable composition of the present invention contains (B) a dispersing agent. (B) A known pigment dispersing agent or a surfactant is used as the dispersing agent. As the knife agent, various compounds are used, for example, Listed ugly phthalocyanine derivatives (commercial product EFKA-745 (manufactured by café, s〇lsperse 5〇〇〇75 201213336 (made by Lubrizol Co., Ltd.); organic poly oxyhydrogenated polymer KP341 (Shin-Etsu Chemical Co., Ltd.) Manufactured, (mercapto) malonic acid (co)polymer Polyflow Νο.75, Νο.90, Ν〇·95 (above manufactured by Kyoeisha Chemical Co., Ltd.), wool (袼商股份有限公/ Is a cationic surfactant; polyoxyethylene lauryl scale, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, Polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, etc. Ionic surfactant; W004, W005, W017 (above manufactured by Yushang Co., Ltd.) and other anionic surfactants; EFKA-46, EFKA-47, EFKA_47EA, EFKA polymer 1〇〇, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (above manufactured by Morishita Industrial Co., Ltd.) and other polymer dispersants; Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 and other Solsperse dispersants (manufactured by Sakamoto Lubrizol Co., Ltd.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L1 (U, P103, F108, L12, P- 123 (above manufactured by ADEKA Co., Ltd.) and isonet S-20 (manufactured by Sanyo Chemical Co., Ltd.). The content of the (B) dispersant of the present invention in the colored curable composition is preferably from 1 wt% to 80 wt%, more preferably from 5 wt% to 70 wt%, based on the pigment. Wt%~60 wt%. [(C) Polymerizable Compound] The colored curable composition of the present invention contains (C) at least one selected from the group consisting of polymerizable compounds represented by the following formula 76 201213336 37723pif (MO-1) to (MO-5) 1 compound. [化 59] 〒 (1) Juemin
Rfr]-GH2-c-eH2ip|rR rn-i) CH神RRfr]-GH2-c-eH2ip|rR rn-i) CH God R
CH2-f-TtR R#)iCH2-Q~GH2-^-CH2-C-CH2-HfrR (HO-2) ch2 蝴; GH2-fT^R R 斜 CH? CH24-T-tR —0-CH2 ~c—ch2^t4-r (MO-3) R-fT^.GHj CH2f%R ch2-Hr 1 (»〇-4) R~HCH2- 〇丫 Ny〇 -N r4_2-n 丫 n'chA 0 、CH24TtR (MO-5) [化 60] ch3. R: H2C*CH-C-0- H2C-C-C-0- -〇^C-fCH2^-a-pH -0-C-^iH-(CH2^COH -OH T: . —〇CH2~ t —OCH2CH2- ^ —OCHsCHjCHj- , —OCHjCHjCHjCHj- Z: -Q-CrNH-(:CH3^NH-€-0-- 於通式(MO-1)〜通式(MO-5)中,n為0〜14之 77 201213336 ^// ^^υιϊ 整數,ml〜m4為丨〜8之整數。於同一分子内多個存在之 R及T可個別相同亦可不同。 而且,於通式(MO-1)〜通式(M0_5)所表示之聚 合性化合物之各個中,多個存在之R中的至少丨個表示 (MO-2)中,Z為·〇·之情形時’以上,或者w_〇c( = o)ch=ch2以外之基。 外^本說明#中,有時將丙_基與曱基丙烯醯 基總稱記載為(甲基)丙_基,且將 酸酯總稱記載為(甲基)丙烯酸酯。 /、甲基丙烯 )中,較佳之η為0 。而且,較佳為ml〜 於通式(MO-1)〜通式(M〇_5 〜14之整數,更佳的是〇〜2之整數 m4為1〜8之整數,更佳的是丨〜2。 〜通式(购)中之r,於同 刀子内多個存在之R中的至少i個可 ch2、或-0C(=0)C(CH3)=CH2。其他 意者’較佳為下述基。 』马上江T之 [化 61] 0CH2-f-TtR R#)iCH2-Q~GH2-^-CH2-C-CH2-HfrR (HO-2) ch2 butterfly; GH2-fT^RR oblique CH? CH24-T-tR —0-CH2 ~c —ch2^t4-r (MO-3) R-fT^.GHj CH2f%R ch2-Hr 1 (»〇-4) R~HCH2- 〇丫Ny〇-N r4_2-n 丫n'chA 0 , CH24TtR (MO-5) [Chem. 60] ch3. R: H2C*CH-C-0- H2C-CC-0- -〇^C-fCH2^-a-pH -0-C-^iH-(CH2^COH -OH T: . -〇CH2~ t -OCH2CH2- ^ -OCHsCHjCHj- , -OCHjCHjCHjCHj- Z: -Q-CrNH-(:CH3^NH-€-0-- in general formula (MO-1)~ (MO-5), n is 0 to 14 of 77 201213336 ^// ^^υιϊ integer, ml~m4 is an integer of 丨~8. Multiple R and T existing in the same molecule may be the same or different Further, in each of the polymerizable compounds represented by the general formula (MO-1) to the general formula (M0_5), at least one of the plurality of R present is represented by (MO-2), and Z is ··· In the case of the above, or w_〇c(=o)ch=ch2. In addition, in the description #, the general name of the propyl group and the fluorenyl acryl group are sometimes described as (meth) propyl _ And the general name of the acid ester is described as (meth) acrylate. /, methacrylic), preferably η 0. Moreover, it is preferably ml~ from the general formula (MO-1) to the general formula (M〇_5 to 14 integers, more preferably 〇~2, the integer m4 is an integer of 1 to 8, more preferably Is 丨~2. ~ r in the general formula (purchased), at least i of the plurality of R existing in the same knife can be ch2, or -0C(=0)C(CH3)=CH2. Other meanings' It is preferably the following group. 』 即江T之[化61] 0
•OH 及f t基及m2為1〜8之整數。較佳為ml 及m2為1〜2之整數。 T,上述結 作為通式(MO-1)〜通式(M〇_5)中之 78 201213336 3 Ί /Ζόρΐί 構中較佳為-(CH2)m-、-〇CH2_,特佳的是-(CH2)m_。 而且,Z較佳為-〇-。 於同-分子内多個存在之R及τ可個勸同亦可不 同,自合成之容易性考慮,較佳為相同。 於通式(ΜΟ-1)〜通式(Μ〇_5)所表示之聚合性化 合物中,較佳為通式(Μ(Μ)、㉟式(Μαι)所表示之化 合物’特佳的是通式(ΜΟ-2)所表示之化合物。 其中’特佳的是以通式(Μ0·2)所表示,且通式(μ〇 2) 中所存在之至少-個述所示之任意基的 [化 62]• OH and f t groups and m2 are integers from 1 to 8. Preferably, ml and m2 are integers of 1 to 2. T, the above-mentioned knot is 78 of the general formula (MO-1) to the general formula (M〇_5). 201213336 3 Ί /Ζόρΐί The structure is preferably -(CH2)m-, -〇CH2_, particularly preferably - (CH2)m_. Moreover, Z is preferably -〇-. The presence of multiple R and τ in the same-molecule may be different, and is preferably the same from the standpoint of ease of synthesis. In the polymerizable compound represented by the formula (ΜΟ-1) to the formula (Μ〇_5), it is preferred that the compound represented by the formula (Μ(Μ), 35 ((αα)) is particularly preferable. a compound represented by the formula (ΜΟ-2), wherein 'excellent is represented by the formula (Μ0·2), and at least one of the groups represented by the formula (μ〇2) [化62]
'Q"?^CH2fcrf0H 於上述之基中,ml及m2個別為〗〜8之整數。 -物:〜通式(M0_5)所表示之聚合性化 口物之:、體例表不如下。本發明並不岐於該些具體例。 丙婧=化異三聚氰酸三丙烯酸酯、8-己内_改質三_(2· 基乙基)異氛酸醋、乙氧基化丙三醇三_旨、 Ϊ t 丙_醋、三經甲基丙朗烯酸酯、二三經曱 、元四丙烯1^旨、乙氧基化季戊四醇四丙烯酸自旨、季戍 ^^_酯、二季細醇六丙烯_旨、二季戊四醇五 =烯H六(丙稀醯氧基乙基乙氧基)二季戊四醇、二季 五丙歸_之_酸單g|、三”基丙烧三甲基丙 79 201213336 本發明之著色硬化性組成物含有(c)通 〜通式(MO-5)所表示之至少1種聚合性化^ M〇-l) 有2種以上而構成。於2種以上之情形時, 亦可含 式所表不之2種以上聚合性化合物,亦可為不同诵二目:通 示之2種以上聚合性化合物。 武所表 另外,本發明之著色硬化性組成物亦可 (MCM)〜通式(M〇_5)所表示之聚合性化合物 其他結構的聚合性化合物。 卜之 作為通式(MO-1)〜通式(MO_5)所表示之聚人性 化合物以外之其他結構之聚合性化合物(以下適宜稱為;其 他聚合性化合物」),可列舉不飽和魏(例如丙_/甲 基丙烯酸、伊康酸、巴豆酸、異丁烯酸、馬來酸等)或其 酯類、醯胺類,較佳為使用不飽和羧酸與脂肪族多元醇化 合物之酯、不飽和羧酸與脂肪族多元胺化合物之醯胺類。 而且,具有羥基或胺基、巯基等親核性取代基之不飽和羧 酸醋或酿胺類與單官能或多官能異氰酸酯類或環氧類之加 成反應生成物、及與單官能或多官能羧酸之脫水縮合反應 生成物等亦可作為適宜之其他聚合性化合物而併用。 而且’作為其他聚合性化合物,具有異氰酸酯基或環 氧基等親電子性取代基之不飽和羧酸酯或醯胺類與單官能 或多官能之醇類、胺類、硫醇類的加成反應物,另外具有 i基或甲苯磺醯氧基等脫離性取代基之不飽和羧酸酯或醯 胺類與單官能或多官能之醇類 、胺類、琉醇類之取代反應 物亦較佳。而且,作為其他例,亦可使用對不飽和膦酸、 201213336 ± 苯乙稀、乙烯醚等進行取代而成之化合物群代替上 和羧酸。 至於脂肪族多元醇化合物與不飽和繞酸之酯之單體的 具體例,作為丙烯酸酯,有乙二醇二丙烯酸酯、三乙二醇 二丙烯酸酯、1,3_丁二醇二丙烯酸酯、:^冬丁二醇二丙烯酸 酯、丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、三羥甲基 丙烷三丙烯酸酯、三羥曱基丙烷三(丙烯醯氧基丙基)醚: 己二醇二丙烯酸酯、1,4-環己二醇二丙烯酸酯、四乙二醇 二丙烯酸酯、四季戊四醇聚丙烯酸酯(丙烯酸酯基數為i 〜10)、五季戊四醇聚丙烯酸酯(丙烯酸酯基數為i〜i2)、 山梨糖醇三丙婦酸酯、山梨糖醇四丙烯酸酯、山梨糖醇五 丙烯酸酯、山梨糖醇六丙烯酸酯、聚酯丙烯酸酯寡聚物等。 一作為曱基丙烯酸酯,有1,4-丁二醇二曱基丙烯酸脂、 三乙二醇二甲基丙烯酸酯、新戊二醇二曱基丙烯酸脂、三 羥甲基丙烷三甲基丙烯酸酯、三羥曱基乙烷三甲基^烯^ 酯、乙二醇二曱基丙烯酸酯、1,3-丁二醇二甲基丙烯酸脂、 己二醇二曱基丙烯酸脂、山梨糖醇三曱基丙烯酸酯、山梨 糖醇四曱基丙烯酸酯、雙[對(3·甲基丙烯醯氧基_2_羥基丙 氧基)苯基]二曱基甲烷、雙-[對(甲基丙烯醯氧基乙氧苯 基]二曱基曱烷等。 Α 作為伊康酸酯,有乙二醇二伊康酸酯、丙二醇二伊康 酸醋、1,3-丁二醇二伊康酸酯、l,4-丁二醇二伊康酸醋 (l,4-butanediol diitaconate )、伸 丁二醇二伊康酸酉匕 (tetmmethylene glycol diitaconate)、季戊四醇二伊康酸 201213336 37723pif 酯、山梨糖醇四伊康酸醋等。作為 巴豆酸醋、认丁二醇二巴豆酸醋、W,有乙二醇二 山梨糖醇四二巴豆酸酉旨等 ^ 一巴豆酸酯、 、季戍四醇:異二乙二醇二 酸醋等。作為馬來酸酿,有乙二醇二馬=醇四異丁婦 等。 戊叫—馬來_、山錄醇四馬來酸醋 作為其他酷之例,例如亦可適 賤说號公報、日本專利特_ 57 j 公昭 ==族醇系_,或曰本專利特開昭上= 報、日本專利特開昭59-5241號公報 唬么 2專=?中所記載之具有芳香族系骨架== 專利特開千1.165613號公報巾所記載之 = 等。另外,前述之醋單體亦可製成混合物而使用。土-曰 =且’至於其錄合性化合物,作為脂職多元胺化 。物與不麵紐之_之單體的具_,有錐 丙稀酿胺、亞甲基雙甲基丙_胺、W六亞甲基雙_土丙^ =胺:1,6_六亞甲基雙曱基丙_胺、二乙三胺三丙_ 胺、本二曱基雙丙烯醯胺、苯二甲基雙甲基丙_胺等。 作為其他較佳之軸轉體之例,可縣日本專公日刀 54-2Π26號公報中所絲之具有伸環已基結構之醯胺系^ 體。 另外,作為其他聚合性化合物,使用異氛酸醋與經基 之加成反應而製造的聚胺酯系加成聚合性化合物亦較佳, 82 201213336 ^ / /z^pif 作為此種具體例,例如可列^日本專婦公㈣_41708 號公報t所記載之於丨分子具有2 _上異級醋基之聚 異氰酸醋化合物上加成下述通式(v)所表示之含有經基 η:體而成的於i分子中含有2個以上聚合性乙二 基之乙烯基胺基甲酸酯化合物等。 [化 63] CH. im) CO:aeH^G:H (R;^j OH; 通式(V) CHi 其中,通式(V)中之^及尺5個別獨立地表示11或 〇 ,,而且下述文獻所記載之化合物中的通式(M〇_l )〜 ϋϋ5)所表示之聚合性化合物以外之其他結構的聚 5性化σ物亦可與本發明之聚合性化合 色硬化性組成物中。 优用於耆 日本專利特開BS 51·37193號公報、日本專利特公平 2-32293 f虎公報、日本專利特公平2_16765號公報中所記載 之丙烯酸胺基甲酸_,或日本專利特公昭58·49860號公 報、日本專利特公昭56-176Μ f虎公報、日本專利特公昭 日本專公昭62_39418號公報中所1°己 衣氧乙燒系骨架之胺基曱酸酯化合物類,另外, 日本專利特開昭63_277653號公報、日本專 ㈣0909八號公報、日本專利特開平μ〇52職公 °己載之於分子内具有胺基結構或硫醚結構之加成聚合性化 83 201213336 合物類,日本專利特開昭48侦83號公報、日本 公報、日本專彻公昭52_3_號公報之 ^所記载之聚醋丙焊酸醋類、環氧樹脂與(甲基 ”而所得之環氧丙烯酸酯類等多官能丙烯醆酯:戈甲 基丙烯酸S旨,日本專利特公昭46_43946號公報、日本專 公報、日本_公平MG336 f_ 斤。己載之特疋之不飽和化合物,曰本專利特開平2_ U報中所e載之乙稀基膦酸系化合物, 號公報中所記載之含有全氟烧基之結構 曰本接者協會志VO1.20、Να7、第3〇〇〜3〇8頁(198 中作為光硬化性單财絲物而介紹之化合物。 作為著色硬化性組成物的所有固形物中的聚合性化合 、之,量(於2種以上之情形時為總含量),並無特別& 疋’自更有效地獲得本發明之效果之觀財慮,較佳 職〜80 wt%,更佳的是15糾%〜75㈣ 是'Q"?^CH2fcrf0H In the above base, ml and m2 are each an integer of 〜8. - Object: ~ The polymerizable substance represented by the formula (M0_5): The system is not as follows. The present invention is not limited to these specific examples. Propionate=Diisocyanuric acid triacrylate, 8-hexene_modified tris-(2·ylethyl)isophthalic acid vinegar, ethoxylated glycerol three-purpose, Ϊ t propylene vinegar , tri-methyl methacrylate, di-trimperanthene, tetra-tetrapropene, ethoxylated pentaerythritol tetraacrylic acid, quaternary oxime, diquaternary hexapropene, dipentaerythritol Five = olefin H hexa(propylene oxyethyl ethoxy) dipentaerythritol, two quarters pentacene _ _ acid mono g |, trisyl propyl trimethyl propyl 79 201213336 The color hardening composition of the present invention The compound contains at least one type of polymerizable compound represented by the formula (MO-5) and is composed of two or more types. In the case of two or more types, the formula may be The two or more kinds of polymerizable compounds may be different from the above two types: two or more kinds of polymerizable compounds which are shown. In addition, the colored hardening composition of the present invention may also be (MCM) to the formula (M). (5) Polymerizable compound having a structure other than the polymerizable compound represented by the formula (5), which is a polymerizable property other than the poly-human compound represented by the formula (MO-1) to the formula (MO_5) The compound (hereinafter referred to as "other polymerizable compound") may, for example, be an unsaturated Wei (for example, C-/methacrylic acid, itaconic acid, crotonic acid, methacrylic acid or maleic acid) or an ester thereof or an anthracene thereof. The amine is preferably an ester of an unsaturated carboxylic acid and an aliphatic polyol compound, an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound. Further, an addition reaction product of an unsaturated carboxylic acid vinegar or a urethane having a nucleophilic substituent such as a hydroxyl group, an amine group or a fluorenyl group with a monofunctional or polyfunctional isocyanate or an epoxy group, and a monofunctional or polyfunctional group The product of dehydration condensation reaction of a functional carboxylic acid or the like may be used in combination as another suitable polymerizable compound. Further, 'as another polymerizable compound, an unsaturated carboxylic acid ester having an isocyanate group or an electrophilic substituent such as an epoxy group or an oxime amine and an addition of a monofunctional or polyfunctional alcohol, an amine or a thiol The reactants, in addition to the derivatized substituents such as i groups or tosyloxy groups, the unsaturated carboxylic acid esters or guanamines and the monofunctional or polyfunctional alcohols, amines, sterols, substituted reactants good. Further, as another example, a compound group obtained by substituting an unsaturated phosphonic acid, 201213336 ± styrene, vinyl ether or the like may be used instead of the upper carboxylic acid. As specific examples of the monomer of the aliphatic polyol compound and the unsaturated acid-free ester, as the acrylate, there are ethylene glycol diacrylate, triethylene glycol diacrylate, and 1,3-butanediol diacrylate. , : ^butanediol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trishydroxypropyl propane tris(propylene oxypropyl) ether: Diol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol polyacrylate (acrylate number i 10), pentaerythritol polyacrylate (acrylate number) It is i~i2), sorbitol tripropionate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, polyester acrylate oligomer, and the like. As a mercapto acrylate, there are 1,4-butanediol dimercapto acrylate, triethylene glycol dimethacrylate, neopentyl glycol dimercapto acrylate, trimethylolpropane trimethacrylate Ester, trihydroxydecylethane trimethyl methacrylate, ethylene glycol dimercapto acrylate, 1,3-butylene glycol dimethacrylate, hexanediol dimercapto acrylate, sorbitol Tridecyl acrylate, sorbitol tetradecyl acrylate, bis[p-(3·methacryloxy-2-hydroxypropyloxy)phenyl]dimercaptomethane, bis-[pair (methyl Acryloxyethoxyphenyl]didecyldecane, etc. Α As an isoconate, there are ethylene glycol di-conconate, propylene glycol diconic acid vinegar, and 1,3-butylene glycol diacon Acid ester, l,4-butanediol diitaconate, tetmmethylene glycol diitaconate, pentaerythritol diconic acid 201213336 37723pif ester, sorbus Sugar alcohol, tetraconcanic acid vinegar, etc. As crotonic acid vinegar, butyl diol dicroton vinegar, W, ethylene glycol disorbitol tetradecanoate, etc. Bean ester, quaternary tetraol: iso-diethylene glycol diacid vinegar, etc. As a maleic acid, there are ethylene glycol di horse = alcohol tetraisobutylate, etc. Penta-Malay _, Shanxu alcohol Four Malay sour vinegar as another cool example, for example, it can also be used in the Japanese version of the bulletin, the Japanese patent special _ 57 j public Zhao == family alcohol system _, or the patent special opening Kai = Shang, Japanese patent special opening Zhao Japanese Patent Publication No. 59-5241, No. 2, No. 2, which has an aromatic skeleton, == described in Japanese Patent Publication No. 1.165613, and the like, and the vinegar monomer can also be used as a mixture.土-曰= and 'As for its recorded compound, as a polyamine for the aliphatic occupation. _, with a monomer of _ _ _, has a cone of acrylamide, methylene bismethyl propyl _ Amine, W hexamethylene bis- oxalate = amine: 1,6-hexamethylene bis-decyl propylamine, diethylenetriamine tripropylamine, the present dimercapto bis acrylamide, benzene Methyl dimethyl propyl amide, etc. As an example of another preferred axial rotator, a sulphate structure having a stretched ring structure as disclosed in Japanese Unexamined Japanese Patent Publication No. 54-2Π26. As other aggregation A compound, a polyurethane-based addition polymerizable compound produced by an addition reaction of an oleic acid vinegar and a base group is also preferred, and 82 201213336 ^ / /z^pif is exemplified as such a specific example, for example, a Japanese woman (4) The polyisocyanate compound having a 2 _ upper hetero- hydroxy group in the oxime molecule described in Japanese Patent Publication No. _41708 is added to the i molecule containing the η group represented by the following formula (v) A vinyl urethane compound containing two or more polymerizable ethylenediyl groups, etc. [Chem. 63] CH. im) CO: aeH^G: H (R; ^j OH; Formula (V) CHi In the formula (V), the ruthenium and the ruthenium 5 each independently represent 11 or ruthenium, and other than the polymerizable compound represented by the formula (M〇_l) to ϋϋ5) in the compounds described in the following documents. The poly-5-formed σ material of another structure may also be combined with the polymerizable color-curable composition of the present invention. It is preferably used in the Japanese Patent Laid-Open Publication No. H07-37193, the Japanese Patent Laid-Open No. 2-32293, and the Japanese Patent Publication No. Hei 2_16765, or the Japanese Patent Publication No. Sho. Japanese Patent Publication No. 49,860, Japanese Patent Publication No. Sho 56-176, pp. H-Han, and Japanese Patent Publication No. Sho 62-39418, the amine phthalate compound of the 1 octyl oxyethylene skeleton, and the Japanese patent Japanese Patent No. 63_277653, Japanese Special (4) No. 0909-8, and Japanese Patent Special Kaiping No. 52, which are contained in the molecule, have an amine group structure or an thioether structure, and are added and polymerized. 83 201213336 Compound, Japan Polypropylene acrylate vinegar, epoxy resin and (meth) epoxide acrylate described in Japanese Patent Publication No. 83, Japanese Gazette, Japanese Gazette No. 52_3_ Polyfunctional propylene oxime esters such as methacrylic acid S, Japanese Patent Publication No. Sho 46_43946, Japanese Special Publications, Japan _ Fair MG336 f_ jin. Unsaturated compounds of the special enthalpy, 曰本专利专开平2_The ethylidene phosphonic acid compound contained in the U report, the structure containing the perfluoroalkyl group described in the Japanese Patent Publication No. VO1.20, Να7, and the third 〇〇~3〇8 pages ( a compound which is described as a photocurable monofilament in 198. The polymerizable compound in all the solids of the colored curable composition, the amount (the total content in the case of two or more kinds), is not particularly & 疋 'from the more effective way to obtain the effect of the invention, better job ~ 80 wt%, more preferably 15 correction % ~ 75 (four) is
Wt% 〜6〇wt〇/o。 耵疋 20 [(D)光聚合起始劑] 本發明之著色硬化性組成物含有(D)光聚合起始劑。 光聚合起始劑只要為可使上述(c)選自所述通 (=_υ〜通式(MO_5)所表示之聚合性化合物的至少 物聚合之化合物’職鱗別限制,較佳為以特 ^、開始效率、吸收波長、獲得性、成本稍點選擇。 為光聚合起始劑,例如可列舉:選自_甲基。惡二唾 化a物及Μ基·均三魏合物之至少丨種活性齒化合 84 201213336 物、3-芳基取代香豆素化合物、咯吩2聚體、二苯甲酮化 合物、苯乙酮化合物及其衍生物、環戊二烯_苯_鐵錯合物 及其鹽、將糸化合物等。關於光聚合起始劑之具體例,可 列舉日本專利特開2004-295116號公報之段落[〇〇7〇]〜 D077]中所記載之化合物。其中’自聚合反應迅速之方面 等考慮,較佳為肟系化合物。 作為所述肟系化合物(以下亦稱為「肟系光聚合起始 劑」),並無特別限定’例如可列舉曰本專利特開2〇〇〇_8〇〇68 號公報、W002/100903A卜日本專利特開2001-233842號 公報等中所記載之肟系化合物。 具體例可列舉:2-(0-苯曱醯肟)_1-[4-(苯硫基)苯 基]-1,2·丁二酮、2-(0-苯曱醯肟)-1-[4-(苯硫基)苯基]_152_ 戊一酮、2·(0-笨曱醯月亏)-1-[4_(苯硫基)笨基]-i,2_己二酮、 2-(0-笨甲醯肪)·ι·[4_(苯琉基)苯基]-1,2-庚二酮、2-(〇-苯曱 酿蔣)-1-[4-(苯硫基)苯基]·1,2-辛二酮、2-(〇_苯曱醯 两)小[4-(甲基苯硫基)苯基]-1,2-丁二酮、2-(〇-苯曱醯 肟M-[4-(乙基苯硫基)苯基]-1,2-丁二酮、2-(〇_苯曱醯 將)-1-[4-( 丁基基苯硫基)苯基]-1,2-丁二酮、〖_(〇_乙醯 躬·)-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-叶·β坐-3-基]乙g同、 1_(〇-乙酿肪)-1-[9·曱基-6-(2-曱基苯甲醯基)_9H-味唾-3-基] 乙酮、1-(〇_乙醯肟)小[9-丙基-6-(2-曱基苯甲酿基)_9H-咔 唾-3-基]乙酿j、ι_(〇_乙醯躬τ)-1-[9-乙基-6·(2-乙基苯曱醯 基)-9Η-咔峻-3-基]乙酮、1-(〇-乙酿肪)-1-[9-乙基-6-(2-丁基 本甲醯基)-9H-味α坐-3-基]乙酮專。但並不限定於該些化合 85 201213336 物。 該些化合物中,就以更少之曝光量而獲得形狀(特別 是於固體攝影元件之情形時為圖案之矩形性)良好之圖案 之方面而言,特佳的是2_(0_苯甲醯肟)-1·[4-(苯硫基)笨 基]―1,2-辛二酮、1-(〇·乙醯肪)-Η9-乙基-6-(2-甲基苯甲醯 基)-9H_咔唑-3-基]乙酮等肪-Ο醯基系化合物,具體而言, 例如可列舉OXE-01、oxE-02 (以上由BASF公司製造) 等。 而且,於本發明中,自感光度、經時穩定性、且 用於彩色i慮光片製作時的 叫遇 所表示之化合物。 慮,聘系化合物更佳的是下、Π.、、、、時的箸色防止之觀點考 V通式(d_1)〜通式(d-4) 201213336 37723pif [化 64]Wt% ~6〇wt〇/o.耵疋 20 [(D) Photopolymerization initiator] The color hardening composition of the present invention contains (D) a photopolymerization initiator. The photopolymerization initiator is preferably one which can limit the above-mentioned (c) compound which is selected from the above-mentioned (=_υ~polymerizable compound represented by the general formula (MO_5)). ^, start efficiency, absorption wavelength, availability, and cost are selected. For the photopolymerization initiator, for example, at least one selected from the group consisting of _methyl group, oxadi-salt a substance, and decyl-s-trimide活性Active tooth combination 84 201213336, 3-aryl substituted coumarin compound, phenanthrene 2 mer, benzophenone compound, acetophenone compound and its derivative, cyclopentadiene _ benzene-iron And a salt thereof, a ruthenium compound, etc. Specific examples of the photopolymerization initiator include the compounds described in paragraphs [〇〇7〇] to D077] of JP-A-2004-295116. The ruthenium-based compound (hereinafter also referred to as "anthraquinone photopolymerization initiator") is not particularly limited as long as it is rapid in terms of the polymerization reaction, etc. Open 2〇〇〇_8〇〇68 Bulletin, W002/100903ABu Japanese Patent Special Open 2 An anthraquinone compound described in 001-233842 or the like. Specific examples thereof include 2-(0-benzoquinone)-1-[4-(phenylthio)phenyl]-1,2·butanedione , 2-(0-benzoquinone)-1-[4-(phenylthio)phenyl]-152_pentanone, 2·(0-曱醯月曱醯 deficit)-1-[4_(phenylthio) ) stupid]-i, 2_hexanedione, 2-(0-abbreviated), ι·[4_(phenylhydrazo)phenyl]-1,2-heptanedion, 2-(〇- Benzoquinone-branched acetonitrile--1-[4-(phenylthio)phenyl]·1,2-octanedione, 2-(indole-benzoquinone) small [4-(methylphenylthio)benzene 1,2-butanedione, 2-(〇-benzoquinone M-[4-(ethylphenylthio)phenyl]-1,2-butanedione, 2-(〇_benzene -1-[)(4-(butylphenylphenyl)phenyl]-1,2-butanedione, _(〇_乙醯躬·)-1-[9-ethyl-6 -(2-methylbenzhydryl)-9H-leaf·β--3-yl]ethyl g, 1_(〇-乙糖)-1-[9·曱基-6-(2-曱Benzomethanyl)_9H-flavor-3-yl] ethyl ketone, 1-(〇_乙醯肟) small [9-propyl-6-(2-mercaptobenzoyl)_9H-咔-3-yl]ethyl brewing j, ι_(〇_乙醯躬τ)-1-[9-ethyl-6·(2-ethylbenzoinyl)-9Η-咔峻-3-yl]B Ketone, 1-(〇-乙糖)-1-[9-ethyl-6-( 2-butylbenzimidyl)-9H-flavor α-yl-3-yl]ethanone, but not limited to the compounds 85 201213336. In these compounds, the shape is obtained with less exposure. (especially in the case of solid-state imaging elements, the rectangular shape of the pattern). In terms of a good pattern, it is particularly preferable that 2_(0_benzamide)-1·[4-(phenylthio)phenyl ]-1,2-octanedione, 1-(〇·乙醯肥)-Η9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]ethanone, etc. Specific examples of the fat-hydrazine-based compound include OXE-01 and oxE-02 (all manufactured by BASF Corporation). Further, in the present invention, the self-sensitivity, the stability over time, and the compound represented by the sensation when used in the production of a color i-ray sheet. Considering that it is better to hire a compound, the viewpoint of the prevention of bleed, Π., ,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,
通式(屮General formula
通式(d-4) 於上述通式(d-1)〜通式(d-4)中,R22及X22個別 獨立地表示1價取代基,A22表示2價有機基,Ar表示芳 基。η為1〜5之整數。多個之R22、X22、A22、及Ar可個 別相同亦可不同。 作為R22,自高感光度化之方面而言,較佳為醯基, 87 201213336 具體而言較佳為乙醯基、丙醯基、笨曱醯基、甲苯甲酿基。 作為A22,自提高感度,抑制加熱隨時間經過所造成 之著色的方面考慮,較佳為未經取代之伸烧基、經烧基(例 如甲基、乙基、第三丁基、十二烷基)取代之伸烷經 婦基(例如乙烯基、烯丙基)取代之伸烧基、經芳基(例 如苯基、對甲苯基、二曱苯基、異丙苯基、萘基、蒽基、 菲基、苯乙烯基)取代之伸烷基。 作為Ar,自提高感度,抑制加熱隨時間經過所造成之 著色的方面考慮,較佳為經取代或未經取代之苯基。於經 取代之苯基之情形時,其取代基例如較佳魏原子 ' 氯原 子、溴原子、碘原子等鹵基。 一作為X22,自提高溶劑溶解性與長波長區域之吸收效 率之方面而言,較佳為亦可具有取代基之烷基、亦可具有 取代基之芳基、亦可具有取代基之雜、亦可具有取代基 之炔基、亦可具有取代基之烧氧基、亦可具有取代基之芳 ,基亦可具有取代基之烧基硫g同基、亦可具有取代基之 芳基硫鴨、亦可具有取代基之絲。、 而且較佳為通式(d-Ι)〜通式(d-4)中之n為1 〜2之整數。 〃 τ η上 之且Hi將通式⑷)〜通式(d_4)所表示之化合物 八彳表示如下,但本發明並不限定於該些具體例。 88 201213336 37723pif [化 65]In the above formula (d-1) to formula (d-4), R22 and X22 each independently represent a monovalent substituent, A22 represents a divalent organic group, and Ar represents an aryl group. η is an integer of 1 to 5. A plurality of R22, X22, A22, and Ar may be the same or different. R22 is preferably a mercapto group from the viewpoint of high sensitivity, and is particularly preferably an ethyl sulfonyl group, a propyl fluorenyl group, a ruthenium group or a toluene group. As A22, from the viewpoint of improving the sensitivity and suppressing the coloring caused by heating over time, an unsubstituted extended alkyl group, a burnt group (for example, methyl group, ethyl group, tert-butyl group, dodecane group) is preferred. a substituted alkyl group substituted with a benzyl group (eg, a vinyl group, an allyl group), an aryl group (eg, phenyl, p-tolyl, diphenyl, cumyl, naphthyl, anthracene) Alkyl, phenanthryl, styryl) substituted alkyl. As Ar, a substituted or unsubstituted phenyl group is preferred from the viewpoint of improving sensitivity and suppressing coloration caused by heating over time. In the case of a substituted phenyl group, the substituent is preferably, for example, a halogen atom such as a chlorine atom, a chloro atom, a bromine atom or an iodine atom. In the case of X22, from the viewpoint of improving solvent solubility and absorption efficiency in a long wavelength region, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent may be preferable. An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a base which may have a substituent, a thiol group having a substituent, and an aryl group which may have a substituent Ducks may also have a silk of substituents. Further, it is preferred that n in the formula (d-Ι) to (d-4) is an integer of from 1 to 2. The compound represented by the formula (4)) to the formula (d_4) is represented by the following, but the present invention is not limited to these specific examples. 88 201213336 37723pif [化65]
89 201213336 [化 66] Ο89 201213336 [化66] Ο
ClCl
而且 於本毛月之著色硬化性組成物中,除了上述光 聚合起始劑以外’亦可使用日本專利特開2004-295116號 公報之段落_9]中所記載之其他公知之光聚合起始劑。 光聚合起始劑可單獨含有1種或者組合含有2種以上。 旧^有效地獲得本發明之絲之觀財慮,著色硬化 成物之所有固形物中的光聚合起始劑之含#(於2種 201213336 以上之情形時為總含量)較佳為3 wt%〜20 wt%,更佳的 是4 wt%〜19 wt% ’特佳的是5 wt%〜18 wt%。 -增感色素- 本發明之著色硬化性組成物亦可視需要而添加增感色 素。增感色素可由於該增感色素可吸收之波長的曝光而促 進上述光聚合起始劑之自由基產生反應等或由此而造成之 所述光聚合性化合物之聚合反應。 作為此種增感色素,可列舉公知之分光增感色素或染 料、或吸收光而與光聚合起始劑相互作用之染料或顏料。 (分光增感色素或染料) 可作為本發明中所使用之增感色素而較佳之分光增咸 色素或染料可列舉多核芳香族類(例如芘、茈、聯伸三苯)、 二苯并哌喃類(例如螢光素、曙紅、赤蘚紅、玫魂紅B、 孟加拉玫瑰紅)、花青類(例如噻碳花青、噁碳花青)、部 花青類(例如部花青、碳部花青)、噻嗪類(例如硫堇、^ I基藍、曱苯絲)"丫销(例如^丫錄、氣黃素、十定 =素)、酞菁類(例如酞菁、金屬酞菁)、卟啉類(例如四 笨基外琳、中心、金屬取代„卜琳)、葉綠素類(例如葉綠素、 葉綠酸、中心金屬取代葉綠素)、金屬錯合物(例如、述 ,、葱麵、(例如葱酉昆)、斯誇琳(_Further, in the color hardening composition of the present invention, other known photopolymerization initiations as described in paragraph _9 of JP-A-2004-295116 may be used in addition to the above-mentioned photopolymerization initiator. Agent. The photopolymerization initiator may be contained alone or in combination of two or more. The effect of the silk of the present invention is effectively obtained, and the content of the photopolymerization initiator in all the solids of the colored hardened product (the total content in the case of two kinds of 201213336 or more) is preferably 3 wt. %~20 wt%, more preferably 4 wt%~19 wt% 'extra good is 5 wt%~18 wt%. - Sensitizing dye - The coloring composition of the present invention may also contain a sensitizing dye as needed. The sensitizing dye can promote the radical polymerization reaction of the photopolymerization initiator or the like, or the polymerization reaction of the photopolymerizable compound, by exposure to a wavelength at which the sensitizing dye can be absorbed. Examples of such a sensitizing dye include known spectroscopic dyes or dyes, or dyes or pigments which absorb light and interact with a photopolymerization initiator. (Specifying sensitizing dye or dye) The sensitizing dye used in the present invention is preferably a spectroscopic coloring dye or a dye, and examples thereof include polynuclear aromatics (for example, ruthenium, osmium, and terphenyl), and dibenzopyran. Classes (such as luciferin, blush, red erythro, red rose B, bengal rose red), cyanine (such as thiocyanine, carbocyanine), merocyanine (such as merocyanine, Carbon (Cyanine), thiazides (such as thioindigo, ^ I-blue, fluorene) "quote (such as ^ 丫 recorded, aflatoxin, decantane = prime), phthalocyanines (such as phthalocyanine) , metal phthalocyanine), porphyrins (such as four stupid base, center, metal substitution „Blin), chlorophyll (such as chlorophyll, chlorophyllin, central metal instead of chlorophyll), metal complex (for example, , onion noodles, (such as green onion), Squarlin (_
如斯誇琳)等。 以貝U歹J 以下例示更佳之分光增感色素料之例。 “可列舉:日本專利特公平π·4號公報中所 本乙烯基系色素;日本專利特_ 62-M3044號公報中所 91 201213336 5己載之陽離子染料;日本專利特 記载之㈣琳舰;日本專利=;:f24147號公報中所 記載之新亞曱基藍化合物;=4侧4號公報中所 報中所記载之葱日本專開昭64韻7號公 記載之苯并氧雜葱染料;曰號公報中所 及日本專鄕開平2_226149 2福148號公報 本專利特公昭4〇-2_號公報中定類;曰 特開平號中所記載之中苯之f青類·,日本專利 開平2-85858號公報、曰^^并°夫°南色素;曰本專利特 =咖曰本專利特開 桂皮二==:==記載之偶氮亞 之議色素;曰本專利=3 == 二:專 ==報:所記載之_乙稀二 2-244㈣號公報中所記载之部花青色素: : 59-28326 1 虎公報令所記裁 2 =公昭 ==所記載“ = -1292^公報中所記狀部花青色素; : 8_334897號公報令所記載之苯并t南系色素。特開千 (於35〇nm〜45〇nm具有極大吸收波長之色素) 92 201213336 J/VZJpif 合:增=其他較佳態樣,可列舉屬於以下之化 素。 且於35G⑽〜450 nm具有極大吸收波長之色 例,可列舉··多核芳香族類(例 -本开派翻(例如螢光素 北㈣一本)、 孟加拉玫瑰紅)、花青類1、玫瑰紅β、 甲基藍、甲苯胺藍;、二:=== 黃素丄,類⑺如㈣)、斯誇琳 述之增感色素,可以改良本發明之著色硬化性 =物之特性為目的而進行如下所述之各種化學二生 ^h=lcal m〇dification)。例如,藉由共價鍵、離子鍵、 虱鍵專方法而使增感色素與加成聚合性化合物 丙_基或甲基丙烯醯基)鍵結,藉此而可獲得提高交聯 硬化膜之南強度化或者抑制色素不必要地自交聯硬化膜 出的效果。 、 增感色素之含量相對於著色硬化性組成物之所有固形 物而言較佳為0.01 wt%〜20 wt%,更佳的是〇 〇1 wt%〜^ wt% ’進一步更佳的是(u wt%〜5 wt%。 ° 藉由使增感色素之含量為該範圍,則對於超高壓水銀 燈之曝光波長的感光度高,獲得膜深部硬化性,並且於顯 影界限(development margin)、圖案形成性之方面而古較 佳。 •供氫性化合物- 93 201213336 物。於本^明n者色硬化性組成物含有供氫性化合 素或光聚合起始劑物具有如下作用:使增感色 高,或者__細糾之歧進一步提 作為此種供氫合物之聚合阻礙等。 M.R.Sander等人著之之^列,可列舉胺類,例如 Society)」第10盎铱问刀子予會會刊(Journal〇fP〇lymer 44-20139 ^ 1 號公報、日本專利特^2、日本專利特開昭59_138205 昭62-18537號八郝Γ ^ 4305號公報、日本專利特開 (RelearchDiLost!^ ^31°4 ' 合物等,具體之化 乙醋'她基二甲基笨胺、甲酸 =氫性化合物之其他例,可類, =舉曰本專利特開昭號公報、曰本專利二 戶^己# $ Π號公報、日本專利特開平Η42772號公報中 斤^载之硫醇化合物、日本專利特開昭Μ·號公報之 合物等,具體而言可列舉2_疏基苯并射、2_疏 基本并噁唑、2-酼基苯并咪唑 疏基萘等。 料Η 2·_·4_·料琳、β· 醢化,i/作為供氮性化合物之進而其他例,可列舉胺基 物(例如N-苯甘胺酸等)、日本專利特公昭48 42965 號么報中所記載之有機金屬化合物(例如乙酸三丁基锡 94 201213336 曰Ιίΐ利特公昭55-34414號公報中所記載之供氫 Λ 6-308727 ι例如二°塞燒等)等。 2料歧速度與鏈轉移之平_硬化速度提高之 成物些供氫性化合物之含量相對於著色硬化性組 範=ΐ形物之重量而言較佳為m wt%〜3g⑽之 ,更佳的是1 Wt。/。〜25 Wt%之範圍,進一步更佳的 •5 wt%〜2〇 wt%之範圍。 [(E)有機溶劑] f發明之著色硬化性組成物含有(E)有機溶劑。 若為可滿足所並存之各成分解性或 性組成物時之塗佈性的有機_,職本上益特 而加、以選^的是考慮黏合狀溶雜、塗佈性、安全性 至於有機溶劑,作為醋類,例如可列舉乙酸乙酉旨、乙 ^ 丁S日、乙酸異丁§旨、甲酸細旨、乙酸異摘、乙酸異 酽甲丙,丁知、丁酸異丙酯、丁酸乙酯、丁酸丁酯、乳 ‘、童曰、,乙酯、氧化乙酸烷基酯類(例如氧化乙酸曱 ‘乙化t酸乙酷、氧化乙酸丁S旨(具體而言可列舉甲氧 酸曱§日、甲氧基乙酸乙醋、曱氧基乙酸丁醋、乙氧美 如-I酯、乙氧基乙酸乙酯等))、3_氧基丙酸烷基酯類(二 3 ·基丙酸曱酉旨、3_氧基丙酸乙料(具體而言可列舉 酷氧基丙酸甲_、3·曱氧基丙酸乙自旨、3·乙氧基丙酸甲 9、3_乙氧基丙酸乙酯等))、2·氧基丙酸烷基酯類(例如 95 201213336 2-氧基丙酸曱酯、2-氧基丙酸乙酯、2-氧基丙酸丙酯等(具 體而言可列舉2-曱氧基丙酸曱酯、2-曱氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸曱酯、2-乙氧基丙酸乙酯 等))、2-氧基-2-曱基丙酸曱酯、2-氧基-2-曱基丙酸乙酯(具 體而言可列舉2-曱氧基-2-曱基丙酸曱酯、2-乙氧基-2-曱基 丙酸乙酯等)、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙 醯乙酸曱酯、乙醯乙酸乙酯、2-側氧丁酸曱酯、2-側氧丁 酸乙酯等。 而且,作為醚類,例如可列舉二乙二醇二曱醚、四氫 呋喃、乙二醇單甲醚、乙二醇單***、甲基賽路蘇乙酸酯、 乙基赛路蘇乙酸酯、二乙二醇單曱醚、二乙二醇單***、 二乙二醇單丁醚、丙二醇單曱醚、丙二醇單甲醚乙酸酯、 丙二醇單***乙酸酯、丙二醇單丙醚乙酸酯等。 作為酮類,例如可列舉丁酮、環己酮、2-庚酮、3-庚 酮等。 作為芳香族烴類,例如可適宜列舉曱苯、二曱苯等。 作為該些有機溶劑,自前述各成分之溶解性、及於包 含鹼可溶性黏合劑之情形時其溶解性、塗佈面狀之改良等 觀點考慮,亦較佳為將2種以上加以混合。於此情形時, 特佳的是包含選自3-乙氧基丙酸曱酯、3-乙氧基丙酸乙 酯、乙基賽路蘇乙酸酯、乳酸乙酯、二乙二醇二曱醚、乙 酸丁酯、3-甲氧基丙酸甲酯、2-庚酮、環己酮、乙基卡必 醇乙酸酯、丁基卡必醇.乙酸酯、丙二醇甲醚、及丙二醇曱 醚乙酸酯之2種以上的混合溶液。 96 201213336 植成有機溶劑於著色硬化性組成物中之含量,較佳為 所有固形物濃度成為10 Wt%〜80 wt%之量,更 之Ϊ疋确物中之所有固形物濃度成為15 wt%〜60 wt% [(F)其他成分] 可於明之著色硬化性組成物除了上述各成分以外,亦 、不知及本發明之絲的_ 合劑、交聯轉其他成分。 r ^ -鹼可溶性黏合劑_ 定,敕11黏合劑除了具有驗可溶性m卜並無特別限 :、、可根據耐熱性、顯影性、獲得性等觀點而選擇。 可溶於黏合劑是線狀有機高分子聚合物,且較佳為 有機^八二劑、可藉由祕性水溶液而進行顯影的線狀 列舉有機高分子聚合物,可 59-446M% 羧 I合物,例如日本專利特開昭 昭58-12577\Γ本專利特公昭A34327號、日本專利特公 ^門日1 ^、曰本專利特公昭54·25957號、曰本專利 =戶^己都53836 !虎、日本專利特開昭59_71048號之各公 基丙賊共聚物、丙稀酸共聚物、伊康酸 &物/碰共聚物、馬麵料物、部錢化馬來酸 囉地亦可使用於嗔具有魏之酸性纖維素 使用之驗可溶性黏合劑,亦可 有絲之聚δ物上加成酸奸而成的化合物等、或 97 201213336 聚輕基苯乙婦請脂、聚魏燒系樹脂、聚((曱基)丙稀酸 ,經基乙醋)、聚乙烯吼洛。定酮或聚環氧乙烧、聚乙稀醇 等。而且,線狀有機高分子聚合物亦可為具有親水性之單 體共聚而成之聚合物。其例可列舉(曱基)⑽酸烧氧基烧 基醋、(曱基)丙稀酸經基烧基醋、丙三醇(甲基)丙稀酸醋、 (曱基)丙烯醯胺、N-羥甲基丙烯醯胺、2級或3級烷基丙烯 醯胺、(甲基)丙烯酸二烷基胺基烷基酯、嗎啉(甲基)丙烯酸 酯、N-乙烯基吡咯啶酮、N-乙烯基己内醯胺、乙烯基咪唑、 乙烯基***、(曱基)丙烯酸曱酯、(曱基)丙烯酸乙酯、支鏈 或直鍵之(曱基)丙稀酸丙g旨、支鍵或直鍵之丁基(甲基)丙稀 酸酉曰、或(甲基)丙婦酸苯氧基經基丙醋等。另外,作為具 有親水性之單體,亦可使用包含四氫呋喃曱基、磷酸基、 磷酸酯基、四級銨鹽基、伸乙基氧基鏈、伸丙基氧基鏈、 磺酸基及源自其鹽之基、N-嗎啉基乙基等的單體等。 而且,鹼可溶性黏合劑為了提高交聯效率而亦可於侧 鏈具有聚合性基’例如亦可使用於侧鏈含有烯丙基、(甲基) 丙稀基、稀丙氧基烧基等之聚合物等。作為含有上述聚合 性基之聚合物例’可列舉市售品之KS resist-106 (大阪有 機化學工業股份有限公司製造)、Cyclomer P系列(DAICEL CHEMICAL INDUSTRIES,LTD.製造)等。而且,為 了提 尚硬化皮膜之強度’亦可使用醇可溶性尼龍或2,2-雙-(4-羥基苯基)-丙烷與表氣醇之聚醚等。 於該些各種驗可溶性黏合劑中,自耐熱性之觀點考 慮’較佳為聚羥基苯乙烯系樹脂、聚矽氧烷系樹脂、丙烯 98 201213336 酸系樹脂、丙烯醯胺系樹脂、_⑽、/丙烯軸共聚物樹 ,,自顯影性控制之觀點考慮,較佳為丙稀酸系樹脂、丙 烯醯胺系樹脂、丙烯酸系/丙烯醯胺共聚物樹脂。 作為所述丙烯酸系樹脂,較佳為由選自(甲基)丙烯酸 苄基酯、(曱基)丙烯酸、(甲基)丙烯酸羥基乙酯、(甲基)丙 烯醯胺等之單體所形成之共聚物,或市售品之Ks resist-106 (大阪有機化學工業股份有限公司製造)、Such as Squarlin) and so on. An example of a better spectroscopic sensitizing pigment is exemplified below. "The vinyl-based coloring matter of the Japanese Patent Publication No. π. 4, Japanese Patent Publication No. 62-M3044, No. 91, 201213336, the cationic dye contained in the Japanese Patent Publication No. 62-M3044; Japanese Patent No.: the new indenyl blue compound described in the publication No. F24147; the benzoxene onion described in the No. 4, No. 4, No. 4 publication Dyes; in the 曰 公报 公报 日本 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 148 Patent Kaiping 2-85858, 曰^^ and °funan pigment; 曰本专利特=咖曰本本专开桂皮二==:== Recorded azo-Asian pigment; 曰本专利=3 == 2:Special ==Report: The merocyanine pigments described in the _Ethylene 2-244 (4) bulletin: 59-28326 1 The official statement of the tiger's bulletin 2 = Gong Zhao == recorded = -1292^ The phthalocyanine pigment recorded in the publication of the publication; benzoxanthene pigment described in the publication No. 8_334897. Special open thousand (pigment with a maximum absorption wavelength at 35〇nm~45〇nm) 92 201213336 J/VZJpif Combination: increase = other preferred aspects, which can be listed as the following compounds. Examples of the color having a maximum absorption wavelength at 35G (10) to 450 nm include polynuclear aromatics (for example, the present invention (for example, fluorescein North (four) one), the bengal rose red), and the cyanine class 1. Rose red β, methyl blue, toluidine blue; two: === flavonoid, class (7) (4), squarin sensitizing pigment, can improve the color hardening property of the present invention Various chemical biochemicals as described below were carried out ^h=lcal m〇dification). For example, by bonding a sensitizing dye to an addition polymerizable compound propyl group or methacryl oxime group by a covalent bond, an ionic bond or a hydrazone bond, a crosslinked cured film can be obtained. The effect of the south strength or the suppression of the pigment from the self-crosslinking hardening film is unnecessarily. The content of the sensitizing dye is preferably 0.01 wt% to 20 wt%, more preferably 〇〇1 wt% to ^ wt%, based on all solids of the colored curable composition. Further preferably ( u wt% 〜5 wt%. ° By setting the content of the sensitizing dye to this range, the sensitivity to the exposure wavelength of the ultrahigh pressure mercury lamp is high, and the film deep hardenability is obtained, and the development margin and pattern are obtained. It is also preferred in terms of formability. • Hydrogen-donating compound - 93 201213336. In the present invention, the color-hardening composition contains a hydrogen-donating chemical or a photopolymerization initiator having the following effects: sensitization The color height, or __ 细 之 进一步 进一步 进一步 进一步 进一步 进一步 进一步 进一步 进一步 进一步 进一步 进一步 进一步 进一步 进一步 。 。 。 。 。 M M M M M M M M M M M M M M M M M M M M M M M M M M Journal publication (Journal〇fP〇lymer 44-20139 ^1 bulletin, Japanese patent special ^2, Japanese patent special open 59_138205 Zhao 62-18537 No. 8 Hao Hao ^ 4305 bulletin, Japanese patent special open (RelearchDiLost!^ ^31°4' compound, etc., specific vinegar 'heryl dimethyl sulfonamide Formic acid = other examples of hydrogen compounds, can be classified as follows: 曰 专利 专利 专利 专利 专利 昭 公报 曰 曰 曰 曰 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 专利 硫 硫 硫 硫 硫 、 、 、 、 、 、 、 、 、 、 、 、 、 、 Specific examples of the compound, the compound of Japanese Patent Laid-Open Publication No. JP-A No. 2-3, and the like, and the like are, for example, 2 - thiol benzopyrazine, 2 - hydrazino oxazolidine, 2-mercaptobenzimidazole sulfaphthalene, and the like. Η 2·_·4_· _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The organometallic compound described in the report (for example, tributyltin acetate 94 201213336 曰Ι ΐ 特 特 55 55 55-34414 供 供 Λ - - - - - - - - 55 55 Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ Λ - - - - - 。 。 。 。 。 。 。 。 。 。 。 The content of the hydrogen-donating compound with respect to the chain transfer is preferably m wt% to 3 g (10), more preferably 1 Wt, with respect to the weight of the color hardening property. ~. ~25 Wt% range, further better • 5 wt% ~ 2〇wt% range. [(E) Organic Solvent] f Invention The colored curable composition contains (E) an organic solvent. If it is an organic _ which satisfies the coating properties of the respective decomposable or sexual compositions, the merits of the work are to be considered. The binder is miscible, the coating property, and the safety are as long as the organic solvent. Examples of the vinegar include ethyl acetate, ethyl acetate, acetic acid, acetic acid, acetic acid, and acetic acid. C, Dingzhi, isopropyl butyrate, ethyl butyrate, butyl butyrate, milk ', nursery rhyme, ethyl ester, alkyl acetate oxidized (such as oxidized acetic acid 乙 'acetylated t-acid cool, The oxidized acetic acid butyl S (specifically, methoxy day, methoxyacetic acid ethyl acetate, methoxyacetic acid butyl vinegar, ethoxymethan-I ester, ethyl ethoxyacetate, etc.), 3_oxypropionic acid alkyl esters (dibenzylidene propionate, 3-oxypropionic acid) (specifically, alkoxypropionic acid methyl, 3, methoxypropionic acid B, 3, ethoxylated acid methyl 9, 3 - ethoxy propionate ethyl ester, etc.), 2 · oxypropionic acid alkyl esters (such as 95 201213336 2-oxopropionate, 2-oxygen Ethyl propionate, propyl 2-oxypropionate, etc. (specifically, decyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.), 2-oxo-2-mercaptopropionate, ethyl 2-oxy-2-mercaptopropionate (Specifically, decyl 2-nonyloxy-2-mercaptopropionate, ethyl 2-ethoxy-2-mercaptopropionate, etc.), methyl pyruvate, ethyl pyruvate, pyruvic acid Propyl ester, acetamidine acetate, ethyl acetate, ethyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like. Further, examples of the ethers include diethylene glycol dioxime ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl stilbene acetate, and ethyl stilbene acetate. Diethylene glycol monoterpene ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monoterpene ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Wait. Examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone. Examples of the aromatic hydrocarbons include decene, diphenylbenzene, and the like. In view of the solubility of the above-mentioned respective components and the solubility in the case of containing an alkali-soluble binder, and the improvement of the coating surface, it is preferred to mix two or more kinds of these organic solvents. In this case, it is particularly preferred to comprise a decyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celecoxib acetate, ethyl lactate, diethylene glycol Anthracene ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol, acetate, propylene glycol methyl ether, and A mixed solution of two or more kinds of propylene glycol oxime ether acetate. 96 201213336 The content of the organic solvent to be colored in the curable composition is preferably such that all solids concentration is from 10 Wt% to 80% by weight, and further, all solid concentrations in the confirmed substance are 15 wt%. ~60 wt% [(F) Other components] In addition to the above respective components, the color-curable composition of the present invention may not be known as a conjugate or a cross-linking component of the present invention. r ^ - alkali-soluble binder _ The 敕11 binder is not particularly limited in addition to the solubility m, and can be selected from the viewpoints of heat resistance, developability, and availability. The soluble binder is a linear organic high molecular polymer, and is preferably an organic compound, which can be developed by a secret aqueous solution. The organic polymer can be 59-446M%. Compounds, for example, Japanese Patent Laid-Open No. 58-12577 Γ 专利 专利 专利 343 343 343 A34327, Japanese Patent Special ^ 日 日 1 ^, 曰 专利 专利 54 54 54 54·25957, 曰 本 patent = household ^ 己53833 ! Tiger, Japanese Patent Laid-Open No. 59_71048, each of the public base thief copolymer, acrylic acid copolymer, itaconic acid & material / touch copolymer, horse fabric, Ministry of money, maleic acid, can also be used It can be used as a soluble binder for the use of Wei's acid cellulose, or as a compound for the addition of sorrel on the poly-delta of the silk, or 97 201213336 Polylight-based benzophenone, fat, and Weiwei Resin, poly((mercapto)acrylic acid, base ethyl vinegar), polyethylene strontium. Ketone or polyethylene oxide, polyethylene glycol, and the like. Further, the linear organic high molecular polymer may be a polymer obtained by copolymerizing a hydrophilic monomer. Examples thereof include (indenyl) (10) acid alkoxy ketone, (mercapto) acrylic acid sulfonic acid vinegar, glycerol (meth) acrylic acid vinegar, (mercapto) acrylamide, N-methylol acrylamide, 2 or 3 alkyl acrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinyl pyrrolidone , N-vinyl caprolactam, vinyl imidazole, vinyl triazole, (decyl) decyl acrylate, (mercapto) ethyl acrylate, branched or straight-bonded (fluorenyl) acrylate A butyl (meth) acrylate or a (meth) propyl acetophenoxy phenoxy propyl acetonate or the like. Further, as the monomer having hydrophilicity, a tetrahydrofuranyl group, a phosphate group, a phosphate group, a quaternary ammonium salt group, an extended ethyloxy chain, a propyloxy chain, a sulfonic acid group, and a source may also be used. A monomer such as a salt thereof or a N-morpholinylethyl group. Further, the alkali-soluble binder may have a polymerizable group in the side chain in order to increase the crosslinking efficiency. For example, the side chain may be an allyl group, a (meth) propyl group or a dipropyloxy group. Polymers, etc. As a polymer example containing the above-mentioned polymerizable group, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by DAICEL CHEMICAL INDUSTRIES, LTD.), and the like are commercially available. Further, in order to improve the strength of the hardened film, alcohol-soluble nylon or a polyether of 2,2-bis-(4-hydroxyphenyl)-propane and epigas alcohol may be used. Among these various soluble binders, from the viewpoint of heat resistance, 'preferably polyhydroxystyrene resin, polyoxyalkylene resin, propylene 98 201213336 acid resin, acrylamide resin, _(10), / The propylene shaft copolymer tree is preferably an acrylic acid resin, an acrylamide resin, or an acrylic/acrylamide copolymer resin from the viewpoint of self-developability control. The acrylic resin is preferably formed of a monomer selected from the group consisting of benzyl (meth)acrylate, (mercapto)acrylic acid, hydroxyethyl (meth)acrylate, and (meth)acrylamide. Copolymer, or Ks resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.),
Cyclomer P 系列(DAICEL CHEMICAL INDUSTRIES LTD 製造)等。 ’ 自顯影性、液體黏度等觀點考慮,鹼可溶性黏合劑較 佳為重量平均分子量(藉由GPC法而測定之聚苯乙烯換算 值)為1000〜2xl05之聚合物,更佳的是2〇〇〇〜1χ1〇5之 聚合物,特佳的是5000〜5xl〇4之聚合物。 -交聯劑- 於本發明之著色硬化性組成物中亦可補足性地使用交 聯劑’從而進一步提高著色硬化性組成物硬化而成之著色 硬化膜的硬度。 作為交聯劑’若為可藉由交聯反應而進行膜硬化者, 則並無特別限定,例如可列舉環氧樹脂、被選自 羥曱基、烷氧基曱基、及醯氧基曱基之至少丨個取代基取 代之三聚氰胺化合物、胍胺化合物、甘脲化合物或脲化合 物、(c)被選自羥曱基、烷氧基曱基、及醯氧基曱基之至 乂 1個取代基取代之酚化合物、萘紛化合物或經基惹化合 物。其中,較佳為多官能環氧樹脂。 99 201213336 37/23pit 關於交聯劑之具體例等之詳細内容,可參考日本專利 特開2004-295116號公報之段落[0134]〜[0147]之記載。 -其他添加物- 於著色硬化性組成物中,可視需要而調配各種添加 物,例如:填充劑、上述以外之高分子化合物、界面活性 劑、密接促進劑、抗氧化劑、紫外線吸收劑、凝聚抑制劑、 顯影促進劑等。該些添加物可列舉日本專利特開 2004-295116號公報之段落[0155]〜[〇156]中所記載之化合 物。 (界面活性劑) 作為可於上述本發明之著色硬化性組成物中添加之界 面活性劑,自使塗佈性進—步提高之觀點考慮,可添加各 種界面活性劑。作為界面活性劑,可使用氟系界面活性劑、 非離子系界©活性劑、陽離子轉面活性劑、陰離子系界 面活性劑、聚魏系界面活性鮮各種界面活性劑/、1 祕本發,著色硬鎌組成物含有氟系界 ' 可1提面製備為塗佈液時之液體特性(特 =是流動性)’因此可進—步改善塗佈厚度之均-性或省液 、、/即1於㈣塗佈液(所述塗佈液適时含氣系界3 活性劑之著色硬錄組絲)㈣彡鎖之情,你㈣ 佈面與塗佈狀界祕力降低,由此而㈣皮^ 由少量之液量而形成數_左右之薄膜二= 100 201213336 J / / JiJlJll 宜地形成厚度不均較小的均一厚度的膜之方面而言有效。 氟系界面活性劑中之氟含有率較佳為3 wt%〜40 wt% ’更佳的是5 wt%〜30 wt%,特佳的是7 wt%〜25 wt%。氟含有率為該範圍内的氟系界面活性劑於塗佈膜厚 度之均一性或省液性之方面而言有效果,於著色硬化性組 成物中之溶解性亦良好。 氟系界面活性劑例如可列舉Megafac F171、Megafac F172、Megafac F173、Megafac F176、Megafac F177、Megafac F141'Megafac FI42'Megafac FI43'Megafac FI44'Megafac R30、Megafac F437、Megafac F475、Megafac F479、Megafac F482、Megafac F780、Megafac F781 (以上由 DIC 股份有 限公司製造)、Fluorad FC430、Fluorad FC431、Fluorad FC171 (以上由住友3]y[股份有限公司製造)、Surflon S-382 - Surflon SC-101 ' Surflon SC-103 ' Surflon SC-104 'Cyclomer P series (manufactured by DAICEL CHEMICAL INDUSTRIES LTD). The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by a GPC method) of 1000 to 2×10 5 , more preferably 2 观点 from the viewpoints of self-developability, liquid viscosity, and the like. 〇~1χ1〇5 of the polymer, particularly preferably a polymer of 5000~5xl〇4. - Crosslinking agent - The coloring-curable composition of the present invention can also be used in a complementary manner to further improve the hardness of the colored cured film obtained by curing the colored curable composition. The crosslinking agent is not particularly limited as long as it can be cured by a crosslinking reaction, and examples thereof include an epoxy resin selected from a hydroxy group, an alkoxy group, and an anthracene group. a melamine compound, a guanamine compound, a glycoluril compound or a urea compound substituted with at least one substituent, and (c) a thiol group, an alkoxy fluorenyl group, and a fluorenyl fluorenyl group A substituted phenolic compound, a naphthalene compound or a genomic compound. Among them, a polyfunctional epoxy resin is preferred. 99 201213336 37/23pit For details of specific examples of the crosslinking agent, etc., reference is made to paragraphs [0134] to [0147] of JP-A-2004-295116. -Other Additives - Various additives such as a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and aggregation inhibition may be blended in the coloring-curable composition. Agent, development accelerator, and the like. The compounds described in paragraphs [0155] to [〇156] of JP-A-2004-295116 can be cited as such additives. (Interacting Agent) As the surfactant which can be added to the colored curable composition of the present invention, various surfactants can be added from the viewpoint of further improving the coatability. As the surfactant, a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, a poly-wet interface active fresh surfactant, and a secret carrier can be used. The colored hard ruthenium composition contains a fluorine-based boundary. The liquid property (special = fluidity) when the surface is prepared as a coating liquid can be improved to improve the uniformity of the coating thickness or the liquid-saving, / That is, in (4) the coating liquid (the coating liquid contains the gas-lined 3 active agent in the coloring hard recording group) (4) the shackles, you (4) the cloth surface and the coating boundary boundary are reduced, thereby And (4) Skin ^ is formed by a small amount of liquid to form a film of about _ = 100 201213336 J / / JiJlJll It is effective to form a film of uniform thickness having a small thickness unevenness. The fluorine content in the fluorine-based surfactant is preferably from 3 wt% to 40 wt%, more preferably from 5 wt% to 30 wt%, particularly preferably from 7 wt% to 25 wt%. The fluorine-containing surfactant having a fluorine content in this range is effective in terms of uniformity of coating film thickness or liquid-repellent property, and is also excellent in solubility in a coloring-curable composition. Examples of the fluorine-based surfactant include Megafac F171, Megafac F172, Megafac F173, Megafac F176, Megafac F177, Megafac F141'Megafac FI42'Megafac FI43'Megafac FI44'Megafac R30, Megafac F437, Megafac F475, Megafac F479, Megafac F482, Megafac F780, Megafac F781 (manufactured by DIC Corporation), Fluorad FC430, Fluorad FC431, Fluorad FC171 (above Sumitomo 3]y [manufactured by Suisse Co., Ltd.), Surflon S-382 - Surflon SC-101 ' Surflon SC- 103 ' Surflon SC-104 '
Surflon SC-105、Surflon SC 1068、Surflon SC-381、Surflon SC-383、Surflon S393、Surflon KH-40 (以上由旭硝子股份 有限公司製造)等。 非離子系界面活性劑具體可列舉:丙三醇、三羥曱基 丙烷、三羥甲基乙烷以及該些之乙氧基化物及丙氧基化物 (例如丙三醇丙氧基化物、丙三醇乙氧基化物等)、聚氧乙 烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚、聚氧 乙埽辛基苯基崎、聚氧乙稀壬基苯基醚、聚乙二醇二月桂 酸酯、聚乙二醇二硬脂酸酯、山梨糖醇酐脂肪酸酯(BASF 公司製造之 Pluronic L10、L31、L61、L62、10R5、17R2、 101 201213336 25R2、Tetronic 304、7(U、704、901、904、150R1、Solsperse 20000 (日本Lubrizol股份有限公司製造)等。 陽離子系界面活性劑具體可列舉酞菁衍生物(商品 名:EFKA-745、森下產業股份有限公司製造)、有機聚矽 氧烷聚合物KP341 (信越化學工業股份有限公司製造)、 (曱基)丙烯酸系(共)聚合物Polyflow No.75、No.90、No.95 (共榮社化學股份有限公司製造)、W001 (裕商股份有限 公司製造)等。 陰離子系界面活性劑具體可列舉W004、W005、W017 (裕商股份有限公司製造)等。 聚矽氧系界面活性劑例如可列舉東麗道康寧股份有限 公司製造之「Toray Silicone DC3PA」、「Toray Silicone SH7PA」、「Toray Silicone DC11PA」、「Toray Silicone SH21PA」、「Toray Silicone SH28PA」、「Toray Silicone SH29PA」、「Toray Silicone SH30PA」、「Toray Silicone SH8400」、Momentive Performance Materials Inc.製造之 「TSF_4440」、「TSF-4300」、「TSF-4445」、「TSF-4460」、 「TSF-4452」、信越矽利光股份有限公司製造之「KP341」、 「KF6001」、「KF6002」、BYK Chemie 公司製造之 「BYK307」、「BYK323」、「BYK330」等。 界面活性劑可僅使用1種,亦可組合使用2種以上。 (熱聚合抑制劑) 另外,於本發明之著色硬化性組成物中,可含有曰本 專利特開2004-295116號公報之段落[0078]中所記載之增 102 201213336 37723pif 卿^^^^2·295116綱之段 硬化i:成二中’為了於著色 要的想的是添加少量=二:物之不必 二紛、對甲氧基苯紛、二第三,可列舉對苯 第三丁基兒茶盼、苯醒;、 盼)、2,2,-亞曱基雙(4_甲其6笛代雙(#3·甲基_6_第三丁基苯 基經胺亞#鹽等。A帛二丁基核)、N·亞石肖基苯 熱聚合抑制劑之添加量相對於著色硬化性 量而言較佳為約O.Oi祕〜約5祕。 ' (顯影促進劑) 而且,於促進非曝光區域之驗溶解性, 性組成物之顯雜线—线高讀科,村於該组成 麵以下之有機紐、分子量為_ ;1下之丙二醇丙氧基化物(例如丙三醇丙氧 土化物(Mw 1500)、丙三醇丙氧基化物(Mw咖)、丙 =丙氧基化物(Mw75〇)、丙三醇丙氧基化物(歸侧) 作為所述分子量為麵以下之有機羧酸,例如可 甲酸、乙酸、丙酸、丁酉复、戊酸、特戊酸、己酸、二乙其 乙酸:庚酸、辛酸等脂肪族單鎖;草酸、丙二酸、號二 酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、 103 201213336 十二烧二酸、甲基丙二酸、乙基丙二酸、二f基丙二酸、 甲基琥珀酸、四甲基琥珀酸、檸康酸等脂肪族二羧酸;丙 二甲酸、烏頭酸、降莰三酸等脂肪族三羧酸;苯甲酸、 苯甲酸、菌香酸、2,3-二甲基苯甲酸、3,5_二甲苯甲酸等芳 香族單羧酸;鄰苯二f酸、間苯二甲酸、對苯二甲酸、偏 苯三f酸、1’3’5-苯三甲酸、1,2,3’5_苯四甲酸、苯均四酸等 芳香族多羧酸,·苯乙酸、氫化阿托酸、氫化肉桂酸、苦杏 仁酸、苯基琥珀酸、阿托酸、肉桂酸、肉桂酸甲酯、肉桂 酸苄酯 '次肉桂基乙酸、香豆酸、繳形酸(Umbdlic ad 等其他羧酸。 [著色熱硬化性組成物之製備方法] 本發明之著色熱硬化性組成物可將前述之必須成分、 以及視需要之任意成分加以混合而製備。 另外,於製備著色硬化性組成物時,可將構成著色硬 化f生、、且成物之各成分總括調配,亦可使各成分溶解、分散 於溶劑巾之後進行逐次娜。而且,於繼時之投入順序 或作業條件並不!^特別制約。例如,可將全部成分同時溶 ,、分散於溶劑中而製備組成物,亦可視需要將各成分適 宜製成2個以上溶液、分散液,於使用時(塗佈時)將該 些加以混合而製備為組成物。 如上所述而製備之著色硬化性組成物,可使用較佳為 孔徑為0.01 μιη〜3 〇 μιη、更佳的是孔徑為〇 〇5叫〜〇 5 μ'左右之冲(聚丙烯)、ΡΕ (聚乙稀)、尼龍等材質的過 濾器等而進行過濾分離後,供於使用。 104 201213336 本發明之著色硬化性組成物由於保存穩定性優異、另 外可形成耐光性優異之著色硬化膜,因此可適宜用以形成 液晶顯示裝置、有機EL顯示裝置等顯示裝置或固體攝影 =件(例如CCD、CMOS等)中所使用之彩色濾光片等的 著色畫素,而且可適宜用作印刷墨水、噴墨墨水、及塗料 等之製作用途。特別是可適宜用於形成CCD及CM〇s等 固體攝影元件用著色晝素。 《彩色濾光片及其製造方法》 其次,對使用本發明之著色硬化性組成物而製造彩色 遽光片之方法(本發明之彩色滤光片的製造方法)加 明。 本發明之彩色據光片的製造方法具有:步驟(A),於 支樓體上塗佈本發明之著色硬化性組錢 性組成物層;步驟⑻,介隔遮罩對步驟H)色: 色硬化性組成物層進行曝光後,進行顯影而形成著 而且 是更且之彩色航片的製造方法中,特佳的 照㈡二步驟⑻中所形成之著色圖案 系卜線,步驟(D),對該步驟(c)中之 線之著色圖案進行加熱處理。 、各卜 之說γ ’對本發私彩色就0製造方法加以更具體 -步驟(Α)- 於本發明之彩色遽光片的製造方法中,首先藉由旋 105 201213336 37723pif 塗、流鑄塗佈、輥塗等塗佈方法將所述之本發明之著色硬 化性組成物塗佈於支撐體上,形成著色硬化性組成物層’ 其後’視需要進行預備硬化(預供烤),使該著色硬化性組 成物層乾燥。 作為本發明之彩色濾光片的製造方法中所使用之支撐 體,例如可列舉液晶顯示裝置等中所使用之鈉玻璃、無驗 玻,、硼矽玻璃(派瑞克斯(PYREX)(註冊商標)玻璃)、 石英玻璃、及於該些玻璃上附著有透明導電膜者,或固體 攝影元件等中所使用之光電轉換元件基板、例如石夕基板等 或者互補性金騎倾半導體(CMGS)基㈣。該些基 板亦存在形成對各畫素進行隔離之黑色條紋之情形。二 且,於該些支撐體上,亦可視需要為了與上部層之密接改 良、物質之擴散防止、或表面之平坦化而設置下塗層。 可藉由旋塗、狹縫塗佈、流鑄塗佈、輥塗、棒塗、喷 f等塗佈方法財侧之著色魏性組錢直接或者介隔 其他層而塗佈於基板上,形成著色硬化性組成物之塗佈膜。 另外於將著色硬化性組成物旋塗於支樓體上時為 了,低液體之滴加量,於滴加著色硬化性組成物時,滴加 機溶劑而使其旋轉,由此可使著色硬化性組成物 於支撐體上之親合性變佳。 於7nt為上述預烘烤之條件,可列舉使用加熱板或供箱, 於7〇C〜130C下加熱〇5分鐘〜15分鐘左右的條件。 物声硬化性組成物所形成之著色硬化性組成 曰之厚度可根據目的而適宜選擇,通常於固體攝影元件 106Surflon SC-105, Surflon SC 1068, Surflon SC-381, Surflon SC-383, Surflon S393, Surflon KH-40 (above manufactured by Asahi Glass Co., Ltd.), etc. Specific examples of the nonionic surfactant include glycerin, trihydroxydecylpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, C). Triol ethoxylate, etc., polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl sulphate, polyoxyethylene decyl phenyl ether , polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2, 101 201213336 25R2, Tetronic manufactured by BASF Corporation) 304, 7 (U, 704, 901, 904, 150R1, Solsperse 20000 (made by Lubrizol Co., Ltd., Japan), etc. Specific examples of the cationic surfactant are phthalocyanine derivatives (trade name: EFKA-745, Morishita Industrial Co., Ltd.) Manufactured by the company), organopolyoxyalkylene polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (fluorenyl) acrylic (co)polymer Polyflow No.75, No.90, No.95 (Kyoeisha Chemical Co., Ltd.) Manufacturing Co., Ltd.), W001 (Yu Shang Co., Ltd. Specific examples of the anionic surfactants include W004, W005, W017 (manufactured by Yusei Co., Ltd.), etc. Examples of the polyoxo-based surfactants include "Toray Silicone DC3PA" manufactured by Toray Dow Corning Co., Ltd. , manufactured by Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400, Momentive Performance Materials Inc. "TSF_4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF-4452", "KP341", "KF6001", "KF6002", BYK Chemie manufactured by Shin-Etsu Trading Co., Ltd. "BYK307", "BYK323", "BYK330", etc. manufactured by the company. The surfactants may be used alone or in combination of two or more. (Thermal polymerization inhibitor) Further, the color-curable composition of the present invention The increase may be as described in paragraph [0078] of the Japanese Patent Laid-Open Publication No. 2004-295116. 201213336 37723pif 卿^^^^2·295116 The hardening of the section of the section i: into the second part of the 'in order to coloring is to add a small amount = two: the thing does not have two, p-methoxybenzene, two third, can be cited benzene tert-butyl tea Hope, benzene awake;, hope), 2, 2, - yttrium bis (4 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The addition amount of the A帛 dibutyl nucleus) and the N· succinyl benzene thermal polymerization inhibitor is preferably about O.Oi secret to about 5 sec. with respect to the amount of the coloring hardenability. '(Development accelerator) Moreover, in promoting the solubility in the non-exposed area, the odor of the composition is high-line, the organic nucleus below the composition surface, the molecular weight is _; Oxide (eg glycerol propoxylate (Mw 1500), glycerol propoxylate (Mw), propane-propoxylate (Mw75), glycerol propoxylate (back side) As the organic carboxylic acid having a molecular weight of less than or equal to the surface, for example, formic acid, acetic acid, propionic acid, butyl valproate, valeric acid, pivalic acid, hexanoic acid, diethyl acetic acid: heptanoic acid, octanoic acid, etc.; Oxalic acid, malonic acid, oxalic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 103 201213336 12-burned diacid, methylmalonic acid, ethyl An aliphatic dicarboxylic acid such as malonic acid, dif-propionic acid, methyl succinic acid, tetramethyl succinic acid or citraconic acid; an aliphatic tricarboxylic acid such as malonic acid, aconitic acid or decyl tricarboxylic acid; An aromatic monocarboxylic acid such as benzoic acid, benzoic acid, bactericinic acid, 2,3-dimethylbenzoic acid or 3,5-xylenecarboxylic acid; phthalic acid; Aromatic polycarboxylic acid such as dicarboxylic acid, terephthalic acid, trimellitic acid, 1'3'5-benzenetricarboxylic acid, 1,2,3'5-benzenetetracarboxylic acid, pyromellitic acid, phenylacetic acid , hydrogenated atropic acid, hydrogenated cinnamic acid, bitter almond acid, phenyl succinic acid, atopic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, decyl cinnamic acid, coumaric acid, diced acid (Umbdlic Other carboxylic acid, etc. [Preparation method of coloring thermosetting composition] The colored thermosetting composition of the present invention can be prepared by mixing the above-mentioned essential components and optional components as needed. In the case of a composition, the components which are constitutively colored and hardened, and the components of the product can be collectively formulated, and the components can be dissolved and dispersed in the solvent towel to be successively subjected to the step of arranging. It is not particularly limited. For example, all components may be simultaneously dissolved, dispersed in a solvent to prepare a composition, and each component may be suitably prepared into two or more solutions and dispersions as needed (at the time of coating) ) mixing these to prepare The color-hardening composition prepared as described above may preferably be a polypropylene having a pore diameter of 0.01 μm to 3 〇μηη, more preferably a pore diameter of 〇〇5 to 〇5 μ' (polypropylene). And the color-curable composition of the present invention is excellent in storage stability and can also form a color excellent in light resistance. Since the cured film is suitable for forming a coloring element such as a display device such as a liquid crystal display device or an organic EL display device, or a color filter used in a solid-state imaging device (for example, CCD or CMOS), and can be suitably used. It is used in the production of printing inks, inkjet inks, and paints. In particular, it can be suitably used for forming colored halogens for solid-state imaging elements such as CCD and CM〇s. <<Color filter and method for producing the same>> Next, a method of producing a color calender using the colored curable composition of the present invention (method for producing a color filter of the present invention) will be described. The method for producing a color light-receiving sheet of the present invention comprises: step (A), applying a colored hardenable composition layer of the present invention on a support body; and step (8), separating the mask to the step H): In the method for producing a colored aerial sheet, after the exposure of the color-curable composition layer, the colored pattern is formed in the second step (8), and the step (D) is performed. And heating the colored pattern of the line in the step (c). 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Coating method such as roll coating, the above-described colored curable composition of the present invention is applied onto a support to form a colored curable composition layer 'subsequent', and preliminary hardening (pre-bake) is performed as needed. The colored curable composition layer is dried. Examples of the support used in the method for producing a color filter of the present invention include soda glass used in liquid crystal display devices and the like, and glass-free glass, and porphyrin glass (PYREX) (registered). (trademark) glass, quartz glass, and a transparent conductive film attached to the glass, or a photoelectric conversion element substrate used in a solid-state imaging device or the like, for example, a stone substrate or a complementary gold riding semiconductor (CMGS) Base (four). These substrates also have a black stripe that forms a barrier to each pixel. Further, on the support members, an undercoat layer may be provided in order to improve adhesion to the upper layer, prevent diffusion of the substance, or planarize the surface. The coating method of spin coating, slit coating, flow casting coating, roll coating, bar coating, spray coating, etc. can be applied to the substrate directly or through other layers by the coating method. A coating film for coloring the curable composition. In addition, when the colored curable composition is spin-coated on the support body, the amount of the low-liquid drop is added, and when the colored curable composition is dropped, the solvent is added dropwise to rotate the machine to cause color hardening. The affinity of the composition on the support becomes better. The conditions for pre-baking at 7 nt include a heating plate or a supply box, and heating at 〇C to 130 C for 5 minutes to 15 minutes. The color hardening composition formed by the acoustic hardening composition can be appropriately selected depending on the purpose, usually on the solid-state imaging element 106.
201213336 J / /jLJpiL 用H慮光片專中較佳為0 2 μπι〜5·〇 μυ!,更佳的是 μΜ〜2·5 μΐη,最佳的是0.3 μηι〜1.5 μηι。而且,於液晶顯 示裝置用彩色滤光>{料,較佳為Q 2叫〜5抑⑺,更佳 的是1·〇 μιη〜4.0 μηι,最佳的是j 5 μηι〜3 5 μιη。 另外,此處所謂之著色硬化性組成物層之厚度是預烘 烤後之膜厚。 " -步驟(Β)- 其次,於本發明之彩色濾光片的製造方法中,對形成 於支撐體上之著色硬化性組成物層,介隔遮罩而進行曝光。 作為可適用於曝光之光或放射線,較佳為g線、h線、 i線、KrF光、ArF光’特佳的是土線。於照射光使用土線 之情形時,較佳為以l〇〇mj/cm2〜10000 mJ/cm2之曝光量 進行照射。 ’ 而且,作為其他曝光光線,亦可使用超高壓、高壓、 中壓、低壓之各水銀燈、化學燈、碳弧燈、氙氣燈、金屬 鹵素燈、可見及紫外之各種雷射光源、螢光燈、鎢燈、太 陽光等。 (使用雷射光源之曝光步驟) 於本發明之使用雷射光源之曝光方式中,使用紫外光 雷射作為光源。雷射(LASER)是英語之Light Amplification by Stimulated Emission of Radiation (由於受激發射而光增 幅)之縮寫。具有利用於具有反轉分布之物質中產生的受 激發射之現象,作出由於光波之放大、振盪而使干涉性與 指向性進一步更強之單色光的振盪器及放大器,作為激發 107 201213336 37723pif 媒體之結晶、玻璃、液體、色素、氣體等,由於該些媒質 而可使用固體雷射、液體雷射、氣體雷射、半導體雷射等 公知之於紫外光中具有發射波長之雷射。其中,自雷射之 輸出及發射波長之觀點考慮,較佳為固體雷射、氣體雷射。 作為本發明中可使用之波長,自與抗蝕之感光波長符 合之方面考慮,較佳為300 nm〜380 nm之範圍的波長範 圍的紫外光雷射,更佳的是3〇〇 nm〜360 nm之範圍的波 長的紫外光雷射。 具體而言,特別是可適宜使用輸出大、比較廉價之固 體雷射的Nd : YAG雷射之第三諧波(355 nm)、或準分子 雷射之 XeCl (308nm)、XeF (353 nm)。 作為被曝光物(圖案)之曝光量,為1 mJ/cm2〜100 mJ/cm2之範圍,更佳的是1 mJ/cm2〜50 mJ/cm2之範圍。 若曝光量為該範圍,則於圖案形成之生產性之方面而言較 佳0 作為本發明中可使用之曝光裝置,無特別限制,市售 之曝光裝置可使用Callisto (V Technology Co.,Ltd·製造)201213336 J / /jLJpiL The H-light film is preferably 0 2 μπι 5·〇 μυ!, more preferably μΜ~2·5 μΐη, and most preferably 0.3 μηι~1.5 μηι. Further, in the liquid crystal display device, color filter > {material, preferably Q 2 is called 5 to 5 (7), more preferably 1·〇 μηη to 4.0 μηι, and most preferably j 5 μηι to 3 5 μιη. Further, the thickness of the color hardening composition layer referred to herein is the film thickness after prebaking. <Step (Β) - Next, in the method of producing a color filter of the present invention, the colored curable composition layer formed on the support is exposed through a mask. As the light or radiation which can be applied to the exposure, it is preferable that the g-line, the h-line, the i-line, the KrF light, and the ArF light are earth lines. In the case where the soil line is used for the irradiation light, it is preferably irradiated with an exposure amount of l〇〇mj/cm2 to 10000 mJ/cm2. ' Moreover, as other exposure light, you can also use ultra-high pressure, high pressure, medium pressure, low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, visible and ultraviolet laser light sources, fluorescent lamps. , tungsten light, sunlight, etc. (Exposure step using a laser light source) In the exposure mode using the laser light source of the present invention, an ultraviolet laser is used as a light source. Laser (LASER) is an abbreviation for Light Amplification by Stimulated Emission of Radiation in English. An oscillator and an amplifier for monochromatic light that is made more intense in interference and directivity due to amplification and oscillation of light waves, as an excitation 107 201213336 37723pif Crystals of the medium, glass, liquid, pigment, gas, etc., due to the medium, a solid laser, a liquid laser, a gas laser, a semiconductor laser, or the like, which is known to have an emission wavelength in ultraviolet light, can be used. Among them, solid lasers and gas lasers are preferred from the viewpoint of laser output and emission wavelength. As the wavelength which can be used in the present invention, from the viewpoint of conforming to the photosensitive wavelength of the resist, it is preferably an ultraviolet laser having a wavelength range of from 300 nm to 380 nm, more preferably from 3 〇〇 nm to 360. Ultraviolet laser at a wavelength in the range of nm. Specifically, in particular, a third harmonic of a Nd:YAG laser having a large output and a relatively inexpensive solid laser (355 nm), or a XeCl (308 nm) of a pseudo-molecular laser, and a XeF (353 nm) can be suitably used. . The exposure amount of the object to be exposed (pattern) is in the range of 1 mJ/cm 2 to 100 mJ/cm 2 , and more preferably in the range of 1 mJ/cm 2 to 50 mJ/cm 2 . When the exposure amount is in this range, it is preferably 0 in terms of productivity in pattern formation. The exposure apparatus usable in the present invention is not particularly limited, and a commercially available exposure apparatus can use Callisto (V Technology Co., Ltd). ·Manufacturing)
或 EGIS ( V Technology Co.,Ltd.製造)或 DF2200G (0窪丨1^卩〇113〇^11^^.(:〇.,1^(1.製造)等。而且,亦可適 宜使用上述以外之裝置。 而且’可使用發光二極體(LED)及雷射二極體(LD) 作為活性放射線源。特別是於需要紫外線源之情形時,可 使用紫外LED及紫外LD。例如,日亞化學股份有限公司 上市了主發射光譜具有365 nm與420 nm之間波長的紫色 108 201213336 第6二=一之波長之情形時,美國專利編號 4,250號說明書中揭示了一種可發射中心處於3〇〇 nm與370 nm之間的活性放射線的咖。而且,其他紫外 可獲得,可照料同之料_帶之放射。本發明 中特佳之活性放射線源是UV_LED,特佳的是於34〇 m〜 370 m具有峰值波長之UV-LED。 、紫外光祕㈣平行度良好,因此树糾即使不使 ^遮罩亦可進订圖案曝光。然而,於使用遮罩而對圖案進 行曝光之情形時’圖案之直線性進—步變高而更佳。 且’進行了曝光之著色硬化性組成物層,可於隨後 之顯影處理前使用加熱板或烘箱,於机〜則加敎 0.5分鐘〜15分鐘左右。 … 而且,為了抑制著色硬化性組成物層中之有色材料之 氧化褪色,可於腔室内一面流通氮氣一面進行曝光。 〃繼而,顯影液中對曝光後之著色硬化性組成物層進 行顯影。藉此可形成負型或正型之著色圖案(抗蝕圖案)。 顯影液若為可溶解著色硬化性組成物層之未硬化部 (未曝光部),且不溶解硬化部(曝光部)之顯影液,則^ 使用各種錢溶劑之組合級性水溶液。於㈣液為驗性 水溶液之情形時,進行調整以使鹼濃度成為較佳為pH為 11〜13 ’更佳的是pH為11.5〜12.5。 所述鹼性水溶液例如可列舉氫氧化鈉、氫氧化鉀、碳 酸鈉、碳酸氫鈉、矽酸鈉、偏矽酸鈉、氨水、乙基胺、一 乙基胺、二甲基乙醇胺、四曱基氫氧化銨、四乙基氫氧化 109 201213336 irrupii =隹膽驗、鱗n 二氮雜雙環·[5,綱·7_十 烯4驗性水溶液。 灭 。特別是可使用將四乙基氫氧化錄調整為濃度為〇Or EGIS (manufactured by V Technology Co., Ltd.) or DF2200G (0洼丨1^卩〇113〇^11^^. (: 〇., 1^(1. manufactured)), etc. In addition to the device, 'light-emitting diode (LED) and laser diode (LD) can be used as the active radiation source. Especially in the case where an ultraviolet source is required, ultraviolet LED and ultraviolet LD can be used. For example, Asia Chemical Co., Ltd. has listed a purple emission of the wavelength of 365 nm and 420 nm at the wavelength of 365 nm and 420 nm. The US Patent No. 4,250 discloses that an emission center is at 3 〇. The active radiation between 〇nm and 370 nm. Moreover, other ultraviolet rays can be obtained, and the radiation of the same material can be taken care of. The preferred active radiation source in the present invention is UV_LED, especially preferably 34〇m~ 370 m UV-LED with peak wavelength. UV-visual (4) parallelism is good, so even if you don't make the mask, you can also order the pattern exposure. However, when using the mask to expose the pattern, ' The linearity of the pattern is higher and the step is higher. Preferably, the layer of the color-hardening composition which has been exposed can be used in a heating plate or an oven before the subsequent development treatment, and is applied to the machine for about 0.5 minutes to 15 minutes. Moreover, in order to suppress the coloring hardenability composition The oxidative fading of the colored material in the layer can be exposed while flowing nitrogen gas in the chamber. Then, the exposed color-curable composition layer is developed in the developer, thereby forming a negative or positive type. Coloring pattern (resist pattern). If the developing solution is an uncured portion (unexposed portion) in which the colored curable composition layer is soluble, and the developing solution of the hardened portion (exposure portion) is not dissolved, then various solvent solvents are used. When the (IV) liquid is an aqueous test solution, it is adjusted so that the alkali concentration is preferably pH 11 to 13'. More preferably, the pH is 11.5 to 12.5. Sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium citrate, sodium metasilicate, aqueous ammonia, ethylamine, monoethylamine, dimethylethanolamine, tetradecyl ammonium hydroxide, tetraethyl hydrogen Oxidation 109 201213336 irrupii = sputum test, scale n diazabicyclo] [5, s-7 7 decene 4 aqueous solution. Off. In particular, the use of tetraethyl hydrazine can be adjusted to a concentration of 〇
10 wt/。、較佳為〇 〇1 wt%〜5 wt%之鹼性水溶 為顯影液。 W …貝〜時間較佳為3〇秒〜3〇〇秒,更佳的是3〇秒〜 秒。顯影溫度較佳為2(rc〜4(rc,更佳的是23艺。 顯影可藉由浸置方式、淋浴方式、喷霧方式等而進行。 而且,較佳為於使用驗性水溶液而進行顯影之後 由水進行清洗。清洗方式亦根據目的而適宜選擇,可藉由 1〇 rpm〜500 rpm之轉速使石夕晶圓基板等支撐體旋轉^ 旋轉中心之上方’自喷出管嘴淋綠地供給純水而進行沖 洗處理。 其後’於本發明之彩色遽光片的製造方法中,亦可視 需要對藉由随而形成之著色圖案進行後期加熱及 期曝光,從而促進著色圖案之硬化。 -步驟(C)- 特別是於本發明之彩色濾光片的製造方法中對由本 發明之著色硬化性組成物所形成之著色圖案(晝素 利用紫外線照射之㈣曝光,可有效地抑制對於鄰接之竺 素或所積層之上下層之色移。該色移是如本發明之著色$ 化性組成物般,於使用如特定錯合物般的染料作 料之情形時所產生之特有的問題,該色移可藉由如下所述 之利用紫外線照射之後期曝光而減低。 110 201213336 (利用紫外線照射之後期曝光) 、於利用紫外線照射之後期曝光中,較佳為對如上所述 而=行顯影處理後的著色圖案照射顯影前之曝光處理的曝 光里[mj/cm ]之1 〇倍以上照射光量[mj/cm2]的紫外光(uv 光)。 另外’於顯影處理與後述之步驟(D)之加熱處理之10 wt/. Preferably, 〇 1 wt% to 5 wt% of alkaline water is dissolved as a developing solution. W ... Bay ~ time is preferably 3 seconds ~ 3 seconds, more preferably 3 seconds ~ seconds. The development temperature is preferably 2 (rc 4 4 (rc, more preferably 23 art). Development can be carried out by a dipping method, a shower method, a spray method, etc. Further, it is preferably carried out using an aqueous solution After the development, it is cleaned by water. The cleaning method is also suitable according to the purpose. The support of the Shixi wafer substrate can be rotated by the rotation speed of 1 rpm to 500 rpm. The pure water is supplied and rinsed. Thereafter, in the method for producing a color calender of the present invention, the colored pattern formed by the subsequent coloring may be subjected to post-heating and exposure, thereby promoting the hardening of the colored pattern. -Step (C) - In particular, in the method for producing a color filter of the present invention, the colored pattern formed by the colored curable composition of the present invention (the exposure of the halogen to the ultraviolet light (four) is effectively suppressed for the adjacent The color shift of the element or the lower layer of the layer. The color shift is a characteristic of the coloring composition of the present invention, which is produced when a dye composition such as a specific complex is used. The problem is that the color shift can be reduced by the subsequent exposure by ultraviolet irradiation as described below. 110 201213336 (exposure after exposure to ultraviolet light), in the subsequent exposure by ultraviolet irradiation, preferably as described above = The coloring pattern after the development processing is irradiated with ultraviolet light (uv light) of 1 m times or more of the exposure light amount [mj/cm] in the exposure process before development, and the development process and the steps described later. (D) heat treatment
間,藉由對顯影後之著色圖案照射規定時間之紫外光(UV 光)’可有效地防止其後進行加熱時產生色移,從而使耐光 性提兩。 照射紫外光之光源例如可使用超高壓水銀燈、高壓水 銀燈、低壓水銀燈、深紫外線燈(DeepUVlamp)等。其 中’較佳為於所照射之紫外光中包含275 nm以下波長之 光’且可照射275 nm以下波長之光的照射照度[mW/cm2] 相對於紫外光中之所有波長之光的積分照射照度而言為 5%以上的光。藉由使紫外光中之275 nm以下波長之光的 恥射照度為5%以上,可進一步提高對於鄰接之晝素間或 者上下層之色移的抑制效果及耐光性之提高效果。 自該方面而言,較佳為使用與前述之步驟(B)中之 曝光所使用i線等明線等之光源不同之光源、具體而言為 高壓水銀燈、低壓水銀燈等而進行利用紫外線照射之後期 曝光。其中,由於與上述同樣之理由,275 nm以下波長之 光的照射照度[mW/cm2]相對於紫外光中之所有波長之光 的積分照射照度而言較佳為7%以上。而且,275 nm以下 波長之光的照射照度之上限較理想的是25%以下。 111 201213336 37723pif 另外,所謂積分照射照度是指於繪出以每個分光波長 之照度(單位時間内通過單位面積之放射能量; 為縱轴,以光之波長[nm]為橫軸的曲線之情形時,照射光 中所含之各波長光之照度之和(面積)。 紫外光之照射較佳為設為前述步驟(B)中之曝光時 之曝光量的10倍以上之照射光量[mj/cm2]而進行。本步驟 (C)中之照射光量若不足前述步驟(B)中之曝光時之曝 光量的10倍,則存在如下情形:不能防止鄰接之晝素間或 上下層間的色移,而且耐光性亦惡化。 其中,备'外光之照射光量較佳為前述步驟(B)中之 曝光時之曝光量的12倍以上200倍以下,更佳的是15倍 以上1〇〇倍以下。 於此情形時,較佳為所照射之紫外光的積分照射照度 為200 mW/cm2以上。若積分照射照度為2〇〇 mW/cm2以 上,則可更有效地提南對於鄰接之晝素間或上下層的色移 之抑制效果及耐光性之提高效果。其中,較佳為25〇 mW/cm2〜2000 mW/cm2 ’ 更佳的是 300 mW/cm2〜1〇〇〇 mW/cm2 ° -步驟(D)- 對於如上所述般進行了利用紫外線照射之後期曝光的 著色圖案,較佳為進行加熱處理。藉由對_成之著色圖 案進行加熱(所謂之後靖),可使著色畴進—步硬化。 該加熱處理例如可藉由加熱板、各種加熱器、供箱等 而進行。 112 201213336. 加熱處理時之溫度較佳為l〇〇°C〜3〇〇艺,更佳的是 150°C〜250°C。而且,加熱時間較佳為3〇秒〜3〇〇〇〇秒, 更佳的是60秒〜1000秒。 於本發明之彩色滤光片的製造方法中,亦可進行利用 g線、h線、i線、KrF、ArF、電子束、X射線等之後期曝 光而代替如前述之步驟(C)那樣的利用紫外線照射之後 期曝光。 於利用§亥些手段之後期曝光之情形時,照射時間為 秒〜180秒,較佳為20秒〜120秒,更佳的是3〇秒〜6〇 秒。 而且,於本發明之彩色濾光片的製造方法中,亦可並 不進行如前述步驟(C)那樣的利用紫外線照射之後期曝 光,而是僅進行如前述步驟(D)那樣的後期曝光。' 另外,作為後期曝光與後期加熱,先進行任一者均可, 但較佳為於後期加熱之前實施後期曝光。其原因在於:藉 由=後期曝光而促進硬化,可抑制於後期加熱過程中所^ 之著色圖案之過熱(矩形圖案之球形化)或褶邊(圖案下 層部之回流化)所造成之形狀變形。 ’、 如上所述而所得之著色圖案構成彩色濾光片中之金 素。 息 於具有多種色調之晝素的彩色濾光片之製作中,可根 據所,月望之|貞色數*反覆進行前述步驟(A)、步驟(b)、 以及視需要之步驟(C)或步驟(D)。 另外,可於每次單色之著色硬化性組成物層之形成、 113 201213336 曝光、顯影結束時(每i色),進 驟(D),亦可於』1芡驟(〇及/或步 層之形成、曝纟/望之顏色數之財著&硬化性組成物 及/或步影結束後’總括地進行前述步驟⑹ 光片1 明^彩色濾、光片的製造方法而所得之彩色滤 组成物〗H*之彩色滤光片)使用了本發明之著色硬化性 ,、且成物,因此變得耐光性優異。 CCD?上成本發明之彩色濾光片可用於液晶顯示裝置或 龄ΓΓίΓ11、CMGS f彡像制11 _體_元件及使 二固職影元件之照相機系統中,其巾,適於以微少 ^寸而於薄膜上形成著色圖案,且要求良好之矩形剖面輪 廓的固體攝影元件用途,特別是超過100萬晝素之高解像 度之CCD元件或CMOS等之用途。 《固體攝影元件》 本發明之固體攝影元件具有本發明之彩色濾光片。本 發明之彩色濾光片具有高的耐光性,具有該彩色濾光片之 固體攝影元件變得可獲得優異之色再現性。 作為固體攝影元件之構成,若為具有本發明之彩色濾 光片,作為固體攝影元件而發揮功能之構成則並無特別限 定’例如可列舉如下所述之構成。 亦即’於支撐體上具有轉移電極(所述轉移電極包含 構成CCD影像感測器(固體攝影元件)之受光區域的多 個光電二極體及多晶矽等)’且於其上設置本發明之彩色滤 光片’其次積層微透鏡的構成。 114 201213336 ,且,作為具有本發明之彩色滤光片之照相機By irradiating the developed color pattern with ultraviolet light (UV light) for a predetermined period of time, it is possible to effectively prevent the color shift from occurring after heating, thereby improving the light resistance. As the light source that illuminates the ultraviolet light, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a deep ultraviolet lamp or the like can be used. Wherein 'preferably is light having a wavelength of 275 nm or less in the irradiated ultraviolet light' and illumination illuminance of the light having a wavelength of 275 nm or less [mW/cm2] is integrated with respect to light of all wavelengths in the ultraviolet light In terms of illuminance, it is 5% or more of light. By making the irradiance of light having a wavelength of 275 nm or less in the ultraviolet light 5% or more, the effect of suppressing the color shift between the adjacent pixels or the upper and lower layers and the effect of improving the light resistance can be further enhanced. In this respect, it is preferable to use a light source different from a light source such as an i-line or the like used for the exposure in the step (B), specifically, a high-pressure mercury lamp, a low-pressure mercury lamp, or the like, and to perform ultraviolet irradiation. Late exposure. Among them, for the same reason as described above, the irradiation illuminance [mW/cm2] of light having a wavelength of 275 nm or less is preferably 7% or more with respect to the integrated illuminance of light of all wavelengths in the ultraviolet light. Further, the upper limit of the irradiation illuminance of the light having a wavelength of 275 nm or less is preferably 25% or less. 111 201213336 37723pif In addition, the so-called integral illumination illuminance refers to the case where the illuminance per wavelength (the radiation energy per unit area per unit time; the vertical axis, the wavelength of the light [nm]) is plotted. The sum of the illuminances of the respective wavelengths of light contained in the illumination light (area). The irradiation of the ultraviolet light is preferably set to be more than 10 times the amount of exposure at the time of exposure in the above step (B) [mj/ If the amount of the illumination light in the step (C) is less than 10 times the exposure amount in the exposure in the above step (B), there is a case where the color shift between adjacent pixels or between the upper and lower layers cannot be prevented. Moreover, the light resistance is also deteriorated. Among them, the amount of the external light is preferably 12 times or more and 200 times or less, more preferably 15 times or more and 1 times as much as the exposure amount in the exposure in the above step (B). In this case, it is preferable that the integrated irradiation illuminance of the ultraviolet light to be irradiated is 200 mW/cm 2 or more. If the integrated illumination illuminance is 2 〇〇 mW/cm 2 or more, the south can be more effectively extracted. Suppression of color shift between prime or upper and lower layers The effect of improving the light resistance is preferably 25 〇 mW/cm 2 to 2000 mW/cm 2 ' more preferably 300 mW/cm 2 〜 1 〇〇〇 mW/cm 2 ° - step (D) - for the above As described above, the coloring pattern which is exposed after the ultraviolet irradiation is preferably subjected to heat treatment, and the colored domain can be further hardened by heating the colored pattern (so-called sufficiency). It can be carried out by a heating plate, various heaters, a supply box, etc. 112 201213336. The temperature during the heat treatment is preferably from 10 ° C to 3 °, more preferably from 150 ° C to 250 ° C. Further, the heating time is preferably 3 sec to 3 sec, more preferably 60 sec to 1000 sec. In the method of manufacturing the color filter of the present invention, the g line and the h line can also be used. Subsequent exposure of i-line, KrF, ArF, electron beam, X-ray, etc. instead of exposure after ultraviolet irradiation as in the above step (C). When using the later exposure of some means, the irradiation time It is seconds to 180 seconds, preferably 20 seconds to 120 seconds, and more preferably 3 seconds to 6 inches. Further, in the method of manufacturing a color filter of the present invention, it is also possible to perform the post-exposure by ultraviolet irradiation as in the above step (C), but only to perform the post-exposure as in the above step (D). In addition, as the post-exposure and post-heating, either of them may be performed first, but it is preferable to perform the post-exposure before the post-heating. The reason is that the hardening is promoted by the late exposure, and the post-heating process can be suppressed. Shape deformation caused by overheating (sphericalization of a rectangular pattern) or hem (reflow of a lower layer of the pattern) of the colored pattern. The colored pattern obtained as described above constitutes the gold in the color filter. In the production of a color filter having a plurality of shades of color, the above steps (A), (b), and optionally (C) may be repeatedly performed according to the number of colors* Or step (D). In addition, it can be formed in each of the monochromatic color hardening composition layers, 113 201213336 exposure, and development end (per color), and can be advanced (D), or in 』1 steps (〇 and/or steps) The formation of the layer, the color of the exposure/exposure color & the curable composition and/or the step shadow after the completion of the above steps (6) the light sheet 1 clear color filter, the method of manufacturing the light sheet In the color filter composition of the color filter composition H*, the color hardening property of the present invention is used, and it is excellent in light resistance. CCD? The color filter of the invention can be used for liquid crystal display devices or ΓΓ Γ 、 、 、 、 、 CM CM CM CM 及 及 及 及 及 及 及 及 及 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机 照相机The use of a solid-state imaging element that forms a colored pattern on a film and requires a good rectangular cross-sectional profile, in particular, a CCD element or a CMOS having a high resolution of more than one million elements. <<Solid Photographic Element>> The solid-state imaging element of the present invention has the color filter of the present invention. The color filter of the present invention has high light resistance, and the solid-state imaging element having the color filter can obtain excellent color reproducibility. The configuration of the solid-state imaging device is not particularly limited as long as it has the color filter of the present invention and functions as a solid-state imaging device. For example, the following configuration can be cited. That is, 'the transfer electrode has a transfer electrode (the transfer electrode includes a plurality of photodiodes and polycrystalline germanium constituting a light receiving region of a CCD image sensor (solid-state imaging device)), and the present invention is disposed thereon The color filter is composed of the second laminated microlens. 114 201213336 and as a camera having the color filter of the present invention
ίΐΛ材料之光褪色性之觀點考慮,理想的是照相機透# 或m截止膜具有進行了雙色塗佈H 其材料之光學特性理想的是吸收彻nm以下之且 部分或全部。,作為照相機純之結構,為了 =料之氧倾色,較佳為成為對彩色滤光片之氧 氮氣密封。 、相機系奴付或全體被 <液晶顯示裝置、有機a顯示裝置等顯示裝置> 置具有…示裝置等顯示裝 (液======液晶顯示器 壯μ、 有機EL顯不器(有機EL顯千 =)、液晶投影儀、職機用顯示裝置、 動 終端用顯示裝置、數位城則括裝置、 2動 裝置等顯轉置,_是純顯林置較佳用顯不 顯示裝置之定義或各顯示襞置之說明例如 :;置;佐f木昭夫著、工業調查會股份有限公= 仃顯不農置(伊吹順章著、產業圖書股份有限In view of the light fading property of the material, it is desirable that the camera or the m-cut film has a two-color coating H. The optical properties of the material are preferably partially or wholly absorbed below nm. As a pure structure of the camera, it is preferable to form an oxygen-nitrogen seal to the color filter in order to make the oxygen color of the material. , the camera is a slave or the whole is displayed by a display device such as a liquid crystal display device or an organic a display device, etc. (liquid======liquid crystal display, strong organic display device) Organic EL display thousand =), liquid crystal projector, display device for job machine, display device for mobile terminal, digital city device, 2 mobile device, etc., _ is pure display, better display device The definitions or descriptions of the display devices are as follows:; set; Zuo Fukio, the Industrial Research Association, the limited company = 仃显不农 (I Bing Shunzhang, the industry book shares limited
Si t年發行)」等中有所記載。而且,關於液晶顯 不裝置’例如於「下一代液晶顯示器技術(内 集、工業啦纽份有限公3、剛年發行)」中有所纪 ^。可適用本發明之液晶顯示裝置並無特別限制,例如 週用上述「下—代液晶顯示器技術」中所記栽之各種方式 115 201213336 3//23pif 之液晶顯示裝置。 作為本u之彩色遽H其巾制是對於彩色TFT 月液B0H置而言有效。關於彩色TFT方式之液晶 j =置’例如於「彩& T F τ液晶顯示器(共立出版股份 、“司19%年發行)」中有所記載。另外,本發明亦 :適用於ips等橫向電場驅動方式、mva等晝素分割方式 *視角得$|丨擴大的液晶顯示裝置,或stn、、VA、〇cs、 FFS、及 R-〇cb 等中。 而且本發明之彩色濾光片亦可供於明亮且高精細之 =〇A (C〇l〇r_filter 〇n An:ay,彩色遽光片陣列)方式中。 =0A :¾式之液晶顯示裝置+,對彩色縣片層之要求 、除了如上所述之通常之要求特性以外,還必須對層間 絕緣膜之要求特性,亦即低介電f數及_綱受性。作 為本發月之彩色遽光片,除了利用紫外光雷射之曝光方法 =外’本發明藉由選擇規定之晝素之色調或膜厚而提高 作為曝光之光的紫外光雷射之透過性。藉此,可使著色畫 素之硬化性提高’形成紐損或祕、雛之晝素,因此 ^接,接地設於TFT基板上之著色層的特別是剝離液耐 生提㊅’可用於c〇A方式之液晶顯示裝置中。為了滿 =介電常數之要求特性,亦可於彩色濾光片層上設置樹 脂覆膜。 —另外,於藉由C〇A方式而形成之著色層中,為了使 :色層上所配置之IT0電極與著色層下方之驅動用基板之 端子導通’必須形成-邊之長度為^瓜〜心⑺左右之矩 116 201213336 形通孔或口字型之凹坑等導通路,導通路之尺寸(亦即— 邊之長度)特佳的是設為5 μπι以下,藉由使用本發明, 亦可形成5 μηι以下之導通路。 _。關於該郷軸*方^,例如於「EL、PDP、LCD顯 示器技術與市场之最新動向_( T〇ray Research center調查 研究部門、_年發行)」之第43頁等中有所記載。 本發明之液晶顯示裝置除了本發明之彩色遽光片以 外,亦包含電極基板、偏紐、相位差膜、背舰、間隔 物、視角保障膜等各種部件。本發明之彩色濾光片可適用 於包含該些公知之部件的液晶顯示裝置中。 ^於該些部件,例如於「,94液晶顯示器周邊材料、化 學市場(島健太郎、CMC股份有限公司、1994年發行)」、 「2003液晶關聯市場之現狀與將來展望(下卷)(表良 吉、Fuji Chimera Research Institute,Inc.、2003 年發行) 中有所記載。 關於背光源,於SID會議精要(SID meeting Diges〇 1380 ( 2005 ) ( A.Konno專人)、或顯示器月刊細5年 月號之第18〜24頁(島康裕)、顯示器月刊2005年12 月號之第25〜30頁(八木隆明)等中有所記載。 若將本發明之彩色濾光片用於液晶顯示裝置中,則斑 先前公知之冷陰極管的三波長管組合時可實現高的對^匕 度,另外藉由將紅、綠、藍之LED光源(RGB_LED)作 為背光源’可提供亮度高、而且色純度高之色再現性良好 的液晶顯不襄置。 117 201213336 37723pif 而且右用於有機见顯示裝置中 比度,且可提供亮度高、而 的對 有機EL顯示裝置。 巴$^之色再現性良好的 [實例] 乂下,藉由貫例對本發明加以更 明只要不超過其主旨,則並不岐於明=本發 無特別說明,則「份」、「%」均為重量^例。另外,若 (實例1) -1·著色硬化性組成物之製備^ 將下述各成分加以混合,進行分 得著色硬化性組成物1。 ' 合、過濾而獲 • (A-2)顏料藍_i5 : 6分散液 度為 17··、顏、It is recorded in the Si t year issue). Further, regarding the liquid crystal display device, for example, "the next generation of liquid crystal display technology (inner set, industrial 纽 份 3 3, just issued). The liquid crystal display device to which the present invention is applicable is not particularly limited. For example, the liquid crystal display device of the various methods described in the above-mentioned "lower generation liquid crystal display technology" is used. As a color 遽H, the towel system is effective for the color TFT moon liquid B0H. The color TFT type liquid crystal j = set is described, for example, in the "Color & T F τ liquid crystal display (Kyoritsu Publishing Co., Ltd., "19% annual release"). In addition, the present invention is also applicable to a horizontal electric field driving method such as ips, a pixel division method such as mva, a liquid crystal display device with a viewing angle of $|丨, or stn, VA, 〇cs, FFS, and R-〇cb. in. Moreover, the color filter of the present invention is also available in a bright and high-precision = 〇A (C〇l〇r_filter 〇n An:ay, color enamel array) mode. =0A : 3⁄4 type liquid crystal display device +, the requirements for the color county layer, in addition to the usual required characteristics as described above, the required characteristics of the interlayer insulating film, that is, the low dielectric f number and the Receptive. As the color light-emitting sheet of the present month, in addition to the exposure method using ultraviolet laser light, the present invention improves the transmittance of ultraviolet laser light as exposure light by selecting the color tone or film thickness of the specified element. . In this way, the hardenability of the coloring pixels can be improved, and the defects of the coloring or the secrets can be formed. Therefore, the coloring layer which is grounded on the TFT substrate, especially the stripping liquid resistant to the skin can be used for c. 〇A mode liquid crystal display device. A resin film may also be provided on the color filter layer in order to satisfy the required characteristics of the dielectric constant. - In addition, in the coloring layer formed by the C〇A method, in order to make the ITO electrode disposed on the color layer and the terminal of the driving substrate below the coloring layer conductive, the length of the side must be formed. The moment of the heart (7) 116 201213336 The shape of the via hole or the mouth type pit, etc., the size of the conduction path (that is, the length of the side) is particularly preferably set to 5 μπι or less, by using the present invention, A conduction path of 5 μηι or less can be formed. _. This axis is described in, for example, "The latest development of EL, PDP, LCD display technology and market _ (T〇ray Research center, research and development department, _year issue)", page 43 and the like. The liquid crystal display device of the present invention includes various components such as an electrode substrate, a eccentricity, a retardation film, a backing, a spacer, and a viewing angle securing film in addition to the color grading sheet of the present invention. The color filter of the present invention can be applied to a liquid crystal display device including such known components. ^For these components, for example, "94 LCD Peripheral Materials, Chemical Markets (Island Kentaro, CMC Co., Ltd., issued in 1994)", "2003 LCD Related Markets Status and Future Outlook (Volume 2) , documented by Fuji Chimera Research Institute, Inc., issued in 2003. About the backlight, at the SID meeting (SID meeting Diges〇1380 (2005) (A.Konno), or the monthly display of the display for 5 years No. 18 to 24 (Island Kang Yu), Display Monthly, December 2005, No. 25 to 30 (Yumu Longming), etc. If the color filter of the present invention is used in a liquid crystal display device The combination of the three-wavelength tube of the previously known cold cathode tube can achieve high contrast, and the red, green and blue LED light source (RGB_LED) can be used as a backlight to provide high brightness and color. Liquid crystal display with good purity and high reproducibility. 117 201213336 37723pif And right for organic display device, and can provide high brightness, organic EL display device. [Examples] The present invention will be further clarified by the following examples. As long as the subject matter is not exceeded, it is not clear that the present invention has no special description, and the "parts" and "%" are weights ^ In addition, (Example 1) -1·Preparation of coloring curable composition ^ The following components are mixed and the coloring curable composition 1 is obtained. 'Combination, filtration and obtaining (A-2) Pigment blue _i5: 6 dispersion liquid is 17 · ·, color,
• A-1)特定錯合物(例示化合物Μ) 〇84份 •()先聚合起始劑(下述結構之起始劑U • (C)聚合性化合物(單體0.27伤 •⑹聚合性化合物(單體^ 0.20份 •驗可溶性黏合劑:甲基丙稀”自旨/甲基丙騎之丑 聚物20%環己聰液(莫耳比為7g:3g : 量為:_二下稱為「樹,) 〇,〇/ (E ) >合劑·丙一^醇js甲嘛,私 ΓΡΟΜΕΑ,) 知’乙酸醋(以下稱為 , 10.25 份 另外’上述所使用之顏料藍七:6分散液是使用直徑 118 201213336 為0.5 mm之氧化鍅顆粒,於分散機(商品名:Dispermat, GETZMANN公司製造)中對以下配方之組成物實施2小 時之分散處理而獲得。 •著色劑:顏料藍-15 : 6 59.00份 •樹脂溶液(曱基丙烯酸苄酯/曱基丙烯酸共聚物、莫 耳比為80/20、Mw為10000、樹脂固形物濃度為30%、溶 劑為 PGMEA70% ) 19.65 份 342.7 份• A-1) Specific complex (exemplified compound Μ) 〇 84 parts • () First polymerization initiator (starting agent U of the following structure: • (C) polymerizable compound (monomer 0.27 wound • (6) polymerizability Compound (monomer ^ 0.20 part • test soluble binder: methyl propylene) from the purpose / methyl propylene riding ugly polymer 20% cyclohexidine solution (Mo Erbi is 7g: 3g: amount is: _ two It is called "tree," 〇, 〇 / (E ) > mixture · propyl alcohol j js, private ΓΡΟΜΕΑ,) know 'acetic acid vinegar (hereinafter, 10.25 copies of the other used pigment blue seven: 6 Dispersion liquid is obtained by using a cerium oxide particle having a diameter of 118 201213336 of 0.5 mm, and dispersing the composition of the following formulation in a dispersing machine (trade name: Dispermat, manufactured by GETZMANN Co., Ltd.) for 2 hours. Blue-15 : 6 59.00 parts • Resin solution (benzyl methacrylate / mercaptoacrylic acid copolymer, molar ratio of 80/20, Mw of 10,000, resin solids concentration of 30%, solvent PGMEA 70%) 19.65 parts 342.7 servings
•溶劑:PGMEA •分散劑:BYK-161 (BYK公司製造)30〇/〇溶液(溶 劑為PGMEA、乙酸丁酯) 78.65份 (著色硬化性組成物2〜著色硬化性組成物1〇之製 備) 於著色硬化性組成物1之製備中,如表丨所示那樣個 別變更顏料分散液、特定錯合物、光聚合起始劑、聚人性 化合物、聚合物、及溶劑之種類與量,除此以外與實例上 之著色硬化性組成物之製備同樣地進行而製備菩备 組成物2〜著色硬化性組成物10。 更化性 另外,於表1中記載有2種聚合性化合物之實例、表 考例表示併用2種。另外’()内是使用量,為重量換算, 而且’「樹脂A」表示實例i中之鹼可溶性黏合° cyH」為環己酮。 119 201213336 Α· .• Solvent: PGMEA • Dispersant: BYK-161 (manufactured by BYK) 30 〇 / 〇 solution (solvent is PGMEA, butyl acetate) 78.65 parts (preparation of colored curable composition 2 to colored curable composition 1 )) In the preparation of the colored curable composition 1, the types and amounts of the pigment dispersion liquid, the specific complex compound, the photopolymerization initiator, the polytropic compound, the polymer, and the solvent are individually changed as shown in Table ,. In the same manner as in the preparation of the colored curable composition of the example, the bodhisattva composition 2 to the colored curable composition 10 were prepared. Further, Table 1 shows an example of two kinds of polymerizable compounds, and the test examples show two types in combination. Further, '() is the amount used, and is converted into weight, and 'Resin A' indicates that the alkali-soluble adhesion ° cyH" in the example i is cyclohexanone. 119 201213336 Α· .
[表l] 顏料分散液 特定錯合 物 光聚合起始劑 聚合性化合物 聚合物 溶劑 著色硬化性組 成物1 PB15:6 (17.04) la-5 (0.84) 起始劑1 (0.27) 單體A (0.20) 樹脂A (0.10) PGMEA (10.25) 單體F (0.64) 著色硬化性組 成物2 PB15:6 (17.04) III-3 (0.84) 起始劑1 (0.27) 單體B (0.40) - PGMEA (10.25) 單體F (0.44) 著色硬化性組 成物3 PB15:6 (17.04) III-5 (0.84) 起始劑1 (0.15) 單體C (0.40) - PGMEA (6.25) 起始劑2 (0.12) 單體F (0.44) CyH (4.00) 著色硬化性組 成物4 PB15:6 (17.04) ΙΙΙ-Α (0.84) 起始劑2 (0.27) 單體D (0.50) PGMEA (6.25) 單體F (0.34) 2-庚酮 (4.00) 著色硬化性組 成物5 PB15:6 (17.04) ΙΙΙ-45 (0.84) 起始劑3 (0.27) 單逋E (0.84) - PGMEA (10.25) 著色硬化性組 成物6 PB15:6 (17.04) ΙΙΙ-Α (0.84) 起始劑2 (0.27) 單體C (0.84) - PGMEA (10.25) 著色硬化性組 成物7 PB15:6 (17.04) ΙΙΙ-65 (0.84) •" 丨 起始劑1 (0.27) 單體E (0.50) 樹脂A (0.10) PGMEA (10.25) 單體F (0.34) 著色硬化性組 成物8 PB15:6 (17.04) ΙΙΙ-68 (0.84) 起始劑1 (0.27) 單體D (0.84) - PGMEA (10.25) 著色硬化性組 成物9 PB15 (17.04) ΙΙΙ-Β (0.84) 起始劑2 (0.27) 單體E (0.30) - PGMEA (10.25) 單體F (0.54) 著色硬化性組 成物10 PB15:3 (17.04) ΙΙΙ-47 (0.84) 起始劑3 (0.27) 單體E (0.20) - PGMEA (10.25) 單體F (0.64) 著色硬化性組成物1之製備及表1中所使用之聚合性 化合物、光聚合起始劑之起始劑1〜起始劑3如下所述。 單體A〜單體D、及單體F是本發明之聚合性化合物,但 120 201213336 單體D與本發明之聚合性化合物不同。 聚合性化合物: 單體A:乙氧基化異三聚氰酸三丙烯酸酯 單體B:季戊四醇三丙烯酸酯 單體C :季戊四醇四丙烯酸酯 單體D:下述結構 [化 67][Table 1] Pigment Dispersion Specific Complex Photopolymerization Initiator Polymerizable Compound Polymer Solvent Colored Curable Composition 1 PB15:6 (17.04) la-5 (0.84) Starting Agent 1 (0.27) Monomer A (0.20) Resin A (0.10) PGMEA (10.25) Monomer F (0.64) Colored hardening composition 2 PB15:6 (17.04) III-3 (0.84) Starting agent 1 (0.27) Monomer B (0.40) - PGMEA (10.25) Monomer F (0.44) Colored hardening composition 3 PB15:6 (17.04) III-5 (0.84) Starting agent 1 (0.15) Monomer C (0.40) - PGMEA (6.25) Starting agent 2 (0.12) Monomer F (0.44) CyH (4.00) Colored hardening composition 4 PB15:6 (17.04) ΙΙΙ-Α (0.84) Starting agent 2 (0.27) Monomer D (0.50) PGMEA (6.25) Monomer F (0.34) 2-heptanone (4.00) colored curable composition 5 PB15:6 (17.04) ΙΙΙ-45 (0.84) initiator 3 (0.27) monoterpene E (0.84) - PGMEA (10.25) color hardening Composition 6 PB15:6 (17.04) ΙΙΙ-Α (0.84) Starting agent 2 (0.27) Monomer C (0.84) - PGMEA (10.25) Colored hardening composition 7 PB15:6 (17.04) ΙΙΙ-65 (0.84 ) •" 丨Starter 1 (0.27) Monomer E (0.50) Resin A (0.10) PGMEA (10.25) Monomer F (0.34) Colored hardening composition 8 PB15:6 (17.04) ΙΙΙ-68 (0.84) Starting agent 1 (0.27) Monomer D (0.84) - PGMEA (10.25) Colored curable composition 9 PB15 (17.04) ΙΙΙ -Β (0.84) Starting agent 2 (0.27) Monomer E (0.30) - PGMEA (10.25) Monomer F (0.54) Colored curable composition 10 PB15:3 (17.04) ΙΙΙ-47 (0.84) Starting agent 3 (0.27) Monomer E (0.20) - PGMEA (10.25) Monomer F (0.64) Preparation of colored curable composition 1 and polymerizable compound used in Table 1, initiator of photopolymerization initiator 1 ~Starter 3 is as follows. Monomer A to monomer D and monomer F are the polymerizable compounds of the present invention, but 120 201213336 monomer D is different from the polymerizable compound of the present invention. Polymerizable compound: Monomer A: Ethoxylated isocyanuric acid triacrylate Monomer B: Pentaerythritol triacrylate Monomer C: Pentaerythritol tetraacrylate Monomer D: The following structure [Chem. 67]
單體E:二季戊四醇六丙烯酸酯 單體F:下述結構 [化 68]Monomer E: dipentaerythritol hexaacrylate monomer F: the following structure [Chem. 68]
121 201213336 _ . - - [化 69]121 201213336 _ . - - [Chem. 69]
起始劑1Starting agent 1
起始劑2Starting agent 2
另外’於表1中,顏料分散液之攔的「PB15 : 6」表 示所述顏料藍-15 : 6分散液。而且,「pBl5」及rpBl5 : 3」是指於顏料藍-15 : 6分散液之製備中,個別使用顏料 ΡΒ15、及顏料ΡΒ15 : 3而代替作為顏料之顏料藍_15 : 6, 除此以外與顏料藍-15 : 6分散液之製備同樣地進行而所得 之顏料分散液。 (實例2〜實例9、參考例〇 實例2〜實例9、參考例1使用表2中所示之各著色硬 化性組成物。 如下所述那樣評價實例1〜實例9、參考例i中之各著 色硬化性組成物的耐光性、及顯影時間依存性,將結果示 於表2。 122 201213336 ό//zjpif _單色彩色滤光片之製作與耐光性之評價_ 使用旋轉式塗佈機’將上述所得之各著色硬化性组成 物以乾燥後之膜厚成為0.6 μΐη之方式塗佈於玻璃基板 ί色進行12°秒之_烤,獲得耐光性評價用 早色彩色濾光片。 =所得之耐光性評·單色彩⑽光片,藉由氣氣燈 以10萬1似照射20小時(相當於2〇〇萬lux · h)。測 氣燈照射前後之單色彩色滤光片之色差(δε*Α值 耐光性指標H ΔΕΜ值越小’則耐光性越良好,判 斷基準如下所述。將結果示於表2中。 〜判定基準〜 △E*ab 值< 1 ^△E*ab 值<3 3$站*沾值$10 10<^*ab 值 X : -顯影時間依存性之評價- (1)抗蝕溶液A (下塗液)之製備 將下述成分加以混合而使其溶解,製備抗餘 * PGMEA 5.20 份 • 52.60 份 •黏合劑 30.50份 (甲基丙烯酸节i旨/曱基丙烯酸/曱基丙稀酸_2老美乙 物、莫耳比為60: 20: 2〇、重量平均分子量為‘ο (I本乙烯換异)、41%環己目同溶液) 123 201213336 •二季戊四醇六丙烯酸酯 10.20份 •聚合抑制劑(對甲氧基苯酚) 0.006份 •氟系界面活性劑(DIC股份有限公司製造之ρ_475 ) 0.80 份 •光聚合起始劑:4-苯并四氫咬喃-2,6-雙(三氣曱基)_ 均三喚(Midori Kagaku Co.,Ltd.製造之 TAZ-107) 0.58 份 (2) 附有下塗層之玻璃基板之製作 將玻璃基板(康寧公司製造之1737)於0.5%NaOH水 中進行超音波清洗後,進行水洗、脫水烘烤 (200°C/20min)。其次,使用旋轉式塗佈機’將上述(丄) 所得之抗蝕溶液A以乾燥後之膜厚成為2 μιη之方式塗佈 於進行了清洗之玻璃基板上,於220°C下使其加熱乾燥i 小時,製備附有下塗層之玻璃基板。 (3) 顯影時間依存性之評價 於(2)中所得之附有下塗層之矽晶圓基板的下塗層 上’以各自之塗佈膜的乾燥膜厚成為0.7 μηχ之方式塗佈著 色硬化性組成物’形成光硬化性著色硬化性組成物層。繼 而’使用100°C之加熱板而進行120秒之加熱處理(預烘 烤)。其次,使用i線步進機曝光裝置FPA-3000i5 + ( Canon 股份有限公司製造)’通過圖案為1.2 μιη之四方的島_分 布狀圖案遮罩,於100 mJ/cm2〜2500 mJ/cm2之範圍使曝光 量每次變化100 mJ/cm2地照射365 nm波長之光。其後, 將形成有塗佈膜之石夕晶圓基板載置於旋轉、喷淋顯影機 124 201213336Further, in Table 1, "PB15: 6" of the pigment dispersion was expressed as the pigment blue-15:6 dispersion. Further, "pBl5" and rpBl5: 3" mean that in the preparation of the pigment blue-15:6 dispersion, the pigment ΡΒ15 and the pigment ΡΒ15:3 are used instead of the pigment blue _15: 6, otherwise The pigment dispersion obtained in the same manner as in the preparation of the pigment blue-15:6 dispersion. (Example 2 to Example 9, Reference Example 2 to Example 9, and Reference Example 1 Each of the colored curable compositions shown in Table 2 was used. Each of Examples 1 to 9 and Reference Example i was evaluated as follows. The light resistance and development time dependence of the coloring curable composition were shown in Table 2. 122 201213336 ό//zjpif _ Monochrome color filter production and evaluation of light resistance _ Using a rotary coater Each of the colored curable compositions obtained above was applied to a glass substrate to have a film thickness of 0.6 μΐ after drying, and baked for 12° seconds to obtain an early color filter for evaluation of light resistance. Light resistance evaluation · Single color (10) light film, which is illuminated by a gas lamp for 100 hours (equivalent to 2 million lux · h). The color difference of the monochrome color filter before and after the gas meter illumination (The smaller the δ ε * 耐 value light resistance index H Δ ΕΜ value is, the better the light resistance is, and the judgment criteria are as follows. The results are shown in Table 2. ~ Determination criterion ~ ΔE*ab value < 1 ^ △ E* Ab value <3 3$ station* dip value $10 10<^*ab value X: - evaluation of development time dependence - (1) Preparation of etching solution A (undercoating solution) The following components were mixed and dissolved to prepare an anti-residue * PGMEA 5.20 parts • 52.60 parts • 30.50 parts of a binder (methacrylic acid / methacrylic acid / mercaptopropyl Dilute acid _2 old US, molar ratio of 60: 20: 2 〇, weight average molecular weight is 'ο (I vinyl interchange), 41% cycloheximide solution) 123 201213336 • dipentaerythritol hexaacrylate 10.20 parts • polymerization inhibitor (p-methoxyphenol) 0.006 parts • fluorine-based surfactant (ρ_475, manufactured by DIC Corporation) 0.80 parts • photopolymerization initiator: 4-benzotetrahydrocarbamate-2, 6-double (three gas sulfhydryl)_ 均三唤 (TAZ-107 manufactured by Midori Kagaku Co., Ltd.) 0.58 parts (2) Preparation of glass substrate with undercoat layer Glass substrate (manufactured by Corning Incorporated) 1737) After ultrasonic cleaning in 0.5% NaOH water, washing with water and dehydration baking (200 ° C / 20 min). Next, using the rotary coater 'to dry the resist solution A obtained above (丄) The film thickness was applied to the glass substrate to be cleaned at a film thickness of 2 μm, and the film was allowed to stand at 220 ° C. The glass substrate with the undercoat layer was prepared by heating and drying for 1 hour. (3) The development time dependence was evaluated on the undercoat layer of the underlying coated wafer substrate obtained in (2) The coloring curable composition was applied to form a photocurable coloring curable composition layer so that the dried film thickness of the coating film was 0.7 μηη. Then, heat treatment (pre-baking) was carried out for 120 seconds using a hot plate of 100 °C. Next, the i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Co., Ltd.) was used to cover the islands of the 1.2 μm pattern with a patterned pattern of the pattern, in the range of 100 mJ/cm 2 to 2500 mJ/cm 2 . The 365 nm wavelength light was irradiated by changing the exposure amount by 100 mJ/cm 2 at a time. Thereafter, the Shihua wafer substrate on which the coating film is formed is placed on the rotary and spray developing machine 124 201213336
J / /ZjpiI (DW-30逛;Chemitronics Co·,Ltd·製造)之水平方疋轉台 上,使用 CD-2000 (FUJIFILM Electronic Materials 股份有 限公司製造)而於23°C下進行30秒及120秒之浸置式顯 影’於石夕晶圓基板上形成著色圖案。藉由下述式而評價顯 影時間之依存性。 顯影時間依存性(%) =|D120-D3〇|/D12〇x1〇0 D30 :於進行3〇秒之顯影之情形時,形成1.2 μιη圖 案之曝光量 D12〇 :於進行120秒之顯影之情形時,形成1.2 μπι 圖案之曝光量 〜判定基準〜 ◎:不足5% 〇 : 5%以上、不足1〇0/〇 △ : 10%以上、不足15% X : 15%以上 125 201213336 [表2] 著色硬化性組成物 耐光性 顯影時間依存性 實例1 著色硬化性組成物1 〇 ◎ 實例2 著色硬化性組成物2 0 ◎ 實例3 著色硬化性組成物3 〇 ◎ 實例4 著色硬化性組成物4 〇 ◎ 實例5 著色硬化性組成物7 〇 ◎ 實例6 著色硬化性組成物9 〇 ◎ 實例7 著色硬化性組成物10 〇 ◎ 實例8 著色硬化性組成物6 〇 〇 實例9 著色硬化性組成物8 〇 〇 參考例1 著色硬化性組成物5 〇 Δ 根據表1及表2之結果可知:藉由使用本發明之著色 硬化性組成物,可獲得顯影時間依存性小、且耐光性良好 之彩色濾光片。 【圖式簡單說明】 無。 【主要元件符號說明】 無0 126On the horizontal turntable of J / /ZjpiI (DW-30, manufactured by Chemitronics Co., Ltd.), using CD-2000 (manufactured by FUJIFILM Electronic Materials Co., Ltd.) at 23 ° C for 30 seconds and 120 seconds The dip-type development 'forms a colored pattern on the Shi Xi wafer substrate. The dependence of the development time was evaluated by the following formula. Development time dependence (%) =|D120-D3〇|/D12〇x1〇0 D30: In the case of 3 seconds of development, an exposure amount of D1 is formed in a 1.2 μm pattern: development is performed for 120 seconds. In the case of the case, the exposure amount of the pattern of 1.2 μπι is formed. ~: 5%: less than 5% 〇: 5% or more, less than 1〇0/〇 Δ: 10% or more, less than 15% X: 15% or more 125 201213336 [Table 2 Coloring Curable Composition Light Resistance Development Time Dependence Example 1 Coloring Curable Composition 1 〇 ◎ Example 2 Coloring Curable Composition 2 0 ◎ Example 3 Coloring Curable Composition 3 〇 ◎ Example 4 Coloring Curable Composition 4 〇 ◎ Example 5 Colored curable composition 7 〇 ◎ Example 6 Colored curable composition 9 〇 ◎ Example 7 Colored curable composition 10 〇 ◎ Example 8 Colored curable composition 6 〇〇 Example 9 Colored curable composition 8 〇〇Reference Example 1 Colored curable composition 5 〇Δ According to the results of Tables 1 and 2, it is understood that by using the color-curable composition of the present invention, color filter having small development time dependency and good light resistance can be obtained. Light film. [Simple description of the diagram] None. [Main component symbol description] None 0 126
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