TW201700484A - Squarylium compounds used for LCD color filters - Google Patents

Squarylium compounds used for LCD color filters Download PDF

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TW201700484A
TW201700484A TW105109421A TW105109421A TW201700484A TW 201700484 A TW201700484 A TW 201700484A TW 105109421 A TW105109421 A TW 105109421A TW 105109421 A TW105109421 A TW 105109421A TW 201700484 A TW201700484 A TW 201700484A
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alkyl
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胡小鏈
李揚
廖桂紅
張楷男
馬修 瑞米
何超
任華
劉安棟
許之
凱西 法納
何義勇
伊莉莎白 史文森
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陶氏全球科技公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0874—Reactions involving a bond of the Si-O-Si linkage
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Optical Filters (AREA)

Abstract

Squarylium compounds suitable for forming color filters used for a liquid crystal display device, a method for synthesis of the squarylium compounds, a composition containing a resin and the squarylium compounds, an article having a polymer layer containing the compounds and a resin, and color filters containing the compounds are provided.

Description

用於LCD彩色濾光片的方酸鹽化合物 Squanate compound for LCD color filters

本發明係關於適合於形成用於液晶顯示器裝置之彩色濾光片之方酸鹽化合物及其混合物、一種用於合成方酸鹽化合物之方法、一種含有樹脂及方酸鹽化合物之組成物、一種具有由該組成物形成之聚合物層之物品，以及包含方酸鹽化合物之彩色濾光片。 The present invention relates to a squary acid salt compound suitable for forming a color filter for a liquid crystal display device, a mixture thereof, a method for synthesizing a squary acid salt compound, a composition containing a resin and a squary acid salt compound, and the like An article having a polymer layer formed of the composition, and a color filter comprising a squaraine compound.

液晶顯示器(liquid crystal display；LCD)裝置當前由於其極佳顯示特性(諸如，能效色彩純度及/或纖細性)而在顯示器市場占主導地位。作為LCD裝置之關鍵組件，半透明彩色濾光片起到藉由過濾來自背板之白光而產生紅/綠/藍光的關鍵作用。此能力來源於包含在彩色濾光片單元中之紅/綠/藍著色劑。各著色劑具有特性吸收光譜且當用波長在380nm至780nm範圍內之白色可見光照明時會展示三種原色中之一種。受控地混合來自每一彩色濾光片單元之由著色劑產生之原色將產生像素之最終色彩。因此，彩色濾光片之效率直接影響LCD的效能。 Liquid crystal display (LCD) devices currently dominate the display market due to their excellent display characteristics such as energy efficiency color purity and/or slenderness. As a key component of LCD devices, translucent color filters play a key role in producing red/green/blue light by filtering white light from the backsheet. This ability is derived from the red/green/blue colorants contained in the color filter unit. Each colorant has a characteristic absorption spectrum and exhibits one of three primary colors when illuminated with white visible light having a wavelength in the range of 380 nm to 780 nm. Controlled mixing of the primary colors produced by the colorant from each color filter unit will produce the final color of the pixel. Therefore, the efficiency of the color filter directly affects the performance of the LCD.

顏料及染料為著色劑之兩個主要類型。顏料針對熱、光及化學物質具有良好穩定性。歸因於顏料的固有不可溶性，顏料在被添加到色彩抗蝕劑中以製成彩色濾光片之前必須被研磨成微/奈米粒子。著色劑之聚集粒子造成光散射。因此，光信號會損失且透射率低，且必須施加較多光 能以向LCD提供足夠亮度。 Pigments and dyes are the two main types of colorants. Pigments have good stability against heat, light and chemicals. Due to the inherent insolubility of the pigment, the pigment must be ground into micro/nano particles before being added to the color resist to form a color filter. Aggregated particles of the colorant cause light scattering. Therefore, the optical signal is lost and the transmittance is low, and more light must be applied. Can provide sufficient brightness to the LCD.

與顏料對比，染料在許多材料中可溶以使得其以分子級分散。若染料代替顏料用於彩色濾光片中，則光散射將明顯地縮減。基於染料的彩色濾光片可能具有較高透射率，且能量成本可能因此極大地縮減。然而，染料針對光、熱之穩定性及耐化學性一般不如顏料。因此，目前商品化之LCD彩色濾光片主要為顏料加上少許顏料染料混合物。 In contrast to pigments, dyes are soluble in many materials such that they are dispersed at the molecular level. If the dye is used in the color filter instead of the pigment, the light scattering will be significantly reduced. Dye-based color filters may have higher transmission rates and energy costs may therefore be greatly reduced. However, dyes are generally inferior to pigments for light, heat stability and chemical resistance. Therefore, currently commercialized LCD color filters are mainly pigments plus a small pigment dye mixture.

方酸鹽化合物為具有良好熱穩定性之著色劑。一些方酸鹽化合物係用於LCD彩色濾光片，參見(例如)WO2013/094827A、WO2013/047859A、WO2013/047860A、JP2012168258A、JP2006079011A、JP2006079012A、WO2008/035554A、JP2008275726A、JP2009040860A、US2007212622A、JP2012013945A、JP2004238606A和JP2004258514A，但彼等化合物一般在用於彩色濾光片之共同有機溶劑中具有不充分可溶性。 The squaraine compound is a coloring agent with good thermal stability. Some of the squaraine compounds are used in LCD color filters, see, for example, WO 2013/094827 A, WO 2013/047859 A, WO 2013/047860 A, JP 2012 168 258 A, JP 2006 079 011 A, JP 2006 079 012 A, WO 2008/035554 A, JP 2008 275 726 A, JP 2009 040 860 A, US 2007212622 A, JP 201 2013 945 A, JP 2004 238 606 A JP2004258514A, but their compounds generally have insufficient solubility in a common organic solvent for color filters.

因此，仍需要既穩定亦在有機溶劑中具有令人滿意的可溶性之方酸鹽化合物。 Therefore, there is still a need for a squary acid salt compound which is both stable and has satisfactory solubility in an organic solvent.

本發明之發明人已發現具有矽氧烷或矽烷基醚側鏈之新方酸鹽化合物，該等方酸鹽化合物為穩定的且在用於彩色濾光片之有機溶劑中具有良好可溶性。本發明之發明人已進一步發現：(1)具有矽氧烷或矽烷基醚側鏈之不對稱方酸鹽化合物展示與通常用於彩色濾光片中之丙烯酸酯樹脂的經改良之相容性，且亦比對稱方酸鹽化合物展示較深藍色；以及(2)諸如側鏈上之丙烯酸酯或環氧基的可交聯基團改良與丙烯酸酯樹脂之相容性。 The inventors of the present invention have found a novel squary acid salt compound having a side chain of a decane or a decyl ether which is stable and has good solubility in an organic solvent used for a color filter. The inventors of the present invention have further found that: (1) an asymmetric squary acid salt compound having a side chain of a decane or a decyl ether exhibits improved compatibility with an acrylate resin generally used in a color filter. And also exhibits a darker blue color than the symmetric squary acid salt compound; and (2) a crosslinkable group such as an acrylate or epoxy group on the side chain improves the compatibility with the acrylate resin.

因此，本發明之一個態樣係關於一種具有矽氧烷或矽烷基醚結構且由通式(1)表示之方酸鹽化合物： Accordingly, one aspect of the present invention relates to a squary acid salt compound having the structure of a decane or a decyl ether and represented by the formula (1):

其中R1至R6係選自由氫、羥基、醯胺、胺、矽烷基、烷基磺醯基、具有1至20個碳原子之經取代或未經取代之烷氧基及具有1至20個碳原子之經取代或未經取代之烷基組成的群組，烷氧基或烷基之取代基為-OCOR28，其中R28為飽和或不飽和烴，R1至R3中之至少一者及R4至R6中之至少一者為由NR7R8表示之胺，其中R7及R8係選自由具有1至20個碳原子之經取代或非經取代之烷基、烯基、芳基、雜芳基、氫、甲醯基及-L-S1組成的群組，烷基之取代基為-OCOR28，L為選自直接鍵、氧原子及具有1至20個碳原子之可含有雜原子之飽和或不飽和烴之二價鍵聯基團，S1為由以下式(3)至式(5)表示之含有矽氧烷或矽烷基醚的基團： Wherein R 1 to R 6 are selected from the group consisting of hydrogen, hydroxy, decylamine, amine, decylalkyl, alkylsulfonyl, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms and having 1 to 20 a group consisting of a substituted or unsubstituted alkyl group of a carbon atom, the substituent of the alkoxy group or the alkyl group being -OCOR 28 , wherein R 28 is a saturated or unsaturated hydrocarbon, and at least R 1 to R 3 And one of R 4 to R 6 is an amine represented by NR 7 R 8 , wherein R 7 and R 8 are selected from substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms, a group consisting of an alkenyl group, an aryl group, a heteroaryl group, a hydrogen group, a methyl group and a -L-S1 group, the substituent of the alkyl group is -OCOR 28 , and L is selected from a direct bond, an oxygen atom, and has 1 to 20 a carbon atom which may contain a divalent linking group of a saturated or unsaturated hydrocarbon of a hetero atom, and S1 is a group containing a decane or a decyl ether represented by the following formula (3) to formula (5):

其中R9至R11、R13至R16、R18至R23及R25至R27為具有1至20 個碳原子之烷基，n及m為自0至10之整數，R12、R17及R24為具有1至20個碳原子之烷基或G，G為具有環氧基、丙烯酸酯、丙烯醯胺及烯系不飽和基團中之至少一者之可交聯基團，*意謂鍵結至L之位置，且R7至R8中之至少一者為-L-S1。 Wherein R 9 to R 11 , R 13 to R 16 , R 18 to R 23 and R 25 to R 27 are alkyl groups having 1 to 20 carbon atoms, and n and m are integers from 0 to 10, R 12 , R 17 and R 24 are an alkyl group having 1 to 20 carbon atoms or G, and G is a crosslinkable group having at least one of an epoxy group, an acrylate, an acrylamide, and an ethylenically unsaturated group. , * means the position of the bond to L, and at least one of R 7 to R 8 is -L-S1.

本發明之另一態樣係關於一種上文所揭示之用於合成方酸鹽化合物之方法，該方法包含使具有烯系不飽和基團之方酸鹽化合物與具有氫原子之矽氧烷或矽烷基醚化合物接觸之步驟。 Another aspect of the invention relates to a method for synthesizing a squaraine compound disclosed above, which comprises reacting a squaraine compound having an ethylenically unsaturated group with a oxane having a hydrogen atom or The step of contacting the decyl ether compound.

本發明之又其他態樣係關於：一種包含樹脂及該方酸鹽化合物之組成物；一種具有由上文所揭示之該組成物形成之聚合物層之物品；以及一種包含該方酸鹽化合物中之至少一者之彩色濾光片。 Still other aspects of the invention relate to: a composition comprising a resin and the squary acid salt compound; an article having a polymer layer formed from the composition disclosed above; and a compound comprising the squary acid salt At least one of the color filters.

本發明之另一及其他態樣係關於一種自以下步驟獲得之方酸鹽化合物混合物：(a)使5-(二烯丙胺基)苯-1,3-二醇與方酸(squaric acid)接觸以獲得反應產物A；及(b)在存在催化劑之情況下使反應產物A與具有氫原子之矽氧烷或矽烷基醚化合物接觸。 Another and other aspects of the invention relate to a mixture of squaraine compounds obtained from the following steps: (a) 5-(diallylamino)benzene-1,3-diol and squaric acid Contacting to obtain the reaction product A; and (b) contacting the reaction product A with a oxane or a decyl ether compound having a hydrogen atom in the presence of a catalyst.

圖1為由實例1獲得之方酸鹽化合物之混合物(混合物B)的HPLC圖表。 Figure 1 is an HPLC chart of a mixture (mixture B) of the squaraine compound obtained in Example 1.

圖2為由實例3獲得之方酸鹽混合物(化合物8)之NMR光譜。 2 is an NMR spectrum of a squaraine salt mixture (Compound 8) obtained in Example 3.

圖3a及圖3b為展示由方酸鹽化合物及丙烯酸酯樹脂形成之彩色膜的相片。 3a and 3b are photographs showing a color film formed of a squarate compound and an acrylate resin.

如本說明書通篇所用，除非上下文明確指示，否則以下所給出之縮寫具有以下含義：g=公克；mg=毫克；mm=毫米；min.=分鐘；s=秒；hr.=小時；rpm=每分鐘轉數；℃=攝氏度。在本說明書通篇中，「(甲基)丙烯酸」用於指示「丙烯酸」或「甲基丙烯酸」官能基可能存在。如本說明書通篇所用，詞語「樹脂」及「聚合物」可被互換地使用。詞語「鹼溶性樹脂」及「黏合劑」可被互換地使用。 As used throughout this specification, the abbreviations given below have the following meanings unless the context clearly indicates: g = grams; mg = milligrams; mm = millimeters; min. = minutes; s = seconds; hr. = hours; rpm = revolutions per minute; °C = degrees Celsius. Throughout this specification, "(meth)acrylic acid" is used to indicate that "acrylic" or "methacrylic" functional groups may be present. As used throughout this specification, the terms "resin" and "polymer" are used interchangeably. The words "alkali-soluble resin" and "binder" can be used interchangeably.

方酸鹽化合物 Squanate compound

本發明提供由通式(1)表示之方酸鹽化合物。 The present invention provides a squary acid salt compound represented by the general formula (1).

在式(1)中，R1至R6係獨立地選自由氫、羥基、醯胺、胺、矽烷基、烷基磺醯基、具有1至20個碳原子之經取代或未經取代之烷氧基，及具有1至20個碳原子之經取代或未經取代之烷基組成的群組。烷氧基或烷基之取代基為-OCOR28。R28為飽和或不飽和烴。 In the formula (1), R 1 to R 6 are independently selected from hydrogen, hydroxy, decylamine, amine, decylalkyl, alkylsulfonyl, substituted or unsubstituted having 1 to 20 carbon atoms. An alkoxy group, and a group consisting of substituted or unsubstituted alkyl groups having 1 to 20 carbon atoms. The substituent of the alkoxy group or the alkyl group is -OCOR 28 . R 28 is a saturated or unsaturated hydrocarbon.

烷基具有至少1個碳原子，且具有小於20個碳原子，較佳小於8個碳原子。烷基之實例為：甲基、乙基、丙基、丁基、己基、辛基、癸基、十二基、十六基、十八基、異丙基、第二丙基、第二丁基、第三丁基、2-乙基己基、環己基、1-降冰片烷基及1-金剛烷基。 The alkyl group has at least one carbon atom and has less than 20 carbon atoms, preferably less than 8 carbon atoms. Examples of alkyl groups are: methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecanyl, octadecyl, isopropyl, second propyl, second butyl Base, tert-butyl, 2-ethylhexyl, cyclohexyl, 1-norbornyl and 1-adamantyl.

烷氧基具有至少1個碳原子，且具有小於20個碳原子，較佳小於8個碳原子。烷氧基之實例為：甲氧基、乙氧基、丙氧基、丁氧基、己氧基、辛氧基、第二丁氧基及第三丁氧基。 The alkoxy group has at least one carbon atom and has less than 20 carbon atoms, preferably less than 8 carbon atoms. Examples of alkoxy groups are: methoxy, ethoxy, propoxy, butoxy, hexyloxy, octyloxy, second butoxy and tert-butoxy.

在式(1)中，R1至R3中之至少一者及R4至R6中之至少一 者為由式(2)表示之胺。較佳地，R3及R6為由式(2)表示之胺。 In the formula (1), at least one of R 1 to R 3 and at least one of R 4 to R 6 are an amine represented by the formula (2). Preferably, R 3 and R 6 are an amine represented by the formula (2).

在式(2)中，R7及R8係選自由具有1至20個碳原子之經取代或未經取代之烷基、烯基、芳基、雜芳基、氫、甲醯基及-L-S1組成的群組。R7及R8中之至少一者為-L-S1。烷基之取代基為-OCOR28.L為選自直接鍵、氧原子及具有1至20個碳原子之可含有雜原子之飽和或不飽和烴的二價鍵聯基團。較佳地，L為具有1至5個碳原子之伸烷基或 In the formula (2), R 7 and R 8 are selected from substituted or unsubstituted alkyl, alkenyl, aryl, heteroaryl, hydrogen, formazan and - having from 1 to 20 carbon atoms. A group consisting of L-S1. At least one of R 7 and R 8 is -L-S1. The substituent of the alkyl group is -OCOR 28. L is a divalent linking group selected from a direct bond, an oxygen atom, and a saturated or unsaturated hydrocarbon having 1 to 20 carbon atoms which may contain a hetero atom. Preferably, L is an alkylene group having 1 to 5 carbon atoms or

S1為由以下式(3)至式(5)表示之含有矽氧烷或矽烷基醚之基團。 S1 is a group containing a decane or a decyl ether represented by the following formula (3) to formula (5).

在式(3)至式(5)中，*意謂鍵結至L之位置。R9至R11、R13至R16、R18至R23及R25至R27為具有1至20個碳原子之烷基。n及m為自0至10之整數。較佳地，n為小於4之整數且m為小於2之整數。R12、R17 及R24為具有1至20個碳原子之烷基或G。G為具有環氧基、丙烯酸酯、丙烯醯胺及烯系不飽和基團中之至少一者之可交聯基團。較佳地，G為具有環氧基或丙烯酸酯基團之可交聯基團。 In the formulas (3) to (5), * means a position bonded to L. R 9 to R 11 , R 13 to R 16 , R 18 to R 23 and R 25 to R 27 are an alkyl group having 1 to 20 carbon atoms. n and m are integers from 0 to 10. Preferably, n is an integer less than 4 and m is an integer less than 2. R 12 , R 17 and R 24 are an alkyl group having 1 to 20 carbon atoms or G. G is a crosslinkable group having at least one of an epoxy group, an acrylate, an acrylamide, and an ethylenically unsaturated group. Preferably, G is a crosslinkable group having an epoxy group or an acrylate group.

本發明之方酸鹽化合物可用作混合物。方酸鹽化合物中之兩者或更多者之混合物可增加化合物在各種有機溶劑中之可溶性。 The squaraine compound of the present invention can be used as a mixture. Mixtures of two or more of the squaraine compounds increase the solubility of the compounds in various organic solvents.

由式(1)表示之方酸鹽化合物適用於LCD之彩色濾光片中，此係由於本發明之方酸鹽化合物具有極佳熱穩定性且針對用於LCD之製造中之有機溶劑(諸如，丙二醇單甲醚乙酸酯(propylene glycol monomethyl ether acetate；PGMEA))具有足夠高可溶性。另外，具有不對稱矽氧烷、矽烷/矽烷基側鏈之方酸鹽化合物在彩色濾光片中展示經改良之透射率。當由式(1)表示之化合物具有G(可交聯基團)，諸如丙烯酸酯或環氧基時，方酸鹽化合物展示與通常用於彩色濾光片之樹脂的經改良之相容性。 The squary acid salt compound represented by the formula (1) is suitable for use in a color filter of an LCD because the squary acid salt compound of the present invention has excellent thermal stability and is suitable for an organic solvent used in the manufacture of an LCD (such as , propylene glycol monomethyl ether acetate (PGMEA) has a sufficiently high solubility. Additionally, a squaraine compound having an asymmetric oxane, decane/decane alkyl side chain exhibits improved transmittance in a color filter. When the compound represented by the formula (1) has a G (crosslinkable group) such as an acrylate or an epoxy group, the squary acid salt compound exhibits improved compatibility with a resin generally used for a color filter. .

本發明之方酸鹽化合物可藉由具有氫原子之矽氧烷或矽烷基醚化合物與具有烯系不飽和基團之對應方酸鹽化合物反應而合成。詳言之，該反應包括在存在催化劑之情況下使由以下式(6)表示之化合物(A)與式(7)至式(9)表示之矽氧烷或矽烷基醚化合物(B)接觸。 The squary acid salt compound of the present invention can be synthesized by reacting a decane or a decyl ether compound having a hydrogen atom with a corresponding squary acid salt compound having an ethylenically unsaturated group. In particular, the reaction involves contacting the compound (A) represented by the following formula (6) with the oxirane or decyl ether compound (B) represented by the formula (7) to the formula (9) in the presence of a catalyst. .

在式(6)中，R1至R6係選自由氫、羥基、醯胺、胺、矽烷基、烷基磺醯基、具有1至20個碳原子之經取代或未經取代之烷氧基，及具有1至20個碳原子之經取代或未經取代之烷基組成的群組。烷氧基或烷基之取代基為-OCOR28，其中R28為飽和或不飽和烴。R1至R3中之至少一者及R4至R6中之至少一者為展示為NR7R8之胺，其中R7及R8係選自由具有1至20個碳原子之經取代或未經取代之烷基、烯基、芳基、雜芳基、氫、甲醯基及-L-X組成的群組。烷基之取代基為-OCOR28。L為選自直接鍵、氧原子及具有1至20個碳原子之可含有雜原子之飽和或不飽和烴的二價鍵聯基團。X為具有烯系不飽和基團之基團。R7及R8中之至少一者為-L-X。 In the formula (6), R 1 to R 6 are selected from the group consisting of hydrogen, hydroxy, decylamine, amine, decylalkyl, alkylsulfonyl, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms. a group consisting of a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. The substituent of the alkoxy or alkyl group is -OCOR 28 wherein R 28 is a saturated or unsaturated hydrocarbon. At least one of R 1 to R 3 and at least one of R 4 to R 6 are amines exhibiting NR 7 R 8 wherein R 7 and R 8 are selected from substituted with from 1 to 20 carbon atoms. Or a group of unsubstituted alkyl, alkenyl, aryl, heteroaryl, hydrogen, formazan and -LX groups. The substituent of the alkyl group is -OCOR 28 . L is a divalent linking group selected from a direct bond, an oxygen atom, and a saturated or unsaturated hydrocarbon having 1 to 20 carbon atoms which may contain a hetero atom. X is a group having an ethylenically unsaturated group. At least one of R 7 and R 8 is -LX.

在式(7)至式(9)中，R9至R11、R13至R16、R18至R23及R25至R27為具有1至20個碳原子之烷基。n及m為自0至10之整數。R12、R17及R24為具有1至20個碳原子之烷基或G。G為具有環氧基、丙烯酸酯、丙烯醯胺及烯系不飽和基團中之至少一者之可交聯基團。 In the formulae (7) to (9), R 9 to R 11 , R 13 to R 16 , R 18 to R 23 and R 25 to R 27 are an alkyl group having 1 to 20 carbon atoms. n and m are integers from 0 to 10. R 12 , R 17 and R 24 are an alkyl group having 1 to 20 carbon atoms or G. G is a crosslinkable group having at least one of an epoxy group, an acrylate, an acrylamide, and an ethylenically unsaturated group.

當R12、R17及R24中之至少一者為G時，可使用下文所揭示 之矽氧烷化合物。 When at least one of R 12 , R 17 and R 24 is G, the oxoxane compound disclosed below can be used.

(CAS登記號：17980-29-9) (CAS registration number: 17980-29-9)

(CAS登記號：623932-34-3) (CAS registration number: 623932-34-3)

(CAS登記號：140404-94-0) (CAS registration number: 140404-94-0)

(CAS登記號：96474-12-3) (CAS registration number: 96474-12-3)

此等化合物市售可得或可合成。 These compounds are commercially available or can be synthesized.

催化劑較佳為矽氫化催化劑(Pt、Pd、Rh或Ru催化劑)。催化劑之實例包括卡爾施泰特氏(Karstedt)催化劑(具有分子式C24H54O3Pt2Si6 之有機鉑化合物)、氯鉑酸及威京森(Wilkinson)催化劑。作為本發明之催化劑，卡爾施泰特氏催化劑係較佳的。催化劑之量基本上為10ppm至1000ppm(呈莫耳形式)，較佳為40ppm至200ppm。 The catalyst is preferably a rhodium hydrogenation catalyst (Pt, Pd, Rh or Ru catalyst). Examples of the catalyst include a Karlstedt catalyst (organoplatinum compound having a molecular formula of C 24 H 54 O 3 Pt 2 Si 6 ), chloroplatinic acid, and a Wilkinson catalyst. As a catalyst of the present invention, a Karlstedt catalyst is preferred. The amount of the catalyst is substantially from 10 ppm to 1000 ppm (in the form of a mole), preferably from 40 ppm to 200 ppm.

由式(6)表示之化合物與由式(7)、式(8)或式(9)表示之化合物之莫耳比取決於式(6)化合物之烯系不飽和基團之數目。當由式(6)表示之化合物具有四個烯系不飽和基團時，由式(6)表示之化合物與由式(7)、式(8)或式(9)表示之化合物之莫耳比基本上為1：1至1：20，較佳為1：2至1：10，更佳為1：2至1：6。 The molar ratio of the compound represented by the formula (6) to the compound represented by the formula (7), the formula (8) or the formula (9) depends on the number of ethylenically unsaturated groups of the compound of the formula (6). When the compound represented by the formula (6) has four ethylenically unsaturated groups, the compound represented by the formula (6) and the compound represented by the formula (7), the formula (8) or the formula (9) The ratio is substantially from 1:1 to 1:20, preferably from 1:2 to 1:10, more preferably from 1:2 to 1:6.

該反應在溶劑中進行。可使用任何已知溶劑，除非該溶劑不與該反應中所用的組分反應。溶劑之實例包括正丁醇、N-甲基吡咯啶酮(NMP)、N,N-二甲基甲醯胺(DMF)、四氫呋喃(THF)、二甲亞碸(DMSO)、異丙醇、戊醇、二噁烷、己醇及其混合物。 The reaction is carried out in a solvent. Any known solvent can be used unless the solvent does not react with the components used in the reaction. Examples of the solvent include n-butanol, N-methylpyrrolidone (NMP), N,N-dimethylformamide (DMF), tetrahydrofuran (THF), dimethyl hydrazine (DMSO), isopropyl alcohol, Pentanol, dioxane, hexanol and mixtures thereof.

反應溫度較佳為20℃或20℃以上，更佳為50℃或50℃以上。反應溫度較佳為200℃或200℃以下，更佳為180℃或180℃以下。反應時間較佳為3小時或3小時以上，更佳為8小時或8小時以上。反應時間較佳為48小時或48小時以下，更佳為24小時或24小時以下。所得產物可藉由再結晶或管柱層析法分離。 The reaction temperature is preferably 20 ° C or more, more preferably 50 ° C or more. The reaction temperature is preferably 200 ° C or lower, more preferably 180 ° C or lower. The reaction time is preferably 3 hours or more, more preferably 8 hours or more. The reaction time is preferably 48 hours or less, more preferably 24 hours or less. The resulting product can be isolated by recrystallization or column chromatography.

由式(6)表示之化合物藉由經取代或未經取代之羥基苯、二烯丙基胺及方酸之反應合成。下文展示反應之實例。 The compound represented by the formula (6) is synthesized by a reaction of a substituted or unsubstituted hydroxybenzene, diallylamine and squaric acid. Examples of reactions are shown below.

在以上反應期間，可形成三個異構物(異構物A、異構物B及異構物C)。彼等異構物可藉由再結晶或管柱層析法分離，或可用作混合物。在本申請案中，混合物亦被稱作「反應產物A」。異構物A、異構物B及異構物C之間的莫耳比隨著反應條件(諸如溶劑或溫度)變化。通常，在純化步驟(再結晶)之前的莫耳比為異構物A：異構物B：異構物C=1：0.15-0.40：0.01-0.04。 During the above reaction, three isomers (isomer A, isomer B, and isomer C) can be formed. The isomers may be separated by recrystallization or column chromatography or may be used as a mixture. In the present application, the mixture is also referred to as "reaction product A". The molar ratio between isomer A, isomer B, and isomer C varies with reaction conditions such as solvent or temperature. Typically, the molar ratio prior to the purification step (recrystallization) is isomer A: isomer B: isomer C = 1: 0.15-0.40: 0.01-0.04.

當在存在催化劑之情況下使反應產物A與由上文所揭示之式(7)至式(9)表示之矽氧烷或矽烷基醚化合物接觸時，所獲得之方酸鹽化合物混合物可含有以下三種化合物。 When the reaction product A is contacted with a oxoxane or a decyl ether compound represented by the above formula (7) to formula (9) in the presence of a catalyst, the obtained squary acid salt compound mixture may contain The following three compounds.

在式(10)至式(12)中，S1為含有矽氧烷或矽烷基醚之基團。含有彼等矽氧烷或矽烷基醚之基團對應於含有由上文所揭示之式(3)至式(5)表示之矽氧烷或矽烷基醚的基團。另外，方酸鹽化合物混合物可包含用於具有一個不反應烯系不飽和鍵之結構的異構物。 In the formulae (10) to (12), S1 is a group containing a decane or a decyl ether. The group containing these decane or decyl ether corresponds to a group containing a decane or a decyl ether represented by the above formula (3) to formula (5). Further, the squaraine compound mixture may contain an isomer for a structure having an unreacted ethylenically unsaturated bond.

組成物 Composition

本發明之組成物包含式(1)之化合物及樹脂。樹脂較佳為鹼溶性樹脂。該組成物較佳另外包含交聯劑(cross-linker/cross-linking agent)、溶劑及諸如光引發劑之輻射敏感化合物。該組成物可形成適用於彩色濾光片之膜。 The composition of the present invention comprises a compound of the formula (1) and a resin. The resin is preferably an alkali-soluble resin. The composition preferably further comprises a cross-linker/cross-linking agent, a solvent and a radiation-sensitive compound such as a photoinitiator. The composition can form a film suitable for a color filter.

本發明之組成物中之式(1)之化合物的含量取決於各莫耳吸收係數及所需的光譜特性、膜厚度或其類似者而變化，但以該組成物之總固體含量計其較佳為至少1wt%、更佳為至少2wt%、最佳為至少5wt%。以組成物之總固體含量計，較佳含量為小於55wt%、更佳為小於45wt%、最佳為小於35wt%。 The content of the compound of the formula (1) in the composition of the present invention varies depending on each molar absorption coefficient and desired spectral characteristics, film thickness or the like, but is calculated by the total solid content of the composition. It is preferably at least 1% by weight, more preferably at least 2% by weight, most preferably at least 5% by weight. The preferred content is less than 55 wt%, more preferably less than 45 wt%, most preferably less than 35 wt%, based on the total solids content of the composition.

本發明之組成物可包含除如式(1)中所述之組成物以外的其他著色材料。通常，額外著色材料之使用係自待由該組成物形成之材料的所需光譜特性來判定。 The composition of the present invention may contain other coloring materials than the composition as described in the formula (1). Generally, the use of additional coloring materials is determined by the desired spectral characteristics of the material to be formed from the composition.

在此技術領域中，鹼溶性樹脂亦稱為「黏合劑」。較佳地，將鹼溶性樹脂溶解於有機溶劑中。鹼溶性樹脂可在形成膜之後經諸如氫氧 化四甲基銨(tetramethyl ammonium hydroxide；TMAH)水溶液之鹼溶液顯影。 In this technical field, alkali-soluble resins are also referred to as "adhesives". Preferably, the alkali-soluble resin is dissolved in an organic solvent. The alkali-soluble resin may be subjected to, for example, hydrogen and oxygen after forming the film. Development of an alkali solution of an aqueous solution of tetramethyl ammonium hydroxide (TMAH).

鹼溶性樹脂(黏合劑)通常為直鏈有機聚合物。黏合劑視情況在聚合物結構內具有可交聯基團。當本發明之組成物用作負型感光性組成物時，此可交聯基團可藉由曝光或加熱來反應且形成交聯以使得黏合劑變為不可溶於鹼之聚合物。 The alkali-soluble resin (binder) is usually a linear organic polymer. The binder optionally has crosslinkable groups within the polymer structure. When the composition of the present invention is used as a negative photosensitive composition, the crosslinkable group can be reacted by exposure or heating and formed into a crosslink such that the binder becomes an alkali-insoluble polymer.

在此項技術中已知許多種類之黏合劑。此黏合劑之實例為：(甲基)丙烯酸系樹脂、丙烯醯胺樹脂、苯乙烯系樹脂、環氧樹脂、聚矽氧烷樹脂、酚系樹脂、清漆型酚醛樹脂及彼等樹脂之共聚物或混合物。在本申請案中，(甲基)丙烯酸系樹脂(聚合物)包括(甲基)丙烯酸或其酯及一或多種其他可聚合單體之共聚物。舉例而言，丙烯酸系樹脂可自丙烯酸及/或丙烯酸酯及任何其他可聚合單體(諸如苯乙烯、經取代之苯乙烯、順丁烯二酸或(甲基)丙烯酸縮水甘油酯)聚合。 Many types of adhesives are known in the art. Examples of the binder are: (meth)acrylic resin, acrylamide resin, styrene resin, epoxy resin, polyoxyalkylene resin, phenol resin, varnish type phenol resin, and copolymers thereof. Or a mixture. In the present application, the (meth)acrylic resin (polymer) includes a copolymer of (meth)acrylic acid or an ester thereof and one or more other polymerizable monomers. For example, the acrylic resin can be polymerized from acrylic acid and/or acrylate and any other polymerizable monomer such as styrene, substituted styrene, maleic acid or glycidyl (meth)acrylate.

藉由使用聚苯乙烯作為標準品之GPC方法量測，黏合劑較佳具有至少1,000之重量平均分子量(Mw)，更佳具有至少2,000之Mw。同時，藉由上文所描述之相同方法量測，黏合劑較佳具有小於200,000之Mw、更佳小於100,000之Mw。 The binder preferably has a weight average molecular weight (Mw) of at least 1,000, more preferably a Mw of at least 2,000, as measured by a GPC method using polystyrene as a standard. At the same time, the binder preferably has a Mw of less than 200,000, more preferably less than 100,000 Mw, as measured by the same method as described above.

本發明之組成物中所用的黏合劑之量以組成物之總固體含量計較佳為至少10wt%、更佳為至少20wt%。同時，以組成物之總固體含量計，黏合劑之較佳量為小於80wt%、更佳為小於50wt%、最佳為小於30wt%。 The amount of the binder used in the composition of the present invention is preferably at least 10% by weight, more preferably at least 20% by weight based on the total solid content of the composition. Meanwhile, the preferred amount of the binder is less than 80% by weight, more preferably less than 50% by weight, most preferably less than 30% by weight based on the total solid content of the composition.

本發明之組成物視情況進一步包含交聯劑以獲得另一硬化材料。其亦稱為自由基可聚合單體。當本發明之組成物用作負型感光性組 成物時，此交聯劑可藉由曝光或加熱形成交聯且有助於獲得另一硬化材料。熟知交聯劑可用於本發明之組成物。交聯劑之實例為：環氧樹脂，諸如雙酚A二縮水甘油醚、乙二醇二縮水甘油醚、丁二醇二縮水甘油醚、二季戊四醇五縮水甘油醚或二季戊四醇六縮水甘油醚；及經取代之含氮化合物，諸如三聚氰胺、脲、胍胺或二醇脲。 The composition of the present invention optionally further comprises a crosslinking agent to obtain another hardening material. It is also known as a free radical polymerizable monomer. When the composition of the present invention is used as a negative photosensitive group In the case of a product, the crosslinking agent can be crosslinked by exposure or heating and contribute to obtaining another hardening material. Well known crosslinkers are useful in the compositions of the present invention. Examples of crosslinking agents are: epoxy resins such as bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether, dipentaerythritol penta glycidyl ether or dipentaerythritol hexa glycidyl ether; And substituted nitrogen-containing compounds such as melamine, urea, guanamine or glycol urea.

本發明之組成物視情況進一步包含溶劑。待用於組成物之溶劑不受限，但較佳基於組成物(諸如黏合劑或方酸鹽染料)之組分之可溶性而選擇。較佳溶劑之實例包括：酯，諸如乙酸乙酯、乙酸正丁酯、甲酸戊酯、丙酸丁酯或3-乙氧基丙酸酯；醚，諸如二乙二醇二甲醚、乙二醇單甲醚或丙二醇***乙酸酯；及酮，諸如甲基乙基酮、環己酮或2-庚酮。丙二醇單甲醚乙酸酯(PGMEA)為較佳溶劑。 The composition of the present invention further comprises a solvent as the case may be. The solvent to be used for the composition is not limited, but is preferably selected based on the solubility of components of the composition such as a binder or a squary acid dye. Examples of preferred solvents include: esters such as ethyl acetate, n-butyl acetate, amyl formate, butyl propionate or 3-ethoxypropionate; ethers such as diethylene glycol dimethyl ether, ethylene Alcohol monomethyl ether or propylene glycol diethyl ether acetate; and a ketone such as methyl ethyl ketone, cyclohexanone or 2-heptanone. Propylene glycol monomethyl ether acetate (PGMEA) is a preferred solvent.

當本發明之組成物為負型輻射敏感組成物時，該組成物較佳包含光引發劑。光引發劑亦稱為光聚合引發劑且包括自由基引發劑、陽離子引發劑及陰離子引發劑。光引發劑之實例包括：肟酯型引發劑、鋶鹽引發劑、碘鹽引發劑及磺酸鹽引發劑。 When the composition of the present invention is a negative radiation-sensitive composition, the composition preferably comprises a photoinitiator. Photoinitiators are also known as photopolymerization initiators and include free radical initiators, cationic initiators, and anionic initiators. Examples of the photoinitiator include an oxime ester type initiator, a cerium salt initiator, an iodonium salt initiator, and a sulfonate initiator.

本發明之組成物可包含諸如輻射敏感樹脂或光酸產生劑之其他輻射敏感化合物。 The composition of the present invention may comprise other radiation-sensitive compounds such as radiation-sensitive resins or photoacid generators.

聚合物層 Polymer layer

上文所描述之本發明之組成物可在物品上形成聚合物層。聚合物層在本說明書中亦被描述為「聚合物膜」。 The composition of the invention described above can form a polymer layer on the article. The polymer layer is also described herein as a "polymer film."

聚合物層中之如式(1)所述之化合物的含量取決於膜之所需色彩，但以聚合物層計至少為1wt%，較佳為至少5wt%。同時，化合物 之含量以聚合物層計小於50wt%，較佳為小於35wt%。聚合物層亦包含上文所揭示之鹼溶性樹脂。 The content of the compound of the formula (1) in the polymer layer depends on the desired color of the film, but is at least 1% by weight, preferably at least 5% by weight, based on the polymer layer. At the same time, compounds The content is less than 50% by weight, preferably less than 35% by weight, based on the polymer layer. The polymer layer also contains the alkali soluble resin disclosed above.

聚合物層視情況包含上文所揭示之光引發劑、光酸產生劑、輻射敏感樹脂及交聯劑。 The polymer layer optionally includes the photoinitiator, photoacid generator, radiation sensitive resin, and crosslinker disclosed above.

在物品上形成聚合物層之方法包含以下步驟：使本發明之方酸鹽化合物與樹脂及溶劑混合，將該混合物塗佈至支撐層之物品上以及加熱該物品以形成聚合物層(膜)。視情況，該方法包含使層(膜)曝光或使層固化以形成交聯穩定層之步驟中之一或多者。 The method of forming a polymer layer on an article comprises the steps of: mixing a squaraine compound of the present invention with a resin and a solvent, applying the mixture to an article of a support layer, and heating the article to form a polymer layer (film) . Optionally, the method comprises one or more of the steps of exposing the layer (film) or curing the layer to form a crosslinked stabilizing layer.

用於形成聚合物層之方法的樹脂及溶劑與上文所揭示之樹脂及溶劑相同。 The resin and solvent used in the method for forming the polymer layer are the same as the resins and solvents disclosed above.

支撐層(膜)之物品之實例為玻璃、金屬、矽基板及經金屬氧化物塗佈之材料。 Examples of articles of the support layer (film) are glass, metal, tantalum substrates, and metal oxide coated materials.

任何塗佈方法可用於塗佈步驟，諸如旋塗、鑄塗或滾塗。 Any coating method can be used for the coating step such as spin coating, cast coating or roll coating.

層(膜)之厚度取決於所需的膜屬性而變化。層之厚度為0.1微米至5微米，較佳為0.5微米至3微米。 The thickness of the layer (film) varies depending on the desired film properties. The thickness of the layer is from 0.1 micron to 5 microns, preferably from 0.5 micron to 3 microns.

層(膜)具有來自本發明之方酸鹽化合物之屬性的高透射率及熱穩定性。方酸鹽化合物可溶解於有機溶劑中且具有高的熱穩定性。因此，染料並不防礙膜之透射率且並不降低膜之熱穩定性。此屬性對於LCD之彩色濾光片為重要的。因此，本發明之層(膜)適用作LCD之彩色濾光片。 The layer (film) has high transmittance and thermal stability from the properties of the squaraine compound of the present invention. The squaraine compound is soluble in an organic solvent and has high thermal stability. Therefore, the dye does not interfere with the transmittance of the film and does not degrade the thermal stability of the film. This property is important for LCD color filters. Therefore, the layer (film) of the present invention is suitable as a color filter for an LCD.

彩色濾光片 Color filter

本發明之彩色濾光片包含如式(1)中所述之化合物。上文所揭示之層 (膜)可用於該彩色濾光片。通常，彩色濾光片具有由包含紅/綠/藍著色劑之有色膜製成的多個單元。 The color filter of the present invention contains a compound as described in the formula (1). The layer disclosed above (Film) can be used for the color filter. Typically, a color filter has a plurality of cells made of a colored film comprising a red/green/blue colorant.

用於彩色濾光片之有色膜中之本發明之方酸鹽化合物的含量與上文所揭示之膜相同，以有色膜之總重量計，至少為1wt%，更佳為至少5wt%。同時，以有色膜之總重量計，該含量小於50wt%，較佳為小於35wt%。 The content of the squaraine compound of the present invention in the colored film for a color filter is the same as that of the film disclosed above, and is at least 1% by weight, more preferably at least 5% by weight based on the total weight of the colored film. At the same time, the content is less than 50% by weight, preferably less than 35% by weight, based on the total weight of the colored film.

用於彩色濾光片之膜可藉由以下步驟形成：塗佈包含如式(1)中所述之化合物、黏合劑、光引發劑及溶劑之溶液以在材料上形成輻射敏感組成物層，使層經由圖案化光罩曝光且用鹼溶液使該層顯影。此外，可視需要在顯影步驟後進行進一步加熱層及/或使層曝光之固化步驟。 The film for a color filter can be formed by coating a solution containing a compound as described in the formula (1), a binder, a photoinitiator, and a solvent to form a radiation-sensitive composition layer on the material. The layer is exposed through a patterned reticle and the layer is developed with an alkaline solution. In addition, it may be desirable to carry out a further step of heating the layer and/or exposing the layer after the development step.

由於彩色濾光片包含含R/G/B著色劑之三種有色膜，因此重複形成每一有色膜之步驟，接著獲得具有此三種有色膜之彩色濾光片。 Since the color filter contains three colored films containing R/G/B colorant, the step of forming each colored film is repeated, followed by obtaining a color filter having the three colored films.

實例 Instance

實例1 Example 1

製備方酸鹽化合物之混合物。 A mixture of squaraine compounds is prepared.

a.四烯丙基方酸鹽化合物(烯丙基-SQ)之製備 a. Preparation of tetraallyl citrate compound (allyl-SQ)

在乾燥氮氣氛圍下，將1,3,5-三羥基苯(11.88g，94.2mmol)、二烯丙基胺(18.27g，188.4mmol)、正丁醇(75mL)及甲苯(225mL)之混合物在水之共沸蒸餾下回流持續6h。接著冷卻黃色溶液，且將包括過量二烯丙基胺之溶劑在減壓下蒸發以給出黃色黏性液體。接著，在乾燥氮氣氛圍下攪拌所有以上5-(二烯丙胺基)苯-1,3-二醇、方酸(5.0g，43.8mmol)、正丁醇(90mL)及甲苯(270mL)之混合物且在水之共沸蒸餾下將其回流持續6h。冷 卻後，過濾綠色沈澱且用異丙醇及甲醇洗滌，從而得到13.7g結晶反應產物A-1。產率：63%。1H NMR(CDCl3,ppm)：11.00(s,4H)，5.83(s,4H)，5.81(ddt,4H)，5.25(dd,4H)，5.16(dd,4H)，3.99(d,8H)。 a mixture of 1,3,5-trihydroxybenzene (11.88 g, 94.2 mmol), diallylamine (18.27 g, 188.4 mmol), n-butanol (75 mL) and toluene (225 mL) under dry nitrogen atmosphere The reflux was continued for 6 h under azeotropic distillation of water. The yellow solution was then cooled and the solvent including excess diallylamine was evaporated under reduced pressure to give a yellow viscous liquid. Next, a mixture of all of the above 5-(diallylamino)benzene-1,3-diol, squaric acid (5.0 g, 43.8 mmol), n-butanol (90 mL) and toluene (270 mL) was stirred under a dry nitrogen atmosphere. It was refluxed for 6 h under azeotropic distillation of water. After cooling, the green precipitate was filtered and washed with isopropyl alcohol and methanol to give 13.7 g of crystallization reaction product A-1. Yield: 63%. 1 H NMR (CDCl 3 , ppm): 11.00 (s, 4H), 5.83 (s, 4H), 5.81 (dd, 4H), 5.25 (dd, 4H), 5.16 (dd, 4H), 3.99 (d, 8H) ).

b.矽氫化 b. hydrogenation

在乾燥氮氣氛圍下將以上再結晶樣本(烯丙基-SQ，8g，16.3mmol)溶解於無水THF(480mL)中。經由隔壁注射四當量之1,1,1,3,5,5,5-七甲基三矽氧烷(4.00equiv，14.5g)，接著添加卡爾施泰特氏催化劑(二甲苯中之鉑二乙烯四甲基-矽氧烷複合物，3wt%，0.75mL)。在70℃下攪拌所得混合物隔夜。此後，執行四氫呋喃對於酒精之溶劑交換(68℃至70℃，1atm)，接著濃縮溶液(酒精含量為70g)。藉由使溶液對流歷時4小時且被攪拌隔夜而將該溶液冷卻至室溫。經由粗玻璃燒結漏斗過濾所得沈澱。用冷酒精(80g)洗滌所收集的固體，且在40℃真空下使其乾燥以獲得方酸鹽化合物之混合物(混合物A)(7.57g，33%產率)。1H NMR(CDCl3,ppm)：10.96(s,4H)，5.78(s,4H)，3.36(t,8H)，1.55-1.72(m,8H)，0.45(t,8H)，0-0.06(m,84H)。 The above recrystallized sample (allyl-SQ, 8 g, 16.3 mmol) was dissolved in dry THF (480 mL) under dry nitrogen. Four equivalents of 1,1,1,3,5,5,5-heptamethyltrioxane (4.00 equiv, 14.5 g) were injected via the partition, followed by the addition of Karlstedt's catalyst (platinum in xylene) Ethylene tetramethyl-decane complex, 3 wt%, 0.75 mL). The resulting mixture was stirred at 70 ° C overnight. Thereafter, solvent exchange of tetrahydrofuran for alcohol (68 ° C to 70 ° C, 1 atm) was carried out, followed by concentration of the solution (alcohol content: 70 g). The solution was cooled to room temperature by convection of the solution for 4 hours and stirred overnight. The resulting precipitate was filtered through a coarse glass fritted funnel. The collected solid was washed with cold alcohol (80 g) and dried under vacuum at 40 ° C to obtain a mixture of the succinate compound (mixture A) (7.57 g, 33% yield). 1H NMR (CDCl 3 , ppm): 10.96 (s, 4H), 5.78 (s, 4H), 3.36 (t, 8H), 1.55-1.72 (m, 8H), 0.45 (t, 8H), 0-0.06 ( m, 84H).

ESI-MS(m/z，離子，式)：1378，(M+H)+，C56H115N2O14Si12，(質量1377)。 ESI-MS (m/z, ion, formula): 1378, (M+H) + , C 56 H 115 N 2 O 14 Si 12 , (mass 1377).

分析數據展示方酸鹽化合物之混合物(混合物A)含有下文所揭示之以下化合物1a、化合物1b、化合物2、化合物3及化合物4。 The analytical data shows that the mixture of the squaraine compounds (mixture A) contains the following compounds 1a, 1b, 2, 3 and 4 as disclosed below.

可對反應產物A-1執行相同矽氫化步驟且無需再結晶。獲得方酸鹽化合物之混合物(混合物B)。混合物A及混合物B含有如表1中所展示之方酸鹽化合物。根據HPLC區域之比率計算方酸鹽化合物之間的莫耳比。用於混合物B之HPIC圖表在圖2中展示。 The same hydrazine hydrogenation step can be carried out on the reaction product A-1 without recrystallization. A mixture of the squaraine compounds (mixture B) is obtained. Mixture A and Mix B contained the squaraine compound as shown in Table 1. The molar ratio between the squaraine compounds was calculated from the ratio of the HPLC regions. The HPIC chart for Mix B is shown in Figure 2.

實例2 Example 2

合成下文所揭示之方酸鹽化合物。 The squaraine compounds disclosed below were synthesized.

a.不對稱取代方酸(AsySQA)之製備 a. Preparation of asymmetric substituted squaric acid (AsySQA)

在氮氣下向具有磁性攪拌桿之乾燥燒瓶中裝入3-[4-(N,N-二丁胺基)苯基]-4-羥基-環丁烯-1,2-二酮(1.50g，4.98mmol)、5-(二烯丙胺基)-1,3-二羥基苯(1.02g，4.98mmol)、甲苯(50mL)及正丁醇(50mL)。在回流下攪拌反應混合物34h且接著將其冷卻至周圍溫度。藉由過濾獲得藍色晶體且使其乾燥(產率41%)。藉由進一步純化獲得較多產物。在減壓下移除濾液中之溶劑，且殘餘物藉由矽膠管柱層析法純化，用甲醇/二氯甲烷洗提(總產率62%)。1H NMR(CDCl3,ppm)：12.75(s,2H)，8.07(d,2H)，6.67(d,2H)，5.76-5.88(m,4H)，5.21(q,4H)，4.00(d,4H)，3.40(t,4H)，1.63(t,4H)， 1.37(m,4H)，0.98(t,6H)。ESI-MS(m/z，離子，式)：489.2771(M+H)+，C30H37N2O4，(理論質量488.62)。 A dry flask with a magnetic stir bar was charged with 3-[4-(N,N-dibutylamino)phenyl]-4-hydroxy-cyclobutene-1,2-dione (1.50 g) under nitrogen. , 4.98 mmol), 5-(diallylamino)-1,3-dihydroxybenzene (1.02 g, 4.98 mmol), toluene (50 mL) and n-butanol (50 mL). The reaction mixture was stirred at reflux for 34 h and then cooled to ambient temperature. Blue crystals were obtained by filtration and dried (yield 41%). More product was obtained by further purification. The solvent in the filtrate was removed under reduced pressure, and the residue was purified mjjjjjjjjjj 1 H NMR (CDCl 3 , ppm): 12.75 (s, 2H), 8.07 (d, 2H), 6.67 (d, 2H), 5.76-5.88 (m, 4H), 5.21. (q, 4H), 4.00 (d) , 4H), 3.40 (t, 4H), 1.63 (t, 4H), 1.37 (m, 4H), 0.98 (t, 6H). ESI-MS (m/z, mp.): 489.2771 (M+H) + , C 30 H 37 N 2 O 4 , (theoretical mass 488.62).

b.矽氫化 b. hydrogenation

在N2下使AsySQA(0.50g，1.02mmol)溶解於20mL無水THF中。經由隔壁注射1,1,1,3,3-五甲基二矽氧烷(2.20equiv.，0.33g)，接著添加一滴卡爾施泰特氏催化劑(二甲苯中之鉑二乙烯四甲基-矽氧烷複合物，3wt)。在50℃下攪拌所得混合物隔夜。在減壓下蒸發溶液。藉由二氧化矽層析法純化粗產物。1H NMR(CDCl3,ppm)：12.68(s,2H)，7.97(d,2H)，6.60(d,2H)，5.70(s,2H)，3.29(m,8H)，0.90(t,6H)，1.55(m,4H)，1.30(m,4H)，0.80(t,4H)，0.43(t,4H)，0.01-0.04(m,30H)。ESI-MS(m/z，離子，式)：785.422，(M+H)+，C40H69N2O6Si4，(理論質量784.42)。 Under N 2 so AsySQA (0.50g, 1.02mmol) was dissolved in 20mL anhydrous THF. 1,1,1,3,3-pentamethyldioxane (2.20 equiv., 0.33 g) was injected via a partition, followed by the addition of a drop of Karlstedt's catalyst (platinum divinyltetramethyl- in xylene) A siloxane complex, 3 wt). The resulting mixture was stirred at 50 ° C overnight. The solution was evaporated under reduced pressure. The crude product was purified by cerium oxide chromatography. 1 H NMR (CDCl 3 , ppm): 12.68 (s, 2H), 7.97 (d, 2H), 6.60 (d, 2H), 5.70 (s, 2H), 3.29 (m, 8H), 0.90 (t, 6H) ), 1.55 (m, 4H), 1.30 (m, 4H), 0.80 (t, 4H), 0.43 (t, 4H), 0.01-0.04 (m, 30H). ESI-MS (m/z, ion, formula): 785.422, (M+H) + , C 40 H 69 N 2 O 6 Si 4 , (theoretical mass 784.42).

實例3 合成下文所揭示之方酸鹽混合物。 Example 3 The squaraine salt mixture disclosed below was synthesized.

a.甲基丙烯酸甲酯改質的方酸鹽(SQ-MMA)之製備 a. Preparation of methyl methacrylate modified squary salt (SQ-MMA)

將SQ-OH(2,4-雙(4-(雙(2-羥基乙基)胺基)-2,6-二羥基苯基)-3-氧環丁-1-烯醇酯，100mg，0.198mmol)、4-二甲胺基吡啶(DMAP，0.158mmol，19.3mg，0.8equiv.)、三乙胺(Et3N，0.832mmol，84mg，0.12mL，4.2equiv)及二甲基乙醯胺(DMAc，3mL)添加至三頸圓底燒瓶中。在0℃下經由拋棄式注射器將DMAc(0.2mL)中之甲基丙烯酸酐(MMA，0.99mmol，152mg，0.15mL，5equiv.)逐滴添加至反應混合物中。該反應由TLC(2/1 EtOAc/石油醚)監測。6h之後，添加水(200mL)以稀釋整個反應混合物。接著添加飽和NaHCO3(50mL)以促進用於進一步萃取步驟之分離。藉由乙酸乙酯萃取粗混合物。組合有機相且接著在減壓下濃縮該有機相。在移除溶劑之後，混合物在TLC(3/2乙酸乙酯/石油醚)上展示多個點。藉由急驟管柱層析法收集所有餾份。混合物SQ-MMA含有四、三及二-經取代之MMA SQ。粗NMR圖像在圖2中展示。 SQ-OH (2,4-bis(4-(bis(2-hydroxyethyl)amino)-2,6-dihydroxyphenyl)-3-oxocyclobut-1-enolate, 100 mg, 0.198 mmol), 4-dimethylaminopyridine (DMAP, 0.158 mmol, 19.3 mg, 0.8 equiv.), triethylamine (Et 3 N, 0.832 mmol, 84 mg, 0.12 mL, 4.2 equiv) and dimethyl acetonitrile The amine (DMAc, 3 mL) was added to a 3-neck round bottom flask. Methacrylic anhydride (MMA, 0.99 mmol, 152 mg, 0.15 mL, 5 equiv.) in DMAc (0.2 mL) was added dropwise to the reaction mixture via a disposable syringe at 0 °C. The reaction was monitored by TLC (2/1 EtOAc / petroleum ether). After 6 h, water (200 mL) was added to dilute the whole reaction mixture. Saturated NaHCO3 (50 mL) was then added to facilitate separation for further extraction steps. The crude mixture was extracted by ethyl acetate. The organic phase was combined and the organic phase was then concentrated under reduced pressure. After removal of the solvent, the mixture exhibited multiple spots on TLC (3/2 ethyl acetate / petroleum ether). All fractions were collected by flash column chromatography. The mixture SQ-MMA contains four, three and two-substituted MMA SQ. A crude NMR image is shown in Figure 2.

b.矽氫化 b. hydrogenation

於配備有回流冷凝器之三頸圓底燒瓶中在N2下將SQ-MMA之混合物(70mg)溶解於無水甲苯(10mL)中。接著，將五甲基二矽氧 烷(30μL，23mg，0.16mmol)及卡爾施泰特氏催化劑(二甲苯中之鉑二乙烯四甲基-矽氧烷複合物，3wt%，20μL，1.3μmol)添加至反應混合物中。在75℃下攪拌反應混合物15h且接著將其冷卻至室溫。在減壓下移除溶劑。接著經由石油醚藉由短矽管柱層析法純化粗混合物以移除甲苯及二甲苯殘餘物接著移除乙酸乙酯以收集產物混合物化合物8。最終TLC展示確實發生了反應。基於粗略TLC估計，轉化率為約10%-20%。最終產物為可由LC-MS確認之SQ-MMA與化合物5的混合物。ESI-MS(m/z，離子)：777.28及925.33(M+H)+，下文展示理論質量及化學式。 In three necked round bottom flask equipped with a reflux condenser under N 2 of the mixture of SQ-MMA (70 mg of) was dissolved in dry toluene (10 mL) in. Next, pentamethyldioxane (30 μL, 23 mg, 0.16 mmol) and Karlstedt's catalyst (platinum diethylene tetramethyl-decane complex in xylene, 3 wt%, 20 μL, 1.3 μmol) ) is added to the reaction mixture. The reaction mixture was stirred at 75 ° C for 15 h and then cooled to room temperature. The solvent was removed under reduced pressure. The crude mixture was then purified via short flash column chromatography via petroleum ether to remove toluene and toluene residue and then ethyl acetate was removed to collect product mixture compound 8. The final TLC show did react. Based on a rough TLC estimate, the conversion is about 10%-20%. The final product is a mixture of SQ-MMA and Compound 5 which can be confirmed by LC-MS. ESI-MS (m/z, ion): 777.28 and 925.33 (M+H) + , the theoretical mass and chemical formula are shown below.

PGMEA中之混合物的可溶性為2.8wt%。 The solubility of the mixture in PGMEA was 2.8 wt%.

實例4(比較實例) Example 4 (comparative example)

下文所揭示之化合物用於實例4中。 The compounds disclosed below were used in Example 4.

a.化合物9(異丁基-SQ)之合成 a. Synthesis of compound 9 (isobutyl-SQ)

在乾燥氮氣氛圍下，將1,3,5-三羥基苯(3.96g，31.4mmol)、 二異丁基-胺(8.11g，62.8mmol)、正丁醇(25mL)及甲苯(75mL)之混合物在水之共沸蒸餾下回流持續6h。接著冷卻淺棕色溶液，且將包括過量二烯丙基胺之溶劑在減壓下蒸發以給出棕色黏性液體。接著，在乾燥氮氣氛圍下攪拌所有以上5-(二異丁基胺基)苯-1,3-二醇、方酸(1.7g，14.9mmol)、正丁醇(30mL)及甲苯(90mL)之混合物且在水之共沸蒸餾下將其回流持續6h。冷卻後，過濾黃綠色沈澱且用異丙醇及甲醇洗滌，從而得到4.1g結晶產物。產率：50%。1H NMR(CDCl3,ppm)：10.99(s,4H)，5.83(s,4H)，3.26(d,8H)，2.10-2.20(m,4H)，0.92-0.98(m,24H)。 1,3,5-trihydroxybenzene (3.96 g, 31.4 mmol), diisobutyl-amine (8.11 g, 62.8 mmol), n-butanol (25 mL) and toluene (75 mL) under dry nitrogen atmosphere The mixture was refluxed under azeotropic distillation of water for 6 h. The light brown solution was then cooled and the solvent including excess diallylamine was evaporated under reduced pressure to give a brown viscous liquid. Next, all of the above 5-(diisobutylamino)benzene-1,3-diol, squaric acid (1.7 g, 14.9 mmol), n-butanol (30 mL), and toluene (90 mL) were stirred under a dry nitrogen atmosphere. The mixture was refluxed for 6 h under azeotropic distillation of water. After cooling, the yellow-green precipitate was filtered and washed with isopropyl alcohol and methanol to give 4.1 g of a crystalline product. Yield: 50%. 1 H NMR (CDCl 3 , ppm): 10.99 (s, 4H), 5.83 (s, 4H), 3.26 (d, 8H), 2.10-2.20 (m, 4H), 0.92-0.98 (m, 24H).

實例5(比較實例) Example 5 (comparative example)

實例1中經合成之烯丙基-SQ用於實例5中。 The synthesized allyl-SQ in Example 1 was used in Example 5.

實例6(比較實例) Example 6 (comparative example)

實例2中經合成之AsySQA用於實例6中。 The synthesized AsySQA in Example 2 was used in Example 6.

實例7(比較實例) Example 7 (comparative example)

下文所揭示之化合物用於實例7中。 The compounds disclosed below were used in Example 7.

(C.I.顏料藍15：6) (C.I. Pigment Blue 15:6)

方酸鹽化合物及顏料之屬性 Properties of squaraine compounds and pigments

(a)分析(在25℃下)方酸鹽化合物及顏料之(PGMEA中的)可溶性、彼等化合物之UV-Vis吸收及熱穩定性。UV-Vis藉由(此處添加UV-Vis分析器之器具/類型/生產者)分析。熱穩定性在於230℃下烘烤1小時前後 藉由H-NMR及LC-MS分析。 (a) Analysis (at 25 ° C) of the solubility of the squaraine compound and the pigment (in the PGMEA), the UV-Vis absorption and thermal stability of the compounds. UV-Vis is analyzed by (incorporating the appliance/type/producer of the UV-Vis analyzer here). Thermal stability is baked at 230 ° C for 1 hour before and after Analysis by H-NMR and LC-MS.

參考表2，可發現，實例1至實例3與實例4至實例7相比展示在熱穩定性及在PGMEA中之可溶性方面的顯著改良。 Referring to Table 2, it was found that Examples 1 to 3 exhibited significant improvements in thermal stability and solubility in PGMEA compared to Examples 4 to 7.

(b)比較混合物A與化合物7之色彩。混合物A及化合物7分別在PGMEA中溶解。與展示藍綠色之混合物A相比，具有藍移UV-Vis光譜之化合物7展示較深藍色。 (b) Compare the color of mixture A with compound 7. Mixture A and Compound 7 were each dissolved in PGMEA. Compound 7 with a blue shift UV-Vis spectrum exhibited a darker blue color than the mixture A showing blue-green.

(c)測試方酸鹽化合物與丙烯酸酯樹脂之相容性。藉由僅將PGMEA中之化合物7或混合物A之溶液分別與丙烯酸酯樹脂混合來製成簡單調配物。化合物7或混合物A之含量為5wt%。以200rpm旋轉速度將溶液旋塗至乾淨玻璃基板上。所得膜接著在90℃下在空氣氛圍下乾燥100秒。與混合物A相比，化合物7展示與丙烯酸酯樹脂的經改良之相容性。 (c) Testing the compatibility of the squaraine compound with the acrylate resin. A simple formulation is prepared by separately mixing a solution of Compound 7 or Mix A in PGMEA with an acrylate resin. The content of the compound 7 or the mixture A was 5% by weight. The solution was spin coated onto a clean glass substrate at a rotational speed of 200 rpm. The resulting film was then dried at 90 ° C for 100 seconds under an air atmosphere. Compound 7 exhibited improved compatibility with acrylate resin compared to Mixture A.

(d)分析CIE值之色彩。包含化合物7之膜如以上(c)一樣製成。顏料藍與丙烯酸酯樹脂之混合物係用作比較。化合物7或顏料藍之含量為5wt%。分別以200rpm、300rpm 400rpm及500rpm旋轉速度將溶液旋塗至乾淨玻璃基板上。所得膜接著在90℃下在空氣氛圍下乾燥100秒。使用MCPD-6000(日本otsuka electronics)及C2作為光源來量測CIE值(xyY 值)。膜厚度及xyY值在表3中展示，且彼等膜之圖像在圖3中展示。 (d) Analysis of the color of the CIE value. The film containing the compound 7 was produced as in the above (c). A mixture of pigment blue and acrylate resin was used for comparison. The content of Compound 7 or Pigment Blue was 5% by weight. The solution was spin-coated onto a clean glass substrate at 200 rpm, 300 rpm, 400 rpm, and 500 rpm. The resulting film was then dried at 90 ° C for 100 seconds under an air atmosphere. Measurement of CIE value using MCPD-6000 (Japan otsuka electronics) and C2 as light source (xyY value). Film thickness and xyY values are shown in Table 3, and images of these films are shown in Figure 3.

Claims (10)

一種由以下式(1)表示之方酸鹽化合物 其中R1至R6係選自由氫、羥基、醯胺、胺、矽烷基、烷基磺醯基、具有1至20個碳原子之經取代或未經取代之烷氧基及具有1至20個碳原子之經取代或未經取代之烷基組成的群組，該烷氧基或該烷基之取代基為-OCOR28，其中R28為飽和或不飽和烴，R1至R3中之至少一者及R4至R6中之至少一者為由以下式(2)表示之胺 其中R7及R8係選自由具有1至20個碳原子之經取代或未經取代之烷基、烯基、芳基、雜芳基、氫、甲醯基及-L-S1組成的群組，該烷基之取代基為-OCOR28，L為選自直接鍵、氧原子及具有1至20個碳原子之可含有雜原子之飽和或不飽和烴的二價鍵聯基團，S1為由以下式(3)至式(5)表示之含有矽氧烷或矽烷基醚之基團， 其中R9至R11、R13至R16、R18至R23及R25至R27為具有1至20個碳原子之烷基，n及m為自0至10之整數，R12、R17及R24為具有1至20個碳原子之烷基或G，G為具有環氧基、丙烯酸酯、丙烯醯胺及烯系不飽和基團中之至少一者之可交聯基團，*意謂至L之鍵聯，且R7及R8中之至少一者為-L-S1。 A squary acid salt compound represented by the following formula (1) Wherein R 1 to R 6 are selected from the group consisting of hydrogen, hydroxy, decylamine, amine, decylalkyl, alkylsulfonyl, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms and having 1 to 20 a group consisting of a substituted or unsubstituted alkyl group of a carbon atom, the alkoxy group or the substituent of the alkyl group being -OCOR 28 , wherein R 28 is a saturated or unsaturated hydrocarbon, and R 1 to R 3 are At least one of and at least one of R 4 to R 6 is an amine represented by the following formula (2) Wherein R 7 and R 8 are selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, aryl, heteroaryl, hydrogen, formazan and -L-S1 having from 1 to 20 carbon atoms. The substituent of the alkyl group is -OCOR 28 , and L is a divalent linking group selected from a direct bond, an oxygen atom, and a saturated or unsaturated hydrocarbon having 1 to 20 carbon atoms which may contain a hetero atom, S1 a group containing a decane or a decyl ether represented by the following formula (3) to formula (5), Wherein R 9 to R 11 , R 13 to R 16 , R 18 to R 23 and R 25 to R 27 are alkyl groups having 1 to 20 carbon atoms, and n and m are integers from 0 to 10, R 12 , R 17 and R 24 are an alkyl group having 1 to 20 carbon atoms or G, and G is a crosslinkable group having at least one of an epoxy group, an acrylate, an acrylamide, and an ethylenically unsaturated group. , * means a bond to L, and at least one of R 7 and R 8 is -L-S1. 如申請專利範圍第1項之方酸鹽化合物，其中R3及R6為由式(2)表示之胺 其中R7及R8係選自由具有1至20個碳原子之經取代或未經取代之烷基、烯基、芳基、雜芳基、氫、甲醯基及-L-S1組成的群組，該烷基之取代基為-OCOR28，L為選自直接鍵、氧原子及具有1至20個碳原子之可含有雜原子之飽和或不飽和烴的二價鍵聯基團，S1為由以下式(3)至式(5)表示之含有矽氧烷或矽烷基醚之基團， 其中R9至R11、R13至R16、R18至R23及R25至R27為具有1至20個碳原子之烷基，n及m為自0至10之整數，R12、R17及R24為具有1至20個碳原子之烷基或G，G為具有環氧基、丙烯酸酯、丙烯醯胺及烯系不飽和基團中之至少一者之可交聯基團，*意謂至L之鍵聯，且R7及R8中之至少一者為-L-S1。 A compound of the formula of claim 1, wherein R 3 and R 6 are an amine represented by the formula (2) Wherein R 7 and R 8 are selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, aryl, heteroaryl, hydrogen, formazan and -L-S1 having from 1 to 20 carbon atoms. The substituent of the alkyl group is -OCOR 28 , and L is a divalent linking group selected from a direct bond, an oxygen atom, and a saturated or unsaturated hydrocarbon having 1 to 20 carbon atoms which may contain a hetero atom, S1 a group containing a decane or a decyl ether represented by the following formula (3) to formula (5), Wherein R 9 to R 11 , R 13 to R 16 , R 18 to R 23 and R 25 to R 27 are alkyl groups having 1 to 20 carbon atoms, and n and m are integers from 0 to 10, R 12 , R 17 and R 24 are an alkyl group having 1 to 20 carbon atoms or G, and G is a crosslinkable group having at least one of an epoxy group, an acrylate, an acrylamide, and an ethylenically unsaturated group. , * means a bond to L, and at least one of R 7 and R 8 is -L-S1. 如申請專利範圍第1項之方酸鹽化合物，其中R12、R17及R24為具有1至20個碳原子之烷基。 A squaraine compound according to the first aspect of the invention, wherein R 12 , R 17 and R 24 are an alkyl group having 1 to 20 carbon atoms. 如申請專利範圍第1項之方酸鹽化合物，其中R12、R17及R24中之至少一者為G。 A squaraine compound according to claim 1, wherein at least one of R 12 , R 17 and R 24 is G. 一種用於合成如申請專利範圍第1項之方酸鹽化合物之方法，該方法包含以下步驟：在存在催化劑之情況下使由以下式(6)表示之該化合物與由式(7)至式(9)表示之矽氧烷或矽烷基醚化合物接觸， 其中R1至R6係選自由氫、羥基、醯胺、胺、矽烷基、烷基磺醯基、具有1至20個碳原子之經取代或未經取代之烷氧基及具有1至20個碳原子之經取代或未經取代之烷基組成的群組，該烷氧基或該烷基之取代基為-OCOR28，其中R28為飽和或不飽和烴，R1至R3中之至少一者及R4至R6中之至少一者為由以下式(2)表示之胺 其中R7及R8係選自由具有1至20個碳原子之經取代或未經取代之烷基、烯基、芳基、雜芳基、氫、甲醯基及-L-X組成的群組，該烷基之取代基為-OCOR28，L為選自直接鍵、氧原子及具有1至20個碳原子之可含有雜原子之飽和或不飽和烴之二價鍵聯基團，X為具有烯系不飽和基團之基團，且R7及R8中之至少一者為-L-X， 其中R9至R11、R13至R16、R18至R23及R25至R27為具有1至20個碳原子之烷基，n及m為自0至10之整數，R12、R17及R24為具有1至20個碳原子之烷基或G，G為具有環氧基、丙烯酸酯、丙烯醯胺及烯系不飽和基團中之至少一者之可交聯基團。 A method for synthesizing a squary acid salt compound according to the first aspect of the patent application, the method comprising the steps of: reacting the compound represented by the following formula (6) with the formula (7) to the formula in the presence of a catalyst (9) indicating contact with a oxane or a decyl ether compound, Wherein R 1 to R 6 are selected from the group consisting of hydrogen, hydroxy, decylamine, amine, decylalkyl, alkylsulfonyl, substituted or unsubstituted alkoxy having 1 to 20 carbon atoms and having 1 to 20 a group consisting of a substituted or unsubstituted alkyl group of a carbon atom, the alkoxy group or the substituent of the alkyl group being -OCOR 28 , wherein R 28 is a saturated or unsaturated hydrocarbon, and R 1 to R 3 are At least one of and at least one of R 4 to R 6 is an amine represented by the following formula (2) Wherein R 7 and R 8 are selected from the group consisting of substituted or unsubstituted alkyl, alkenyl, aryl, heteroaryl, hydrogen, formazan and -LX having from 1 to 20 carbon atoms. The substituent of the alkyl group is -OCOR 28 , and L is a divalent linking group selected from a direct bond, an oxygen atom, and a saturated or unsaturated hydrocarbon having 1 to 20 carbon atoms which may contain a hetero atom, and X has a group of an ethylenically unsaturated group, and at least one of R 7 and R 8 is -LX, Wherein R 9 to R 11 , R 13 to R 16 , R 18 to R 23 and R 25 to R 27 are alkyl groups having 1 to 20 carbon atoms, and n and m are integers from 0 to 10, R 12 , R 17 and R 24 are an alkyl group having 1 to 20 carbon atoms or G, and G is a crosslinkable group having at least one of an epoxy group, an acrylate, an acrylamide, and an ethylenically unsaturated group. . 一種組成物，其包含樹脂及如申請專利範圍第1項至第4項中任一項之化合物。 A composition comprising a resin and a compound according to any one of claims 1 to 4. 一種物品，其具有由如申請專利範圍第6項之組成物形成的聚合物層。 An article having a polymer layer formed from the composition of claim 6 of the patent application. 一種彩色濾光片，其包含如申請專利範圍第1項至第4項中任一項之化合物中之至少一者。 A color filter comprising at least one of the compounds according to any one of claims 1 to 4. 一種自以下步驟獲得之方酸鹽化合物混合物：(a)使5-(二烯丙胺基)苯-1,3-二醇與方酸(squaric acid)接觸以獲得反應產物A，及(b)在存在催化劑之情況下使該反應產物A與由式(7)至式(9)表示之矽氧烷或矽烷基醚化合物接觸， 其中R9至R11、R13至R16、R18至R23及R25至R27為具有1至20個碳原子之烷基，n及m為自0至10之整數，R12、R17及R24為具有1至20個碳原子之烷基或G，G為具有環氧基、丙烯酸酯、丙烯醯胺及烯系不飽和基團中之至少一者之可交聯基團。 A mixture of a squaraine compound obtained from the following steps: (a) contacting 5-(diallylamino)benzene-1,3-diol with squaric acid to obtain a reaction product A, and (b) The reaction product A is contacted with a oxoxane or a decyl ether compound represented by the formula (7) to the formula (9) in the presence of a catalyst, Wherein R 9 to R 11 , R 13 to R 16 , R 18 to R 23 and R 25 to R 27 are alkyl groups having 1 to 20 carbon atoms, and n and m are integers from 0 to 10, R 12 , R 17 and R 24 are an alkyl group having 1 to 20 carbon atoms or G, and G is a crosslinkable group having at least one of an epoxy group, an acrylate, an acrylamide, and an ethylenically unsaturated group. . 如申請專利範圍第9項之方酸鹽化合物混合物，其中該混合物包含由式(10)至式(12)表示之該等化合物中之至少一者， 其中S1為含有矽氧烷或矽烷基醚之基團。 A compound of a squaraine compound according to claim 9 wherein the mixture comprises at least one of the compounds represented by formula (10) to formula (12). Wherein S1 is a group containing a decane or a decyl ether.
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