TWI790354B - Colorant dispersion, colored curable resin composition, color filter, and display device - Google Patents
Colorant dispersion, colored curable resin composition, color filter, and display device Download PDFInfo
- Publication number
- TWI790354B TWI790354B TW108106773A TW108106773A TWI790354B TW I790354 B TWI790354 B TW I790354B TW 108106773 A TW108106773 A TW 108106773A TW 108106773 A TW108106773 A TW 108106773A TW I790354 B TWI790354 B TW I790354B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- ring
- formula
- compound
- substituent
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B25/00—Quinophthalones
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
- G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Optics & Photonics (AREA)
- Theoretical Computer Science (AREA)
- Structural Engineering (AREA)
- Architecture (AREA)
- Optical Filters (AREA)
- Materials For Photolithography (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本發明提供一種包含C.I.顏料黃138且可形成顯示出良好對比度的彩色濾光片的著色劑分散液、包含該著色劑分散液的著色硬化性樹脂組成物、由該著色劑分散液或該著色硬化性樹脂組成物形成的彩色濾光片、以及包含該彩色濾光片的顯示裝置。本發明提供一種包含作為主成分的C.I.顏料黃138(A)與式(I)所表示的化合物(B)的共分散物的著色劑分散液、包含該著色劑分散液的著色硬化性樹脂組成物、由該著色劑分散液或該著色硬化性樹脂組成物形成的彩色濾光片、以及包含該彩色濾光片的顯示裝置。The present invention provides a colorant dispersion comprising C.I. Pigment Yellow 138 and capable of forming a color filter exhibiting good contrast, a colored curable resin composition comprising the colorant dispersion, the colorant dispersion or the colored A color filter formed of a curable resin composition, and a display device including the color filter. The present invention provides a colorant dispersion comprising a co-dispersion of C.I. Pigment Yellow 138 (A) and a compound (B) represented by formula (I) as main components, and a colored curable resin composition comprising the colorant dispersion A color filter formed from the colorant dispersion or the colored curable resin composition, and a display device including the color filter.
Description
本發明是有關於一種著色劑分散液、著色硬化性樹脂組成物、彩色濾光片及顯示裝置。 The present invention relates to a coloring agent dispersion liquid, a colored curable resin composition, a color filter and a display device.
著色硬化性樹脂組成物用於製造液晶顯示裝置、電致發光(electroluminescence)顯示裝置及電漿顯示器等的顯示裝置中使用的彩色濾光片。使用彩色濾光片的顯示裝置要求有高對比度(contrast)。 The colored curable resin composition is used in the production of color filters used in display devices such as liquid crystal display devices, electroluminescence display devices, and plasma displays. Display devices using color filters require high contrast.
於日本專利特開2002-179979號公報(專利文獻1)中記載,為了改善顯示裝置的對比度,使包含作為黃色顏料的染料索引(color index,C.I.)顏料黃138的色糊(color paste)中進而含有C.I.顏料黃138的磺化衍生物。 It is described in Japanese Patent Application Laid-Open No. 2002-179979 (Patent Document 1), in order to improve the contrast of a display device, the color paste (color paste) containing dye index (color index, C.I.) Pigment Yellow 138 as a yellow pigment Furthermore, it contains a sulfonated derivative of C.I. Pigment Yellow 138.
[專利文獻1]日本專利特開2002-179979號公報 [Patent Document 1] Japanese Patent Laid-Open No. 2002-179979
本發明的目的在於提供一種包含C.I.顏料黃138且可形成顯 示出良好對比度的彩色濾光片的著色劑分散液、包含該著色劑分散液的著色硬化性樹脂組成物、由該著色劑分散液或該著色硬化性樹脂組成物形成的彩色濾光片、以及包含該彩色濾光片的顯示裝置。 The object of the present invention is to provide a kind of containing C.I. Pigment Yellow 138 and can form the Colorant dispersion liquid of a color filter showing good contrast, colored curable resin composition containing the colorant dispersion liquid, color filter formed of the colorant dispersion liquid or the colored curable resin composition, And a display device including the color filter.
本發明提供以下所示的著色劑分散液、著色硬化性樹脂組成物、彩色濾光片及顯示裝置。 The present invention provides a colorant dispersion liquid, a colored curable resin composition, a color filter, and a display device shown below.
[1]一種著色劑分散液,其包含作為主成分的C.I.顏料黃138(A)與式(I)所表示的化合物(B)的共分散物。 [1] A colorant dispersion comprising a co-dispersion of C.I. Pigment Yellow 138 (A) and a compound (B) represented by formula (I) as main components.
[式(I)中,a表示式(I)所表示的化合物所具有的-CO2 -及-S(O)2O-的合計數,且為0~10的任一整數。 [In formula (I), a represents the total number of -CO 2 - and -S(O) 2 O- that the compound represented by formula (I) has, and is any integer of 0-10.
a)於a為1~10的任一整數的情況下,X表示CR8R9,R1表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基或氫原子,該烴基中所含的-CH2-及該雜環基包含並未構成 環的-CH2-時的所述-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 a) When a is any integer from 1 to 10, X represents CR 8 R 9 , and R 1 represents a hydrocarbon group having 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom , the -CH 2 - contained in the hydrocarbon group and the -CH 2 - when the heterocyclic group contains -CH 2 - that does not constitute a ring can be substituted with -O-, -CO-, -S(O ) 2 -or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
R2~R9相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基、硝基、-CO2 -或-S(O)2O-,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 R 2 to R 9 independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group, a nitro group, -CO 2 - or -S (O) 2 O - , when -CH 2 - contained in the hydrocarbon group and -CH 2 - not constituting a ring are included in the heterocyclic group, the -CH 2 - may be substituted with -O-, -CO- , -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
選自由R2與R3、R3與R4、R4與R5、R6與R7、及R8與R9所組成的群組中的至少一組可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該環可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 At least one group selected from the group consisting of R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , and R 8 and R 9 may be bonded to the respective carbon The atoms together form a ring which may have substituents, and the -CH 2 - when the ring contains -CH 2 - which does not constitute a ring may be substituted with -O-, -CO-, -S(O) 2 - or - NR na- . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ring may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
Rna表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基或氫原子,該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。於存在多個Rna的情況下,該些可相同亦可不同。 R na represents a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom. The hydrocarbon group and the heterocyclic group may have a group selected from -CO 2 - and -S(O) 2 O - at least one of the group consisting of. When multiple RNAs are present, these may be the same or different.
Mb+表示氫正離子(hydron)或b價的金屬離子。於存在多個Mb+的情況下,該些可相同亦可不同。於Mb+為氫正離子時,該氫 正離子與所述-CO2 -及-S(O)2O-一起作為-CO2H及S(O)2OH而存在。 M b+ represents a hydrogen ion (hydron) or a b-valent metal ion. When there are a plurality of M b+ , these may be the same or different. When M b+ is a positive hydride ion, the positive hydride ion exists as -CO 2 H and S(O) 2 OH together with the above-mentioned -CO 2 - and -S(O) 2 O - .
b表示1~6的任一整數。 b represents any integer from 1 to 6.
m表示Mb+的個數。 m represents the number of M b+ .
n為滿足n=b×m/a的關係的數。 n is a number satisfying the relationship of n=b×m/a.
b)於a為0的情況下,n表示1,且m表示0。 b) When a is 0, n represents 1, and m represents 0.
R1表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基或氫原子,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-、-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 R 1 represents a hydrocarbon group having 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom, and -CH 2 - contained in the hydrocarbon group and - that do not constitute a ring in the heterocyclic group include In the case of CH 2 -, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 -, -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
R2~R5相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 R 2 to R 5 independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group or a nitro group, and the - When CH 2 - and the heterocyclic group contain -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
選自由R2與R3、R3與R4、及R4與R5所組成的群組中的至少一組可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 At least one group selected from the group consisting of R 2 and R 3 , R 3 and R 4 , and R 4 and R 5 may form a ring that may have a substituent together with the carbon atoms to which they are bonded. When -CH 2 - which does not constitute a ring is included, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
R6表示-CO-ORnb1、-CO-NH2、-CO-NH(Rnb1)、-CO-N(Rnb1)2、-CO-H、-CO-Rnb1或-S(O)2-Rnb1。 R 6 represents -CO-OR nb1 , -CO-NH 2 , -CO-NH(R nb1 ), -CO-N(R nb1 ) 2 , -CO-H, -CO-R nb1 or -S(O) 2 -R nb1 .
其中,於R6表示-CO-NH(Rnb1)的情況下,R2~R5滿足(ib)及(iib)中的至少一者。 Wherein, when R 6 represents -CO-NH(R nb1 ), R 2 to R 5 satisfy at least one of (ib) and (iib).
(ib)R2~R5中的至少一個表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 (ib) At least one of R 2 to R 5 represents a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a halogen atom, a cyano group, or a nitro group, and the hydrocarbon group contained in When -CH 2 - and the heterocyclic group contain -CH 2 - that does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb - . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
(iib)選自由R2與R3、R3與R4、及R4與R5所組成的群組中的至少一組與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。R2~R5中的未形成環者相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 (iib) At least one group selected from the group consisting of R 2 and R 3 , R 3 and R 4 , and R 4 and R 5 forms a ring which may have a substituent together with the carbon atoms to which they are bonded, When the ring contains -CH 2 - which does not constitute the ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ones in R 2 to R 5 that do not form a ring independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group, or a nitro group. -CH 2 - contained in the hydrocarbon group and -CH 2 - when the heterocyclic group contains -CH 2 - that does not constitute a ring may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb- . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
R7表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。另外,R7可與R6及R7鍵結的碳原子一起形成環。 R 7 represents a hydrocarbon group having 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group or a nitro group, and -CH 2 - contained in the hydrocarbon group and the heterocyclic group When the cyclic group contains -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. In addition, R 7 may form a ring together with the carbon atom to which R 6 and R 7 are bonded.
X表示式(1a)所表示的基團。 X represents a group represented by formula (1a).
[式(1a)中, R17b及R18b相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 [In the formula (1a), R 17b and R 18b independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group or a nitro group, -CH 2 - contained in the hydrocarbon group and -CH 2 - when the heterocyclic group contains -CH 2 - that does not constitute a ring may be substituted with -O-, -CO-, -S(O) 2 -or-NR nb- . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
R17b與R18b可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 R 17b and R 18b may form a ring which may have substituents together with the carbon atoms to which they are bonded, and when the ring contains -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
*1表示與異吲哚啉環的結合鍵。] *1 indicates a bond to the isoindoline ring. ]
Rnb表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基或氫原子。於存在多個Rnb的情況下,該些可相同亦可不同。 R nb represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom. When there are multiple R nbs , these may be the same or different.
Rnb1表示可具有取代基的碳數1~35的烴基或可具有取代基的雜環基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb10-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。於存在多個Rnb1的情況下,該些可相同亦可不同。 R nb1 represents a hydrocarbon group having 1 to 35 carbon atoms that may have a substituent or a heterocyclic group that may have a substituent, and -CH 2 - contained in the hydrocarbon group and the heterocyclic group include -CH 2 - that does not constitute a ring The -CH 2 - at the time may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb10 -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. When there are multiple Rnb1s , these may be the same or different.
Rnb10表示可具有取代基的碳數1~35的烴基、可具有取代基的雜環基或氫原子。於存在多個Rnb10的情況下,該些可相同亦可不同。] R nb10 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom. When there are multiple Rnb10s , these may be the same or different. ]
[2]如[1]所述的著色劑分散液,其中,式(1a)所表示的基團為式(2a)所表示的基團。 [2] The colorant dispersion liquid according to [1], wherein the group represented by formula (1a) is a group represented by formula (2a).
[式(2a)中,R19b及R20b相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基或氫原子,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 [In formula (2a), R 19b and R 20b independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom, and the -CH contained in the hydrocarbon group - and when the heterocyclic group contains -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
Rnb表示與前述相同的含義。 R nb represents the same meaning as above.
*2表示與異吲哚啉環的結合鍵。] *2 represents a bond to the isoindoline ring. ]
[3]如[1]或[2]所述的著色劑分散液,其中,式(I)中,a)於a為1~10的任一整數的情況下,R2~R5相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴 基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 [3] The colorant dispersion as described in [1] or [2], wherein, in formula (I), a) when a is any integer from 1 to 10, R 2 to R 5 are mutually independent means a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group or a nitro group, -CH 2 - contained in the hydrocarbon group and the heterocyclic ring When the group contains -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
選自由R2與R3、R3與R4、及R4與R5所組成的群組中的至少一組可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該環可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 At least one group selected from the group consisting of R 2 and R 3 , R 3 and R 4 , and R 4 and R 5 may form a ring that may have a substituent together with the carbon atoms to which they are bonded. When -CH 2 - which does not constitute a ring is contained, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ring may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
R6表示-CO-ORna1、-CO-NH2、-CO-NH(Rna1)、-CO-N(Rna1)2、-CO-H、-CO-Rna1或-S(O)2-Rna1。 R 6 represents -CO-OR na1 , -CO-NH 2 , -CO-NH(R na1 ), -CO-N(R na1 ) 2 , -CO-H, -CO-R na1 or -S(O) 2 -R na1 .
其中,於R6表示-CO-NH(Rna1)的情況下,R2~R5滿足(ia)及(iia)中的至少一者。 Wherein, when R 6 represents -CO-NH(R na1 ), R 2 to R 5 satisfy at least one of (ia) and (iia).
(ia)R2~R5中的至少一個表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 (ia) At least one of R 2 to R 5 represents a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a halogen atom, a cyano group or a nitro group, and the hydrocarbon group contained in When -CH 2 - and the heterocyclic group contain -CH 2 - that does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na - . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
(iia)選自由R2與R3、R3與R4、及R4與R5所組成的群組中的至少一組與各自所鍵結的碳原子一起形成可具有取代基的 環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該環可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。R2~R5中的未形成環者相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 (iia) At least one group selected from the group consisting of R 2 and R 3 , R 3 and R 4 , and R 4 and R 5 forms a ring which may have a substituent together with the carbon atoms to which they are bonded, When the ring contains -CH 2 - which does not constitute the ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ring may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- . The ones in R 2 to R 5 that do not form a ring independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group, or a nitro group. -CH 2 - contained in the hydrocarbon group and -CH 2 - when the heterocyclic group contains -CH 2 - that does not constitute a ring may be substituted with -O-, -CO-, -S(O) 2 - or -NR na- . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
R7表示氰基。 R 7 represents a cyano group.
X表示式(1a-x)所表示的基團。 X represents a group represented by formula (1a-x).
[式(1a-x)中,R21及R22相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自 由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 [In the formula (1a-x), R 21 and R 22 independently represent a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group, or a nitrate When the -CH 2 - contained in the hydrocarbon group and the -CH 2 - that does not constitute a ring are included in the heterocyclic group, the -CH 2 - may be substituted with -O-, -CO-, -S(O ) 2 -or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
R21與R22可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該環可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 R 21 and R 22 may form, together with the carbon atoms to which they are bonded, a ring which may have substituents, and when the ring includes -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ring may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
*1表示與異吲哚啉環的結合鍵。] *1 indicates a bond to the isoindoline ring. ]
Rna表示與前述相同的含義。 R na represents the same meaning as above.
Rna1表示可具有取代基的碳數1~35的烴基或可具有取代基的雜環基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna10-。其中,並未藉由取代-CH2-而形成-COOH及-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。於存在多個Rna1的情況下,該些可相同亦可不同。 R na1 represents a hydrocarbon group having 1 to 35 carbon atoms that may have a substituent or a heterocyclic group that may have a substituent, and -CH 2 - contained in the hydrocarbon group and -CH 2 - that does not constitute a ring in the heterocyclic group include The -CH 2 - at the time may be substituted with -O-, -CO-, -S(O) 2 - or -NR na10 -. Wherein, -COOH and -S(O) 2 OH are not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- . Where there are multiple R na1s , these may be the same or different.
Rna10表示可具有取代基的碳數1~35的烴基或可具有取代基的雜環基,於存在多個Rna10的情況下,該些可相同亦可不同。 R na10 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent, and when a plurality of R na10s exist, these may be the same or different.
b)於a為0的情況下,R7表示氰基。 b) When a is 0, R 7 represents a cyano group.
[4]如[3]所述的著色劑分散液,其中,式(1a-x)所表示的基團為式(2a-x)所表示的基團。 [4] The colorant dispersion liquid according to [3], wherein the group represented by the formula (1a-x) is a group represented by the formula (2a-x).
[式(2a-x)中,R23及R24相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基或氫原子,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 [In the formula (2a-x), R 23 and R 24 independently represent a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom, and the - When CH 2 - and the heterocyclic group contain -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
Rna表示與前述相同的含義。 R na represents the same meaning as above.
*2表示與異吲哚啉環的結合鍵。] *2 represents a bond to the isoindoline ring. ]
[5]如[1]至[4]中任一項所述的著色劑分散液,其進而包含金屬鹽(C),所述金屬鹽(C)含有具有羥基的碳數1~40的脂肪族羧酸的陰離子。 [5] The colorant dispersion according to any one of [1] to [4], further comprising a metal salt (C) containing a C 1-40 fat having a hydroxyl group anions of carboxylic acids.
[6]一種著色硬化性樹脂組成物,其包含:如[1]至[5]中任一項所述的著色劑分散液、以及樹脂(D)。 [6] A colored curable resin composition comprising: the colorant dispersion according to any one of [1] to [5]; and a resin (D).
[7]一種彩色濾光片,其是由如[1]至[5]中任一項所述的著色劑分散液或如[6]所述的著色硬化性樹脂組成物形成。 [7] A color filter formed of the colorant dispersion according to any one of [1] to [5] or the colored curable resin composition according to [6].
[8]一種顯示裝置,其包含如[7]所述的彩色濾光片。 [8] A display device including the color filter according to [7].
根據本發明的著色劑分散液及著色硬化性樹脂組成物,可提供一種顯示出良好對比度的彩色濾光片、以及包含其的顯示裝置。 According to the colorant dispersion liquid and colored curable resin composition of the present invention, a color filter exhibiting good contrast and a display device including the same can be provided.
<著色劑分散液> <Colorant Dispersion>
本發明的著色劑分散液包含C.I.顏料黃138(A)與式(I)所表示的化合物(B)的共分散物。 The colorant dispersion liquid of the present invention contains a co-dispersion of C.I. Pigment Yellow 138 (A) and a compound (B) represented by formula (I).
根據所述著色劑分散液,儘管將C.I.顏料黃138(A)作為主成分,但可使由該著色劑分散液或包含該著色劑分散液的著色硬化性樹脂組成物形成的彩色濾光片及使用其的顯示裝置的對比度變得良好。 According to the colorant dispersion liquid, although C.I. Pigment Yellow 138 (A) is used as the main component, a color filter formed of the colorant dispersion liquid or a colored curable resin composition containing the colorant dispersion liquid can be made And the contrast ratio of the display device using it becomes favorable.
著色劑分散液可進而包含金屬鹽(C),所述金屬鹽(C)含有具有羥基的碳數1~40的脂肪族羧酸的陰離子。以下,亦將含有具有羥基的碳數1~40的脂肪族羧酸的陰離子的金屬鹽(C)稱作「脂肪族羧酸金屬鹽(C)」。 The colorant dispersion liquid may further contain a metal salt (C) containing an anion of an aliphatic carboxylic acid having 1 to 40 carbon atoms having a hydroxyl group. Hereinafter, the metal salt (C) containing an anion of an aliphatic carboxylic acid having 1 to 40 carbon atoms having a hydroxyl group is also referred to as "aliphatic carboxylic acid metal salt (C)".
以下,作為各成分而例示的化合物只要無特別說明,則可單獨使用、或者將多種組合使用。 Hereinafter, unless otherwise specified, the compounds exemplified as each component may be used alone or in combination of multiple types.
〔1〕C.I.顏料黃138(A) 〔1〕C.I. Pigment Yellow 138(A)
共分散物中所含的C.I.顏料黃138(A)為於染料索引(Color Index)(染色與印染工作者協會(The Society of Dyers and Colourists)出版)中被分類為顏料(pigment)的黃色顏料。 C.I. Pigment Yellow 138(A) contained in the co-dispersion is listed on the Color Index (The Society of Dyers and Dyeing Workers A yellow pigment classified as a pigment (pigment) in Colourists Publishing).
〔2〕式(I)所表示的化合物(B) [2] Compound (B) represented by formula (I)
共分散物包含式(I)所表示的化合物(B)。 The codispersion contains compound (B) represented by formula (I).
[式(I)中,a表示式(I)所表示的化合物所具有的-CO2 -及-S(O)2O-的合計數,且為0~10的任一整數。 [In formula (I), a represents the total number of -CO 2 - and -S(O) 2 O- that the compound represented by formula (I) has, and is any integer of 0-10.
a)於a為1~10的任一整數的情況下,X表示CR8R9,R1表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基或氫原子,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 a) When a is any integer from 1 to 10, X represents CR 8 R 9 , and R 1 represents a hydrocarbon group having 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom , when the -CH 2 - contained in the hydrocarbon group and the -CH 2 - contained in the heterocyclic group do not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
R2~R9相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基、硝基、-CO2 - 或-S(O)2O-,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 R 2 to R 9 independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group, a nitro group, -CO 2 - or -S (O) 2 O - , when -CH 2 - contained in the hydrocarbon group and -CH 2 - not constituting a ring are included in the heterocyclic group, the -CH 2 - may be substituted with -O-, -CO- , -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
選自由R2與R3、R3與R4、R4與R5、R6與R7、及R8與R9所組成的群組中的至少一組可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該環可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 At least one group selected from the group consisting of R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , and R 8 and R 9 may be bonded to the respective carbon The atoms together form a ring which may have substituents, and the -CH 2 - when the ring contains -CH 2 - which does not constitute a ring may be substituted with -O-, -CO-, -S(O) 2 - or - NR na- . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ring may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
Rna表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基或氫原子,該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。於存在多個Rna的情況下,該些可相同亦可不同。 R na represents a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom. The hydrocarbon group and the heterocyclic group may have a group selected from -CO 2 - and -S(O) 2 O - at least one of the group consisting of. When multiple RNAs are present, these may be the same or different.
Mb+表示氫正離子或b價的金屬離子。於存在多個Mb+的情況下,該些可相同亦可不同。於Mb+為氫正離子時,該氫正離子與所述-CO2 -及-S(O)2O-一起作為-CO2H及S(O)2OH而存在。 M b+ represents a hydrogen positive ion or a b-valent metal ion. When there are a plurality of M b+ , these may be the same or different. When M b+ is a positive hydride ion, the positive hydride ion exists as -CO 2 H and S(O) 2 OH together with the above-mentioned -CO 2 - and -S(O) 2 O - .
b表示1~6的任一整數。 b represents any integer from 1 to 6.
m表示Mb+的個數。 m represents the number of M b+ .
n為滿足n=b×m/a的關係的數。 n is a number satisfying the relationship of n=b×m/a.
b)於a為0的情況下,n表示1,且m表示0。 b) When a is 0, n represents 1, and m represents 0.
R1表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基或氫原子,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 R 1 represents a hydrocarbon group having 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom, and -CH 2 - contained in the hydrocarbon group and - that do not constitute a ring in the heterocyclic group include The -CH 2 - in the case of CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
R2~R5相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 R 2 to R 5 independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group or a nitro group, and the - When CH 2 - and the heterocyclic group contain -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
選自由R2與R3、R3與R4、及R4與R5所組成的群組中的至少一組可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 At least one group selected from the group consisting of R 2 and R 3 , R 3 and R 4 , and R 4 and R 5 may form a ring that may have a substituent together with the carbon atoms to which they are bonded. When -CH 2 - which does not constitute a ring is included, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
R6表示-CO-ORnb1、-CO-NH2、-CO-NH(Rnb1)、-CO-N(Rnb1)2、-CO-H、-CO-Rnb1或-S(O)2-Rnb1。 R 6 represents -CO-OR nb1 , -CO-NH 2 , -CO-NH(R nb1 ), -CO-N(R nb1 ) 2 , -CO-H, -CO-R nb1 or -S(O) 2 -R nb1 .
其中,於R6表示-CO-NH(Rnb1)的情況下,R2~R5滿足(ib)及(iib)中的至少一者。 Wherein, when R 6 represents -CO-NH(R nb1 ), R 2 to R 5 satisfy at least one of (ib) and (iib).
(ib)R2~R5中的至少一個表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2- 而形成-COOH或-S(O)2OH。 (ib) At least one of R 2 to R 5 represents a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a halogen atom, a cyano group, or a nitro group, and the hydrocarbon group contained in When -CH 2 - and the heterocyclic group contain -CH 2 - that does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb - . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
(iib)選自由R2與R3、R3與R4、及R4與R5所組成的群組中的至少一組與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。R2~R5中的未形成環者相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 (iib) At least one group selected from the group consisting of R 2 and R 3 , R 3 and R 4 , and R 4 and R 5 forms a ring which may have a substituent together with the carbon atoms to which they are bonded, When the ring contains -CH 2 - which does not constitute the ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ones in R 2 to R 5 that do not form a ring independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group, or a nitro group. -CH 2 - contained in the hydrocarbon group and -CH 2 - when the heterocyclic group contains -CH 2 - that does not constitute a ring may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb- . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
R7表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。另外,R7可與R6及R7鍵結的碳原子一起形成環。 R 7 represents a hydrocarbon group having 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group or a nitro group, and -CH 2 - contained in the hydrocarbon group and the heterocyclic group When the cyclic group contains -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. In addition, R 7 may form a ring together with the carbon atom to which R 6 and R 7 are bonded.
X表示式(1a)所表示的基團。 X represents a group represented by formula (1a).
[式(1a)中,R17b及R18b相互獨立地表示可具有取代基的碳數1~40的烴 基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 [In formula (1a), R 17b and R 18b independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group or a nitro group, -CH 2 - contained in the hydrocarbon group and -CH 2 - when the heterocyclic group contains -CH 2 - that does not constitute a ring may be substituted with -O-, -CO-, -S(O) 2 -or-NR nb- . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
R17b與R18b可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 R 17b and R 18b may form a ring which may have substituents together with the carbon atoms to which they are bonded, and when the ring contains -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
*1表示與異吲哚啉環的結合鍵。] *1 indicates a bond to the isoindoline ring. ]
Rnb表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基或氫原子。於存在多個Rnb的情況下,該些可相同亦可不同。 R nb represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom. When there are multiple R nbs , these may be the same or different.
Rnb1表示可具有取代基的碳數1~35的烴基或可具有取代基的雜環基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb10-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。於存在多個Rnb1的情況下,該些可相同亦可不同。 R nb1 represents a hydrocarbon group having 1 to 35 carbon atoms that may have a substituent or a heterocyclic group that may have a substituent, and -CH 2 - contained in the hydrocarbon group and the heterocyclic group include -CH 2 - that does not constitute a ring The -CH 2 - at the time may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb10 -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. When there are multiple Rnb1s , these may be the same or different.
Rnb10表示可具有取代基的碳數1~35的烴基、可具有取代基的雜環基或氫原子。於存在多個Rnb10的情況下,該些可相同亦可不同。] R nb10 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom. When there are multiple Rnb10s , these may be the same or different. ]
式(1a)所表示的基團較佳為式(2a)所表示的基團。 The group represented by formula (1a) is preferably a group represented by formula (2a).
[式(2a)中,R19b及R20b相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基或氫原子,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 [In formula (2a), R 19b and R 20b independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom, and the -CH contained in the hydrocarbon group - and when the heterocyclic group contains -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
Rnb表示與所述相同的含義。 R nb represents the same meaning as above.
*2表示與異吲哚啉環的結合鍵。] *2 represents a bond to the isoindoline ring. ]
〔2-1〕式(I)所表示的化合物(B)的第1態樣 [2-1] The first aspect of the compound (B) represented by the formula (I)
於式(I)所表示的化合物(B)的較佳一態樣即第1態樣中,式(I)中,a)於a為1~10的任一整數的情況下,R2~R5相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 In the preferred aspect of the compound (B) represented by the formula (I), that is, the first aspect, in the formula (I), when a) is any integer from 1 to 10, R 2 ~ R 5 independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group or a nitro group, and -CH 2 - contained in the hydrocarbon group And when the heterocyclic group contains -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
R2與R3、R3與R4、及R4與R5中的至少一組可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該環可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 At least one group of R 2 and R 3 , R 3 and R 4 , and R 4 and R 5 may form a ring that may have a substituent together with the carbon atoms to which they are bonded, and the ring includes - The -CH 2 - in the case of CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ring may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
R6表示-CO-ORna1、-CO-NH2、-CO-NH(Rna1)、-CO-N(Rna1)2、-CO-H、-CO-Rna1或-S(O)2-Rna1。 R 6 represents -CO-OR na1 , -CO-NH 2 , -CO-NH(R na1 ), -CO-N(R na1 ) 2 , -CO-H, -CO-R na1 or -S(O) 2 -R na1 .
其中,於R6表示-CO-NH(Rna1)的情況下,R2~R5滿足(ia)及(iia)中的至少一者。 Wherein, when R 6 represents -CO-NH(R na1 ), R 2 to R 5 satisfy at least one of (ia) and (iia).
(ia)R2~R5中的至少一個表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 (ia) At least one of R 2 to R 5 represents a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a halogen atom, a cyano group or a nitro group, and the hydrocarbon group contained in When -CH 2 - and the heterocyclic group contain -CH 2 - that does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na - . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
(iia)選自由R2與R3、R3與R4、及R4與R5所組成的群組中的至少一組與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該環可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。R2~R5中的未形成環者相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素 原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 (iia) At least one group selected from the group consisting of R 2 and R 3 , R 3 and R 4 , and R 4 and R 5 forms a ring which may have a substituent together with the carbon atoms to which they are bonded, When the ring contains -CH 2 - which does not constitute the ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ring may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- . The ones in R 2 to R 5 that do not form a ring independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group, or a nitro group. -CH 2 - contained in the hydrocarbon group and -CH 2 - when the heterocyclic group contains -CH 2 - that does not constitute a ring may be substituted with -O-, -CO-, -S(O) 2 - or -NR na- . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
R7表示氰基。 R 7 represents a cyano group.
X表示式(1a-x)所表示的基團。 X represents a group represented by formula (1a-x).
[式(1a-x)中,R21及R22相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 [In the formula (1a-x), R 21 and R 22 independently represent a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group, or a nitrate When the -CH 2 - contained in the hydrocarbon group and the -CH 2 - that does not constitute a ring are included in the heterocyclic group, the -CH 2 - may be substituted with -O-, -CO-, -S(O ) 2 -or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
R21與R22可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該環可具有選自由-CO2 -及-S(O)2O-所組成的群組中 的至少一種。 R 21 and R 22 may form, together with the carbon atoms to which they are bonded, a ring which may have substituents, and when the ring includes -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ring may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
*1表示與異吲哚啉環的結合鍵。] *1 indicates a bond to the isoindoline ring. ]
Rna表示與前述相同的含義。 R na represents the same meaning as above.
Rna1表示可具有取代基的碳數1~35的烴基或可具有取代基的雜環基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna10-。其中,並未藉由取代-CH2-而形成-COOH及-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。於存在多個Rna1的情況下,該些可相同亦可不同。 R na1 represents a hydrocarbon group having 1 to 35 carbon atoms that may have a substituent or a heterocyclic group that may have a substituent, and -CH 2 - contained in the hydrocarbon group and -CH 2 - that does not constitute a ring in the heterocyclic group include The -CH 2 - at the time may be substituted with -O-, -CO-, -S(O) 2 - or -NR na10 -. Wherein, -COOH and -S(O) 2 OH are not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- . Where there are multiple R na1s , these may be the same or different.
Rna10表示可具有取代基的碳數1~35的烴基或可具有取代基的雜環基,於存在多個Rna10的情況下,該些可相同亦可不同。 R na10 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent, and when a plurality of R na10s exist, these may be the same or different.
b)於a為0的情況下, R7表示氰基。 b) When a is 0, R 7 represents a cyano group.
式(1a-x)所表示的基團較佳為式(2a-x)所表示的基團。 The group represented by formula (1a-x) is preferably a group represented by formula (2a-x).
[式(2a-x)中,R23及R24相互獨立地表示可具有取代基的碳數1~40的烴 基、可具有取代基的雜環基或氫原子,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 [In the formula (2a-x), R 23 and R 24 independently represent a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom, and the - When CH 2 - and the heterocyclic group contain -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
Rna表示與前述相同的含義。 R na represents the same meaning as above.
*2表示與異吲哚啉環的結合鍵。] *2 represents a bond to the isoindoline ring. ]
〔2-2〕式(I)所表示的化合物(B)的第2態樣 [2-2] The second aspect of the compound (B) represented by the formula (I)
式(I)所表示的化合物(B)的較佳的另一態樣即第2態樣是於所述第1態樣中a為0的式(IIB)所表示的化合物。 Another preferable second aspect of the compound (B) represented by the formula (I) is a compound represented by the formula (IIB) in which a is 0 in the first aspect.
[式(IIB)中,R11b~R15b分別表示與式(I)中a為0時的R1~R5相同的含義。 [In formula (IIB), R 11b to R 15b represent the same meanings as R 1 to R 5 when a is 0 in formula (I), respectively.
選自由R12b與R13b、R13b與R14b、及R14b與R15b所組成的群組中的至少一組可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、 -CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 At least one group selected from the group consisting of R 12b and R 13b , R 13b and R 14b , and R 14b and R 15b may form a ring that may have a substituent together with the carbon atoms to which they are bonded. When -CH 2 - which does not constitute a ring is included, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
R16b表示-CO-ORnb1、-CO-NH2、-CO-NH(Rnb1)、-CO-N(Rnb1)2、-CO-H、-CO-Rnb1或-S(O)2-Rnb1。 R 16b represents -CO-OR nb1 , -CO-NH 2 , -CO-NH(R nb1 ), -CO-N(R nb1 ) 2 , -CO-H, -CO-R nb1 or -S(O) 2 -R nb1 .
其中,於R16b表示-CO-NH(Rnb1)的情況下,R12b~R15b滿足(ixb)及(iixb)中的至少一者。 Wherein, when R 16b represents -CO-NH(R nb1 ), R 12b to R 15b satisfy at least one of (ixb) and (iixb).
(ixb)R12b~R15b中的至少一個表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 (ixb) At least one of R 12b to R 15b represents a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, a halogen atom, a cyano group or a nitro group, and the hydrocarbon group contained in When -CH 2 - and the heterocyclic group contain -CH 2 - that does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb - . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
(iixb)選自由R12b與R13b、R13b與R14b、及R14b與R15b所組成的群組中的至少一組與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH及-S(O)2OH。R12b~R15b中的未形成環者相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 (iixb) At least one group selected from the group consisting of R 12b and R 13b , R 13b and R 14b , and R 14b and R 15b forms a ring that may have a substituent together with the carbon atoms to which they are bonded, When the ring contains -CH 2 - which does not constitute the ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH and -S(O) 2 OH are not formed by substituting -CH 2 -. R 12b to R 15b that do not form a ring independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group, or a nitro group, which -CH 2 - contained in the hydrocarbon group and -CH 2 - when the heterocyclic group contains -CH 2 - that does not constitute a ring may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb- . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
X1b表示式(1a-xb)所表示的基團。 X 1b represents a group represented by the formula (1a-xb).
[式(1a-xb)中,R21b、R22b及*1分別表示與式(1a)中的R17b、R18b及*1相同的含義。] [In formula (1a-xb), R 21b , R 22b and *1 represent the same meanings as R 17b , R 18b and *1 in formula (1a), respectively. ]
Rnb及Rnb1表示與前述相同的含義。] R nb and R nb1 have the same meaning as above. ]
式(IIB)所表示的化合物所具有的-CO2H及-S(O)2OH的合計數為0。 The total number of -CO 2 H and -S(O) 2 OH contained in the compound represented by the formula (IIB) is zero.
式(1a-xb)所表示的基團較佳為式(2a-xb)所表示的基團。 The group represented by formula (1a-xb) is preferably a group represented by formula (2a-xb).
[式(2a-xb)中,R23b、R24b及*2分別表示與式(2a)中的R19b、R20b及*2相同的含義。 [In formula (2a-xb), R 23b , R 24b and *2 represent the same meanings as R 19b , R 20b and *2 in formula (2a), respectively.
Rnb表示與前述相同的含義。] R nb represents the same meaning as above. ]
〔2-3〕式(I)所表示的化合物(B)的第3態樣 [2-3] The third aspect of the compound (B) represented by the formula (I)
式(I)所表示的化合物(B)的較佳的另一態樣即第3態樣 是式(I)中的a(即,式(I)所表示的化合物所具有的-CO2 -及-S(O)2O-的合計數)為1~10的任一整數的式(IA)所表示的化合物。 Another preferred aspect of the compound (B) represented by the formula (I), that is, the third aspect is a in the formula (I) (that is, -CO 2 - and -S(O) 2 O- ) is a compound represented by formula (IA) in which any integer of 1 to 10 is represented.
[式(IA)中,R1a~R9a分別表示與式(I)中a為1~10的任一整數時的R1~R9相同的含義。 [In formula (IA), R 1a to R 9a represent the same meanings as R 1 to R 9 when a is any integer of 1 to 10 in formula (I), respectively.
選自由R2a與R3a、R3a與R4a、R4a與R5a、R6a與R7a、及R8a與R9a所組成的群組中的至少一組可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。該環可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 At least one group selected from the group consisting of R 2a and R 3a , R 3a and R 4a , R 4a and R 5a , R 6a and R 7a , and R 8a and R 9a may be bonded to the respective carbons The atoms together form a ring which may have substituents, and the -CH 2 - when the ring contains -CH 2 - which does not constitute a ring may be substituted with -O-, -CO-, -S(O) 2 - or - NR na- . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ring may have at least one selected from the group consisting of -CO 2 - and -S(O) 2 O- .
Rna及Mb+表示與前述相同的含義。 R na and M b+ represent the same meaning as above.
b表示1~6的任一整數。 b represents any integer from 1 to 6.
aa表示式(IA)所表示的化合物所具有的-CO2 -及-S(O)2O-的合計數,且為1~10的任一整數。 aa represents the total number of —CO 2 — and —S(O) 2 O — that the compound represented by the formula (IA) has, and is any integer of 1 to 10.
ma表示Mb+的個數。 ma represents the number of M b+ .
na為滿足na=b×ma/aa的關係的數。] na is a number satisfying the relationship of na=b×ma/aa. ]
〔2-4〕式(I)所表示的化合物(B)的第4態樣 [2-4] The fourth aspect of the compound (B) represented by the formula (I)
式(I)所表示的化合物(B)的較佳的另一態樣即第4態樣是式(I)中的a為0的式(IB)所表示的化合物。 Another preferred aspect of the compound (B) represented by the formula (I), that is, the fourth aspect is a compound represented by the formula (IB) in which a in the formula (I) is 0.
[式(IB)中,R1b~R5b分別表示與式(I)中a為0時的R1~R5相同的含義。 [In formula (IB), R 1b to R 5b represent the same meanings as R 1 to R 5 when a is 0 in formula (I), respectively.
選自由R2b與R3b、R3b與R4b、及R4b與R5b所組成的群組中的至少一組可與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 At least one group selected from the group consisting of R 2b and R 3b , R 3b and R 4b , and R 4b and R 5b may form a ring that may have a substituent together with the carbon atoms to which they are bonded, and the ring When -CH 2 - which does not constitute a ring is included, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
R6b表示-CO-ORnb1、-CO-NH2、-CO-NH(Rnb1)、-CO-N(Rnb1)2、-CO-H、-CO-Rnb1或-S(O)2-Rnb1。 R 6b represents -CO-OR nb1 , -CO-NH 2 , -CO-NH(R nb1 ), -CO-N(R nb1 ) 2 , -CO-H, -CO-R nb1 or -S(O) 2 -R nb1 .
其中,於R6b表示-CO-NH(Rnb1)的情況下,R2b~R5b滿足(ibb)及(iibb)中的至少一者。 Wherein, when R 6b represents -CO-NH(R nb1 ), R 2b to R 5b satisfy at least one of (ibb) and (iibb).
(ibb)R2b~R5b中的至少一個表示可具有取代基的碳數1~ 40的烴基、可具有取代基的雜環基、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 (ibb) At least one of R 2b to R 5b represents a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, a halogen atom, a cyano group or a nitro group, and the hydrocarbon group contained When -CH 2 - and the heterocyclic group contain -CH 2 - that does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb - . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
(iibb)選自由R2b與R3b、R3b與R4b、及R4b與R5b所組成的群組中的至少一組與各自所鍵結的碳原子一起形成可具有取代基的環,該環包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。R2b~R5b中的未形成環者相互獨立地表示可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 (iibb) at least one group selected from the group consisting of R 2b and R 3b , R 3b and R 4b , and R 4b and R 5b forms a ring that may have a substituent together with the carbon atoms to which they are bonded, When the ring contains -CH 2 - which does not constitute the ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -. The ones in R 2b to R 5b that do not form a ring independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group, or a nitro group, which -CH 2 - contained in the hydrocarbon group and -CH 2 - when the heterocyclic group contains -CH 2 - that does not constitute a ring may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb- . Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
R7b表示與式(I)中a為0時的R7相同的含義。R7b可與R6b及R7b鍵結的碳原子一起形成環。 R 7b represents the same meaning as R 7 when a is 0 in formula (I). R 7b may form a ring together with R 6b and the carbon atom to which R 7b is bonded.
Xb表示與式(I)中a為0時的X相同的含義。 X b represents the same meaning as X when a is 0 in formula (I).
Rnb、Rnb1及Rnb10表示與前述相同的含義。] R nb , R nb1 and R nb10 have the same meanings as above. ]
式(IB)所表示的化合物中所含的-CO2H及-S(O)2OH的合計數為0。 The total number of -CO 2 H and -S(O) 2 OH contained in the compound represented by the formula (IB) is zero.
於式(IB)所表示的化合物中,所述式(1a)所表示的基團較佳為所述式(2a)所表示的基團。 Among the compounds represented by the formula (IB), the group represented by the formula (1a) is preferably the group represented by the formula (2a).
本說明書中,具有取代基的烴基的碳數為經取代基取代 前的烴基的碳數。 In this specification, the carbon number of a hydrocarbon group having a substituent is substituted by a substituent The carbon number of the preceding hydrocarbon group.
烴基中所含的-CH2-經取代為-O-、-CO-、-S(O)2-、-NRna-、-NRnb-、-NRna10-或-NRnb10-等而形成的基團的碳數為經該基團取代前的烴基的碳數。 The -CH 2 - contained in the hydrocarbon group is substituted with -O-, -CO-, -S(O) 2 -, -NR na -, -NR nb -, -NR na10 - or -NR nb10 -, etc. The carbon number of the group is the carbon number of the hydrocarbon group before being substituted by this group.
以下,將藉由烴基中所含的-CH2-經取代為-O-、-CO-、-S(O)2-、-NRna-、-NRnb-、-NRna10-或-NRnb10-而形成的基團亦總稱為「基團(Z)」。 Hereinafter, -CH 2 - contained in the hydrocarbon group is substituted with -O-, -CO-, -S(O) 2 -, -NR na -, -NR nb -, -NR na10 - or -NR The group formed by nb10 - is also collectively referred to as "group (Z)".
〔2-5〕對式(I)所表示的化合物(B)及其第1態樣~第4態樣的化合物所具有的基團的說明 [2-5] Explanation of the groups contained in the compound (B) represented by the formula (I) and the compounds of the first to fourth aspects thereof
R1~R9、R11b~R16b、R1a~R9a、R1b~R7b、Rna、Rnb、Rna1、Rnb1、Rna10、Rnb10、R17b~R24b、R21~R24所表示的基團通常為1價基團。 R 1 ~R 9 , R 11b ~R 16b , R 1a ~R 9a , R 1b ~R 7b , R na , R nb , R na1 , R nb1 , R na10 , R nb10 , R 17b ~R 24b , R 21 The group represented by ~R 24 is usually a monovalent group.
R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24所表示的碳數1~40的烴基、Rna1、Rnb1、Rna10及Rnb10所表示的碳數1~35的烴基可為脂肪族烴基或芳香族烴基,該脂肪族烴基可為飽和或不飽和,亦可為鏈狀或脂環式。 Carbon number represented by R 1 ~R 9 , R 11b ~R 15b , R 1a ~R 9a , R 1b ~R 5b , R 7b , R na , R nb , R 17b ~R 24b , R 21 ~R 241 ~40 hydrocarbon groups, R na1 , R nb1 , R na10 and R nb10 represented by carbon number 1~35 hydrocarbon groups can be aliphatic hydrocarbon groups or aromatic hydrocarbon groups, and the aliphatic hydrocarbon groups can be saturated or unsaturated, or can be chain or alicyclic.
於a為1~10的任一整數的情況下,R1~R9、R1a~R9a、R21~R24及Rna所表示的烴基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 When a is any integer from 1 to 10, the hydrocarbon group represented by R 1 to R 9 , R 1a to R 9a , R 21 to R 24 and R na may have a group selected from -CO 2 - and -S( O) 2 O - at least one of the group consisting of.
作為R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的飽和或不飽和鏈狀烴基,可列舉:甲基、乙基、丙基、丁基、戊基、 己基、庚基、辛基、壬基、癸基、十一基、十二基、十七基、十八基及二十基等的直鏈狀烷基等;異丙基、(2-甲基)丙基、異丁基、第二丁基、第三丁基、(2-乙基)丁基、異戊基、新戊基、第三戊基、(1-甲基)戊基、(2-甲基)戊基、(1-乙基)戊基、(3-乙基)戊基、異己基、(5-甲基)己基、(2-乙基)己基、及(3-乙基)庚基等的分支鏈狀烷基等;乙烯基、1-丙烯基、2-丙烯基(烯丙基)、異丙烯基、(1-甲基)乙烯基、2-丁烯基、3-丁烯基、1,3-丁二烯基、(1-(2-丙烯基))乙烯基、(1,2-二甲基)丙烯基及2-戊烯基等的烯基等。 As R 1 ~R 9 , R 11b ~R 15b , R 1a ~R 9a , R 1b ~R 5b , R 7b , R na , R nb , R 17b ~R 24b , R 21 ~R 24 , R na1 , R The saturated or unsaturated chain hydrocarbon groups represented by nb1 , R na10 and R nb10 include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Straight-chain alkyl groups such as undecyl, dodecyl, heptadecyl, octadecyl and eicosyl; isopropyl, (2-methyl)propyl, isobutyl, second butyl, Tertiary butyl, (2-ethyl) butyl, isopentyl, neopentyl, third pentyl, (1-methyl) pentyl, (2-methyl) pentyl, (1-ethyl) ) pentyl, (3-ethyl) pentyl, isohexyl, (5-methyl) hexyl, (2-ethyl) hexyl, and (3-ethyl) heptyl branched chain alkyl, etc.; Vinyl, 1-propenyl, 2-propenyl (allyl), isopropenyl, (1-methyl)vinyl, 2-butenyl, 3-butenyl, 1,3-butadiene (1-(2-propenyl))ethenyl, (1,2-dimethyl)propenyl, alkenyl such as 2-pentenyl, etc.
R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24所表示的飽和或不飽和鏈狀烴基的碳數較佳為1~30,更佳為1~20,進而佳為1~15,進而更佳為1~10,進而尤佳為1~8,特佳為1~5。 R 1 ~R 9 , R 11b ~R 15b , R 1a ~R 9a , R 1b ~R 5b , R 7b , R na , R nb , R 17b ~R 24b , R 21 ~R 24 are saturated or not The carbon number of the saturated chain hydrocarbon group is preferably 1-30, more preferably 1-20, further preferably 1-15, further preferably 1-10, further preferably 1-8, particularly preferably 1-5 .
Rna1、Rnb1、Rna10及Rnb10所表示的飽和或不飽和鏈狀烴基的碳數較佳為1~28,更佳為1~18,進而佳為1~13,進而更佳為1~8,進而尤佳為1~6,特佳為1~3。 The carbon number of the saturated or unsaturated chain hydrocarbon group represented by R na1 , R nb1 , R na10 and R nb10 is preferably 1-28, more preferably 1-18, further preferably 1-13, further preferably 1 ~8, and the best is 1~6, and the best is 1~3.
作為R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的飽和或不飽和脂環式烴基,可列舉:環丙基、1-甲基環丙基、環丁基、環戊基、環己基、環庚基、1-甲基環己基、2-甲基環己基、3-甲基環己基、4-甲基環己基、1,2-二甲基環己基、1,3-二甲基環己基、1,4-二甲基環己基、2,3-二甲基環己基、2,4-二甲基環己基、2,5-二甲基環己基、2,6-二甲基環己基、3,4-二甲基環己基、3,5- 二甲基環己基、2,2-二甲基環己基、3,3-二甲基環己基、4,4-二甲基環己基、環辛基、2,4,6-三甲基環己基、2,2,6,6-四甲基環己基、3,3,5,5-四甲基環己基、4-戊基環己基、4-辛基環己基及4-環己基環己基等的環烷基;環己烯基(例如環己-2-烯、環己-3-烯)、環庚烯基及環辛烯基等的環烯基;降冰片烷基、金剛烷基、雙環[2.2.2]辛烷等。 As R 1 ~R 9 , R 11b ~R 15b , R 1a ~R 9a , R 1b ~R 5b , R 7b , R na , R nb , R 17b ~R 24b , R 21 ~R 24 , R na1 , R The saturated or unsaturated alicyclic hydrocarbon groups represented by nb1 , R na10 and R nb10 include: cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1 -Methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4 -Dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4 -Dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3,3-dimethylcyclohexyl, 4,4-dimethylcyclohexyl, cyclooctyl , 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl, 4-pentylcyclohexyl, 4- Cycloalkyl groups such as octylcyclohexyl and 4-cyclohexylcyclohexyl; rings such as cyclohexenyl (such as cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl and cyclooctenyl Alkenyl; norbornyl, adamantyl, bicyclo[2.2.2]octane, etc.
所述飽和或不飽和脂環式烴基的碳數較佳為3~30,更佳為3~20,進而佳為4~20,進而更佳為4~15,進而尤佳為5~15,特佳為5~10,其中,特佳為環戊基、環己基、環庚基或環辛基。 The carbon number of the saturated or unsaturated alicyclic hydrocarbon group is preferably 3-30, more preferably 3-20, further preferably 4-20, further preferably 4-15, further preferably 5-15, Especially preferably, it is 5 to 10, especially preferably cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的飽和或不飽和烴基亦可為將所述列舉的鏈狀烴基與脂環式烴基組合而成的基團,例如可列舉:環丙基甲基、環丙基乙基、環丁基甲基、環丁基乙基、環戊基甲基、環戊基乙基、環己基甲基及環己基乙基等的鍵結有一個以上的脂環式烴基的烷基。 R 1 ~R 9 , R 11b ~R 15b , R 1a ~R 9a , R 1b ~R 5b , R 7b , R na , R nb , R 17b ~R 24b , R 21 ~R 24 , R na1 , R nb1 The saturated or unsaturated hydrocarbon group represented by R na10 and R nb10 can also be a group formed by combining the listed chain hydrocarbon group and alicyclic hydrocarbon group, for example: cyclopropylmethyl, cyclopropyl Alkyl groups such as ethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl and cyclohexylethyl to which one or more alicyclic hydrocarbon groups are bonded.
將鏈狀烴基與脂環式烴基組合而成的基團的碳數較佳為4~30,更佳為4~20,進而佳為4~15。 The carbon number of the group formed by combining a chain hydrocarbon group and an alicyclic hydrocarbon group is preferably 4-30, more preferably 4-20, still more preferably 4-15.
作為R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的芳香族烴基,可列舉:苯基、鄰甲苯基、間甲苯基、對甲苯基、2,3-二甲基苯基、2,4-二甲基苯基、2,5-二甲基苯基、2,6-二甲基苯基、3,4-二甲基苯基、3,5-二甲基苯基、鄰異丙基苯基、間異丙基苯基、 對異丙基苯基、鄰-第三丁基苯基、間-第三丁基苯基、對-第三丁基苯基、均三甲苯基(mesityl)、2,6-雙(2-丙基)苯基、2,4,6-三甲基苯基、1-萘基、2-萘基、5,6,7,8-四氫-1-萘基、5,6,7,8-四氫-2-萘基、茀基、菲基及蒽基等的芳香族烴基等。 As R 1 ~R 9 , R 11b ~R 15b , R 1a ~R 9a , R 1b ~R 5b , R 7b , R na , R nb , R 17b ~R 24b , R 21 ~R 24 , R na1 , R The aromatic hydrocarbon groups represented by nb1 , R na10 and R nb10 include: phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2,4-dimethylbenzene base, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, o-isopropylphenyl, m- Isopropylphenyl, p-isopropylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, mesityl, 2, 6-bis(2-propyl)phenyl, 2,4,6-trimethylphenyl, 1-naphthyl, 2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, Aromatic hydrocarbon groups such as 5,6,7,8-tetrahydro-2-naphthyl, fenyl, phenanthrenyl and anthracenyl, etc.
所述芳香族烴基的碳數較佳為6~30,更佳為6~20,進而佳為6~15。 The carbon number of the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, and still more preferably 6-15.
R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的芳香族烴基只要為具有芳香族烴環的烴基,則並無特別限定,亦可為將所述列舉的鏈狀烴基、脂環式烴基、及芳香族烴基的至少一個與所述列舉的芳香族烴基組合而成的基團,例如可列舉:苄基、2-甲基苄基、3-甲基苄基、4-甲基苄基、苯基乙基、苯基丙基及1-甲基-1-苯基乙基等的芳烷基;苯基乙烯基(phenyl ethenyl)(苯基乙烯基(phenyl vinyl))等的芳基烯基;苯基乙炔基等的芳基炔基;聯苯基及聯三苯基等的鍵結有一個以上的苯基的苯基;環己基甲基苯基、苄基苯基、(二甲基(苯基)甲基)苯基等。 R 1 ~R 9 , R 11b ~R 15b , R 1a ~R 9a , R 1b ~R 5b , R 7b , R na , R nb , R 17b ~R 24b , R 21 ~R 24 , R na1 , R nb1 The aromatic hydrocarbon groups represented by R na10 and R nb10 are not particularly limited as long as they are hydrocarbon groups having an aromatic hydrocarbon ring, and may be chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups listed above. At least one group combined with the listed aromatic hydrocarbon groups, for example, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, phenylethyl, Aralkyl such as phenylpropyl and 1-methyl-1-phenylethyl; arylalkenyl such as phenyl ethyl (phenyl vinyl); phenyl acetylene aryl alkynyl groups such as phenyl groups; phenyl groups such as biphenyl and terphenyl groups bonded with more than one phenyl group; cyclohexylmethylphenyl, benzylphenyl, (dimethyl(phenyl) Methyl) phenyl, etc.
將鏈狀烴基、脂環式烴基、及芳香族烴基的至少一個與芳香族烴基組合而成的基團的碳數較佳為7~30,更佳為7~20,進而佳為7~15。 The carbon number of the group formed by combining at least one of a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group with an aromatic hydrocarbon group is preferably 7-30, more preferably 7-20, and still more preferably 7-15 .
另外,R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的烴基可具有1價取代基、或2價取代基。2價取代基較佳為2 個結合鍵鍵結於相同的碳原子上而形成雙鍵的取代基。 In addition, R 1 ~R 9 , R 11b ~R 15b , R 1a ~R 9a , R 1b ~R 5b , R 7b , R na , R nb , R 17b ~R 24b , R 21 ~R 24 , R na1 , The hydrocarbon groups represented by R nb1 , R na10 and R nb10 may have a monovalent substituent or a divalent substituent. The divalent substituent is preferably a substituent in which two bonds are bonded to the same carbon atom to form a double bond.
作為1價取代基,可列舉:甲硫基、乙硫基、丙硫基及丁硫基等的碳數1~10的烷硫基(alkyl sulfanyl);氟原子、氯原子、溴原子及碘原子等的鹵素原子;硝基;氰基;三氟甲基、全氟乙基、全氟丙基、全氟異丙基、全氟丁基、全氟戊基、全氟己基、全氟庚基、全氟辛基、全氟壬基、全氟癸基、全氟環己基及全氟苯基等的氟原子取代全部氫原子而成的碳數1~20、較佳為碳數1~10的烴基;*-CO-SH;*-CO-S-CH3、*-CO-S-CH2CH3、*-CO-S-CH2-CH2-CH3、及*-CO-S-CH2-CH2-CH2-CH3等的與鍵結於烷基(該烷基的碳數為1~10)的硫原子鍵結的羰基;*-CO-S-C6H5等的與鍵結於芳基(該芳基的碳數為6~20)的硫原子鍵結的羰基;*-OP(O)(ORnb2)2;*-Si(Rnb2)(Rnb3)(Rnb4)等。 Examples of the monovalent substituent include: methylthio, ethylthio, propylthio, and butylthio and other C1-C10 alkylsulfanyl groups (alkylsulfanyl); fluorine atom, chlorine atom, bromine atom, and iodine Halogen atom such as atom; nitro group; cyano group; trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl A carbon number of 1 to 20, preferably 1 to 20 carbons, formed by replacing all hydrogen atoms with fluorine atoms such as perfluorooctyl, perfluorononyl, perfluorodecyl, perfluorocyclohexyl, and perfluorophenyl. Hydrocarbyl of 10; *-CO-SH; *-CO-S-CH 3 , *-CO-S-CH 2 CH 3 , *-CO-S-CH 2 -CH 2 -CH 3 , and *-CO- S-CH 2 -CH 2 -CH 2 -CH 3 etc. carbonyl group bonded to sulfur atom bonded to alkyl (the carbon number of the alkyl group is 1~10); *-CO-SC 6 H 5 etc. A carbonyl group bonded to a sulfur atom bonded to an aryl group (the carbon number of the aryl group is 6~20); *-OP(O)(OR nb2 ) 2 ; *-Si(R nb2 )(R nb3 ) (R nb4 ) and so on.
[所述式中,*表示與所述烴基的結合鍵。 [In the formula, * represents a bond with the hydrocarbon group.
Rnb2、Rnb3、Rnb4可相同亦可不同,且相互獨立地表示可具有取代基的碳數1~35的烴基、或可具有取代基的雜環基,該烴基 中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-、-Nnb10-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 R nb2 , R nb3 , and R nb4 may be the same or different, and independently represent a hydrocarbon group having 1 to 35 carbon atoms that may have a substituent, or a heterocyclic group that may have a substituent, and -CH contained in the hydrocarbon group 2 - and when the heterocyclic group contains -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 -, -N nb10 -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
Rnb10表示與前述相同的含義。 Rnb10 represents the same meaning as above.
Rnb2、Rnb3、Rnb4的具體例及較佳的例子與Rnb1相同。] Specific examples and preferred examples of Rnb2 , Rnb3 , and Rnb4 are the same as those of Rnb1 . ]
作為2價取代基,可列舉:硫酮基(thioxo)、亞胺基、取代有碳數1~20(較佳為碳數1~10)的烷基的亞胺基、以及取代有碳數6~20的芳基的亞胺基等。 Examples of the divalent substituent include: a thioxo group, an imino group, an imino group substituted with an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and 6~20 aryl imine groups, etc.
作為取代有烷基的亞胺基,可列舉:CH3-N=、CH3-CH2-N=、CH3-(CH2)2-N=、CH3-(CH2)3-N=等。 Examples of the imino group substituted with an alkyl group include: CH 3 -N=, CH 3 -CH 2 -N=, CH 3 -(CH 2 ) 2 -N=, CH 3 -(CH 2 ) 3 -N = Wait.
作為取代有芳基的亞胺基,可列舉C6H5-N=等。 Examples of the imino group substituted with an aryl group include C 6 H 5 -N= and the like.
作為R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的烴基的取代基,較佳為鹵素原子;硝基;氰基;氟原子取代全部氫原子而成的碳數1~20的烴基;硫代羰基;*-OP(O)(ORnb2)2;*-Si(Rnb2)(Rnb3)(Rnb4)等,更佳為鹵素原子;硝基;氰基;氟原子取代全部氫原子而成的碳數1~20的烴基;硫代羰基等,進而佳為氟原子、氯原子、溴原子;硝基;氰基;氟原子取代全部氫原子而成的碳數1~10的烴基;硫代羰基等。 As R 1 ~R 9 , R 11b ~R 15b , R 1a ~R 9a , R 1b ~R 5b , R 7b , R na , R nb , R 17b ~R 24b , R 21 ~R 24 , R na1 , R The substituents of the hydrocarbon groups represented by nb1 , R na10 and R nb10 are preferably halogen atoms; nitro; cyano groups; hydrocarbon groups with 1 to 20 carbons formed by replacing all hydrogen atoms with fluorine atoms; thiocarbonyl; *- OP(O)(OR nb2 ) 2 ; *-Si(R nb2 )(R nb3 )(R nb4 ), etc., more preferably a halogen atom; a nitro group; a cyano group; a carbon number obtained by replacing all hydrogen atoms with a fluorine atom Hydrocarbyl groups of 1 to 20; thiocarbonyl groups, etc., preferably fluorine atoms, chlorine atoms, bromine atoms; nitro groups; cyano groups; hydrocarbon groups with carbon numbers of 1 to 10 formed by replacing all hydrogen atoms with fluorine atoms; thiocarbonyl groups, etc. .
於a為1~10的任一整數的情況下,R1~R9、R1a~R9a、 R21~R24所表示的烴基中所含的-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 When a is any integer from 1 to 10, the -CH 2 - contained in the hydrocarbon groups represented by R 1 to R 9 , R 1a to R 9a , and R 21 to R 24 may be substituted with -O- , -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
於a為0的情況下,R1~R5、R7、R11b~R15b、R1b~R5b、R7b、R17b~R24b所表示的烴基中所含的-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 When a is 0, -CH 2 - contained in the hydrocarbon groups represented by R 1 ~R 5 , R 7 , R 11b ~R 15b , R 1b ~R 5b , R 7b , R 17b ~R 24b may be Substituted with -O-, -CO-, -S(O) 2 - or -NR nb -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
Rna1所表示的烴基中所含的-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna10-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 -CH 2 - contained in the hydrocarbon group represented by R na1 may be substituted with -O-, -CO-, -S(O) 2 - or -NR na10 -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
Rnb1所表示的烴基中所含的-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb10-。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 -CH 2 - contained in the hydrocarbon group represented by R nb1 may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb10 -. Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
作為藉由烴基中所含的-CH2-經取代為-O-、-CO-、-S(O)2-、-NRna-、-NRnb-、-NRna10-或-NRnb10-而形成的基團(Z),可列舉:甲氧基、乙氧基、丙氧基、異丙氧基、丁氧基、異丁氧基、第二丁氧基、第三丁氧基、戊基氧基、己基氧基、(2-乙基)己基氧基、庚基氧基、辛基氧基、壬基氧基、苯基氧基、及鄰甲苯基氧基等的於單側鍵結有碳數為1~20、更佳為碳數1~10的烴基的氧基;環氧基; 甲醯基;乙醯基、丙醯基、丁醯基、第三丁醯基、戊醯基、己醯基、(2-乙基)己醯基、庚醯基、辛醯基、壬醯基及苯甲醯基等的碳數為2~22、較佳為碳數為2~12的醯基(較佳為烷醯基(alkanoyl));甲氧基羰基、乙氧基羰基、丙氧基羰基、丁氧基羰基、第三丁氧基羰基、戊基氧基羰基、己基氧基羰基、(2-乙基)己基氧基羰基、庚基氧基羰基及辛基氧基羰基、壬基氧基羰基、苯基氧基羰基、及鄰甲苯基氧基羰基等的鍵結有碳數1~20、較佳為碳數1~10的烴基的氧基羰基;胺基;N-甲基胺基、N,N-二甲基胺基、N-乙基胺基、N,N-二乙基胺基、N-丙基胺基、N,N-二丙基胺基、N-異丙基胺基、N,N-二異丙基胺基、N-丁基胺基、N,N-二丁基胺基、N-異丁基胺基、N,N-二異丁基胺基、N-第二丁基胺基、N,N-二第二丁基胺基、N-第三丁基胺基、N,N-二第三丁基胺基、N-戊基胺基、N,N-二戊基胺基、N-(1-乙基丙基)胺基、N,N-二(1-乙基丙基)胺基、N-己基胺基、N,N-二己基胺基、N-(2-乙基)己基胺基、N,N-二(2-乙基)己基胺基、N-庚基胺基、N,N-二庚基胺基、N-辛基胺基、N,N-二辛基胺基、N-壬基胺基、N,N-二壬基胺基、N-苯基胺基、N,N-二苯基胺基、N,N-乙基甲基胺基、N,N-丙基甲基胺基、N,N-異丙基甲基胺基、N,N-丁基甲基胺基、N,N-第三丁基甲基胺基、及N,N-苯基甲基胺基等的經1個或2個碳數1~20、較佳為碳數1~10的烴基取代的胺基; 胺磺醯基;N-甲基胺磺醯基、N,N-二甲基胺磺醯基、N-乙基胺磺醯基、N,N-二乙基胺磺醯基、N-丙基胺磺醯基、N,N-二丙基胺磺醯基、N-異丙基胺磺醯基、N,N-二異丙基胺磺醯基、N-丁基胺磺醯基、N,N-二丁基胺磺醯基、N-異丁基胺磺醯基、N,N-二異丁基胺磺醯基、N-第二丁基胺磺醯基、N,N-二第二丁基胺磺醯基、N-第三丁基胺磺醯基、N,N-二第三丁基胺磺醯基、N-戊基胺磺醯基、N,N-二戊基胺磺醯基、N-(1-乙基丙基)胺磺醯基、N,N-二(1-乙基丙基)胺磺醯基、N-己基胺磺醯基、N,N-二己基胺磺醯基、N-(2-乙基)己基胺磺醯基、N,N-二(2-乙基)己基胺磺醯基、N-庚基胺磺醯基、N,N-二庚基胺磺醯基、N-辛基胺磺醯基、N,N-二辛基胺磺醯基、N,N-辛基甲基胺磺醯基、N-壬基胺磺醯基、N,N-二壬基胺磺醯基、N-苯基胺磺醯基、N,N-二苯基胺磺醯基、N,N-乙基甲基胺磺醯基、N,N-丙基甲基胺磺醯基、N,N-異丙基甲基胺磺醯基、N,N-丁基甲基胺磺醯基、N,N-第三丁基甲基胺磺醯基、及N,N-苯基甲基胺磺醯基等的經1個或2個碳數1~20、較佳為碳數1~10的烴基取代的胺磺醯基;甲醯基胺基;乙醯基胺基、丙醯基胺基、丁醯基胺基、2,2-二甲基丙醯基胺基、戊醯基胺基、己醯基胺基、(2-乙基)己醯基胺基、庚醯基胺基、辛醯基胺基、壬醯基胺基、癸醯基胺基、十一醯基胺基、十二醯基胺基、二十一醯基胺基、及苯甲醯基胺基等的碳數1~22、較佳為碳數1~12的烷醯基胺基; 羥基;甲醯基氧基、乙醯氧基、丙醯基氧基、丁醯基氧基、2,2-二甲基丙醯基氧基、戊醯基氧基、己醯基氧基、(2-乙基)己醯基氧基、庚醯基氧基、辛醯基氧基、壬醯基氧基、及苯甲醯基氧基等的碳數1~20、較佳為碳數1~10的烷醯基氧基;甲基磺醯基、乙基磺醯基、丙基磺醯基、丁基磺醯基、戊基磺醯基、己基磺醯基、(2-乙基)己基磺醯基、庚基磺醯基、辛基磺醯基、壬基磺醯基、癸基磺醯基、苯基磺醯基、及對甲苯基磺醯基等的取代有碳數1~20、較佳為碳數1~10的烴基的磺醯基;胺甲醯基;N-甲基胺甲醯基、N,N-二甲基胺甲醯基、N-乙基胺甲醯基、N,N-二乙基胺甲醯基、N-丙基胺甲醯基、N,N-二丙基胺甲醯基、N-異丙基胺甲醯基、N,N-二異丙基胺甲醯基、N-丁基胺甲醯基、N,N-二丁基胺甲醯基、N-異丁基胺甲醯基、N,N-二異丁基胺甲醯基、N-第二丁基胺甲醯基、N,N-二第二丁基胺甲醯基、N-第三丁基胺甲醯基、N,N-二第三丁基胺甲醯基、N-戊基胺甲醯基、N,N-二戊基胺甲醯基、N-(1-乙基丙基)胺甲醯基、N,N-二(1-乙基丙基)胺甲醯基、N-己基胺甲醯基、N,N-二己基胺甲醯基、N-(2-乙基)己基胺甲醯基、N,N-二(2-乙基)己基胺甲醯基、N-庚基胺甲醯基、N,N-二庚基胺甲醯基、N-辛基胺甲醯基、N,N-二辛基胺甲醯基、N-壬基胺甲醯基、N,N-二壬基胺甲醯基、N-苯基胺甲醯基、N,N-二苯基胺甲醯基、N,N-乙基甲基胺甲醯基、N,N-丙基甲基胺甲醯 基、N,N-異丙基甲基胺甲醯基、N,N-丁基甲基胺甲醯基、N,N-第三丁基甲基胺甲醯基、及N,N-苯基甲基胺甲醯基等的經1個或2個碳數1~20、較佳為碳數1~10的烴基取代的胺甲醯基;*-COCORnb2;*-OCON(Rnb2)2;*-N(Rnb2)COORnb2等。 As -CH 2 - contained in the hydrocarbon group is substituted with -O-, -CO-, -S(O) 2 -, -NR na -, -NR nb -, -NR na10 - or -NR nb10 - And the group (Z) that forms can enumerate: methoxyl group, ethoxyl group, propoxyl group, isopropoxyl group, butoxyl group, isobutoxyl group, second butoxyl group, third butoxyl group, On one side of pentyloxy, hexyloxy, (2-ethyl)hexyloxy, heptyloxy, octyloxy, nonyloxy, phenyloxy, and o-tolyloxy Oxygen group with a carbon number of 1 to 20, more preferably a hydrocarbon group with a carbon number of 1 to 10; epoxy group; formyl group; Hexyl, (2-ethyl)hexyl, heptyl, octyl, nonyl and benzoyl etc. have 2 to 22 carbons, preferably 2 to 12 carbons ( Preferred is alkanoyl (alkanoyl)); methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, ( 2-Ethyl)hexyloxycarbonyl, heptyloxycarbonyl and octyloxycarbonyl, nonyloxycarbonyl, phenyloxycarbonyl, and o-tolyloxycarbonyl, etc. have carbon number 1~ 20. Oxycarbonyl, preferably a hydrocarbon group with 1 to 10 carbons; amine; N-methylamino, N,N-dimethylamino, N-ethylamino, N,N-diethyl Amino, N-propylamino, N,N-dipropylamino, N-isopropylamino, N,N-diisopropylamino, N-butylamino, N,N -Dibutylamino, N-isobutylamino, N,N-diisobutylamino, N-second butylamino, N,N-disecond butylamino, N- Tributylamino, N,N-di-tert-butylamino, N-pentylamino, N,N-dipentylamino, N-(1-ethylpropyl)amino, N, N-di(1-ethylpropyl)amino, N-hexylamino, N,N-dihexylamino, N-(2-ethyl)hexylamino, N,N-di(2-ethyl base) hexylamino, N-heptylamino, N,N-diheptylamino, N-octylamino, N,N-dioctylamino, N-nonylamino, N,N -Dinonylamino, N-phenylamino, N,N-diphenylamino, N,N-ethylmethylamino, N,N-propylmethylamino, N,N- Isopropylmethylamino group, N,N-butylmethylamino group, N,N-tert-butylmethylamino group, and N,N-phenylmethylamino group, etc. through 1 or 2 carbon numbers 1 ~20, preferably an amino group substituted with a hydrocarbon group with 1 to 10 carbons; sulfamoyl group; N-methylsulfamoyl group, N,N-dimethylsulfamoyl group, N-ethylsulfamoyl group Acyl, N,N-diethylsulfamoyl, N-propylsulfamoyl, N,N-dipropylsulfamoyl, N-isopropylsulfamoyl, N,N- Diisopropylsulfamoyl, N-butylsulfamoyl, N,N-dibutylsulfamoyl, N-isobutylsulfamoyl, N,N-diisobutylsulfamoyl Acyl group, N-second butyl sulfamoyl group, N,N-di-second butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N,N-di-tert-butyl sulfamoyl group Acyl, N-pentylsulfamoyl, N,N-dipentylsulfamoyl, N-(1-ethylpropyl)sulfamoyl, N,N-bis(1-ethylpropyl) base) sulfamoyl group, N-hexylsulfamoyl group, N,N-dihexylsulfamoyl group, N-(2-ethyl)hexylsulfamoyl group, N,N-di(2-ethyl )hexylsulfamoyl, N-heptylsulfamoyl, N,N-diheptylsulfamoyl, N-octylsulfamoyl, N,N-dioctylsulfamoyl, N ,N-octylmethylsulfamoyl, N-nonylsulfamoyl, N,N-dinonylsulfamoyl, N-phenylsulfamoyl, N,N-diphenylamine Sulfonyl, N,N-Ethylmethylsulfamoyl, N,N-Propylmethylsulfamoyl, N,N-Isopropylmethylsulfamoyl, N,N-Butylmethyl The sulfamoyl group, N,N-tert-butylmethylsulfamoyl group, and N,N-phenylmethylsulfamoyl group, etc. have 1 or 2 carbon numbers of 1 to 20, preferably carbon number 1~10 hydrocarbyl substituted sulfamoyl group; formylamino group; acetylamino group, propionylamino group, butyrylamino group, 2,2-dimethylpropionylamino group, pentylamino group Amino, caproylamino, (2-ethyl) caproylamino, heptylamino, octaylamino, nonylamino, decylamino, undecylamino, Dodecyl amine, helicyl amine, and benzoyl amine, etc., have a carbon number of 1 to 22, preferably an alkyl amine group with a carbon number of 1 to 12; hydroxyl; formyl Oxygen, acetyloxy, propionyloxy, butyryloxy, 2,2-dimethylacryloxy, pentyloxy, hexyloxy, (2-ethyl)hexyl Cyloxy, heptyloxy, octyloxy, nonyloxy, and benzoyloxy such as alkyloxy having 1 to 20 carbons, preferably alkyloxy having 1 to 10 carbons ;Methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, (2-ethyl)hexylsulfonyl, heptylsulfonyl Acyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, phenylsulfonyl, and p-tolylsulfonyl are substituted with 1 to 20 carbons, preferably 1 carbons Sulfonyl group of hydrocarbon group of ~10; Aminoformyl; N-Methylaminoformyl, N,N-Dimethylaminoformyl, N-Ethylaminoformyl, N,N-Diethyl Aminoformyl, N-propylaminoformyl, N,N-dipropylaminoformyl, N-isopropylaminoformyl, N,N-diisopropylaminoformyl, N-butylaminoformyl, N,N-dibutylaminoformyl, N-isobutylaminoformyl, N,N-diisobutylaminoformyl, N-second butyl Aminoformyl, N, N-disecond-butylaminoformyl, N-tert-butylaminoformyl, N, N-di-tert-butylaminoformyl, N-pentylaminoformyl Acyl, N,N-dipentylaminoformyl, N-(1-ethylpropyl)aminoformyl, N,N-bis(1-ethylpropyl)aminoformyl, N- Hexylaminoformyl, N,N-dihexylaminoformyl, N-(2-ethyl)hexylaminoformyl, N,N-di(2-ethyl)hexylaminoformyl, N- Heptylaminoformyl, N,N-diheptylaminoformyl, N-octylaminoformyl, N,N-dioctylaminoformyl, N-nonylaminoformyl, N ,N-Dinonylaminoformyl, N-phenylaminoformyl, N,N-diphenylaminoformyl, N,N-ethylmethylaminoformyl, N,N-propane N, N-butylmethylcarbamoyl, N, N-butylmethylcarbamoyl, N,N-tert-butylmethylcarbamoyl, and N,N -carbamoyl group substituted by 1 or 2 carbon number 1~20, preferably carbon number 1~10 hydrocarbon groups such as phenylmethylcarbamoyl group; *-COCOR nb2 ; *-OCON(R nb2 ) 2 ; *-N(R nb2 )COOR nb2 etc.
[所述式中,*表示結合鍵。 [In the formula, * represents a bond.
於存在多個Rnb2的情況下,該些Rnb2可相同亦可不同,且表示與前述相同的含義。] When there are a plurality of R nb2 , these R nb2 may be the same or different, and have the same meaning as above. ]
R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的雜環基可為單環亦可為多環,較佳為包含雜原子作為環的構成要素的雜環。作為雜原子,可列舉:氮原子、氧原子及硫原子等。 R 1 ~R 9 , R 11b ~R 15b , R 1a ~R 9a , R 1b ~R 5b , R 7b , R na , R nb , R 17b ~R 24b , R 21 ~R 24 , R na1 , R nb1 The heterocyclic group represented by , R na10 and R nb10 may be a monocyclic ring or a polycyclic ring, and is preferably a heterocyclic ring containing a heteroatom as a constituent element of the ring. As a hetero atom, a nitrogen atom, an oxygen atom, a sulfur atom, etc. are mentioned.
所述雜環基的碳數較佳為2~30,更佳為3~22,進而佳為3~20,進而更佳為3~18,進而尤佳為3~15,特佳為3~14。 The carbon number of the heterocyclic group is preferably 2-30, more preferably 3-22, further preferably 3-20, further preferably 3-18, further preferably 3-15, particularly preferably 3-20 14.
於a為1~10的任一整數的情況下,R1~R9、R21~R24、Rna及Rna1所表示的雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種。 When a is any integer from 1 to 10, the heterocyclic group represented by R 1 to R 9 , R 21 to R 24 , R na and R na1 may have a group selected from -CO 2 - and -S(O ) 2 O - at least one of the group consisting of .
作為僅包含氮原子作為雜原子的雜環,可列舉:氮丙啶、吖丁啶(azetidine)、吡咯啶、哌啶及哌嗪等的單環系飽和雜環;2,5-二甲基吡咯等的吡咯、2-甲基吡唑及3-甲基吡唑等的吡唑、以 及咪唑、1,2,3-***及1,2,4-***等的5員環系不飽和雜環;吡啶、噠嗪及6-甲基嘧啶等的嘧啶、吡嗪、以及1,3,5-三嗪等的6員環系不飽和雜環;吲唑、吲哚啉、異吲哚啉、吲哚、吲哚嗪、苯并咪唑、喹啉、異喹啉、5,6,7,8-四氫(3-甲基)喹噁啉及3-甲基喹噁啉等的喹噁啉、喹唑啉、噌啉、酞嗪(phthalazine)、萘啶、嘌呤、喋啶、苯并吡唑、以及苯并哌啶等的縮合二環系雜環;咔唑、吖啶及啡嗪(phenazine)等的縮合三環系雜環;下述式所表示的環等。 Examples of heterocycles containing only nitrogen atoms as heteroatoms include monocyclic saturated heterocycles such as aziridine, azetidine, pyrrolidine, piperidine, and piperazine; 2,5-dimethyl Pyrrole such as pyrrole, pyrazole such as 2-methylpyrazole and 3-methylpyrazole, and and 5-membered unsaturated heterocycles such as imidazole, 1,2,3-triazole and 1,2,4-triazole; pyrimidine, pyrazine, and 1 , 6-membered unsaturated heterocycles such as 3,5-triazine; indazole, indoline, isoindoline, indole, indoxazine, benzimidazole, quinoline, isoquinoline, 5, 6,7,8-tetrahydro(3-methyl)quinoxaline and quinoxaline such as 3-methylquinoxaline, quinazoline, cinnoline, phthalazine (phthalazine), naphthyridine, purine, pterene Condensed bicyclic heterocycles such as pyridine, benzopyrazole, and benzopiperidine; condensed tricyclic heterocycles such as carbazole, acridine, and phenazine; rings represented by the following formulas; and the like.
[式中,*表示結合鍵。] [In the formula, * represents a bond. ]
作為僅包含氧原子作為雜原子的雜環,可列舉:氧雜環丙烷、氧雜環丁烷、四氫呋喃、四氫吡喃、1,3-二噁烷、1,4-二噁烷、及1-環戊基二氧雜環戊烷等的單環系飽和雜環;1,4-二氧雜螺[4.5]癸烷、及1,4-二氧雜螺[4.5]壬烷等的二環系飽和雜環;α-乙醯內酯、β-丙內酯、γ-丁內酯、及δ-戊內酯等的內酯系雜環;2,3-二甲基呋喃、及2,5-二甲基呋喃等的呋喃等的5員環系不飽和雜環;2H-吡喃、及4H-吡喃等的6員環系不飽和雜環;1-苯并呋喃、及4-甲基苯并吡喃等的苯并吡喃、苯并間二氧雜環戊烯 (benzodioxole)、色原烷(chromane)、以及異色原烷等的縮合二環系雜環;呫噸(xanthene)、及二苯并呋喃等的縮合三環系雜環等。 As a heterocyclic ring containing only an oxygen atom as a heteroatom, oxirane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, and Monocyclic saturated heterocycles such as 1-cyclopentyldioxolane; 1,4-dioxaspiro[4.5]decane and 1,4-dioxaspiro[4.5]nonane, etc. Bicyclic saturated heterocyclic rings; lactone heterocyclic rings such as α-acetyl lactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone; 2,3-dimethylfuran, and 5-membered unsaturated heterocycles such as furan such as 2,5-dimethylfuran; 6-membered unsaturated heterocycles such as 2H-pyran and 4H-pyran; 1-benzofuran, and Benzopyran such as 4-methylbenzopyran, benzodioxole Condensed bicyclic heterocycles such as (benzodioxole), chromane, and isochromane; condensed tricyclic heterocycles such as xanthene and dibenzofuran, etc.
作為僅包含硫原子作為雜原子的雜環,可列舉:二硫雜環戊烷等的5員環系飽和雜環;噻烷(thiane)、1,3-二噻烷、及2-甲基1,3-二噻烷等的6員環系飽和雜環;3-甲基噻吩、及2-羧基噻吩等的噻吩、4H-噻喃(thiopyran)、以及苯并四氫噻喃等的苯并噻喃等的5員環系不飽和雜環;苯并噻吩等的縮合二環系雜環等;噻蒽(thianthrene)、及二苯并噻吩等的縮合三環系雜環等。 Examples of heterocycles containing only sulfur atoms as heteroatoms include: 5-membered saturated heterocycles such as dithiolane; thiane, 1,3-dithiane, and 2-methyl 6-membered saturated heterocycles such as 1,3-dithiane; 3-methylthiophene, thiophene such as 2-carboxythiophene, 4H-thiopyran, and benzene such as benzotetrahydrothiopyran 5-membered unsaturated heterocycles such as thiopyran; condensed bicyclic heterocycles such as benzothiophene; and condensed tricyclic heterocycles such as thianthrene and dibenzothiophene.
作為包含氮原子及氧原子作為雜原子的雜環,可列舉:嗎啉、2-吡咯啶酮、2-甲基-2-吡咯啶酮、2-哌啶酮、2-甲基-2-哌啶酮等的單環系飽和雜環;4-甲基噁唑等的噁唑、2-甲基異噁唑、3-甲基異噁唑等的異噁唑等的單環系不飽和雜環;苯并噁唑、苯并異噁唑、苯并噁嗪、苯并二噁烷、苯并咪唑啉等的縮合二環系雜環;啡噁嗪等的縮合三環系雜環等。 As a heterocyclic ring containing a nitrogen atom and an oxygen atom as a heteroatom, morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, 2-methyl-2- Monocyclic saturated heterocyclic rings such as piperidone; monocyclic unsaturated monocyclic systems such as oxazole such as 4-methyloxazole, 2-methylisoxazole, and 3-methylisoxazole such as isoxazole Heterocycles; condensed bicyclic heterocycles such as benzoxazole, benzisoxazole, benzoxazine, benzodioxane, and benzimidazoline; condensed tricyclic heterocycles such as phenoxazine, etc. .
作為包含氮原子及硫原子作為雜原子的雜環,可列舉:3-甲基噻唑、及2,4-二甲基噻唑等的噻唑等的單環系雜環;苯并噻唑等的縮合二環系雜環;啡噻嗪等的縮合三環系雜環等。 Examples of the heterocycle containing a nitrogen atom and a sulfur atom as a heteroatom include monocyclic heterocycles such as thiazole such as 3-methylthiazole and 2,4-dimethylthiazole; Ring heterocycles; condensed tricyclic heterocycles such as phenthiazine, etc.
所述雜環基亦可為將所述列舉的烴基組合而成的基團,例如可列舉四氫呋喃基甲基、甲基四氫呋喃基等。 The heterocyclic group may be a combination of the hydrocarbon groups listed above, for example, tetrahydrofurylmethyl, methyltetrahydrofuryl, etc. may be mentioned.
再者,所述雜環的鍵結位為各環中所含的任意的氫原子脫離的部分。 In addition, the bonding site of the heterocyclic ring is a part from which any hydrogen atom contained in each ring is removed.
於a為1~10的任一整數的情況下,於R1~R9、R1a~R9a、R21~R24所表示的雜環基包含並未構成環的-CH2-時,該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-,該情況下,該雜環基包含所述基團(Z)。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 When a is any integer from 1 to 10, when the heterocyclic group represented by R 1 to R 9 , R 1a to R 9a , R 21 to R 24 includes -CH 2 - which does not constitute a ring, The -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na -, in which case the heterocyclic group comprises the group (Z). Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
於a為0的情況下,於R1~R5、R7、R11b~R15b、R1b~R5b、R7b、R17b~R24b所表示的雜環基包含並未構成環的-CH2-時,該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb-,該情況下,該雜環基包含所述基團(Z)。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 When a is 0, the heterocyclic group represented by R 1 ~ R 5 , R 7 , R 11b ~ R 15b , R 1b ~ R 5b , R 7b , R 17b ~ R 24b includes those that do not constitute a ring In the case of -CH 2 -, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb -, in this case, the heterocyclic group comprises the group ( Z). Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
於Rna1所表示的雜環基包含並未構成環的-CH2-時,該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna10-,該情況下,該雜環基包含所述基團(Z)。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 When the heterocyclic group represented by R na1 includes -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na10 - , in this case, the heterocyclic group comprises the group (Z). Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
於Rnb1所表示的雜環基包含並未構成環的-CH2-時,該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb10-,該情況下,該雜環基包含所述基團(Z)。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 When the heterocyclic group represented by R nb1 includes -CH 2 - which does not constitute a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb10 - , in this case, the heterocyclic group comprises the group (Z). Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
另外,於所述雜環包含氮原子作為其構成元素的情況下,於該氮原子上亦可鍵結所述R1。 In addition, when the heterocyclic ring contains a nitrogen atom as its constituent element, the R 1 may be bonded to the nitrogen atom.
作為R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的雜 環基的取代基,可列舉與R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的烴基可具有的取代基相同者。 As R 1 ~R 9 , R 11b ~R 15b , R 1a ~R 9a , R 1b ~R 5b , R 7b , R na , R nb , R 17b ~R 24b , R 21 ~R 24 , R na1 , R The substituents of the heterocyclic groups represented by nb1 , R na10 and R nb10 include R 1 to R 9 , R 11b to R 15b , R 1a to R 9a , R 1b to R 5b , R 7b , R na , The hydrocarbon groups represented by R nb , R 17b to R 24b , R 21 to R 24 , R na1 , R nb1 , R na10 and R nb10 may have the same substituents.
於R2與R3、R3與R4、R4與R5、R6與R7、R8與R9、R17b與R18b、R21與R22、R12b與R13b、R13b與R14b、以及R14b與R15b、R2a與R3a、R3a與R4a、R4a與R5a、R6a與R7a、R8a與R9a、R2b與R3b、R3b與R4b、R4b與R5b、R6b與R7b、或者R21b與R22b跟各自所鍵結的碳原子一起形成環的情況下,該環可為烴環,亦可為雜環。作為烴環,可列舉:脂肪族烴環、芳香族烴環等。 R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 8 and R 9 , R 17b and R 18b , R 21 and R 22 , R 12b and R 13b , R 13b and R 14b , and R 14b and R 15b , R 2a and R 3a , R 3a and R 4a , R 4a and R 5a , R 6a and R 7a , R 8a and R 9a , R 2b and R 3b , R 3b When forming a ring with R 4b , R 4b and R 5b , R 6b and R 7b , or R 21b and R 22b together with their respective bonded carbon atoms, the ring may be a hydrocarbon ring or a heterocycle. As a hydrocarbon ring, an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, etc. are mentioned.
作為脂肪族烴環,可列舉:環丙烷環、甲基環丙烷環、環丁烷環、環戊烷環、環己烷環、環庚烷環、甲基環己烷環、1,1-二甲基環己烷環、1,2-二甲基環己烷環、1,3-二甲基環己烷環、1,4-二甲基環己烷環、環辛烷環、1,3,5-三甲基環己烷環、1,1,3,3-四甲基環己烷環、戊基環己烷環、辛基環己烷環、及環己基環己烷環等的環烷烴環;環己烯環、環庚烯環、及環辛烯環等的環烯烴環;降冰片烷、金剛烷、及雙環[2.2.2]辛烷等。 Examples of the aliphatic hydrocarbon ring include: cyclopropane ring, methylcyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, methylcyclohexane ring, 1,1- Dimethylcyclohexane ring, 1,2-dimethylcyclohexane ring, 1,3-dimethylcyclohexane ring, 1,4-dimethylcyclohexane ring, cyclooctane ring, 1 ,3,5-trimethylcyclohexane ring, 1,1,3,3-tetramethylcyclohexane ring, pentylcyclohexane ring, octylcyclohexane ring, and cyclohexylcyclohexane ring Cycloalkane rings such as cyclohexene rings, cycloheptene rings, and cyclooctene rings; norbornane, adamantane, and bicyclo[2.2.2]octane, etc.
脂肪族烴環的碳數例如為3~30,較佳為3~20,更佳為4~20,進而佳為4~15,進而更佳為5~15,特佳為5~10。 The carbon number of the aliphatic hydrocarbon ring is, for example, 3-30, preferably 3-20, more preferably 4-20, still more preferably 4-15, still more preferably 5-15, particularly preferably 5-10.
作為芳香族烴環,可列舉:苯、甲苯、鄰二甲苯、間二甲苯、對二甲苯、異丙基苯、第三丁基苯、均三甲苯、1,5-雙(2-丙基)苯、萘、1,2,3,4-四氫萘、茀、菲、及蒽等。 Examples of the aromatic hydrocarbon ring include: benzene, toluene, o-xylene, m-xylene, p-xylene, cumene, tert-butylbenzene, mesitylene, 1,5-bis(2-propyl ) Benzene, naphthalene, 1,2,3,4-tetrahydronaphthalene, fennel, phenanthrene, and anthracene, etc.
芳香族烴環的碳數例如為6~30,較佳為6~20,更佳為6~ 15。 The carbon number of the aromatic hydrocarbon ring is, for example, 6-30, preferably 6-20, more preferably 6-20 15.
於R2與R3、R3與R4、R4與R5、R6與R7、R8與R9、R17b與R18b、R21與R22、R12b與R13b、R13b與R14b、R14b與R15b、R2a與R3a、R3a與R4a、R4a與R5a、R6a與R7a、R8a與R9a、R2b與R3b、R3b與R4b、R4b與R5b、R6b與R7b、或者R21b與R22b跟各自所鍵結的碳原子一起形成環的情況下,該環可具有取代基。作為該取代基,可列舉與R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的烴基可具有的取代基相同者。 R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 8 and R 9 , R 17b and R 18b , R 21 and R 22 , R 12b and R 13b , R 13b and R 14b , R 14b and R 15b , R 2a and R 3a , R 3a and R 4a , R 4a and R 5a , R 6a and R 7a , R 8a and R 9a , R 2b and R 3b , R 3b and When R 4b , R 4b and R 5b , R 6b and R 7b , or R 21b and R 22b form a ring together with carbon atoms to which they are bonded, the ring may have a substituent. Examples of such substituents include combinations with R 1 to R 9 , R 11b to R 15b , R 1a to R 9a , R 1b to R 5b , R 7b , R na , R nb , R 17b to R 24b , R 21 to The hydrocarbon groups represented by R 24 , R na1 , R nb1 , R na10 and R nb10 may have the same substituents.
於R2與R3、R3與R4、R4與R5、R6與R7、R8與R9、R17b與R18b、R21與R22、R12b與R13b、R13b與R14b、以及R14b與R15b、R2a與R3a、R3a與R4a、R4a與R5a、R6a與R7a、R8a與R9a、R2b與R3b、R3b與R4b、R4b與R5b、R6b與R7b、或R21b與R22b跟各自所鍵結的碳原子一起形成可具有取代基的環的情況下,且於該環包含並未構成環的-CH2-時,該-CH2-可經取代為-O-、-CO-、-S(O)2-、-NRna-或-NRnb-,該情況下,該環包含所述基團(Z)。其中,並未藉由取代-CH2-而形成-COOH或-S(O)2OH。 R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 8 and R 9 , R 17b and R 18b , R 21 and R 22 , R 12b and R 13b , R 13b and R 14b , and R 14b and R 15b , R 2a and R 3a , R 3a and R 4a , R 4a and R 5a , R 6a and R 7a , R 8a and R 9a , R 2b and R 3b , R 3b When R 4b , R 4b and R 5b , R 6b and R 7b , or R 21b and R 22b together with the carbon atoms to which they are bonded together form a ring that may have substituents, and when the ring includes and does not constitute In the case of -CH 2 - of a ring, the -CH 2 - may be substituted with -O-, -CO-, -S(O) 2 -, -NR na - or -NR nb -, in which case the ring contains The group (Z). Wherein, -COOH or -S(O) 2 OH is not formed by substituting -CH 2 -.
於R2與R3、R3與R4、R4與R5、R6與R7、R8與R9、R17b與R18b、R21與R22、R12b與R13b、R13b與R14b、R14b與R15b、R2a與R3a、R3a與R4a、R4a與R5a、R6a與R7a、R8a與R9a、R2b與R3b、R3b與R4b、R4b與R5b、R6b與R7b、或R21b與R22b跟各自所鍵結的碳原子一起形成環的情況下,該環可為雜環。 R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 6 and R 7 , R 8 and R 9 , R 17b and R 18b , R 21 and R 22 , R 12b and R 13b , R 13b and R 14b , R 14b and R 15b , R 2a and R 3a , R 3a and R 4a , R 4a and R 5a , R 6a and R 7a , R 8a and R 9a , R 2b and R 3b , R 3b and When R 4b , R 4b and R 5b , R 6b and R 7b , or R 21b and R 22b form a ring together with the carbon atoms to which they are bonded, the ring may be a heterocyclic ring.
於R2與R3、R3與R4、R4與R5、R12b與R13b、R13b與R14b、R14b與R15b、R2a與R3a、R3a與R4a、R4a與R5a、R2b與R3b、R3b與R4b、或R4b與R5b跟各自所鍵結的碳原子一起形成環的情況下,該雜環基與R2~R5、R12b~R15b、R2a~R5a、或R2b~R5b所鍵結的苯環一併具有2環以上的環結構。作為所述具有2環以上的環結構的雜環,例如可列舉具有下述式的結構的雜環。 In R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 12b and R 13b , R 13b and R 14b , R 14b and R 15b , R 2a and R 3a , R 3a and R 4a , R When 4a and R 5a , R 2b and R 3b , R 3b and R 4b , or R 4b and R 5b form a ring together with the carbon atoms to which they are bonded, the heterocyclic group and R 2 to R 5 , R The benzene rings to which 12b to R 15b , R 2a to R 5a , or R 2b to R 5b are bonded together have a ring structure of two or more rings. Examples of the heterocyclic ring having a ring structure of two or more rings include a heterocyclic ring having a structure of the following formula.
[式中的苯環相當於式(I)所表示的化合物所具有的異吲哚啉結構中的苯環。] [The benzene ring in the formula corresponds to the benzene ring in the isoindoline structure of the compound represented by the formula (I). ]
R1~R9、R17b及R18b中的至少一個、較佳為R6~R9、R17b及R18b中的至少一個、更佳為R6及R7中的一者與R8及R9中的一者、或者R6及R7中的一者與R17b及R18b中的一者較佳為烴基。 At least one of R 1 to R 9 , R 17b and R 18b, preferably at least one of R 6 to R 9 , R 17b and R 18b , more preferably one of R 6 and R 7 and R 8 and one of R 9 , or one of R 6 and R 7 and one of R 17b and R 18b is preferably a hydrocarbon group.
R11b~R16b、R21b及R22b中的至少一個、較佳為R16b、R21b及R22b中的至少一個、更佳為R16b、與R21b及R22b中的一者較佳為烴基。 At least one of R 11b ~R 16b , R 21b and R 22b , preferably at least one of R 16b , R 21b and R 22b , more preferably R 16b , and preferably one of R 21b and R 22b for hydrocarbon groups.
R1a~R9a中的至少一個、較佳為R6a~R9a中的至少一個、更佳為R6a及R7a中的一者與R8a及R9a中的一者較佳為烴基。 At least one of R 1a to R 9a , preferably at least one of R 6a to R 9a , more preferably one of R 6a and R 7a and one of R 8a and R 9a is preferably a hydrocarbon group.
R1b~R7b、R17b及R18b中的至少一個、較佳為R6b、R7b、R17b 及R18b中的至少一個、更佳為R6b及R7b中的一者、R17b及R18b中的一者較佳為烴基。 At least one of R 1b ~ R 7b , R 17b and R 18b , preferably at least one of R 6b , R 7b , R 17b and R 18b , more preferably one of R 6b and R 7b , R 17b and one of R 18b is preferably a hydrocarbon group.
作為-CO-ORna1、-CO-ORnb1,較佳為甲氧基羰基、乙氧基羰基、丙氧基羰基、第三丁氧基羰基、丁氧基羰基、戊基氧基羰基、己基氧基羰基、(2-乙基)己基氧基羰基、庚基氧基羰基、辛基氧基羰基、壬基氧基羰基、癸基氧基羰基、十一基氧基羰基、十二基氧基羰基、苯基氧基羰基及二十基氧基羰基等的鍵結有碳數1~35的烴基的氧基羰基等,更佳為可列舉鍵結有碳數1~10的烴基的氧基羰基等。 -CO-OR na1 and -CO-OR nb1 are preferably methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyl Oxycarbonyl, (2-ethyl)hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxy An oxycarbonyl group bonded to a hydrocarbon group having 1 to 35 carbons such as an oxycarbonyl group, a phenyloxycarbonyl group, and an eicosyloxycarbonyl group, etc., more preferably an oxygen group bonded to a hydrocarbon group having 1 to 10 carbons. carbonyl, etc.
作為-CO-NH(Rna1)、-CO-N(Rna1)2、-CO-NH(Rnb1)、-CO-N(Rnb1)2,較佳為:N-甲基胺甲醯基、N-乙基胺甲醯基、N-丙基胺甲醯基、N-異丙基胺甲醯基、N-丁基胺甲醯基、N-異丁基胺甲醯基、N-第二丁基胺甲醯基、N-第三丁基胺甲醯基、N-戊基胺甲醯基、N-(1-乙基丙基)胺甲醯基、N-己基胺甲醯基、N-(2-乙基)己基胺甲醯基、N-庚基胺甲醯基、N-辛基胺甲醯基、N-壬基胺甲醯基、N-癸基胺甲醯基、N-十一基胺甲醯基、N-十二基胺甲醯基、N-二十基胺甲醯基及N-苯基胺甲醯基等的經1個碳數1~35的烴基取代的胺甲醯基等;N,N-二甲基胺甲醯基、N,N-乙基甲基胺甲醯基、N,N-二乙基胺甲醯基、N,N-丙基甲基胺甲醯基、N,N-二丙基胺甲醯基、N,N-異丙基甲基胺甲醯基、N,N-二異丙基胺甲醯基、N,N-第三丁基甲基胺甲醯基、N,N-二異丁基胺甲醯基、N,N-二第二丁基胺甲醯基、 N,N-二第三丁基胺甲醯基、N,N-丁基甲基胺甲醯基、N,N-二丁基胺甲醯基、N,N-丁基辛基胺甲醯基、N,N-二戊基胺甲醯基、N,N-二(1-乙基丙基)胺甲醯基、N,N-二己基胺甲醯基、N,N-二(2-乙基)己基胺甲醯基、N,N-二庚基胺甲醯基、N,N-辛基甲基胺甲醯基、N,N-二辛基胺甲醯基、N,N-二壬基胺甲醯基、N,N-癸基甲基胺甲醯基、N,N-十一基甲基胺甲醯基、N,N-十二基甲基胺甲醯基、N,N-二十基甲基胺甲醯基、N,N-苯基甲基胺甲醯基及N,N-二苯基胺甲醯基等的經2個碳數1~35的烴基取代的胺甲醯基等,更佳為可列舉經1個或2個碳數1~10的烴基取代的胺甲醯基等。 As -CO-NH(R na1 ), -CO-N(R na1 ) 2 , -CO-NH(R nb1 ), -CO-N(R nb1 ) 2 , preferably: N-methylcarbamoyl Base, N-ethylaminoformyl, N-propylaminoformyl, N-isopropylaminoformyl, N-butylaminoformyl, N-isobutylaminoformyl, N -Second butylaminoformyl, N-tertiary butylaminoformyl, N-pentylaminoformyl, N-(1-ethylpropyl)aminoformyl, N-hexylaminoformyl Acyl, N-(2-ethyl)hexylaminoformyl, N-heptylaminoformyl, N-octylaminoformyl, N-nonylaminoformyl, N-decylaminoformyl Acyl group, N-undecylaminoformyl group, N-dodecylaminoformyl group, N-eicosylaminoformyl group and N-phenylaminoformyl group have a carbon number of 1~ 35 hydrocarbyl substituted aminoformyl, etc.; N,N-dimethylaminoformyl, N,N-ethylmethylaminoformyl, N,N-diethylaminoformyl, N, N-Propylmethylaminoformyl, N,N-Dipropylaminoformyl, N,N-Isopropylmethylaminoformyl, N,N-Diisopropylaminoformyl, N,N-tert-butylmethylaminoformyl, N,N-diisobutylaminoformyl, N,N-disecond-butylaminoformyl, N,N-di-tert-butylamine Formyl, N,N-Butylmethylaminoformyl, N,N-Dibutylaminoformyl, N,N-Butyloctylaminoformyl, N,N-Dipentylaminoformyl N,N-di(1-ethylpropyl)aminoformyl, N,N-dihexylaminoformyl, N,N-di(2-ethyl)hexylaminoformyl, N, N-diheptylaminoformyl, N,N-octylmethylaminoformyl, N,N-dioctylaminoformyl, N,N-dinonylaminoformyl, N,N -Decylmethylcarbamoyl, N,N-undecylmethylcarbamoyl, N,N-dodecylmethylcarbamoyl, N,N-eicosylmethylcarbamoyl carbamoyl group, N,N-phenylmethylaminoformyl group and N,N-diphenylaminoformyl group, etc., which are substituted by two hydrocarbon groups with 1 to 35 carbons, more preferably Examples thereof include carbamoyl groups substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms.
作為-CO-Rna1、-CO-Rnb1,較佳為乙醯基、丙醯基、丁醯基、2,2-二甲基丙醯基、戊醯基、己醯基、(2-乙基)己醯基、庚醯基、辛醯基、壬醯基、癸醯基、十一醯基、十二醯基、二十一醯基、苯甲醯基、苯基甲基羰基、苯基乙基羰基及苯基丙基羰基等的鍵結有為烴基且碳數為1~35的基團的羰基,更佳為可列舉鍵結有為烴基且碳數為1~10的基團的羰基等。 As -CO-R na1 , -CO-R nb1 , preferably acetyl, propionyl, butyryl, 2,2-dimethylacryl, pentyl, hexyl, (2-ethyl )hexyl, heptyl, octyl, nonyl, decanyl, undecyl, dodecyl, undecyl, benzoyl, phenylmethylcarbonyl, phenylethyl Carbonyl, phenylpropylcarbonyl, etc. have a carbonyl group bonded to a hydrocarbon group with a carbon number of 1 to 35, more preferably a carbonyl group bonded to a hydrocarbon group with a carbon number of 1 to 10, etc. .
於鍵結有烴基的羰基即-CO-Rna1、-CO-Rnb1中,該烴基亦可具有:氯原子等的鹵素原子;胺磺醯基;羥基;甲氧基等的於單側鍵結有碳數1~10的烴基的氧基;甲氧基羰基等的鍵結有碳數1~10的烴基的氧基羰基等。 In the carbonyl group bonded with a hydrocarbon group, namely -CO-R na1 and -CO-R nb1 , the hydrocarbon group may also have: a halogen atom such as a chlorine atom; a sulfamoyl group; a hydroxyl group; a methoxy group, etc. Oxygen group bonded to a hydrocarbon group with 1 to 10 carbons; oxycarbonyl group bonded to a hydrocarbon group with 1 to 10 carbons such as methoxycarbonyl.
-CO-Rna1中,於鍵結有烴基的羰基中,該烴基亦可具有-CO2 -及-S(O)2O-等。 In -CO-R na1 , in the carbonyl group to which a hydrocarbon group is bonded, the hydrocarbon group may have -CO 2 - and -S(O) 2 O - and the like.
作為-S(O)2-Rna1、-S(O)2-Rnb1,較佳為甲基磺醯基、乙基 磺醯基、丙基磺醯基、丁基磺醯基、戊基磺醯基、己基磺醯基、(2-乙基)己基磺醯基、庚基磺醯基、辛基磺醯基、壬基磺醯基、癸基磺醯基、十一基磺醯基、十二基磺醯基、二十基磺醯基、苯基磺醯基、及對甲苯基磺醯基等的鍵結有碳數1~35的烴基的磺醯基等,更佳為可列舉鍵結有碳數1~10的烴基的磺醯基等。 -S(O) 2 -R na1 and -S(O) 2 -R nb1 are preferably methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, or pentyl Sulfonyl, Hexylsulfonyl, (2-Ethyl)hexylsulfonyl, Heptylsulfonyl, Octylsulfonyl, Nonylsulfonyl, Decylsulfonyl, Undecylsulfonyl , dodecylsulfonyl, eicosylsulfonyl, phenylsulfonyl, p-tolylsulfonyl, etc., such as a sulfonyl group bonded to a hydrocarbon group with a carbon number of 1 to 35, more preferably Examples thereof include a sulfonyl group to which a hydrocarbon group having 1 to 10 carbon atoms is bonded.
R2與R3、R3與R4、R4與R5、R12b與R13b、R13b與R14b、R14b與R15b、R2a與R3a、R3a與R4a、R4a與R5a、R2b與R3b、R3b與R4b、或R4b與R5b跟各自所鍵結的碳原子一起可形成的環是與式(I)、式(IIB)、式(IA)、或式(IB)的異吲哚啉骨架的苯環縮合。 R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 12b and R 13b , R 13b and R 14b , R 14b and R 15b , R 2a and R 3a , R 3a and R 4a , R 4a The ring that can be formed with R 5a , R 2b and R 3b , R 3b and R 4b , or R 4b and R 5b together with the carbon atoms to which they are bonded is the same as formula (I), formula (IIB), formula (IA ), or the benzene ring condensation of the isoindoline skeleton of formula (IB).
作為R2與R3、R3與R4、R4與R5、R12b與R13b、R13b與R14b、R14b與R15b、R2a與R3a、R3a與R4a、R4a與R5a、R2b與R3b、R3b與R4b、或R4b與R5b跟各自所鍵結的碳原子一起可形成的環與所述苯環的縮合環結構,可列舉:茚(indene)、萘、伸聯苯(biphenylene)、苯并二茚(indacene)、苊(acenaphthylene)、茀、萉(phenalene)、菲、蒽、螢蒽(fluoranthene)、醋菲烯(acephenanthrylene)、醋蒽烯(aceanthrylene)、聯伸三苯(triphenylene)、芘、(chrysene)、N-甲基鄰苯二甲醯亞胺、N-(1-苯基乙基)鄰苯二甲醯亞胺及稠四苯(tetracene)等的烴系縮環結構及其部分還原體(例如,9,10-二氫蒽、1,2,3,4-四氫萘等);吲哚、異吲哚、吲唑、喹啉、異喹啉、酞嗪、喹噁啉、喹唑啉、噌啉、咔唑、咔啉、啡啶(phenanthridine)、吖啶、呸啶(perimidine)、 啡啉、啡嗪等的含氮縮合雜環及其部分還原體;3-氫苯并呋喃2-酮等的含氧縮合雜環及其部分還原體。 As R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 12b and R 13b , R 13b and R 14b , R 14b and R 15b , R 2a and R 3a , R 3a and R 4a , R 4a and R 5a , R 2b and R 3b , R 3b and R 4b , or R 4b and R 5b together with the carbon atoms to which they are bonded and the condensed ring structure of the benzene ring and the benzene ring may include: indene (indene), naphthalene, biphenylene, indacene, acenaphthylene, fennel, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, Aceanthrylene, triphenylene, pyrene, (chrysene), N-methylphthalimide, N-(1-phenylethyl)phthalimide, tetracene and other hydrocarbon-based condensed ring structures and their parts Reduced forms (e.g., 9,10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, etc.); indole, isoindole, indazole, quinoline, isoquinoline, phthalazine, quinoxaline , quinazoline, cinnoline, carbazole, carboline, phenanthridine (phenanthridine), acridine, perimidine (perimidine), phenanthroline, phenanthridine, etc. nitrogen-containing condensed heterocyclic rings and their partial reductions; 3-hydrogen Oxygen-containing condensed heterocycles such as benzofuran 2-one and their partially reduced forms.
R6a與R7a、或R8a與R9a跟各自所鍵結的碳原子一起可形成的環是與式(IA)的異吲哚啉骨架的環外亞甲基(C=CH2)鍵結,且若將該環作為包含該環外亞甲基(C=CH2)的結構而列舉,則可例示例如下述群組A般的羰基與環外亞甲基及羰基依此順序排列的結構。**表示與異吲哚啉骨架的結合鍵。 The ring that can be formed by R 6a and R 7a , or R 8a and R 9a together with the carbon atoms to which they are bonded is the exocyclic methylene (C=CH 2 ) bond with the isoindoline skeleton of formula (IA) If the ring is listed as a structure including the exocyclic methylene group (C=CH 2 ), for example, the carbonyl group, exocyclic methylene group, and carbonyl group in the following group A are arranged in this order Structure. ** indicates a bond to the isoindoline skeleton.
[群組A]
[式中,R25及R26相互獨立地表示可具有取代基的碳數1~35的烴基、可具有取代基的雜環基、或氫原子,該烴基中所含的-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna-。其中,並未藉由取代-CH2-而形成-COOH及-S(O)2OH。該烴基及該雜環基可具有選自由-CO2 -及-S(O)2O-所組成的群組中的至少一種作為取代基。 R25、R26的具體例及較佳的例子與Rna1相同。] [In the formula, R 25 and R 26 independently represent a hydrocarbon group with 1 to 35 carbons that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom, and the -CH 2 - contained in the hydrocarbon group may be Substituted with -O-, -CO-, -S(O) 2 - or -NR na -. Wherein, -COOH and -S(O) 2 OH are not formed by substituting -CH 2 -. The hydrocarbon group and the heterocyclic group may have at least one substituent selected from the group consisting of -CO 2 - and -S(O) 2 O - . Specific examples and preferred examples of R 25 and R 26 are the same as those of R na1 . ]
R21與R22跟各自所鍵結的碳原子一起可形成的環是與式(I)的異吲哚啉骨架的環外亞甲基(C=CH2)鍵結,且若將該環作為包含該環外亞甲基(C=CH2)的結構而列舉,則可例示例如下述群組B般的羰基與環外亞甲基及羰基依此順序排列的結構。**表示與異吲哚啉骨架的結合鍵。 The ring that R 21 and R 22 can form together with the carbon atoms they are bonded to is bonded to the exomethylene group (C=CH 2 ) of the isoindoline skeleton of formula (I), and if the ring As a structure including the exocyclic methylene group (C=CH 2 ), for example, a structure in which a carbonyl group, an exocyclic methylene group, and a carbonyl group are arranged in this order as in Group B below can be exemplified. ** indicates a bond to the isoindoline skeleton.
[群組B]
[式中,R23及R24表示與前述相同的含義。] [In the formula, R 23 and R 24 represent the same meaning as above. ]
R17b與R18b、或R21b與R22b跟各自所鍵結的碳原子一起可形成的環是與式(IIB)的異吲哚啉骨架的環外亞甲基(C=CH2)鍵結,且若將該環作為包含該環外亞甲基(C=CH2)的結構而列舉,則可例示例如下述群組C般的羰基與環外亞甲基及羰基依此 順序排列的結構。**表示與異吲哚啉骨架的結合鍵。 The ring that can be formed by R 17b and R 18b , or R 21b and R 22b together with the carbon atoms to which they are bonded is a bond with the exomethylene group (C=CH 2 ) of the isoindoline skeleton of formula (IIB) If the ring is listed as a structure including the exocyclic methylene group (C=CH 2 ), for example, the carbonyl group, exocyclic methylene group, and carbonyl group in the following group C are arranged in this order Structure. ** indicates a bond to the isoindoline skeleton.
[式中,R23b及R24b表示與前述相同的含義。] [wherein, R 23b and R 24b represent the same meaning as above. ]
R2與R3、R3與R4、R4與R5、R12b與R13b、R13b與R14b、 R14b與R15b、R2a與R3a、R3a與R4a、R4a與R5a、R2b與R3b、R3b與R4b、或R4b與R5b跟各自所鍵結的碳原子一起可形成的環亦可具有取代基。作為該取代基,可列舉與R1~R9、R11b~R15b、R1a~R9a、R1b~R5b、R7b、Rna、Rnb、R17b~R24b、R21~R24、Rna1、Rnb1、Rna10及Rnb10所表示的烴基可具有的取代基相同者。 R 2 and R 3 , R 3 and R 4 , R 4 and R 5 , R 12b and R 13b , R 13b and R 14b , R 14b and R 15b , R 2a and R 3a , R 3a and R 4a , R 4a The ring that may be formed with R 5a , R 2b and R 3b , R 3b and R 4b , or R 4b and R 5b together with carbon atoms to which they are bonded may have a substituent. Examples of such substituents include combinations with R 1 to R 9 , R 11b to R 15b , R 1a to R 9a , R 1b to R 5b , R 7b , R na , R nb , R 17b to R 24b , R 21 to The hydrocarbon groups represented by R 24 , R na1 , R nb1 , R na10 and R nb10 may have the same substituents.
作為R2~R9、R17b、R18b、R21、R22、R12b~R15b、R21b及R22b、R2a~R9a、R2b~R5b及R7b所表示的鹵素原子,可列舉氟原子、氯原子、溴原子及碘原子,較佳為氯原子、溴原子。 As a halogen atom represented by R 2 to R 9 , R 17b , R 18b , R 21 , R 22 , R 12b to R 15b , R 21b and R 22b , R 2a to R 9a , R 2b to R 5b and R 7b , may include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a chlorine atom or a bromine atom.
Mb+較佳為氫正離子或Li+、Na+、K+等的1價金屬離子、2價以上的金屬陽離子,更佳為氫正離子或2價以上的金屬陽離子,進而佳為氫正離子。 M b+ is preferably a hydrogen cation or a monovalent metal ion such as Li + , Na + , K + , a metal cation with a valence of more than 2, more preferably a cation or a metal cation with a valence of more than 2, and more preferably a cation of a metal with a valence of more than 2. ion.
作為2價以上的金屬陽離子,可列舉元素週期表的2族~15族的金屬的陽離子,較佳為可列舉Mg2+、Ca2+、Sr2+、Ba2+、Cd2+、Ni2+、Zn2+、Cu2+、Hg2+、Fe2+、Co2+、Sn2+、Pb2+及Mn2+等的2價的金屬陽離子;Al3+、Fe3+及Cr3+等的3價的金屬陽離子;Sn4+、Mn4+、Ce4+等的4價的金屬陽離子,更佳為可列舉Mg2+、Ca2+、Sr2+、Ba2+、Ni2+、Zn2+、Cu2+、Fe2+、Co2+、Sn2+、Mn2+、Al3+、Fe3+、Cr3+、Sn4+及Mn4+,進而佳為可列舉Mg2+、Ca2+、Sr2+、Ba2+、Zn2+、Cu2+、Fe2+、Mn2+、Al3+、Fe3+、Cr3+及Mn4+。 Examples of metal cations having a divalent or higher valence include cations of metals from Group 2 to Group 15 of the periodic table, preferably Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cd 2+ , and Ni. Divalent metal cations such as 2+ , Zn 2+ , Cu 2+ , Hg 2+ , Fe 2+ , Co 2+ , Sn 2+ , Pb 2+ and Mn 2+ ; Al 3+ , Fe 3+ and Trivalent metal cations such as Cr 3+ ; tetravalent metal cations such as Sn 4+ , Mn 4+ , Ce 4+ , more preferably Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ni 2+ , Zn 2+ , Cu 2+ , Fe 2+ , Co 2+ , Sn 2+ , Mn 2+ , Al 3+ , Fe 3+ , Cr 3+ , Sn 4+ and Mn 4+ , and then Preferably, Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cu 2+ , Fe 2+ , Mn 2+ , Al 3+ , Fe 3+ , Cr 3+ , and Mn 4 + .
再者,於Mb+為氫正離子的情況下,該氫正離子與-CO2 -或-S(O)2O-鍵結而作為-COOH或-S(O)2OH存在。 Furthermore, when M b+ is a positive hydride ion, the positive hydride ion is bonded to -CO 2 - or -S(O) 2 O- to exist as -COOH or -S(O) 2 OH.
a較佳為0~10的任一整數,更佳為0~5的任一整數, 進而佳為0或2~4的任一整數。 a is preferably any integer from 0 to 10, more preferably any integer from 0 to 5, More preferably, it is 0 or any integer of 2-4.
於式(I)所表示的化合物(B)的第1態樣中,R1~R6、R21、R22、Rna1、Rna2、Mb+、a較佳為如下。 In the first aspect of compound (B) represented by formula (I), R 1 to R 6 , R 21 , R 22 , R na1 , R na2 , M b+ , and a are preferably as follows.
作為R1,較佳為氫原子。 R 1 is preferably a hydrogen atom.
作為R2~R5,較佳為:氫原子;丁基等的碳數1~10的烷基;甲氧基等的碳數1~10的烷氧基;三氟甲基等的烷基中所含的氫原子全部經取代為氟原子而成的基團;氯原子、溴原子等的鹵素原子;硝基;-CO2 -;-S(O)2O-等。 R 2 to R 5 are preferably: a hydrogen atom; an alkyl group having 1 to 10 carbons such as a butyl group; an alkoxy group having 1 to 10 carbons such as a methoxy group; an alkyl group such as a trifluoromethyl group A group in which all the hydrogen atoms contained in are substituted with fluorine atoms; halogen atoms such as chlorine atoms and bromine atoms; nitro groups; -CO 2 - ; -S(O) 2 O - and the like.
作為R6,較佳為:-CO-ORna1、-CO-NH2、-CO-NH(Rna1)、-CO-N(Rna1)2或-CO-Rna1。 R 6 is preferably -CO-OR na1 , -CO-NH 2 , -CO-NH(R na1 ), -CO-N(R na1 ) 2 or -CO-R na1 .
於R21及R22未與各自所鍵結的碳原子一起形成環的情況下,作為R21,較佳為-CO-ORna2、-CO-NH2、-CO-NH(Rna2)、-CO-N(Rna2)2、-CO-H、-CO-Rna2或-S(O)2-Rna2,更佳為-CO-ORna2、-CO-NH2、-CO-NH(Rna2)、-CO-N(Rna2)2或-CO-Rna2,作為R22,較佳為可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基、硝基、-CO2 -或-S(O)2O-,更佳為氰基。該情況下,R6與R21較佳為同一基團。 When R 21 and R 22 do not form a ring together with the carbon atoms to which they are bonded, R 21 is preferably -CO-OR na2 , -CO-NH 2 , -CO-NH(R na2 ), -CO-N(R na2 ) 2 , -CO-H, -CO-R na2 or -S(O) 2 -R na2 , more preferably -CO-OR na2 , -CO-NH 2 , -CO-NH (R na2 ), -CO-N(R na2 ) 2 or -CO-R na2 , R 22 is preferably a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, Hydrogen atom, halogen atom, cyano group, nitro group, -CO 2 - or -S(O) 2 O - , more preferably cyano group. In this case, R 6 and R 21 are preferably the same group.
Rna2表示可具有取代基的碳數1~35的烴基、或可具有取代基的雜環基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna10-。其中,並未藉由取代-CH2-而形成-COOH及-S(O)2OH。Rna2的具體例及較佳的例子與Rna1相同。於存在多個Rna2的情況下,該些可相同亦 可不同。 R na2 represents a hydrocarbon group having 1 to 35 carbon atoms that may have a substituent, or a heterocyclic group that may have a substituent, and the hydrocarbon group contains -CH 2 - and the heterocyclic group includes -CH 2 that does not constitute a ring The -CH 2 - in - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na10 -. Wherein, -COOH and -S(O) 2 OH are not formed by substituting -CH 2 -. Specific examples and preferable examples of Rna2 are the same as those of Rna1 . Where multiple Rna2s are present, these may be the same or different.
於R21及R22與各自所鍵結的碳原子一起形成環的情況下,較佳為形成群組B的結構,更佳為形成式(2a-x)所表示的環。式(2a-x)中,作為R23及R24,較佳為氫原子。 When R 21 and R 22 form a ring together with the carbon atoms to which they are bonded, they preferably form a structure of Group B, and more preferably form a ring represented by formula (2a-x). In formula (2a-x), R 23 and R 24 are preferably hydrogen atoms.
R21及R22亦較佳為並未形成環。 R 21 and R 22 are also preferably not forming a ring.
作為Rna1、Rna2,較佳為:甲基、乙基、丁基等的碳數1~10的烷基;苯基、甲苯基、乙基苯基等的碳數6~10的芳香族烴基;苄基(亦稱作苯基甲基)、2-甲基苄基、3-甲基苄基、4-甲基苄基、苯基乙基、苯基丙基等的將鏈狀烴基與芳香族烴基組合而成的基團且為碳數7~15的基團等,該些基團可具有-CO2 -或-S(O)2O-,作為取代基,可具有甲氧基等的碳數1~10的烷氧基;甲氧基羰基等的鍵結有碳數1~10的烴基的氧基羰基;胺磺醯基;羥基;氯原子等的鹵素原子,較佳為具有-CO2 -、-S(O)2O-。 R na1 and R na2 are preferably: an alkyl group having 1 to 10 carbons such as methyl, ethyl, and butyl; an aromatic group having 6 to 10 carbons such as phenyl, tolyl, and ethylphenyl. Hydrocarbyl; benzyl (also known as phenylmethyl), 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, phenylethyl, phenylpropyl, etc. A group combined with an aromatic hydrocarbon group and a group with 7 to 15 carbon atoms, etc., these groups may have -CO 2 - or -S(O) 2 O - as a substituent, may have methoxy an alkoxy group with 1 to 10 carbon atoms such as a methoxycarbonyl group; an oxycarbonyl group bonded with a hydrocarbon group with 1 to 10 carbon atoms such as a methoxycarbonyl group; a sulfamoyl group; a hydroxyl group; a halogen atom such as a chlorine atom, preferably is -CO 2 - , -S(O) 2 O - .
作為Mb+,較佳為選自由氫正離子、Mg2+、Ca2+、Sr2+、Ba2+、Zn2+、Cu2+、Fe2+、Mn2+、Al3+、Fe3+、Cr3+及Mn4+所組成的群組中的一種,更佳為氫正離子。 M b+ is preferably selected from hydrogen cations, Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cu 2+ , Fe 2+ , Mn 2+ , Al 3+ , Fe 3+ , Cr 3+ and Mn 4+ in the group consisting of one, more preferably hydrogen cations.
作為a,較佳為1~10的任一整數,更佳為1~5的任一整數。亦較佳為a為0。 As a, any integer of 1-10 is preferable, and any integer of 1-5 is more preferable. It is also preferable that a is 0.
於式(I)所表示的化合物(B)的第2態樣的式(IIB)所表示的化合物中,R11b~R16b、R21b~R24b、Rnb1、Rnb5較佳為如下。 In the compound represented by formula (IIB) of the second aspect of compound (B) represented by formula (I), R 11b to R 16b , R 21b to R 24b , R nb1 , and R nb5 are preferably as follows.
作為R11b,較佳為氫原子。 R 11b is preferably a hydrogen atom.
作為R12b~R15b,較佳為:氫原子;丁基等的碳數1~10的烷基;甲氧基等的碳數1~10的烷氧基;三氟甲基等的烷基中所含的氫原子全部經取代為氟原子而成的基團;氯原子、溴原子等的鹵素原子;硝基等。 R 12b to R 15b are preferably: a hydrogen atom; an alkyl group having 1 to 10 carbons such as a butyl group; an alkoxy group having 1 to 10 carbons such as a methoxy group; an alkyl group such as a trifluoromethyl group A group in which all the hydrogen atoms contained in are substituted with fluorine atoms; halogen atoms such as chlorine atoms, bromine atoms, etc.; nitro groups, etc.
作為R16b,較佳為:-CO-ORnb1、-CO-NH2、-CO-NH(Rnb1)、-CO-N(Rnb1)2或-CO-Rnb1。 R 16b is preferably -CO-OR nb1 , -CO-NH 2 , -CO-NH(R nb1 ), -CO-N(R nb1 ) 2 or -CO-R nb1 .
於R21b及R22b未與各自所鍵結的碳原子一起形成環的情況下,作為R21b,較佳為-CO-ORnb5、-CO-NH2、-CO-NH(Rnb5)、-CO-N(Rnb5)2、-CO-H、-CO-Rnb5或-S(O)2-Rnb5,更佳為-CO-ORnb5、-CO-NH2、-CO-NH(Rnb5)、-CO-N(Rnb5)2或-CO-Rnb5,作為R22b,較佳為可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,更佳為氰基。該情況下,R16b與R21b較佳為同一基團。 When R 21b and R 22b do not form a ring together with the carbon atoms to which they are bonded, R 21b is preferably -CO-OR nb5 , -CO-NH 2 , -CO-NH(R nb5 ), -CO-N(R nb5 ) 2 , -CO-H, -CO-R nb5 or -S(O) 2 -R nb5 , more preferably -CO-OR nb5 , -CO-NH 2 , -CO-NH (R nb5 ), -CO-N(R nb5 ) 2 or -CO-R nb5 , R 22b is preferably a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, A hydrogen atom, a halogen atom, a cyano group or a nitro group, more preferably a cyano group. In this case, R 16b and R 21b are preferably the same group.
Rnb5表示可具有取代基的碳數1~35的烴基、或可具有取代基的雜環基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb10-。其中,並未藉由取代-CH2-而形成-COOH及-S(O)2OH。Rnb5的具體例及較佳的例子與Rnb1相同。於存在多個Rnb5的情況下,該些可相同亦可不同。 R nb5 represents a hydrocarbon group having 1 to 35 carbon atoms that may have a substituent, or a heterocyclic group that may have a substituent, and -CH 2 - contained in the hydrocarbon group and the heterocyclic group include -CH 2 that does not constitute a ring The -CH 2 - in the case of - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb10 -. Wherein, -COOH and -S(O) 2 OH are not formed by substituting -CH 2 -. Specific examples and preferred examples of Rnb5 are the same as those of Rnb1 . When there are multiple Rnb5s , these may be the same or different.
於R21b及R22b與各自所鍵結的碳原子一起形成環的情況下,較佳為形成群組C的結構,更佳為形成式(2a-xb)所表示的環。式(2a-xb)中,作為R23b及R24b,較佳為氫原子。 When R 21b and R 22b form a ring together with the carbon atoms to which they are bonded, they preferably form a structure of Group C, and more preferably form a ring represented by formula (2a-xb). In formula (2a-xb), R 23b and R 24b are preferably hydrogen atoms.
R21b及R22b亦較佳為並未形成環。 R 21b and R 22b are also preferably not forming a ring.
作為Rnb1、Rnb5,較佳為:甲基、乙基、丁基等的碳數1~10的烷基;苯基、甲苯基、乙基苯基等的碳數6~10的芳香族烴基;苯基甲基、2-甲基苄基、3-甲基苄基、4-甲基苄基、苯基乙基、苯基丙基等的將鏈狀烴基與芳香族烴基組合而成的基團且為碳數7~15的基團等,該些基團中,作為取代基,可具有甲氧基等的碳數1~10的烷氧基;甲氧基羰基等鍵結有碳數1~10的烴基的氧基羰基;胺磺醯基;羥基;氯原子等的鹵素原子。 R nb1 and R nb5 are preferably: an alkyl group having 1 to 10 carbons such as methyl, ethyl, or butyl; an aromatic group having 6 to 10 carbons such as phenyl, tolyl, or ethylphenyl. Hydrocarbyl; phenylmethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, phenylethyl, phenylpropyl, etc. are composed of a chain hydrocarbon group and an aromatic hydrocarbon group and it is a group with 7 to 15 carbons, etc., among these groups, as a substituent, there may be an alkoxy group with 1 to 10 carbons such as methoxy; Oxycarbonyl group of hydrocarbon group with 1 to 10 carbons; sulfamoyl group; hydroxyl group; halogen atom such as chlorine atom.
於式(I)所表示的化合物(B)的第3態樣的式(IA)所表示的化合物中,R1a~R9a、Rna4、Mb+、a較佳為如下。 In the compound represented by the formula (IA) of the third aspect of the compound (B) represented by the formula (I), R 1a to R 9a , R na4 , M b+ , and a are preferably as follows.
作為R1a,較佳為氫原子。 R 1a is preferably a hydrogen atom.
作為R2a~R5a,較佳為:氫原子;丁基等的碳數1~10的烷基;甲氧基等的碳數1~10的烷氧基;三氟甲基等的烷基中所含的氫原子全部經取代為氟原子而成的基團;氯原子、溴原子等的鹵素原子;硝基;-CO2 -;-S(O)2O-等。 R 2a to R 5a are preferably: a hydrogen atom; an alkyl group having 1 to 10 carbons such as a butyl group; an alkoxy group having 1 to 10 carbons such as a methoxy group; an alkyl group such as a trifluoromethyl group A group in which all the hydrogen atoms contained in are substituted with fluorine atoms; halogen atoms such as chlorine atoms and bromine atoms; nitro groups; -CO 2 - ; -S(O) 2 O - and the like.
作為R6a,較佳為-COO-、-CO-ORna4、-CO-NH2、-CO-NH(Rna4)、-CO-N(Rna4)2、-CO-H、-CO-Rna4或-S(O)2-Rna4,更佳為-CO-ORna4、-CO-NH2、-CO-NH(Rna4)、-CO-N(Rna4)2或-CO-Rna4。 R 6a is preferably -COO - , -CO-OR na4 , -CO-NH 2 , -CO-NH(R na4 ), -CO-N(R na4 ) 2 , -CO-H, -CO- R na4 or -S(O) 2 -R na4 , more preferably -CO-OR na4 , -CO-NH 2 , -CO-NH(R na4 ), -CO-N(R na4 ) 2 or -CO- Rna4 .
Rna4表示可具有取代基的碳數1~35的烴基、或可具有取代基的雜環基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRna10-。其中,並未藉由取代-CH2-而形成-COOH及-S(O)2OH。Rna4的具體例及較 佳的例子與Rna1相同。於存在多個Rna4的情況下,該些可相同亦可不同。 R na4 represents a hydrocarbon group having 1 to 35 carbon atoms that may have a substituent, or a heterocyclic group that may have a substituent, and -CH 2 - contained in the hydrocarbon group and -CH 2 that does not constitute a ring in the heterocyclic group include The -CH 2 - in - may be substituted with -O-, -CO-, -S(O) 2 - or -NR na10 -. Wherein, -COOH and -S(O) 2 OH are not formed by substituting -CH 2 -. Specific examples and preferred examples of Rna4 are the same as those of Rna1 . Where multiple Rna4s are present, these may be the same or different.
作為R7a,較佳為可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基、硝基、-CO2 -或-S(O)2O-,更佳為氰基。 R 7a is preferably a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group, a nitro group, -CO 2 - or -S(O ) 2 O - , more preferably cyano.
於R8a及R9a未與各自所鍵結的碳原子一起形成環的情況下,作為R8a,較佳為-COO-、-CO-ORna4、-CO-NH2、-CO-NH(Rna4)、-CO-N(Rna4)2、-CO-H、-CO-Rna4或-S(O)2-Rna4,更佳為-CO-ORna4、-CO-NH2、-CO-NH(Rna4)、-CO-N(Rna4)2或-CO-Rna4,作為R7a,較佳為可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基、硝基、-CO2 -或-S(O)2O-,更佳為氰基。該情況下,R6a與R8a較佳為同一基團。 When R 8a and R 9a do not form a ring together with the carbon atoms to which they are bonded, R 8a is preferably -COO - , -CO-OR na4 , -CO-NH 2 , -CO-NH( R na4 ), -CO-N(R na4 ) 2 , -CO-H, -CO-R na4 or -S(O) 2 -R na4 , more preferably -CO-OR na4 , -CO-NH 2 , -CO-NH(R na4 ), -CO-N(R na4 ) 2 or -CO-R na4 , R 7a is preferably a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a substituent Heterocyclic group, hydrogen atom, halogen atom, cyano group, nitro group, -CO 2 - or -S(O) 2 O - , more preferably cyano group. In this case, R 6a and R 8a are preferably the same group.
於R8a及R9a與各自所鍵結的碳原子一起形成環的情況下,較佳為形成群組A的結構,更佳為形成式(QQ18)所表示的環。式(QQ18)中,作為R25及R26,較佳為氫原子。 When R 8a and R 9a form a ring together with the carbon atoms to which they are bonded, they preferably form a structure of Group A, and more preferably form a ring represented by formula (QQ18). In formula (QQ18), R 25 and R 26 are preferably hydrogen atoms.
R8a及R9a亦較佳為並未形成環。 R 8a and R 9a are also preferably not forming a ring.
作為Rna4,較佳為:甲基、乙基、丁基等的碳數1~10的烷基;苯基、甲苯基、乙基苯基等的碳數6~10的芳香族烴基;苯基甲基、2-甲基苄基、3-甲基苄基、4-甲基苄基、苯基乙基、苯基丙基等的將鏈狀烴基與芳香族烴基組合而成的基團且為碳數7~15的基團等,該些基團可具有-CO2 -或-S(O)2O-,作為取代基,可具有甲氧基等的碳數1~10的烷氧基;甲氧基羰基等的鍵結有碳 數1~10的烴基的氧基羰基;胺磺醯基;羥基;氯原子等的鹵素原子,較佳為具有-CO2 -、-S(O)2O-。 R na4 is preferably: an alkyl group having 1 to 10 carbons such as methyl, ethyl, and butyl; an aromatic hydrocarbon group having 6 to 10 carbons such as phenyl, tolyl, and ethylphenyl; A group composed of a chain hydrocarbon group and an aromatic hydrocarbon group such as methyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, phenylethyl, phenylpropyl, etc. And it is a group having 7 to 15 carbons, etc. These groups may have -CO 2 - or -S(O) 2 O - , and as a substituent, may have an alkane having 1 to 10 carbons such as methoxy Oxygen group; Oxycarbonyl group bonded with a hydrocarbon group having 1 to 10 carbon atoms such as methoxycarbonyl group; Sulfamoyl group; Hydroxyl group; Halogen atom such as chlorine atom, preferably having -CO 2 - , -S( O) 2 O - .
作為Mb+,較佳為選自由氫正離子、Mg2+、Ca2+、Sr2+、Ba2+、Zn2+、Cu2+、Fe2+、Mn2+、Al3+、Fe3+、Cr3+及Mn4+所組成的群組中的一種,更佳為氫正離子。 M b+ is preferably selected from hydrogen cations, Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cu 2+ , Fe 2+ , Mn 2+ , Al 3+ , Fe 3+ , Cr 3+ and Mn 4+ in the group consisting of one, more preferably hydrogen cations.
作為a,較佳為1~5的任一整數。 As a, any integer of 1-5 is preferable.
於式(I)所表示的化合物(B)的第4態樣的式(IB)所表示的化合物中,R1b~R7b、R17b~R18b、Rnb1、Rnb6較佳為如下。 In the compound represented by formula (IB) of the fourth aspect of compound (B) represented by formula (I), R 1b ~ R 7b , R 17b ~ R 18b , R nb1 , R nb6 are preferably as follows.
作為R1b,較佳為氫原子。 R 1b is preferably a hydrogen atom.
作為R2b~R5b,較佳為:氫原子;丁基等的碳數1~10的烷基;甲氧基等的碳數1~10的烷氧基;三氟甲基等的烷基中所含的氫原子全部經取代為氟原子而成的基團;氯原子、溴原子等的鹵素原子;硝基等。 R 2b to R 5b are preferably: a hydrogen atom; an alkyl group having 1 to 10 carbons such as a butyl group; an alkoxy group having 1 to 10 carbons such as a methoxy group; an alkyl group such as a trifluoromethyl group A group in which all the hydrogen atoms contained in are substituted with fluorine atoms; halogen atoms such as chlorine atoms, bromine atoms, etc.; nitro groups, etc.
作為R6b,較佳為:-CO-ORnb1、-CO-NH2、-CO-NH(Rnb1)、-CO-N(Rnb1)2或-CO-Rnb1。 R 6b is preferably -CO-OR nb1 , -CO-NH 2 , -CO-NH(R nb1 ), -CO-N(R nb1 ) 2 or -CO-R nb1 .
作為R7b,較佳為可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基、硝基、-CO2 -或-S(O)2O-,更佳為氰基。 R 7b is preferably a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group, a nitro group, -CO 2 - or -S(O ) 2 O - , more preferably cyano.
於R17b及R18b未與各自所鍵結的碳原子一起形成環的情況下,作為R17b,較佳為-CO-ORnb6、-CO-NH2、-CO-NH(Rnb6)、-CO-N(Rnb6)2、-CO-H、-CO-Rnb6或-S(O)2-Rnb6,更佳為-CO-ORnb6、-CO-NH2、-CO-NH(Rnb6)、-CO-N(Rnb6)2或-CO-Rnb6,作為R18b, 較佳為可具有取代基的碳數1~40的烴基、可具有取代基的雜環基、氫原子、鹵素原子、氰基或硝基,更佳為氰基。該情況下,R6b與R17b較佳為同一基團。 When R 17b and R 18b do not form a ring together with the carbon atoms to which they are bonded, R 17b is preferably -CO-OR nb6 , -CO-NH 2 , -CO-NH(R nb6 ), -CO-N(R nb6 ) 2 , -CO-H, -CO-R nb6 or -S(O) 2 -R nb6 , more preferably -CO-OR nb6 , -CO-NH 2 , -CO-NH (R nb6 ), -CO-N(R nb6 ) 2 or -CO-R nb6 , R 18b is preferably a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, A hydrogen atom, a halogen atom, a cyano group or a nitro group, more preferably a cyano group. In this case, R 6b and R 17b are preferably the same group.
Rnb6表示可具有取代基的碳數1~35的烴基、或可具有取代基的雜環基,該烴基中所含的-CH2-及該雜環基包含並未構成環的-CH2-時的該-CH2-可經取代為-O-、-CO-、-S(O)2-或-NRnb10-。其中,並未藉由取代-CH2-而形成-COOH及-S(O)2OH。Rnb6的具體例及較佳的例子與Rnb1相同。於存在多個Rnb6的情況下,該些可相同亦可不同。 R nb6 represents a hydrocarbon group having 1 to 35 carbon atoms that may have a substituent, or a heterocyclic group that may have a substituent, and the -CH 2 - contained in the hydrocarbon group and the heterocyclic group include -CH 2 that does not constitute a ring The -CH 2 - in the case of - may be substituted with -O-, -CO-, -S(O) 2 - or -NR nb10 -. Wherein, -COOH and -S(O) 2 OH are not formed by substituting -CH 2 -. Specific examples and preferred examples of Rnb6 are the same as those of Rnb1 . When there are multiple Rnb6s , these may be the same or different.
於R17b及R18b與各自所鍵結的碳原子一起形成環的情況下,較佳為形成群組C的結構,更佳為形成式(2a)所表示的環。式(2a)中,作為R19b及R20b,較佳為氫原子。 When R 17b and R 18b form a ring together with the carbon atoms to which they are bonded, they preferably form a structure of Group C, and more preferably form a ring represented by formula (2a). In formula (2a), R 19b and R 20b are preferably hydrogen atoms.
R17b及R18b亦較佳為並未形成環。 R 17b and R 18b are also preferably not forming a ring.
作為Rnb1、Rnb6,較佳為:甲基、乙基、丁基等的碳數1~10的烷基;苯基、甲苯基、乙基苯基等的碳數6~10的芳香族烴基;苯基甲基、2-甲基苄基、3-甲基苄基、4-甲基苄基、苯基乙基、苯基丙基等的將鏈狀烴基與芳香族烴基組合而成的基團且為碳數7~15的基團等,該些基團中,作為取代基,可具有甲氧基等的碳數1~10的烷氧基;甲氧基羰基等的鍵結有碳數1~10的烴基的氧基羰基;胺磺醯基;羥基;氯原子等的鹵素原子。 R nb1 and R nb6 are preferably: an alkyl group having 1 to 10 carbons such as methyl, ethyl, or butyl; an aromatic group having 6 to 10 carbons such as phenyl, tolyl, or ethylphenyl. Hydrocarbyl; phenylmethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, phenylethyl, phenylpropyl, etc. are composed of a chain hydrocarbon group and an aromatic hydrocarbon group and a group with 7 to 15 carbons, etc., among these groups, as a substituent, there may be an alkoxy group with 1 to 10 carbons such as a methoxy group; a bond such as a methoxycarbonyl group Oxycarbonyl group having a hydrocarbon group with 1 to 10 carbons; sulfamoyl group; hydroxyl group; halogen atom such as chlorine atom.
作為-CO-ORna1、-CO-ORna2、-CO-ORnb1、-CO-ORnb5、-CO-ORna4、-CO-ORnb6,較佳為甲氧基羰基、乙氧基羰基等的鍵結 有烷基的碳數為1~10的烴基(尤其為烷基)的氧基羰基。 -CO-OR na1 , -CO-OR na2 , -CO-OR nb1 , -CO-OR nb5 , -CO-OR na4 , -CO-OR nb6 , preferably methoxycarbonyl, ethoxycarbonyl, etc. An oxycarbonyl group of a hydrocarbon group (especially an alkyl group) having 1 to 10 carbon atoms bonded to an alkyl group.
作為-CO-Rna1、-CO-Rna2、-CO-Rnb1、-CO-Rnb5、-CO-Rna4、-CO-Rnb6,較佳為:苯甲醯基等的鍵結有碳數6~10的芳香族環的羰基;乙基羰基、丁基羰基等的鍵結有碳數1~10的烷基的羰基;苯基甲基羰基、苯基乙基羰基、苯基丙基羰基等的鍵結有與碳數1~10的芳香族環鍵結的碳數1~10的烷基的羰基。 As -CO-R na1 , -CO-R na2 , -CO-R nb1 , -CO-R nb5 , -CO-R na4 , -CO-R nb6 , preferably a bond such as a benzoyl group is Carbonyl of an aromatic ring with 6 to 10 carbons; ethylcarbonyl, butylcarbonyl and other carbonyls bonded to an alkyl group with 1 to 10 carbons; phenylmethylcarbonyl, phenylethylcarbonyl, phenylpropyl A carbonyl group having an alkyl group having 1 to 10 carbons bonded to an aromatic ring having 1 to 10 carbons such as a carbonyl carbonyl group.
-CO-Rna1、-CO-Rna2、-CO-Rna4的Rna1、Rna2、Rna4可具有-CO2 -或-S(O)2O-,作為取代基,可具有甲氧基等的碳數1~10的烷氧基;甲氧基羰基等的鍵結有碳數1~10的烴基的氧基羰基;胺磺醯基;羥基;氯原子等的鹵素原子,於鍵結有該芳香族環的羰基;鍵結有烷基的羰基;鍵結有鍵結於芳香族環的烷基的羰基等的碳原子上亦可鍵結有-CO2 -;-S(O)2O-;甲氧基等的碳數1~10的烷氧基;甲氧基羰基等的鍵結有碳數1~10的烴基的氧基羰基;胺磺醯基;羥基;氯原子等的鹵素原子等。 R na1 , R na2 , R na4 of -CO-R na1 , -CO-R na2 , -CO-R na4 may have -CO 2 - or -S(O) 2 O - as a substituent, may have methoxy An alkoxy group with 1 to 10 carbons such as a group; an oxycarbonyl group bonded with a hydrocarbon group with 1 to 10 carbons such as a methoxycarbonyl group; a sulfamoyl group; a hydroxyl group; a halogen atom such as a chlorine atom, in a bond The carbonyl group with the aromatic ring; the carbonyl group with the alkyl group; the carbonyl group with the alkyl group bonded to the aromatic ring, etc. -CO 2 - may also be bonded to the carbon atom; -S(O ) 2 O - ; alkoxy groups with 1 to 10 carbon atoms such as methoxy; oxycarbonyl groups bonded with hydrocarbon groups with 1 to 10 carbon atoms such as methoxycarbonyl; sulfamoyl group; hydroxyl group; chlorine atom Halogen atoms, etc.
作為-CO-NH(Rna1)、-CO-NH(Rna2)、-CO-NH(Rnb1)、-CO-NH(Rnb5)、-CO-NH(Rna4)、-CO-NH(Rnb6),較佳為甲基胺基羰基等的鍵結有碳數1~10的烷基的胺基羰基。另外,於該鍵結有烷基的胺基羰基、鍵結有芳香族烴環的胺基羰基等的碳原子上亦可鍵結-CO2 -。 As -CO-NH(R na1 ), -CO-NH(R na2 ), -CO-NH(R nb1 ), -CO-NH(R nb5 ), -CO-NH(R na4 ), -CO-NH (R nb6 ), preferably an aminocarbonyl group to which an alkyl group having 1 to 10 carbon atoms is bonded, such as a methylaminocarbonyl group. In addition, -CO 2 - may be bonded to a carbon atom such as the aminocarbonyl group bonded to an alkyl group or the aminocarbonyl group bonded to an aromatic hydrocarbon ring.
作為-CO-N(Rna1)2、-CO-N(Rna2)2、-CO-N(Rnb1)2、-CO-N(Rnb5)2、-CO-N(Rna4)2、-CO-N(Rnb6)2,較佳為二甲基胺基羰基等的鍵結有2個碳數1~10的烷基的胺基羰基。 As -CO-N(R na1 ) 2 , -CO-N(R na2 ) 2 , -CO-N(R nb1 ) 2 , -CO-N(R nb5 ) 2 , -CO-N(R na4 ) 2 , -CO-N(R nb6 ) 2 , preferably an aminocarbonyl group in which two alkyl groups having 1 to 10 carbons are bonded, such as a dimethylaminocarbonyl group.
〔2-6〕式(I)所表示的化合物(B)的具體例 [2-6] Specific examples of compound (B) represented by formula (I)
式(I)所表示的化合物(B)的較佳態樣之一為所述〔2-3〕中敘述的第3態樣。第3態樣中較佳為,式(IA)中的aa為2,R1a為氫原子,R6a及R7a中的一者為氰基,R8a及R9a中的一者為氰基,Mb+為氫正離子,b為1,ma為2,na為1。 One of the preferred aspects of the compound (B) represented by the formula (I) is the third aspect described in [2-3]. Preferably in the third aspect, aa in formula (IA) is 2, R 1a is a hydrogen atom, one of R 6a and R 7a is a cyano group, and one of R 8a and R 9a is a cyano group , M b+ is a positive hydrogen ion, b is 1, ma is 2, and na is 1.
式(I)所表示的化合物(B)的更佳的一例為式(P)所表示的化合物。 A more preferable example of the compound (B) represented by formula (I) is a compound represented by formula (P).
[式(P)中,L4及L5相互獨立地表示碳數1~10的2價烴基,於該烴基包含-CH2-的情況下,該-CH2-亦可經取代為-NH-。RP表示氫原子或取代基,p表示1~4的任一整數。波浪線表示E體、Z體、或該兩者。] [In formula (P), L 4 and L 5 independently represent a divalent hydrocarbon group with 1 to 10 carbon atoms, and when the hydrocarbon group contains -CH 2 -, the -CH 2 - may also be substituted with -NH -. R P represents a hydrogen atom or a substituent, and p represents any integer from 1 to 4. Wavy lines indicate E bodies, Z bodies, or both. ]
作為所述2價烴基,例如可列舉:伸烷基、伸芳基(例如伸苯基)。 As said divalent hydrocarbon group, an alkylene group and an arylylene group (for example, a phenylene group) are mentioned, for example.
式(I)所表示的化合物(B)的更佳的另一例為式(P)中2個COOH基經取代為-S(O)2OH基而成的化合物。 Another more preferable example of the compound (B) represented by the formula (I) is a compound in which two COOH groups in the formula (P) are substituted with -S(O) 2 OH groups.
作為式(I)、式(IA)、式(IB)或式(IIB)所表示的 化合物的具體例,例如可列舉:於下述式(Ia)所表示的化合物中,R31、L1、L2、R32、B1B2、n、m及Mb+的組合為表1~表4中記載的任一者的化合物、以及於下述式(Ib)所表示的化合物中,R33、L3、B1B2、n、m及Mb+的組合為表5~表6中記載的任一者的化合物。 Specific examples of compounds represented by formula (I), formula (IA), formula (IB) or formula (IIB) include, for example, among compounds represented by the following formula (Ia), R 31 , L 1 , L 2 , R 32 , B 1 B 2 , n, m, and M b+ are any compound described in Table 1 to Table 4, and in the compound represented by the following formula (Ib), R The combination of 33 , L 3 , B 1 B 2 , n, m, and M b+ is any compound described in Table 5 to Table 6.
再者,R31、R32、R33表示式(HH1)~式(HH18)所表示的任一部分結構。B1B2表示式(BB1)~式(BB9)所表示的任一部分結構。 Furthermore, R 31 , R 32 , and R 33 represent any partial structure represented by formula (HH1) to formula (HH18). B 1 B 2 represents any partial structure represented by formula (BB1) to formula (BB9).
[式中,波浪線表示E體、Z體、或該兩者。] [In the formula, the wavy line represents the E body, the Z body, or both. ]
[表1]
表中示出的化合物中,較佳為化合物編號28~31、37 ~40、46~49、55~58、73~76、82~85、91~94、136~139、154~157、190~193、199~202、208~211、244~247、298~301的化合物。 Among the compounds shown in the table, compound numbers 28-31, 37 are preferred ~40, 46~49, 55~58, 73~76, 82~85, 91~94, 136~139, 154~157, 190~193, 199~202, 208~211, 244~247, 298~301 compound of.
〔2-7〕式(I)所表示的化合物(B)的製造方法 [2-7] Method for producing compound (B) represented by formula (I)
式(I)所表示的化合物(B)可藉由如下方式製造:於R1為氫原子時,使式(pt1)所表示的化合物(以下,有時稱作鄰苯二甲腈化合物)與式(pt2)所表示的化合物(以下,有時稱作烷氧化物化合物)反應後,使式(pt3)所表示的化合物(以下,有時稱作化合物(pt3))與式(pt4)所表示的化合物(以下,有時稱作化合物(pt4))進而於酸存在下反應。 The compound (B) represented by the formula (I) can be produced in the following manner: when R 1 is a hydrogen atom, the compound represented by the formula (pt1) (hereinafter sometimes referred to as a phthalonitrile compound) and After the compound represented by formula (pt2) (hereinafter, sometimes referred to as an alkoxide compound) is reacted, the compound represented by formula (pt3) (hereinafter, sometimes referred to as compound (pt3)) is reacted with the compound represented by formula (pt4). The represented compound (hereinafter, may be referred to as compound (pt4)) is further reacted in the presence of an acid.
[式(pt1)~式(pt8)及式(1)中,R1~R7、X、Mb+、a、m、及n表示與前述相同的含義。 [In formula (pt1) to formula (pt8) and formula (1), R 1 to R 7 , X, M b+ , a, m, and n have the same meanings as above.
R41及R42相互獨立地表示氫原子或碳數1~20的烷基。 R 41 and R 42 independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
M1及M2表示鹼金屬原子。 M 1 and M 2 represent alkali metal atoms.
LG1及LG2相互獨立地表示鹵素原子、甲磺醯基氧基、氯甲基磺醯基氧基、甲苯磺醯基氧基或三氟甲磺醯基氧基。 LG 1 and LG 2 independently represent a halogen atom, methanesulfonyloxy, chloromethylsulfonyloxy, tosyloxy or trifluoromethanesulfonyloxy.
M表示金屬原子。] M represents a metal atom. ]
作為R41、R42所表示的碳數1~20的烷基,可列舉甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基及第三丁基等,較佳為可列舉碳數1~6的烷基。 Examples of the alkyl group having 1 to 20 carbon atoms represented by R 41 and R 42 include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl and third butyl, etc. , preferably an alkyl group having 1 to 6 carbon atoms.
作為M1、M2所表示的鹼金屬原子,可列舉:鋰原子、鈉原子及鉀原子。 Examples of the alkali metal atom represented by M 1 and M 2 include a lithium atom, a sodium atom, and a potassium atom.
相對於式(pt1)所表示的鄰苯二甲腈化合物1莫耳,式(pt2)所表示的烷氧化物化合物的使用量通常為0.1莫耳以上且10莫耳以下,較佳為0.2莫耳以上且5莫耳以下,更佳為0.3莫耳以上且3莫耳以下,進而佳為0.4莫耳以上且2莫耳以下。 The amount of the alkoxide compound represented by the formula (pt2) used is usually 0.1 mole or more and 10 mole or less, preferably 0.2 mole per 1 mole of the phthalonitrile compound represented by the formula (pt1). It is not less than 5 moles and not more than 5 moles, more preferably not less than 0.3 moles and not more than 3 moles, and still more preferably not less than 0.4 moles and not more than 2 moles.
相對於式(pt1)所表示的鄰苯二甲腈化合物1莫耳,化合物(pt3)及化合物(pt4)的使用量的合計通常為2莫耳以上且20莫耳以下,較佳為2莫耳以上且10莫耳以下,更佳為2莫耳以上且6莫耳以下,進而佳為2莫耳以上且4莫耳以下。再者,化合物(pt3)與化合物(pt4)亦可為相同的化合物。 The total amount of compound (pt3) and compound (pt4) used is usually 2 moles or more and 20 moles or less, preferably 2 moles per 1 mole of the phthalonitrile compound represented by formula (pt1). It is more than one mole and not more than 10 moles, more preferably not less than 2 moles and not more than 6 moles, and still more preferably not less than 2 moles and not more than 4 moles. In addition, compound (pt3) and compound (pt4) may be the same compound.
作為酸,可列舉:鹽酸、氫溴酸、氫碘酸、硫酸、硝酸、氟磺酸、磷酸等的無機酸;甲磺酸、三氟甲磺酸及對甲苯磺酸等的磺酸;乙酸、檸檬酸、甲酸、葡萄糖酸、乳酸、乙二酸及酒石酸等的羧酸,較佳為可列舉:鹽酸、氫溴酸、硫酸、甲磺酸、三 氟甲磺酸、對甲苯磺酸及羧酸,更佳為可列舉乙酸。 Examples of the acid include: inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, fluorosulfonic acid, and phosphoric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; acetic acid , citric acid, formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid, etc., preferably carboxylic acids such as hydrochloric acid, hydrobromic acid, sulfuric acid, methanesulfonic acid, tris Fluoromethanesulfonic acid, p-toluenesulfonic acid, and carboxylic acid, more preferably acetic acid.
相對於鄰苯二甲腈化合物1莫耳,酸的使用量通常為1莫耳以上且20莫耳以下,較佳為1莫耳以上且10莫耳以下,更佳為1莫耳以上且8莫耳以下,進而佳為1莫耳以上且6莫耳以下。 The amount of the acid used is usually not less than 1 mole and not more than 20 moles, preferably not less than 1 mole and not more than 10 moles, more preferably not less than 1 mole and not more than 8 moles, relative to 1 mole of the phthalonitrile compound. It is not more than 1 mole, and more preferably not less than 1 mole and not more than 6 moles.
鄰苯二甲腈化合物、烷氧化物化合物、化合物(pt3)及化合物(pt4)的反應通常於溶媒存在下實施。 The reaction of the phthalonitrile compound, the alkoxide compound, the compound (pt3) and the compound (pt4) is usually carried out in the presence of a solvent.
作為溶媒,可列舉:水;乙腈等的腈溶媒;甲醇、乙醇、2-丙醇、1-丁醇、1-戊醇及1-辛醇等的醇溶媒;四氫呋喃等的醚溶媒;丙酮等的酮溶媒;乙酸乙酯等的酯溶媒;己烷等的脂肪族烴溶媒;甲苯等的芳香族烴溶媒;亞甲基氯(methylene chloride)及氯仿等的鹵化烴溶媒;N,N-二甲基甲醯胺及N-甲基吡咯啶酮等的醯胺溶媒;二甲基亞碸等的亞碸溶媒,較佳為可列舉:水、腈溶媒、醇溶媒、醚溶媒、酮溶媒、酯溶媒、芳香族烴溶媒、鹵化烴溶媒、醯胺溶媒及亞碸溶媒,更佳為可列舉:水、乙腈、甲醇、乙醇、2-丙醇、1-丁醇、1-戊醇、1-辛醇、四氫呋喃、丙酮、乙酸乙酯、甲苯、亞甲基氯、氯仿、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基吡咯啶酮、1,3-二甲基-2-咪唑啶酮及1,3-二甲基-3,4,5,6-四氫-2(1H)-嘧啶酮及二甲基亞碸,進而佳為可列舉:水、乙腈、甲醇、乙醇、2-丙醇、1-丁醇、1-戊醇、1-辛醇、丙酮、亞甲基氯、氯仿、N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、1,3-二甲基-2-咪唑啶酮及1,3-二甲基-3,4,5,6-四氫-2(1H)-嘧啶酮、N-甲基吡咯啶酮及二甲基亞碸,特佳為可列舉:水、乙腈、甲醇、乙醇、2-丙醇、 N-甲基吡咯啶酮及二甲基亞碸。 Examples of the solvent include water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, and 1-octanol; ether solvents such as tetrahydrofuran; acetone, etc. ketone solvents such as ethyl acetate; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride and chloroform; Amide solvents such as methylformamide and N-methylpyrrolidone; and amide solvents such as dimethylsulfide, preferably water, nitrile solvents, alcohol solvents, ether solvents, ketone solvents, Ester solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents, and ethylene oxide solvents, more preferably water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1 -octanol, tetrahydrofuran, acetone, ethyl acetate, toluene, methylene chloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone , 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone and dimethylsulfoxide, and further preferred Examples include: water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, methylene chloride, chloroform, N,N-dimethylformamide Amine, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H) -pyrimidinone, N-methylpyrrolidone, and dimethylsulfoxide, particularly preferably, water, acetonitrile, methanol, ethanol, 2-propanol, N-methylpyrrolidone and dimethylsulfoxide.
相對於鄰苯二甲腈化合物1質量份,溶媒的使用量通常為1質量份以上且1000質量份以下。 The usage-amount of a solvent is 1 mass part or more and 1000 mass parts or less normally with respect to 1 mass part of phthalonitrile compounds.
鄰苯二甲腈化合物、烷氧化物化合物、化合物(pt3)及化合物(pt4)的反應溫度通常為0℃以上且200℃以下,較佳為0℃以上且100℃以下,更佳為0℃以上且50℃以下。反應時間通常為0.5小時以上且300小時以下。 The reaction temperature of the phthalonitrile compound, the alkoxide compound, the compound (pt3) and the compound (pt4) is usually 0°C to 200°C, preferably 0°C to 100°C, more preferably 0°C Above and below 50°C. The reaction time is usually not less than 0.5 hours and not more than 300 hours.
進而,藉由使化合物(pt6)反應,可獲得R1並非氫原子的式(I)所表示的化合物(B)。相對於R1為氫原子的式(I)所表示的化合物(B)1莫耳,化合物(pt6)的使用量通常為1莫耳以上且10莫耳以下,較佳為1莫耳以上且5莫耳以下,更佳為1莫耳以上且3莫耳以下,進而佳為1莫耳以上且2莫耳以下。 Furthermore, compound (B) represented by formula (I) in which R 1 is not a hydrogen atom can be obtained by reacting compound (pt6). Relative to 1 mole of the compound (B) represented by the formula (I) in which R is a hydrogen atom, the amount of the compound (pt6) used is usually 1 mole or more and 10 moles or less, preferably 1 mole or more and 5 mol or less, more preferably 1 mol or more and 3 mol or less, still more preferably 1 mol or more and 2 mol or less.
於使化合物(pt6)反應的情況下,較佳為使鹼共存。作為鹼,可列舉:三乙基胺、4-(N,N-二甲基胺基)吡啶、吡啶、哌啶等的有機鹼;甲氧化鈉、乙氧化鈉、第三丁氧化鈉、第三丁氧化鉀等的金屬烷氧化物;丁基鋰、第三丁基鋰及苯基鋰等的有機金屬化合物;氫氧化鋰、氫氧化鈉及氫氧化鉀等的無機鹼。 When making compound (pt6) react, it is preferable to make a base coexist. Examples of the base include organic bases such as triethylamine, 4-(N,N-dimethylamino)pyridine, pyridine, and piperidine; sodium methoxide, sodium ethoxide, sodium tert-butoxide, Metal alkoxides such as potassium tributoxide; organometallic compounds such as butyllithium, tert-butyllithium, and phenyllithium; inorganic bases such as lithium hydroxide, sodium hydroxide, and potassium hydroxide.
相對於R1為氫原子的式(I)所表示的化合物(B)1莫耳,鹼的使用量通常為1莫耳以上且10莫耳以下,較佳為1莫耳以上且5莫耳以下,更佳為1莫耳以上且3莫耳以下,進而佳為1莫耳以上且2莫耳以下。 With respect to 1 mole of the compound (B) represented by the formula (I) in which R is a hydrogen atom, the amount of the base used is usually from 1 mole to 10 moles, preferably from 1 mole to 5 moles. or less, more preferably from 1 mole to 3 moles, still more preferably from 1 mole to 2 moles.
另外,化合物(pt6)的反應通常於溶媒存在下實施。溶 媒可自與前述相同的範圍內選擇。 In addition, the reaction of compound (pt6) is usually carried out in the presence of a solvent. dissolve The media can be selected from the same range as described above.
相對於R1並非氫原子的式(I)所表示的化合物(B)1質量份,溶媒的使用量通常為1質量份以上且1000質量份以下。與化合物(pt6)的反應溫度通常為-90℃以上且200℃以下,較佳為-80℃以上且100℃以下,更佳為0℃以上且50℃以下。反應時間通常為0.5小時以上且300小時以下。 The amount of the solvent used is usually not less than 1 part by mass and not more than 1000 parts by mass relative to 1 part by mass of the compound (B) represented by the formula (I) in which R 1 is not a hydrogen atom. The reaction temperature with the compound (pt6) is usually -90°C to 200°C, preferably -80°C to 100°C, more preferably 0°C to 50°C. The reaction time is usually not less than 0.5 hours and not more than 300 hours.
於式(I)所表示的化合物(B)不具有磺基的情況下,可藉由使式(I)所表示的化合物(B)與發煙硫酸或氯磺酸等的磺化劑反應而導入磺基。 When the compound (B) represented by the formula (I) does not have a sulfo group, it can be obtained by reacting the compound (B) represented by the formula (I) with a sulfonating agent such as oleum or chlorosulfonic acid. Import sulfo group.
相對於式(I)所表示的化合物(B)1莫耳,發煙硫酸中的SO3的使用量通常為1莫耳以上且50莫耳以下,較佳為5莫耳以上且40莫耳以下,更佳為5莫耳以上且30莫耳以下,進而佳為5莫耳以上且25莫耳以下。相對於式(I)所表示的化合物(B)1莫耳,發煙硫酸中的硫酸的使用量通常為1莫耳以上且200莫耳以下,較佳為10莫耳以上且100莫耳以下,更佳為10莫耳以上且75莫耳以下,進而佳為10莫耳以上且50莫耳以下。 The amount of SO in oleum to be used is usually not less than 1 mol and not more than 50 mol, preferably not less than 5 mol and not more than 40 mol, relative to 1 mol of compound (B) represented by formula (I). It is less than or equal to more than 5 mol and not more than 30 mol, and still more preferably not less than 5 mol and not more than 25 mol. The amount of sulfuric acid used in the fuming sulfuric acid is usually not less than 1 mol and not more than 200 mol, preferably not less than 10 mol and not more than 100 mol, relative to 1 mol of compound (B) represented by formula (I). , more preferably not less than 10 mol and not more than 75 mol, still more preferably not less than 10 mol and not more than 50 mol.
相對於式(I)所表示的化合物(B)1莫耳,氯磺酸的使用量通常為1莫耳以上且500莫耳以下,較佳為10莫耳以上且300莫耳以下,更佳為10莫耳以上且200莫耳以下,進而佳為10莫耳以上且150莫耳以下。 With respect to 1 mole of compound (B) represented by formula (I), the usage amount of chlorosulfonic acid is usually more than 1 mole and less than 500 moles, preferably more than 10 moles and less than 300 moles, more preferably It is not less than 10 mol and not more than 200 mol, more preferably not less than 10 mol and not more than 150 mol.
磺化的反應溫度通常為-20℃以上且200℃以下,較佳為-10℃以上且100℃以下,更佳為0℃以上且50℃以下。反應時間 通常為0.5小時以上且300小時以下。 The reaction temperature for sulfonation is generally -20°C to 200°C, preferably -10°C to 100°C, more preferably 0°C to 50°C. Reaction time Usually, it is 0.5 hour or more and 300 hours or less.
於式(I)所表示的化合物(B)具有羧基或磺基的情況下,亦可使化合物(pt7)與化合物(pt8)反應而製造包含金屬離子Mb+的式(I)所表示的化合物(B)。 In the case that the compound (B) represented by the formula (I) has a carboxyl group or a sulfo group, the compound (pt7) and the compound (pt8) can be reacted to produce the compound represented by the formula (I) containing the metal ion M b+ (B).
自反應混合物取出式(I)所表示的化合物(B)的方法並無特別限定,可藉由公知的各種方法取出。例如,可於反應結束後,對反應混合物進行過濾,藉此取出式(I)所表示的化合物(B)。另外,亦可於過濾後利用溶媒對所獲得的殘渣進行清洗。另外,亦可於過濾後,進行管柱層析、再結晶或昇華精製。 The method for extracting the compound (B) represented by the formula (I) from the reaction mixture is not particularly limited, and it can be extracted by various known methods. For example, the compound (B) represented by the formula (I) can be taken out by filtering the reaction mixture after the reaction is completed. In addition, the obtained residue may be washed with a solvent after filtration. In addition, column chromatography, recrystallization or sublimation purification can also be performed after filtration.
〔3〕C.I.顏料黃138(A)與式(I)所表示的化合物(B)的共分散物、以及包含其的著色劑分散液 [3] Codispersion of C.I. Pigment Yellow 138 (A) and compound (B) represented by formula (I), and colorant dispersion containing same
著色劑分散液包含作為主成分的C.I.顏料黃138(A)與式(I)所表示的化合物(B)的共分散物。根據包含該共分散物的著色劑分散液,例如與另行製備C.I.顏料黃138(A)的分散液與式(I)所表示的化合物(B)的分散液並將該些分散液混合而成的著色劑分散液相比,可顯著提昇對比度。 The colorant dispersion contains a co-dispersion of C.I. Pigment Yellow 138 (A) and a compound (B) represented by formula (I) as main components. According to the colorant dispersion liquid containing this co-dispersion, for example, the dispersion liquid of C.I. Pigment Yellow 138 (A) and the dispersion liquid of the compound (B) represented by the formula (I) are prepared separately and these dispersion liquids are mixed Compared with the colorant dispersion liquid, it can significantly improve the contrast ratio.
所謂主成分,是指著色劑分散液中所含的著色劑中,含有率(質量基準)最高的成分。 The term "main component" refers to a component having the highest content rate (mass basis) among the colorants contained in the colorant dispersion liquid.
所謂著色劑,是指以顏料及染料為代表的色素的總稱。 The term "colorant" is a general term for pigments represented by pigments and dyes.
共分散物可藉由使C.I.顏料黃138(A)與式(I)所表示的化合物(B)一併視需要於分散劑共存下、或者進而視需要於樹脂共存下分散於溶劑中而製備。 The co-dispersion can be prepared by dispersing C.I. Pigment Yellow 138 (A) and the compound (B) represented by formula (I) together in the presence of a dispersant if necessary, or in a solvent if necessary in the presence of a resin .
作為分散劑,例如可列舉:陽離子系、陰離子系、非離子系、兩性、聚酯系、多胺系、丙烯酸系等的界面活性劑等。該些分散劑可單獨使用,亦可組合使用兩種以上。 Examples of the dispersant include cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, acrylic-based, and other surfactants. These dispersants may be used alone or in combination of two or more.
樹脂亦可自後述樹脂(D)中選擇。溶劑亦可自後述溶劑(G)中選擇。 The resin can also be selected from resins (D) described later. The solvent can also be selected from solvents (G) described later.
共分散物例如可藉由如下方式而製備:使C.I.顏料黃138(A)及式(I)所表示的化合物(B)與溶劑(G)的一部分或全部混合,並視需要於分散劑共存下、或者進而視需要於樹脂(D)的一部分或全部的共存下,使用珠磨機等使其分散,直至著色劑的平均粒徑成為0.2μm以下左右。 The co-dispersion can be prepared, for example, by mixing C.I. Pigment Yellow 138 (A) and the compound (B) represented by the formula (I) with part or all of the solvent (G), and coexisting with a dispersant if necessary Next, or further if necessary, in the coexistence of a part or all of the resin (D), it is dispersed using a bead mill or the like until the average particle diameter of the colorant becomes about 0.2 μm or less.
於使用分散劑的情況下,其使用量相對於著色劑的總量,較佳為1質量%以上且100質量%以下,更佳為5質量%以上且80質量%以下。若分散劑的使用量處於所述範圍內,則有容易獲得均勻的分散狀態的共分散物的傾向。 When a dispersant is used, the amount used is preferably from 1% by mass to 100% by mass, more preferably from 5% by mass to 80% by mass, based on the total amount of the colorant. When the usage-amount of a dispersing agent exists in the said range, it exists in the tendency which becomes easy to obtain the co-dispersion of a uniform dispersion state.
於使用樹脂的情況下,其使用量相對於著色劑的總量,較佳為1質量%以上且100質量%以下,更佳為5質量%以上且80質量%以下。若樹脂的使用量處於所述範圍內,則有容易獲得均勻的分散狀態的共分散物的傾向。 When a resin is used, the amount used is preferably from 1% by mass to 100% by mass, more preferably from 5% by mass to 80% by mass, based on the total amount of the colorant. When the usage-amount of resin exists in the said range, it exists in the tendency which becomes easy to obtain the co-dispersion of a uniform dispersion state.
於共分散物及著色劑分散液中,就提高對比度的觀點而言,C.I.顏料黃138(A)的含量於C.I.顏料黃138(A)及式(I)所表示的化合物(B)的合計量100質量份中較佳為50.1質量份以上且99.9質量份以下,更佳為60質量份以上且99質量份以下, 進而佳為85質量份以上且99質量份以下。 In the co-dispersion and the colorant dispersion, from the viewpoint of improving the contrast, the content of C.I. Pigment Yellow 138 (A) is greater than the total of C.I. Pigment Yellow 138 (A) and the compound (B) represented by the formula (I) The amount is preferably 50.1 mass parts or more and 99.9 mass parts or less in 100 mass parts, more preferably 60 mass parts or more and 99 mass parts or less, More preferably, it is 85 mass parts or more and 99 mass parts or less.
於共分散物及著色劑分散液中,就提高對比度的觀點而言,式(I)所表示的化合物(B)的含量於C.I.顏料黃138(A)及式(I)所表示的化合物(B)的合計量100質量份中較佳為0.1質量份以上且49.9質量份以下,更佳為1質量份以上且40質量份以下,進而佳為1質量份以上且15質量份以下。 In the co-dispersion and the colorant dispersion, from the viewpoint of improving the contrast, the content of the compound (B) represented by the formula (I) is higher than that of the compound (B) represented by C.I. Pigment Yellow 138 (A) and the formula (I) The total amount of B) is preferably 0.1 to 49.9 parts by mass, more preferably 1 to 40 parts by mass, still more preferably 1 to 15 parts by mass, per 100 parts by mass.
共分散物及著色劑分散液分別可包含C.I.顏料黃138(A)及式(I)所表示的化合物(B)以外的其他成分。 The co-dispersion and the colorant dispersion liquid may contain components other than C.I. Pigment Yellow 138 (A) and the compound (B) represented by the formula (I), respectively.
作為其他成分,可列舉:C.I.顏料黃138(A)及式(I)所表示的化合物(B)以外的其他著色劑(顏料、染料)、溶劑、分散劑、樹脂、脂肪族羧酸金屬鹽(C)等。關於脂肪族羧酸金屬鹽(C),於後文敘述。 Examples of other components include: C.I. Pigment Yellow 138 (A) and other colorants (pigments, dyes) other than the compound (B) represented by formula (I), solvents, dispersants, resins, aliphatic carboxylic acid metal salts (C) etc. The aliphatic carboxylic acid metal salt (C) will be described later.
共分散物及著色劑分散液分別可僅包含一種其他成分,亦可包含兩種以上。 Each of the co-dispersion and the colorant dispersion liquid may contain only one kind of other components, or may contain two or more kinds thereof.
作為其他顏料,並無特別限定,可使用公知的顏料,例如可列舉染料索引(染色與印染工作者協會(The Society of Dyers and Colourists)出版)中被分類為顏料(pigment)的顏料。 It does not specifically limit as another pigment, A well-known pigment can be used, For example, the pigment classified as a pigment (pigment) is mentioned in the dye index (published by The Society of Dyers and Colourists).
作為顏料,例如可列舉:C.I.顏料黃1、3、12、13、14、15、16、17、20、24、31、53、83、86、93、94、109、110、117、125、128、137、139、147、148、150、153、154、166、173、185、194、214等的黃色顏料;C.I.顏料橙(Pigment Orange)13、31、36、38、40、42、43、 51、55、59、61、64、65、71、73等的橙色顏料;C.I.顏料紅(Pigment Red)9、97、105、122、123、144、149、166、168、176、177、180、192、209、215、216、224、242、254、255、264、265等的紅色顏料;C.I.顏料藍(Pigment Blue)15、15:3、15:4、15:6、60等的藍色顏料;C.I.顏料紫(Pigment Violet)1、19、23、29、32、36、38等的紫色顏料;C.I.顏料綠(Pigment Green)7、36、58、59等的綠色顏料;C.I.顏料棕(Pigment Brown)23、25等的棕色顏料;C.I.顏料黑(Pigment Black)1、7等的黑色顏料等。 Examples of pigments include: C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; C.I. Pigment Orange (Pigment Orange) 13, 31, 36, 38, 40, 42, 43 , Orange pigments of 51, 55, 59, 61, 64, 65, 71, 73, etc.; C.I. Pigment Red (Pigment Red) 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180 , 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. red pigments; C.I. Pigment Blue (Pigment Blue) 15, 15:3, 15:4, 15:6, 60, etc. blue C.I. Pigment Violet (Pigment Violet) 1, 19, 23, 29, 32, 36, 38 etc. purple pigments; C.I. Pigment Green (Pigment Green) 7, 36, 58, 59 etc. green pigments; C.I. Pigment Brown Brown pigments such as (Pigment Brown) 23, 25, etc.; black pigments such as C.I. Pigment Black (Pigment Black) 1, 7, etc.
其他顏料可與C.I.顏料黃138(A)及式(I)所表示的化合物(B)一併共分散於共分散物中,亦可添加於包含C.I.顏料黃138(A)及式(I)所表示的化合物(B)的共分散物中並包含於著色劑分散液中。 Other pigments can be co-dispersed together with C.I. Pigment Yellow 138 (A) and the compound (B) represented by formula (I) in the co-dispersion, and can also be added to the compound containing C.I. Pigment Yellow 138 (A) and formula (I) The indicated compound (B) is contained in the co-dispersion of the colorant dispersion liquid.
C.I.顏料黃138(A)、式(I)所表示的化合物(B)及其他顏料視需要亦可實施松香處理、使用導入有酸性基或鹼性基的顏料衍生物等進行的表面處理、利用高分子化合物等對顏料表面進行的接枝處理、利用硫酸微粒化法等進行的微粒化處理、或者用以將雜質去除的利用有機溶劑或水等進行的清洗處理、離子性雜質的利用離子交換法等進行的去除處理等。 C.I. Pigment Yellow 138 (A), compound (B) represented by formula (I), and other pigments may also be subjected to rosin treatment, surface treatment using pigment derivatives introduced with acidic or basic groups, etc. Grafting treatment of pigment surface with polymer compounds, micronization treatment by sulfuric acid micronization method, etc., or cleaning treatment with organic solvent or water to remove impurities, ion exchange of ionic impurities Removal treatment, etc. by law, etc.
作為染料,並無特別限定,可使用公知的染料,例如可列舉:溶劑染料、酸性染料、直接染料、媒染染料等。 It does not specifically limit as a dye, A well-known dye can be used, For example, a solvent dye, an acid dye, a direct dye, a mordant dye, etc. are mentioned.
作為染料,例如可列舉染料索引(染色與印染工作者協會(The Society of Dyers and Colourists)出版)及染色筆記(色染(Shikisensha)公司)中記載的公知的染料。 Examples of dyes include known dyes described in Dye Index (published by The Society of Dyers and Colourists) and Dyeing Notebook (Shikisensha).
另外,根據化學結構,染料可列舉:偶氮染料、花青染料(cyanine dye)、三苯基甲烷染料、呫噸氧雜蒽染料、酞青染料、蒽醌染料、萘醌染料、醌亞胺染料、次甲基染料、偶氮次甲基染料(azomethine dye)、方酸內鎓染料(squarylium dye)、吖啶染料、苯乙烯基染料、香豆素染料、喹啉染料及硝基染料等。該些染料中,較佳為有機溶劑可溶性染料。 In addition, examples of dyes depending on the chemical structure include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, and quinone imines. Dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, etc. . Among these dyes, organic solvent-soluble dyes are preferred.
染料可包含於共分散物中,亦可添加於共分散物中並包含於著色劑分散液中。 The dye can be included in the co-dispersion, or it can be added to the co-dispersion and included in the colorant dispersion.
樹脂亦可自後述樹脂(D)中選擇。溶劑亦可自後述溶劑(G)中選擇。 The resin can also be selected from resins (D) described later. The solvent can also be selected from solvents (G) described later.
C.I.顏料黃138(A)及式(I)所表示的化合物(B)的合計含量於共分散物或著色劑分散液中所含的著色劑100質量份中較佳為5質量份以上,更佳為10質量份以上,進而佳為30質量份以上,進而更佳為50質量份以上,尤佳為80質量份以上,最佳為90質量份以上。所述合計含量於共分散物或著色劑分散液中所含的著色劑100質量份中亦可為100質量份。 The total content of C.I. Pigment Yellow 138 (A) and the compound (B) represented by the formula (I) is preferably 5 parts by mass or more in 100 parts by mass of the colorant contained in the co-dispersion or the colorant dispersion, more preferably It is preferably at least 10 parts by mass, more preferably at least 30 parts by mass, still more preferably at least 50 parts by mass, particularly preferably at least 80 parts by mass, most preferably at least 90 parts by mass. The said total content may be 100 mass parts with respect to 100 mass parts of colorants contained in a codispersion or a colorant dispersion liquid.
C.I.顏料黃138(A)及式(I)所表示的化合物(B)的 合計含量於共分散物或著色劑分散液中所含的固體成分的總量100質量份中較佳為10質量份以上且90質量份以下,更佳為15質量份以上且80質量份以下,進而佳為20質量份以上且70質量份以下。 C.I. Pigment Yellow 138 (A) and Compound (B) represented by Formula (I) The total content is preferably not less than 10 parts by mass and not more than 90 parts by mass, more preferably not less than 15 parts by mass and not more than 80 parts by mass, based on 100 parts by mass of the total amount of solids contained in the co-dispersion or colorant dispersion liquid, More preferably, it is 20 mass parts or more and 70 mass parts or less.
本說明書中,所謂共分散物、著色劑分散液或著色硬化性樹脂組成物中所含的「固體成分的總量」,是指自共分散物、著色劑分散液或著色硬化性樹脂組成物的總量中去除溶劑含量而得到的量。固體成分的總量以及相對於其的各成分的含量可藉由例如液相層析法或氣相層析法等的公知的分析手段進行測定。 In this specification, the "total amount of solid content" contained in a co-dispersion, a colorant dispersion, or a colored curable resin composition refers to a self-co-dispersion, a colorant dispersion, or a colored curable resin composition. The amount obtained by removing the solvent content from the total amount. The total amount of solid content and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography.
〔4〕脂肪族羧酸金屬鹽(C) 〔4〕Metal salt of aliphatic carboxylic acid (C)
著色劑分散液可包含脂肪族羧酸金屬鹽(C)作為所述其他成分。進而含有脂肪族羧酸金屬鹽(C)有利於提昇對比度。 The colorant dispersion liquid may contain an aliphatic carboxylic acid metal salt (C) as the other component. Furthermore, the inclusion of the aliphatic carboxylic acid metal salt (C) contributes to enhancement of contrast.
脂肪族羧酸金屬鹽(C)可包含於共分散物中,亦可添加於共分散物中並包含於著色劑分散液中。 The aliphatic carboxylic acid metal salt (C) may be contained in the co-dispersion, or may be added to the co-dispersion and contained in the colorant dispersion liquid.
脂肪族羧酸金屬鹽(C)為包含金屬陽離子、與具有羥基的碳數1~40的脂肪族羧酸的陰離子的鹽。以下,亦將具有羥基的碳數1~40的脂肪族羧酸稱作「脂肪族羧酸(X)」。 The aliphatic carboxylic acid metal salt (C) is a salt containing a metal cation and an anion of an aliphatic carboxylic acid having 1 to 40 carbon atoms having a hydroxyl group. Hereinafter, an aliphatic carboxylic acid having 1 to 40 carbon atoms having a hydroxyl group is also referred to as "aliphatic carboxylic acid (X)".
本說明書中所謂「脂肪族羧酸」,是指不具有芳香環的羧酸。 The term "aliphatic carboxylic acid" in this specification refers to a carboxylic acid not having an aromatic ring.
本發明的著色硬化性樹脂組成物可僅包含一種脂肪族羧酸金屬鹽(C),亦可包含兩種以上。 The colored curable resin composition of the present invention may contain only one type of aliphatic carboxylic acid metal salt (C), or may contain two or more types.
脂肪族羧酸(X)的亦包含羧基的碳在內的碳數為1~40,可為直鏈狀,亦可為分支鏈狀,亦可為環狀,亦可為將選自 由直鏈狀結構、分支鏈結構及環狀結構所組成的群組中的兩種以上的結構組合而成者。 The carbon number of the aliphatic carboxylic acid (X) including the carbon of the carboxyl group is 1 to 40, and may be linear, branched, or cyclic, or may be selected from Combination of two or more structures in the group consisting of linear structure, branched chain structure and cyclic structure.
脂肪族羧酸(X)亦可包含不飽和鍵。 The aliphatic carboxylic acid (X) may also contain unsaturated bonds.
脂肪族羧酸(X)於分子內具有一個以上的羥基。 Aliphatic carboxylic acid (X) has one or more hydroxyl groups in a molecule|numerator.
脂肪族羧酸(X)於分子內具有一個以上的羧基。羧基的數量通常為10以下。 The aliphatic carboxylic acid (X) has one or more carboxyl groups in the molecule. The number of carboxyl groups is usually 10 or less.
就提高對比度的觀點而言,脂肪族羧酸(X)的碳數為1~40,較佳為10~36,更佳為12~24。 The carbon number of the aliphatic carboxylic acid (X) is 1-40, preferably 10-36, and more preferably 12-24 from the viewpoint of improving contrast.
脂肪族羧酸金屬鹽(C)具有至少一個脂肪族羧酸(X)的陰離子即可。於脂肪族羧酸金屬鹽(C)所具有的金屬陽離子的價數為2以上的情況下,脂肪族羧酸金屬鹽(C)可具有兩種以上的脂肪族羧酸(X)的陰離子,亦可具有脂肪族羧酸(X)的陰離子、與脂肪族羧酸(X)的陰離子以外的其他陰離子。 It is sufficient that the aliphatic carboxylic acid metal salt (C) has at least one anion of the aliphatic carboxylic acid (X). In the case where the metal cation of the aliphatic carboxylic acid metal salt (C) has a valence of 2 or more, the aliphatic carboxylic acid metal salt (C) may have two or more anions of the aliphatic carboxylic acid (X), An anion other than the anion of the aliphatic carboxylic acid (X) and the anion of the aliphatic carboxylic acid (X) may be included.
作為所述其他陰離子,並無特別限制,可為鹵素離子、硝酸根離子、硫酸根離子等,較佳為脂肪族羧酸(X)以外的脂肪族羧酸的陰離子。 The other anions are not particularly limited, and may be halogen ions, nitrate ions, sulfate ions, etc., and are preferably anions of aliphatic carboxylic acids other than the aliphatic carboxylic acid (X).
所謂脂肪族羧酸(X)以外的脂肪族羧酸,是指不具有羥基的脂肪族羧酸,例如可列舉除了不具有羥基以外具有與脂肪族羧酸(X)相同的結構者。 The aliphatic carboxylic acid other than the aliphatic carboxylic acid (X) refers to an aliphatic carboxylic acid not having a hydroxyl group, and examples thereof include those having the same structure as the aliphatic carboxylic acid (X) except not having a hydroxyl group.
脂肪族羧酸金屬鹽(C)所具有的陰離子較佳為僅包含脂肪族羧酸(X)的陰離子。 It is preferable that the anion which the aliphatic carboxylic acid metal salt (C) has contains only an anion of aliphatic carboxylic acid (X).
就提高對比度的觀點而言,脂肪族羧酸金屬鹽(C)所 具有的金屬陽離子較佳為2價以上且10價以下的金屬陽離子。作為2價以上的金屬陽離子,可列舉屬於元素週期表的2族~15族的金屬的陽離子。金屬陽離子較佳為2價以上且6價以下的金屬陽離子。 From the viewpoint of improving the contrast ratio, the aliphatic carboxylic acid metal salt (C) The metal cation to have is preferably a metal cation having a valence of 2 or more and a valence of 10 or less. Examples of the divalent or higher metal cation include cations of metals belonging to Group 2 to Group 15 of the periodic table. The metal cation is preferably a metal cation having a valence of 2 or more and a valence of 6 or less.
金屬陽離子 metal cation
更佳為Mg2+、Ca2+、Sr2+、Ba2+、Cd2+、Ni2+、Zn2+、Cu2+、Hg2+、Fe2+、Co2+、Sn2+、Pb2+及Mn2+等的2價的金屬陽離子;Al3+、Fe3+、Co3+及Cr3+等的3價的金屬陽離子;Sn4+及Mn4+等的4價的金屬陽離子,進而佳為Mg2+、Ca2+、Sr2+、Ba2+、Ni2+、Zn2+、Cu2+、Fe2+、Co2+、Sn2+、Mn2+、Al3+、Fe3+、Co3+、Cr3+、Sn4+及Mn4+,尤佳為Mg2+、Ca2+、Sr2+、Ba2+、Ni2+、Zn2+、Cu2+、Fe2+、Co2+、Mn2+、Al3+、Fe3+、Co3+、Cr3+及Mn4+,進一步較佳為Fe2+、Co2+、Fe3+及Co3+。 More preferably Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cd 2+ , Ni 2+ , Zn 2+ , Cu 2+ , Hg 2+ , Fe 2+ , Co 2+ , Sn 2+ Divalent metal cations such as , Pb 2+ and Mn 2+ ; trivalent metal cations such as Al 3+ , Fe 3+ , Co 3+ and Cr 3+ ; tetravalent metal cations such as Sn 4+ and Mn 4+ metal cations, preferably Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ni 2+ , Zn 2+ , Cu 2+ , Fe 2+ , Co 2+ , Sn 2+ , Mn 2+ , Al 3+ , Fe 3+ , Co 3+ , Cr 3+ , Sn 4+ and Mn 4+ , especially Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ni 2+ , Zn 2 + , Cu 2+ , Fe 2+ , Co 2+ , Mn 2+ , Al 3+ , Fe 3+ , Co 3+ , Cr 3+ and Mn 4+ , more preferably Fe 2+ , Co 2+ , Fe 3+ and Co 3+ .
脂肪族羧酸金屬鹽(C)亦可具有兩種以上的金屬陽離子。 The aliphatic carboxylic acid metal salt (C) may have two or more metal cations.
脂肪族羧酸金屬鹽(C)具體而言可為以下的式(Aa)所表示的化合物。 The aliphatic carboxylic acid metal salt (C) may specifically be a compound represented by the following formula (Aa).
[式(Aa)中, D表示具有羥基的脂肪族烴。 [In formula (Aa), D represents an aliphatic hydrocarbon having a hydroxyl group.
a表示1~10的任一整數,較佳為1~3的任一整數。於存在多個a時,該些可彼此相同亦可不同。 a represents any integer of 1-10, preferably any integer of 1-3. When there are a plurality of a, these may be the same as or different from each other.
D的碳數+a為1~40的任一整數。 The carbon number of D + a is any integer from 1 to 40.
b表示1以上的任一整數。於b表示2以上的任一整數時,『[D]-(CO2 -)a』可彼此相同亦可不同。 b represents any integer of 1 or more. When b represents any integer of 2 or more, "[D]-(CO 2 - ) a " may be the same as or different from each other.
Jk-表示『[D]-(CO2 -)a』以外的陰離子。 J k- represents anion other than "[D]-(CO 2 - ) a ".
k表示1~10的任一整數,較佳為1~6的任一整數。 k represents any integer of 1-10, preferably any integer of 1-6.
m表示0以上的任一整數。於m表示2以上的任一整數時,『Jk-』可彼此相同亦可不同。 m represents any integer of 0 or more. When m represents any integer of 2 or more, "J k- " may be the same or different from each other.
Ac+表示c價的金屬陽離子,具體例如上所述。 A c+ represents a c-valent metal cation, and specific examples are as described above.
c表示2~10的任一整數,較佳為2~6的任一整數。 c represents any integer of 2-10, preferably any integer of 2-6.
d表示1以上的任一整數。於d表示2以上的任一整數時,『Ac+』可彼此相同亦可不同。 d represents any integer of 1 or more. When d represents any integer of 2 or more, "A c+ " may be the same or different from each other.
其中,
脂肪族羧酸金屬鹽(C)例如可作為藉由使脂肪族羧酸(X)溶解於鹼水溶液中之後添加具有金屬陽離子的鹽(例如鹵化物等)而產生的沈澱物而獲得。所獲得的脂肪族羧酸金屬鹽(C)視需要亦可供於清洗等的精製處理。 The aliphatic carboxylic acid metal salt (C) can be obtained, for example, as a precipitate produced by dissolving the aliphatic carboxylic acid (X) in an aqueous alkali solution and then adding a salt having a metal cation (such as a halide, etc.). The obtained aliphatic carboxylic acid metal salt (C) can also be used for purification processes, such as washing|cleaning, as needed.
作為脂肪族羧酸金屬鹽(C),具體而言例如可列舉:下述式(AA)中M、L、p及q分別由下述[表A]表示的化合物、[表A]的化合物AA1~化合物AA22中M代替Fe2+而為Mg2+、Ca2+、Sr2+、Ba2+、Cd2+、Ni2+、Zn2+、Cu2+、Hg2+、Co2+、Sn2+、Pb2+、或Mn2+的化合物、[表B]所表示的化合物、[表B]的化合物AA23~化合物AA44中M代替Fe3+而為Al3+、Co3+或Cr3+的化合物、以及[表C]所表示的化合物。 As the aliphatic carboxylic acid metal salt (C), specifically, for example, a compound represented by the following [Table A] in M, L, p, and q in the following formula (AA), and a compound in [Table A] In AA1~Compound AA22, M replaces Fe 2+ to Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cd 2+ , Ni 2+ , Zn 2+ , Cu 2+ , Hg 2+ , Co 2 + , Sn 2+ , Pb 2+ , or Mn 2+ compounds, compounds represented in [Table B], compounds AA23 to AA44 in [Table B], in which M replaces Fe 3+ to Al 3+ , Co 3 + or Cr 3+ compounds, and compounds represented by [Table C].
MpLq (AA) MpLq (AA)
另外,作為具有脂肪族羧酸(X)的陰離子、與脂肪族羧酸(X)的陰離子以外的其他陰離子的脂肪族羧酸金屬鹽(C),例如可列舉下述式所表示的鹽。 In addition, examples of the aliphatic carboxylic acid metal salt (C) having an anion of the aliphatic carboxylic acid (X) and an anion other than the anion of the aliphatic carboxylic acid (X) include salts represented by the following formulas.
於共分散物或著色劑分散液包含脂肪族羧酸金屬鹽(C)的情況下,脂肪族羧酸金屬鹽(C)的含量於共分散物或著色劑分散液中所含的固體成分的總量100質量份中較佳為0.01質量份以上且25質量份以下,更佳為0.1質量份以上且20質量份以下,進而佳為0.2質量份以上且15質量份以下,尤佳為0.3質量份以上且10質量份以下。若脂肪族羧酸金屬鹽(C)的含量處於所述範圍內,則可顯著提昇對比度。 In the case where the co-dispersion or the colorant dispersion contains the aliphatic carboxylic acid metal salt (C), the content of the aliphatic carboxylic acid metal salt (C) is equal to the solid content contained in the co-dispersion or the colorant dispersion. The total amount of 100 parts by mass is preferably from 0.01 to 25 parts by mass, more preferably from 0.1 to 20 parts by mass, still more preferably from 0.2 to 15 parts by mass, most preferably 0.3 parts by mass Part or more and 10 parts by mass or less. When the content of the aliphatic carboxylic acid metal salt (C) is within the above range, the contrast can be significantly improved.
另外,相對於C.I.顏料黃138(A)及式(I)所表示的化合物(B)的合計量100質量份,脂肪族羧酸金屬鹽(C)的含量較佳為0.1質量份以上且20質量份以下,更佳為0.3質量份以上且15質量份以下,進而佳為0.5質量份以上且13質量份以下。 In addition, the content of the aliphatic carboxylic acid metal salt (C) is preferably at least 0.1 parts by mass and 20 parts by mass relative to 100 parts by mass of the total amount of the compound (B) represented by C.I. Pigment Yellow 138 (A) and formula (I). It is not more than 0.3 parts by mass and not more than 15 parts by mass, more preferably not less than 0.5 parts by mass and not more than 13 parts by mass.
<著色硬化性樹脂組成物> <Colored curable resin composition>
著色硬化性樹脂組成物包含所述著色劑分散液與樹脂(D)。 The colored curable resin composition contains the above-mentioned colorant dispersion liquid and resin (D).
著色硬化性樹脂組成物較佳為進而包含聚合性化合物(E)及聚合起始劑(F),更佳為進而包含聚合性化合物(E)、聚合起始劑(F)及溶劑(G)。 The colored curable resin composition preferably further includes a polymerizable compound (E) and a polymerization initiator (F), more preferably further includes a polymerizable compound (E), a polymerization initiator (F) and a solvent (G) .
著色硬化性樹脂組成物亦可進而包含聚合起始助劑(F1)及/或調平劑(H)。 The colored curable resin composition may further contain a polymerization initiation aid (F1) and/or a leveling agent (H).
根據所述著色硬化性樹脂組成物,可使由其形成的彩色濾光片及使用其的顯示裝置的對比度變得良好。 According to the said colored curable resin composition, the contrast of the color filter formed from it and the display device using it can be made favorable.
以下,作為各成分而例示的化合物只要無特別說明,則可單獨使用、或者將多種組合使用。 Hereinafter, unless otherwise specified, the compounds exemplified as each component may be used alone or in combination of multiple types.
〔1〕著色硬化性樹脂組成物中的著色劑分散液的含量 [1] Content of colorant dispersion in colored curable resin composition
就亮度的觀點而言,著色劑分散液是以其中所含的著色劑的含量(或C.I.顏料黃138(A)及式(I)所表示的化合物(B)的合計含量)於著色硬化性樹脂組成物的固體成分的總量100質量份中成為較佳為0.1質量份以上且90質量份以下、更佳為0.5質量份以上且80質量份以下、進而佳為1質量份以上且70質量份以下的方式包含於著色硬化性樹脂組成物中。 From the viewpoint of brightness, the content of the colorant contained in the colorant dispersion liquid (or the total content of the compound (B) represented by C.I. Pigment Yellow 138 (A) and formula (I)) is based on the coloring curability. The total amount of solid content of the resin composition is preferably 0.1 to 90 parts by mass, more preferably 0.5 to 80 parts by mass, and still more preferably 1 to 70 parts by mass in a total amount of 100 parts by mass. Parts or less are included in the colored curable resin composition.
〔2〕樹脂(D) 〔2〕Resin (D)
樹脂(D)並無特別限定,較佳為鹼可溶性樹脂,更佳為具有源自選自由不飽和羧酸及不飽和羧酸酐所組成的群組中的至少一種(a)(以下有時稱作「(a)」)的結構單元的樹脂。 The resin (D) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as A resin used as a structural unit of "(a)").
樹脂(D)進而佳為具有選自由如下結構單元所組成的群組中的至少一種結構單元:源自具有碳數2~4的環狀醚結構與乙烯性不飽和鍵的單量體(b)(以下有時稱作「(b)」)的結構單元、源自可與(a)共聚的單量體(c)(其中,與(a)及(b)不同)(以下有時稱作「(c)」)的結構單元、以及於側鏈具有乙烯性不飽和鍵的結構單元。 The resin (D) further preferably has at least one structural unit selected from the group consisting of the following structural units: a monomer derived from a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b ) (hereinafter sometimes referred to as "(b)"), derived from a monomer (c) (which is different from (a) and (b)) that can be copolymerized with (a) (hereinafter sometimes referred to as as "(c)"), and a structural unit having an ethylenically unsaturated bond in a side chain.
作為(a),例如可列舉:丙烯酸、甲基丙烯酸、馬來酸 酐、衣康酸酐、3,4,5,6-四氫鄰苯二甲酸酐、丁二酸單〔2-(甲基)丙烯醯基氧基乙基〕酯等,較佳為丙烯酸、甲基丙烯酸、馬來酸酐。 Examples of (a) include: acrylic acid, methacrylic acid, maleic acid anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono[2-(meth)acryloxyethyl]ester, etc., preferably acrylic acid, methyl Acrylic acid, maleic anhydride.
(b)較佳為具有碳數2~4的環狀醚結構(例如,選自由氧雜環丙烷環、氧雜環丁烷環及四氫呋喃環所組成的群組中的至少一種)與(甲基)丙烯醯基氧基的單量體。 (b) is preferably a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and (form base) a monomer of acryloxy.
再者,本說明書中所謂「(甲基)丙烯酸」,表示選自由丙烯酸及甲基丙烯酸所組成的群組中的至少一種。「(甲基)丙烯醯基」及「(甲基)丙烯酸酯」等的表述亦具有相同的含義。 In addition, "(meth)acrylic acid" in this specification means at least 1 sort(s) selected from the group which consists of acrylic acid and methacrylic acid. Expressions such as "(meth)acryl" and "(meth)acrylate" also have the same meaning.
作為(b),例如可列舉:(甲基)丙烯酸縮水甘油酯、乙烯基苄基縮水甘油醚、(甲基)丙烯酸3,4-環氧三環[5.2.1.02,6]癸酯、3-乙基-3-(甲基)丙烯醯基氧基甲基氧雜環丁烷、(甲基)丙烯酸四氫糠酯等,較佳為(甲基)丙烯酸縮水甘油酯、(甲基)丙烯酸3,4-環氧三環[5.2.1.02,6]癸酯、3-乙基-3-(甲基)丙烯醯基氧基甲基氧雜環丁烷。 Examples of (b) include glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate, 3-Ethyl-3-(meth)acryloxymethyl oxetane, tetrahydrofurfuryl (meth)acrylate, etc., preferably glycidyl (meth)acrylate, (meth) ) 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane.
作為(c),例如可列舉:(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸環己酯、(甲基)丙烯酸2-甲基環己酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-8-基酯、(甲基)丙烯酸苄酯、(甲基)丙烯酸2-羥基乙酯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺、苯乙烯、乙烯基甲苯等,較佳為以苯乙烯、乙烯基甲苯、(甲基)丙烯酸2-羥基乙酯、N-苯基馬來醯亞胺、N-環己基馬來醯亞胺、N-苄基馬來醯亞胺等為宜。 Examples of (c) include: methyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, (meth)acrylate ) Tricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, N-phenylmaleimide, N -cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyl toluene, etc., preferably styrene, vinyl toluene, 2-hydroxyethyl (meth)acrylate, N -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, etc. are preferable.
具有於側鏈具有乙烯性不飽和鍵的結構單元的樹脂可 藉由使(b)加成於(a)與(c)的共聚物、或使(a)加成於(b)與(c)的共聚物而製造。該樹脂亦可為使(a)加成於(b)與(c)的共聚物並進而使羧酸酐反應所得的樹脂。 A resin having a structural unit having an ethylenically unsaturated bond in a side chain can be Manufactured by adding (b) to a copolymer of (a) and (c), or adding (a) to a copolymer of (b) and (c). This resin may be a resin obtained by adding (a) to a copolymer of (b) and (c), and further reacting a carboxylic anhydride.
樹脂(D)的聚苯乙烯換算的重量平均分子量較佳為3000以上且100000以下,更佳為5000以上且50000以下,進而佳為5000以上且30000以下。 The polystyrene equivalent weight average molecular weight of the resin (D) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000.
樹脂(D)的分散度[重量平均分子量(Mw)/數量平均分子量(Mn)]較佳為1.1以上且6以下,更佳為1.2以上且4以下。 The degree of dispersion of the resin (D) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is preferably from 1.1 to 6, more preferably from 1.2 to 4.
樹脂(D)的酸價以固體成分換算計較佳為20mg-KOH/g以上且170mg-KOH/g以下,更佳為30mg-KOH/g以上且150mg-KOH/g以下,進而佳為40mg-KOH/g以上且135mg-KOH/g以下。 The acid value of the resin (D) is preferably 20 mg-KOH/g or more and 170 mg-KOH/g or less in terms of solid content, more preferably 30 mg-KOH/g or more and 150 mg-KOH/g or less, still more preferably 40 mg-KOH/g or less. KOH/g or more and 135 mg-KOH/g or less.
酸價是作為中和樹脂(D)1g所需的氫氧化鉀的量(mg)而測定的值,例如可藉由使用氫氧化鉀水溶液進行滴定而求出。 The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (D), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.
於著色硬化性樹脂組成物的固體成分的總量100質量份中,樹脂(D)的含量較佳為7質量份以上且65質量份以下,更佳為13質量份以上且60質量份以下,進而佳為17質量份以上且55質量份以下。 The content of the resin (D) is preferably not less than 7 parts by mass and not more than 65 parts by mass, more preferably not less than 13 parts by mass and not more than 60 parts by mass, per 100 parts by mass of the total solid content of the colored curable resin composition, More preferably, it is 17 mass parts or more and 55 mass parts or less.
〔3〕聚合性化合物(E) [3] Polymerizable compound (E)
聚合性化合物(E)為可藉由自聚合起始劑(F)產生的活性自由基及/或酸而聚合的化合物,例如可列舉具有聚合性的乙烯性不飽和鍵的化合物等,較佳為(甲基)丙烯酸酯化合物。 The polymerizable compound (E) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (F), for example, compounds having polymerizable ethylenically unsaturated bonds, etc., are preferred. It is a (meth)acrylate compound.
其中,聚合性化合物(E)較佳為具有三個以上的乙烯性不飽和鍵的聚合性化合物。作為此種聚合性化合物,例如可列舉:三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等。 Among them, the polymerizable compound (E) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. ester, dipentaerythritol hexa(meth)acrylate, etc.
聚合性化合物(E)的重量平均分子量較佳為150以上且2900以下,更佳為250以上且1500以下。 The weight average molecular weight of the polymerizable compound (E) is preferably from 150 to 2900, more preferably from 250 to 1500.
聚合性化合物(E)的含量於著色硬化性樹脂組成物的固體成分的總量100質量份中較佳為7質量份以上且65質量份以下,更佳為13質量份以上且60質量份以下,進而佳為15質量份以上且55質量份以下。 The content of the polymerizable compound (E) is preferably not less than 7 parts by mass and not more than 65 parts by mass, more preferably not less than 13 parts by mass and not more than 60 parts by mass, based on 100 parts by mass of the total solid content of the colored curable resin composition. , and more preferably not less than 15 parts by mass and not more than 55 parts by mass.
〔4〕聚合起始劑(F) [4] Polymerization initiator (F)
聚合起始劑(F)若為可藉由光或熱的作用而產生活性自由基、酸等並開始聚合的化合物則並無特別限定,可使用公知的聚合起始劑。作為產生活性自由基的聚合起始劑,例如可列舉:N-苯甲醯基氧基-1-(4-苯硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯基氧基-1-(4-苯硫基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯基氧基-1-(4-苯硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺、2-甲基-2-嗎啉基-1-(4-甲硫基苯基)丙烷-1-酮、2-二甲基胺基-1-(4-嗎啉基苯基)-2-苄基丁烷-1-酮、1-羥基環己基苯基酮、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三嗪、2,4,6-三甲基苯甲醯基二苯基膦氧化物、2,2'-雙(2-氯苯基)-4,4'5,5'-四苯基聯咪唑等。 The polymerization initiator (F) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc. by the action of light or heat to initiate polymerization, and known polymerization initiators can be used. Examples of polymerization initiators that generate active radicals include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzene Formyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)- 3-cyclopentylpropan-1-one-2-imine, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamine Base-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,4-bis(trichloromethyl)-6-piperonyl -1,3,5-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis(2-chlorophenyl)-4,4'5, 5'-Tetraphenylbiimidazole, etc.
相對於樹脂(D)及聚合性化合物(E)的合計量100質量份,聚合起始劑(F)的含量較佳為0.1質量份以上且30質量份以下,更佳為1質量份以上且20質量份以下。若聚合起始劑(F)的含量處於所述範圍內,則有發生高感度化而曝光時間縮短的傾向,因此,彩色濾光片的生產性提昇。 The content of the polymerization initiator (F) is preferably at least 0.1 parts by mass and at most 30 parts by mass, more preferably at least 1 part by mass and at most 100 parts by mass of the total amount of resin (D) and polymerizable compound (E). 20 parts by mass or less. When content of a polymerization initiator (F) exists in the said range, since there exists a tendency for high sensitivity to occur and exposure time shortening, the productivity of a color filter improves.
〔5〕聚合起始助劑(F1) 〔5〕Polymerization initiation aid (F1)
聚合起始助劑(F1)為用以促進已藉由聚合起始劑(F)開始聚合的聚合性化合物(E)的聚合的化合物、或增感劑。於包含聚合起始助劑(F1)的情況下,通常與聚合起始劑(F)組合使用。 The polymerization initiation aid (F1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound (E) whose polymerization has been initiated by the polymerization initiator (F). In the case of containing the polymerization initiation aid (F1), it is usually used in combination with the polymerization initiator (F).
作為聚合起始助劑(F1),可列舉:4,4'-雙(二甲基胺基)二苯甲酮(通稱為米氏酮(Michler's ketone))、4,4'-雙(二乙基胺基)二苯甲酮、9,10-二甲氧基蒽、2,4-二乙基噻噸酮、N-苯基甘胺酸等。 Examples of the polymerization initiation aid (F1) include: 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), Ethylamino) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine, etc.
於使用聚合起始助劑(F1)的情況下,其含量相對於樹脂(D)及聚合性化合物(F)的合計量100質量份而較佳為0.1質量份~30質量份,更佳為1質量份~20質量份。若聚合起始助劑(F1)的量處於該範圍內,則可進而以高感度形成著色圖案,且有彩色濾光片的生產性提昇的傾向。 In the case of using a polymerization initiation aid (F1), its content is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass to 20 parts by mass. When the quantity of a polymerization initiation auxiliary agent (F1) exists in this range, a colored pattern can be formed with high sensitivity, and there exists a tendency for the productivity of a color filter to improve.
〔6〕溶劑(G) 〔6〕Solvent (G)
溶劑(G)並無特別限定,可使用該領域中通常使用的溶劑。例如可列舉:酯溶劑(於分子內包含-COO-且不包含-O-的溶劑)、醚溶劑(於分子內包含-O-且不包含-COO-的溶劑)、醚酯溶劑(於分子內包含-COO-與-O-的溶劑)、酮溶劑(於分子內包含-CO-且不 包含-COO-的溶劑)、醇溶劑(於分子內包含OH且不包含-O-、-CO-及-COO-的溶劑)、芳香族烴溶劑、醯胺溶劑、二甲基亞碸等。 The solvent (G) is not particularly limited, and solvents generally used in this field can be used. For example, ester solvents (solvents containing -COO- and not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether ester solvents (solvents containing -O- in the molecule Solvents containing -COO- and -O-), ketone solvents (containing -CO- and not Solvents containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide, and the like.
作為溶劑(G),可列舉:乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸正丁酯、丁酸乙酯、丁酸丁酯、丙酮酸乙酯、乙醯乙酸甲酯、環己醇乙酸酯及γ-丁內酯等的酯溶劑(於分子內包含-COO-且不包含-O-的溶劑);乙二醇單丁醚、二乙二醇單甲醚、丙二醇單甲醚、3-甲氧基-1-丁醇、二乙二醇二甲醚、二乙二醇甲基***等的醚溶劑(於分子內包含-O-且不包含-COO-的溶劑);3-甲氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-甲氧基丁基乙酸酯、丙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單***乙酸酯等的醚酯溶劑(於分子內包含-COO-與-O-的溶劑);4-羥基-4-甲基-2-戊酮、庚酮、4-甲基-2-戊酮、環己酮等的酮溶劑(於分子內包含-CO-且不包含-COO-的溶劑);丁醇、環己醇、丙二醇等的醇溶劑(於分子內包含OH且不包含-O-、-CO-及-COO-的溶劑);N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基吡咯啶酮等的醯胺溶劑等。 Examples of the solvent (G) include: ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetylacetate Ester solvents such as esters, cyclohexanol acetate, and γ-butyrolactone (solvents containing -COO- and not containing -O- in the molecule); ethylene glycol monobutyl ether, diethylene glycol monomethyl ether , propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, etc. (contains -O- and does not contain -COO- in the molecule solvents); methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate Ether ester solvents such as esters and diethylene glycol monoethyl ether acetate (solvents containing -COO- and -O- in the molecule); 4-hydroxy-4-methyl-2-pentanone, heptanone, 4 - Ketone solvents such as methyl-2-pentanone and cyclohexanone (solvents that contain -CO- and do not contain -COO- in the molecule); alcohol solvents such as butanol, cyclohexanol, and propylene glycol (solvents that contain -CO- in the molecule Solvents containing OH and excluding -O-, -CO- and -COO-); N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, etc. amide solvents, etc.
作為溶劑(G),更佳為丙二醇單甲醚乙酸酯、丙二醇單甲醚、乳酸乙酯、3-乙氧基丙酸乙酯及4-羥基-4-甲基-2-戊酮。 The solvent (G) is more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, and 4-hydroxy-4-methyl-2-pentanone.
於包含溶劑(G)的情況下,於著色硬化性樹脂組成物 的總量100質量份中,溶劑(G)的含量較佳為70質量份以上且95質量份以下,更佳為75質量份以上且92質量份以下。換言之,於著色硬化性樹脂組成物的總量100質量份中,著色硬化性樹脂組成物的固體成分的總量較佳為5質量份以上且30質量份以下,更佳為8質量份以上且25質量份以下。 In the case of containing the solvent (G), in the colored curable resin composition The content of the solvent (G) is preferably not less than 70 parts by mass and not more than 95 parts by mass, more preferably not less than 75 parts by mass and not more than 92 parts by mass, per 100 parts by mass of the total amount. In other words, the total amount of solid content of the colored curable resin composition is preferably at least 5 parts by mass and at most 30 parts by mass, more preferably at least 8 parts by mass and at most 100 parts by mass of the total amount of the curable colored resin composition. 25 parts by mass or less.
若溶劑(G)的含量處於所述範圍內,則有如下傾向:塗佈時的平坦性變良好,另外於形成彩色濾光片時色濃度不會不足,因而顯示特性變良好。 When the content of the solvent (G) is within the above range, the flatness at the time of coating tends to be good, and the display characteristics tend to be good because the color density does not become insufficient when forming a color filter.
〔7〕調平劑(H) 〔7〕Leveling agent (H)
作為調平劑(H),可列舉:矽酮系界面活性劑、氟系界面活性劑及具有氟原子的矽酮系界面活性劑等。該些亦可於側鏈具有聚合性基。 Examples of the leveling agent (H) include silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having a fluorine atom, and the like. These may have a polymeric group in a side chain.
作為矽酮系界面活性劑,可列舉分子內具有矽氧烷鍵的界面活性劑等。具體而言,可列舉:東麗矽酮(Toray Silicone)DC3PA、東麗矽酮(Toray Silicone)SH7PA、東麗矽酮(Toray Silicone)DC11PA、東麗矽酮(Toray Silicone)SH21PA、東麗矽酮(Toray Silicone)SH28PA、東麗矽酮(Toray Silicone)SH29PA、東麗矽酮(Toray Silicone)SH30PA、東麗矽酮(Toray Silicone)SH8400(商品名:東麗道康寧(Toray Dow Corning)(股)製造);KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業(股)製造);TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF4446、TSF4452及TSF4460(日本邁圖高新材料 (Momentive Performance Materials Japan)有限責任公司製造)等。 Examples of the silicone-based surfactant include those having a siloxane bond in the molecule, and the like. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone Ketone (Toray Silicone) SH28PA, Toray Silicone (Toray Silicone) SH29PA, Toray Silicone (Toray Silicone) SH30PA, Toray Silicone (Toray Silicone) SH8400 (trade name: Toray Dow Corning (shares) ) manufacturing); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); material (manufactured by Momentive Performance Materials Japan Co., Ltd.), etc.
作為氟系界面活性劑,可列舉分子內具有氟碳鏈的界面活性劑等。具體而言,可列舉:弗拉德(Fluorad)(註冊商標)FC430、弗拉德(Fluorad)FC431(住友3M(股)製造)、美佳法(Megafac)(註冊商標)F142D、美佳法(Megafac)F171、美佳法(Megafac)F172、美佳法(Megafac)F173、美佳法(Megafac)F177、美佳法(Megafac)F183、美佳法(Megafac)F554、美佳法(Megafac)R30、美佳法(Megafac)RS-718-K(迪愛生(DIC)(股)製造)、艾福拓(Eftop)(註冊商標)EF301、艾福拓(Eftop)EF303、艾福拓(Eftop)EF351、艾福拓(Eftop)EF352(三菱材料電子化成(股)製造)、沙福隆(Surflon)(註冊商標)S381、沙福隆(Surflon)S382、沙福隆(Surflon)SC101、沙福隆(Surflon)SC105(旭硝子(股)製造)及E5844(大金精細化學品研究所(股)製造)等。 Examples of the fluorine-based surfactant include those having a fluorocarbon chain in the molecule, and the like. Specifically, examples include: Fluorad (registered trademark) FC430, Fluorad (Fluorad) FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac )F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop ) EF352 (manufactured by Mitsubishi Materials Corporation), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass (stock) manufacturing) and E5844 (daikin Institute of Fine Chemicals (stock) manufacturing), etc.
作為具有氟原子的矽酮系界面活性劑,可列舉分子內具有矽氧烷鍵及氟碳鏈的界面活性劑等。具體而言,可列舉:美佳法(Megafac)(註冊商標)R08、美佳法(Megafac)BL20、美佳法(Megafac)F475、美佳法(Megafac)F477及美佳法(Megafac)F443(迪愛生(股)製造)等。 Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, examples include: Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (DIS (shares) ) Manufacturing) etc.
於包含調平劑(H)的情況下,於著色硬化性樹脂組成物的總量100質量份中,調平劑(H)的含量較佳為0.001質量份以上且0.2質量份以下,更佳為0.002質量份以上且0.1質量份以 下。再者,所述含量中不包含分散劑的含量。若調平劑(H)的含量處於所述範圍內,則可使彩色濾光片的平坦性良好。 When the leveling agent (H) is included, the content of the leveling agent (H) is preferably not less than 0.001 parts by mass and not more than 0.2 parts by mass, more preferably not less than 0.2 parts by mass, based on 100 parts by mass of the total amount of the colored curable resin composition 0.002 mass parts or more and 0.1 mass parts or less Down. Furthermore, the content of the dispersant is not included in the said content. When content of a leveling agent (H) exists in the said range, the flatness of a color filter can be made favorable.
〔8〕其他成分 [8] Other ingredients
著色硬化性樹脂組成物視需要亦可包含填充劑、其他高分子化合物、密接促進劑、抗氧化劑、光穩定劑、鏈轉移劑等該技術領域中公知的添加劑。 The colored curable resin composition may contain fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, and other known additives in the technical field as needed.
該添加劑亦可包含於所述著色劑分散液或共分散物中。 This additive may also be included in the colorant dispersion or co-dispersion.
〔9〕著色硬化性樹脂組成物的製造方法 [9] Method for producing colored curable resin composition
著色硬化性樹脂組成物可藉由將著色劑分散液及樹脂(D)、以及視需要使用的聚合性化合物(E)、聚合起始劑(F)、溶劑(G)、聚合起始助劑(F1)、調平劑(H)及其他成分混合而製備。 The colored curable resin composition can be obtained by mixing a colorant dispersion liquid, a resin (D), and optionally a polymerizable compound (E), a polymerization initiator (F), a solvent (G), and a polymerization initiation aid. (F1), leveling agent (H) and other components are mixed and prepared.
<彩色濾光片的製造方法> <Manufacturing method of color filter>
作為由著色劑分散液或著色硬化性樹脂組成物製造著色圖案的方法,可列舉:光微影法、噴墨法、印刷法等。其中,較佳為光微影法。 Examples of the method for producing a colored pattern from a colorant dispersion or a colored curable resin composition include photolithography, inkjet, and printing. Among them, photolithography is preferred.
藉由著色劑分散液或著色硬化性樹脂組成物包含所述共分散物,可製作對比度優異的彩色濾光片。該彩色濾光片作為顯示裝置(例如液晶顯示裝置、有機EL裝置、電子紙等)及固體攝像元件中使用的彩色濾光片而有用。 When the colorant dispersion or the colored curable resin composition contains the co-dispersion, a color filter excellent in contrast can be produced. This color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices.
以下,藉由實施例對本發明進行更詳細的說明。例中的「%」及「份」只要無特別說明則為質量%及質量份。 Hereinafter, the present invention will be described in more detail with examples. "%" and "parts" in the examples refer to mass % and mass parts unless otherwise specified.
<合成例1:化合物(I)的製備> <Synthesis Example 1: Preparation of Compound (I)>
將鄰苯二甲腈(東京化成工業(股)製造)3份與甲醇300份混合。一面將所獲得的混合物的溫度保持為5℃以下,一面花30分鐘滴加28%甲氧化鈉甲醇溶液(和光純藥工業(股)製造)2.71份,於5℃下攪拌6小時。一面將所獲得的混合物的溫度保持為5℃以下,一面加入乙酸14份。於所獲得的混合物中加入4-(2-氰基乙醯基)苯甲酸(依照US2680731中記載的方法而合成)14份,於45℃下攪拌26小時。對所獲得的混合物進行過濾,對殘渣按照水300份、甲醇300份、N,N-二甲基甲醯胺15份的順序進行清洗。將所獲得的殘渣於60℃下減壓乾燥,獲得10份下述式所表示的化合物(I)(產率83%)。 3 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 parts of methanol were mixed. While keeping the temperature of the obtained mixture at 5° C. or lower, 2.71 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 30 minutes, and stirred at 5° C. for 6 hours. While keeping the temperature of the obtained mixture at 5° C. or lower, 14 parts of acetic acid were added. 14 parts of 4-(2-cyanoacetyl)benzoic acid (synthesized according to the method described in US2680731) were added to the obtained mixture, and it stirred at 45 degreeC for 26 hours. The obtained mixture was filtered, and the residue was washed in the order of 300 parts of water, 300 parts of methanol, and 15 parts of N,N-dimethylformamide. The obtained residue was dried under reduced pressure at 60° C. to obtain 10 parts of compound (I) represented by the following formula (83% yield).
[化合物(I)的鑑定] [Identification of compound (I)]
(質量分析)離子化模式=電灑游離(electrospray ionization,ESI)+:m/z=[M+H]+ 490精確質量(Exact Mass):489 (Mass Analysis) Ionization Mode = Electrospray ionization (ESI) +: m/z = [M+H] + 490 Exact Mass: 489
<合成例2:化合物(II)的製備> <Synthesis Example 2: Preparation of Compound (II)>
將鄰苯二甲腈(東京化成工業(股)製造)7.02份與甲醇61.6份混合。一面將所獲得的混合物的溫度保持為2℃,一面花1小時30分鐘滴加28%甲氧化鈉甲醇溶液(和光純藥工業(股)製造)8.20份與甲醇74.6份。將所獲得的混合物於2℃下攪拌6小時15分鐘。一面將所獲得的混合物的溫度保持為4℃以下,一面加入乙酸10.7份。向所獲得的混合物中加入苯甲醯乙腈(東京化成工業(股)製造)17.6份,於室溫下攪拌44小時。對所獲得的混合物進行過濾,利用甲醇800份對殘渣進行清洗。將所獲得的殘渣於60℃下減壓乾燥,獲得18.0份下述式所表示的化合物(IIa)。 7.02 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 61.6 parts of methanol were mixed. While keeping the temperature of the obtained mixture at 2° C., 8.20 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 74.6 parts of methanol were added dropwise over 1 hour and 30 minutes. The obtained mixture was stirred at 2°C for 6 hours and 15 minutes. While keeping the temperature of the obtained mixture at 4°C or lower, 10.7 parts of acetic acid was added. To the obtained mixture was added 17.6 parts of benzoylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at room temperature for 44 hours. The obtained mixture was filtered, and the residue was washed with 800 parts of methanol. The obtained residue was dried under reduced pressure at 60° C. to obtain 18.0 parts of a compound (IIa) represented by the following formula.
[化合物(IIa)的鑑定] [Identification of compound (IIa)]
(質量分析)離子化模式=ESI+:m/z=[M+H]+ 402精確質量(Exact Mass):401 (Mass Analysis) Ionization Mode = ESI+: m/z = [M+H] + 402 Exact Mass (Exact Mass): 401
繼而,一面對3℃的發煙硫酸(25%)(和光純藥工業(股)製造)7.6份進行攪拌,一面加入以上所獲得的化合物(IIa)0.513份。向所獲得的混合物中加入發煙硫酸(25%)(和光純藥工業(股)製造)3.8份。一面對所獲得的混合物進行攪拌,一面花3小時30 分鐘提高至15℃。向所獲得的混合物中加入冰水139份,進而加入氯化鈉38.2份。對所獲得的混合物進行過濾,利用21.5%氯化鈉水溶液64份對所獲得的殘渣進行清洗。將所獲得的殘渣於60℃下減壓乾燥,獲得1.02份下述式所表示的化合物(II)(於化合物(IIa)上鍵結2個磺基而成的化合物)。 Next, 0.513 parts of the compound (IIa) obtained above was added while stirring 7.6 parts of oleum (25%) (manufactured by Wako Pure Chemical Industries, Ltd.) at 3°C. To the obtained mixture was added 3.8 parts of oleum (25%) (manufactured by Wako Pure Chemical Industries, Ltd.). While stirring the obtained mixture, spend 3 hours 30 minutes to increase to 15 °C. To the obtained mixture were added 139 parts of ice water, and further 38.2 parts of sodium chloride were added. The obtained mixture was filtered, and the obtained residue was washed with 64 parts of 21.5% sodium chloride aqueous solution. The obtained residue was dried under reduced pressure at 60° C. to obtain 1.02 parts of compound (II) represented by the following formula (compound in which two sulfo groups were bonded to compound (IIa)).
[化合物(II)的鑑定] [Identification of compound (II)]
(質量分析)離子化模式=ESI-:m/z=[M-H]- 560精確質量(Exact Mass):561 (Mass Analysis) Ionization Mode = ESI-: m/z = [MH] - 560 Exact Mass (Exact Mass): 561
<合成例3:樹脂(D)的製備> <Synthesis Example 3: Preparation of Resin (D)>
於具備回流冷卻器、滴加漏斗及攪拌機的燒瓶內流通適量氮氣而成為氮氣環境,放入丙二醇單甲醚乙酸酯280份,一面攪拌一面加熱至80℃。繼而,使用滴加泵花約5小時向該燒瓶內滴加將丙烯酸38份、丙烯酸3,4-環氧三環[5.2.1.02,6]癸烷-8-基酯及丙烯酸3,4-環氧三環[5.2.1.02,6]癸烷-9-基酯的混合物(含有率為1:1)289份溶解於丙二醇單甲醚乙酸酯125份中而成的溶液。另一方 面,使用其他滴加泵花約6小時向燒瓶內滴加將聚合起始劑2,2-偶氮雙(2,4-二甲基戊腈)33份溶解於丙二醇單甲醚乙酸酯235份中而成的溶液。滴加結束後,以該溫度保持4小時,之後冷卻至室溫,獲得固體成分為35.1%的共聚物(樹脂(D))溶液。所生成的共聚物的重量平均分子量Mw為9200,分散度為2.08,固體成分換算的酸價為77mg-KOH/g。樹脂(D)具有下述結構單元。 An appropriate amount of nitrogen gas was passed through a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to form a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was put in, and it was heated to 80° C. while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate and 3,4 -A solution in which 289 parts of a mixture of epoxytricyclo[5.2.1.0 2,6 ]decane-9-yl ester (content ratio 1:1) was dissolved in 125 parts of propylene glycol monomethyl ether acetate. On the other hand, 33 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in propylene glycol monomethyl ether ethyl alcohol was added dropwise to the flask over about 6 hours using another dropping pump. A solution formed in 235 parts of acid ester. After completion of the dropwise addition, the temperature was maintained for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (D)) solution having a solid content of 35.1%. The weight average molecular weight Mw of the produced copolymer was 9200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. The resin (D) has the following structural units.
樹脂的重量平均分子量(Mw)及數量平均分子量(Mn)的測定是使用GPC法並於以下條件下進行。 The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of resin was performed on the following conditions using the GPC method.
裝置:K2479(島津製作所(股)製造) Device: K2479 (manufactured by Shimadzu Corporation)
管柱:島津(SHIMADZU)Shim-pack GPC-80M Column: Shimadzu (SHIMADZU) Shim-pack GPC-80M
管柱溫度:40℃ Column temperature: 40°C
溶媒:四氫呋喃(tetrahydrofuran,THF) Solvent: tetrahydrofuran (tetrahydrofuran, THF)
流速:1.0mL/min Flow rate: 1.0mL/min
檢測器:RI Detector: RI
校正用標準物質:TSK標準聚苯乙烯(STANDARD POLYSTYRENE)F-40、F-4、F-288、A-2500、A-500(東曹(Tosoh) (股)製造) Standard material for calibration: TSK standard polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (Tosoh) (share) manufacturing)
將所述獲得的聚苯乙烯換算的重量平均分子量(Mw)與數量平均分子量(Mn)之比(Mw/Mn)設為分散度。 The ratio (Mw/Mn) of the obtained polystyrene-equivalent weight average molecular weight (Mw) to the number average molecular weight (Mn) was defined as the degree of dispersion.
<合成例4:脂肪族羧酸金屬鹽(C)分散液(分散液(C))的製備> <Synthesis Example 4: Preparation of Aliphatic Carboxylate Metal Salt (C) Dispersion (Dispersion (C))>
(脂肪族羧酸金屬鹽(C)的合成) (Synthesis of aliphatic carboxylic acid metal salt (C))
於燒杯中將100份的純水及5份的12-羥基硬脂酸(東京化成工業(股)製造)混合。於70℃下向該混合物中加入1%氫氧化鈉水溶液65份。一面將其保持為70℃~75℃,一面花約2小時30分鐘滴加硝酸鐵(III)九水合物(和光純藥工業(股)製造)2份與水40份的混合物。將該混合物一面保持為70℃~75℃一面攪拌約1小時。將該混合物冷卻至35℃並進行過濾。 100 parts of pure water and 5 parts of 12-hydroxystearic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in a beaker. To this mixture was added 65 parts of 1% aqueous sodium hydroxide solution at 70°C. While keeping it at 70° C. to 75° C., a mixture of 2 parts of iron (III) nitrate nonahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 40 parts of water was added dropwise over about 2 hours and 30 minutes. The mixture was stirred for about 1 hour while maintaining the temperature at 70°C to 75°C. The mixture was cooled to 35°C and filtered.
利用水245份將所獲得的殘渣清洗3次,並於60℃下減壓乾燥,獲得包含12-羥基硬脂酸陰離子作為陰離子成分的羧酸鐵(III)鹽(下述式(c)所表示的鹽)。以下,將該鹽稱作脂肪族羧酸金屬鹽(C)。 The obtained residue was washed 3 times with 245 parts of water, and dried under reduced pressure at 60°C to obtain an iron (III) carboxylate salt (formulated by the following formula (c)) containing 12-hydroxystearic acid anion as an anion component. indicated salt). Hereinafter, this salt is called an aliphatic carboxylic acid metal salt (C).
(分散液(C)的製備) (Preparation of Dispersion (C))
將脂肪族羧酸金屬鹽(C) 2.50份;分散劑1 4.00份;溶劑(G):PGMEA 68.50份;以及溶劑(G):DAA 25.00份混合,並使脂肪族羧酸金屬鹽(C)分散,藉此獲得分散液(C)。 Mix 2.50 parts of aliphatic carboxylic acid metal salt (C); 4.00 parts of dispersant 1; solvent (G): 68.50 parts of PGMEA; and solvent (G): DAA 25.00 parts, and make aliphatic carboxylic acid metal salt (C) dispersed, whereby a dispersion liquid (C) is obtained.
調配成分的詳細情況如下。 The details of the blended ingredients are as follows.
〔1〕脂肪族羧酸金屬鹽(C):合成例4中獲得的脂肪族羧酸金屬鹽(C) [1] Aliphatic carboxylic acid metal salt (C): Aliphatic carboxylic acid metal salt (C) obtained in Synthesis Example 4
〔2〕分散劑1:分散劑(迪斯帕畢克(DISPERBYK)-111;日本畢克化學(BYK-chemie Japan)(股)製造) [2] Dispersant 1: Dispersant (DISPERBYK-111; manufactured by BYK-chemie Japan Co., Ltd.)
〔3〕PGMEA:丙二醇單甲醚乙酸酯 〔3〕PGMEA: Propylene Glycol Monomethyl Ether Acetate
〔4〕DAA:二丙酮醇(4-羥基-4-甲基-2-戊酮) 〔4〕DAA: diacetone alcohol (4-hydroxy-4-methyl-2-pentanone)
<實施例1~實施例7、比較例1~比較例5:著色劑分散液的製備> <Example 1 to Example 7, Comparative Example 1 to Comparative Example 5: Preparation of Colorant Dispersion>
將表7所示的著色劑、分散劑2、合成例3中獲得的樹脂(D)溶液、合成例4中獲得的分散液(C)〔有未使用的例子〕、以及表7所示的溶劑(G)混合,使用珠磨機而獲得各著色劑分散液。 The coloring agent shown in Table 7, dispersant 2, the resin (D) solution obtained in Synthesis Example 3, the dispersion liquid (C) obtained in Synthesis Example 4 [there are unused examples], and the resin shown in Table 7 The solvent (G) was mixed, and each colorant dispersion was obtained using a bead mill.
實施例1、實施例4、實施例6及比較例2的著色劑分散液包含兩種著色劑的共分散物。實施例2、實施例3、實施例5、實施 例7、比較例3及比較例4的著色劑分散液包含兩種著色劑的共分散物及分散液(C)(脂肪族羧酸金屬鹽(C)分散液)。 The colorant dispersions of Example 1, Example 4, Example 6, and Comparative Example 2 contain a co-dispersion of two kinds of colorants. Embodiment 2, embodiment 3, embodiment 5, implementation The colorant dispersions of Example 7, Comparative Example 3, and Comparative Example 4 include a co-dispersion of two kinds of colorants and a dispersion (C) (aliphatic carboxylic acid metal salt (C) dispersion).
將各實施例、比較例中獲得的著色劑分散液的組成示於表7。表7的數值的單位為質量份。表7中的溶劑(G)中包含樹脂(D)溶液中及分散液(C)中的溶劑。 Table 7 shows the compositions of the colorant dispersions obtained in Examples and Comparative Examples. The unit of the numerical value in Table 7 is a mass part. The solvent (G) in Table 7 includes the solvent in the resin (D) solution and the dispersion liquid (C).
著色劑分散液中所含的調配成分的詳細情況如下。 The details of the compounded components contained in the colorant dispersion liquid are as follows.
〔1〕Y138:C.I.顏料黃138 [1] Y138: C.I. Pigment Yellow 138
〔2〕Y185:C.I.顏料黃185 [2] Y185: C.I. Pigment Yellow 185
〔3〕化合物(I):合成例1中獲得的化合物(I) [3] Compound (I): Compound (I) obtained in Synthesis Example 1
〔4〕化合物(II):合成例2中獲得的化合物(II) [4] Compound (II): Compound (II) obtained in Synthesis Example 2
〔5〕脂肪族羧酸金屬鹽(C):合成例4中獲得的脂肪族羧酸金屬鹽(C) [5] Aliphatic carboxylic acid metal salt (C): the aliphatic carboxylic acid metal salt (C) obtained in Synthesis Example 4
〔6〕分散劑2:分散劑(畢克(BYK)-LP N 6919;日本畢 克化學(BYK-chemie Japan)(股)製造) 〔6〕Dispersant 2: Dispersant (BYK (BYK)-LP N 6919; Japanese Bi BYK-chemie Japan (manufactured by BYK-chemie Japan)
〔7〕樹脂(D):合成例3中獲得的樹脂(D)溶液中所含的樹脂(D) [7] Resin (D): Resin (D) contained in the resin (D) solution obtained in Synthesis Example 3
〔8〕PGMEA:丙二醇單甲醚乙酸酯 [8] PGMEA: Propylene Glycol Monomethyl Ether Acetate
〔9〕DAA:二丙酮醇(4-羥基-4-甲基-2-戊酮) 〔9〕DAA: diacetone alcohol (4-hydroxy-4-methyl-2-pentanone)
<實施例8~實施例16、比較例6~比較例10> <Example 8~Example 16, Comparative Example 6~Comparative Example 10>
(1)著色硬化性樹脂組成物的製備 (1) Preparation of colored curable resin composition
於實施例8~實施例14及比較例6~比較例10中,分別將實施例1~實施例7、比較例1~比較例5的著色劑分散液、與樹脂(D)溶液、聚合性化合物(E)、聚合起始劑(F)及調平劑(H)混合而獲得著色硬化性樹脂組成物。 In embodiment 8~embodiment 14 and comparative example 6~comparative example 10, the colorant dispersion liquid of embodiment 1~embodiment 7, comparative example 1~comparative example 5, and resin (D) solution, polymerizability Compound (E), polymerization initiator (F) and leveling agent (H) are mixed to obtain a colored curable resin composition.
於實施例15及實施例16中,將實施例1的著色劑分散液、與合成例4中獲得的分散液(C)、以及樹脂(D)溶液、聚合性化合物(E)、聚合起始劑(F)及調平劑(H)混合而獲得著色硬化性樹脂組成物。 In Examples 15 and 16, the colorant dispersion in Example 1, the dispersion (C) obtained in Synthesis Example 4, and the resin (D) solution, polymerizable compound (E), polymerization initiator The agent (F) and the leveling agent (H) are mixed to obtain a colored curable resin composition.
再者,當製備著色硬化性樹脂組成物時,以使著色硬化性樹脂組成物的固體成分成為20質量%的方式添加丙二醇單甲醚乙酸酯(PGMEA)。 In addition, when preparing a colored curable resin composition, propylene glycol monomethyl ether acetate (PGMEA) was added so that the solid content of the colored curable resin composition might become 20 mass %.
各實施例、比較例中所使用的著色劑分散液、以及各實施例、比較例中所獲得的著色硬化性樹脂組成物中的將溶劑(G)除外的組成示於表8及表9。表8及表9中各成分的調配量的單位為質量份。 Table 8 and Table 9 show the colorant dispersion liquid used in each Example and Comparative Example, and the composition excluding the solvent (G) in the colored curable resin composition obtained in each Example and Comparative Example. The unit of the compounding quantity of each component in Table 8 and Table 9 is mass parts.
聚合性化合物(E)、聚合起始劑(F)及調平劑(H)的詳細情況如下。 The details of the polymerizable compound (E), the polymerization initiator (F) and the leveling agent (H) are as follows.
〔1〕聚合性化合物(E):二季戊四醇六丙烯酸酯(卡亞拉得(KAYARAD)DPHA;日本化藥(股)製造) [1] Polymerizable compound (E): Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
〔2〕聚合起始劑(F):N-苯甲醯基氧基-1-(4-苯硫基苯基)辛烷-1-酮-2-亞胺(豔佳固(Irgacure)(註冊商標)OXE-01;日本巴斯夫(BASF Japan)公司製造) [2] Polymerization initiator (F): N-benzoyloxy-1-(4-phenylthiophenyl) octane-1-one-2-imine (Irgacure ( registered trademark) OXE-01; manufactured by BASF Japan)
〔3〕調平劑(H):聚醚改質矽油(東麗矽酮(Toray Silicone)SH8400;東麗道康寧(Toray Dow Corning)(股)製造) [3] Leveling agent (H): polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning (stock))
(2)著色塗膜的製作 (2) Preparation of colored coating film
於5cm見方的玻璃基板(益格(eagle)2000;康寧(Corning)公司製造)上藉由旋塗法塗佈著色硬化性樹脂組成物,之後於100℃下預烘烤3分鐘,形成著色組成物層。放置冷卻後,使用曝光機(TME-150RSK;拓普康(Topcon)(股)製造)於大氣環境下以150mJ/cm2的曝光量(365nm基準)進行光照射。將光照射後的著色組成物層於包含非離子系界面活性劑0.12%與氫氧化鉀0.04%的水系顯影液中於24℃下浸漬顯影10秒鐘,水洗後,於烘箱中於230℃下進行30分鐘後烘烤,從而獲得著色塗膜。 On a 5 cm square glass substrate (eagle 2000; manufactured by Corning Corporation), the colored curable resin composition was coated by spin coating, and then prebaked at 100°C for 3 minutes to form a colored composition object layer. After leaving to cool, it irradiated with light at an exposure amount of 150 mJ/cm 2 (365 nm basis) in an air environment using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). Immerse and develop the colored composition layer after light irradiation in an aqueous developer solution containing 0.12% non-ionic surfactant and 0.04% potassium hydroxide at 24°C for 10 seconds, wash it with water, and place it in an oven at 230°C Post-baking was performed for 30 minutes to obtain a colored coating film.
(3)膜厚測定 (3) Film thickness measurement
對於所述(2)中獲得的著色塗膜,使用膜厚測定裝置(DEKTAK3;日本真空技術(股)製造)來測定膜厚。 The film thickness of the colored coating film obtained in (2) above was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).
所獲得的著色塗膜的膜厚於任一實施例及比較例中均為2.0 μm。 The film thickness of the colored coating film that obtains is all 2.0 in any embodiment and comparative example μm.
(4)色度評價 (4) Chromaticity evaluation
對於所述(2)中獲得的著色塗膜,使用測色機(OSP-SP-200;奧林巴斯(Olympus)(股)製造)測定分光,使用C光源的特性函數來測定國際照明學會(Commission Internationale de I'Eclairage,CIE)的XYZ表色系統中的XY色度坐標(x,y)。將結果示於表8及表9。 For the colored coating film obtained in the above (2), use a color measuring machine (OSP-SP-200; manufactured by Olympus (Olympus) Co., Ltd.) to measure the spectrum, and use the characteristic function of the C light source to measure the XY chromaticity coordinates (x, y) in the XYZ colorimetric system of the Commission Internationale de I'Eclairage, CIE. The results are shown in Table 8 and Table 9.
(5)對比度評價 (5) Contrast evaluation
對於所述(2)中獲得的著色塗膜,使用對比度計(CT-1:壺阪電機公司製造、色彩色差計BM-5A:拓普康(Topcon)公司製造、光源:F-10、偏光膜:壺阪電機(股)製造)並將空白值設為30000來測定對比度。將結果示於表8及表9。可以說,若著色塗膜中的對比度高,則著色圖案中亦同樣為高對比度。 For the colored coating film obtained in (2), a contrast meter (CT-1: manufactured by Tsubosaka Electric Co., Ltd., color difference meter BM-5A: manufactured by Topcon Corporation, light source: F-10, polarizing film : manufactured by Tsubusaka Electric Co., Ltd.) and the contrast was measured with a blank value of 30000. The results are shown in Table 8 and Table 9. It can be said that if the contrast in the colored coating film is high, the contrast will also be high in the colored pattern.
根據本發明,可提供一種改善了對比度的彩色濾光片、以及包含其的顯示裝置。 According to the present invention, a color filter with improved contrast and a display device including the same can be provided.
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018-039681 | 2018-03-06 | ||
JP2018039681 | 2018-03-06 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201938531A TW201938531A (en) | 2019-10-01 |
TWI790354B true TWI790354B (en) | 2023-01-21 |
Family
ID=67846487
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW108106773A TWI790354B (en) | 2018-03-06 | 2019-02-27 | Colorant dispersion, colored curable resin composition, color filter, and display device |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP7241566B2 (en) |
KR (1) | KR102637673B1 (en) |
CN (1) | CN111836859B (en) |
TW (1) | TWI790354B (en) |
WO (1) | WO2019171999A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2024058001A1 (en) * | 2022-09-16 | 2024-03-21 | 富士フイルム株式会社 | Coloring composition, film, optical filter, solid-state imaging element, image display device, and compound |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012236882A (en) * | 2011-05-10 | 2012-12-06 | Dainippon Printing Co Ltd | Yellow pigment dispersed liquid, yellow photosensitive resin composition for color filter, color filter, liquid crystal display and organic light emitting display device |
CN107586469A (en) * | 2016-07-07 | 2018-01-16 | 住友化学株式会社 | Color compositions, coloured composition and cured composition for color |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5334624B2 (en) * | 2008-03-17 | 2013-11-06 | 富士フイルム株式会社 | Colored curable composition, color filter, and method for producing color filter |
JP5728336B2 (en) * | 2011-08-31 | 2015-06-03 | 富士フイルム株式会社 | Color filter manufacturing method and solid-state image sensor manufacturing method |
KR102092910B1 (en) * | 2015-06-30 | 2020-03-24 | 동우 화인켐 주식회사 | Colored photosensitive resin composition, color filter and display device |
JP6799949B2 (en) * | 2015-07-21 | 2020-12-16 | 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. | Color curable resin composition, color filter and display device |
TWI712654B (en) * | 2016-02-01 | 2020-12-11 | 日商住友化學股份有限公司 | Compound and coloring composition |
KR102378450B1 (en) * | 2016-03-31 | 2022-03-23 | 스미또모 가가꾸 가부시끼가이샤 | Colored curable resin composition |
KR102583553B1 (en) * | 2016-07-28 | 2023-09-27 | 엘지디스플레이 주식회사 | Colorant, colored resin composition comprising the same and color filter |
-
2019
- 2019-02-25 KR KR1020207028203A patent/KR102637673B1/en active IP Right Grant
- 2019-02-25 WO PCT/JP2019/006984 patent/WO2019171999A1/en active Application Filing
- 2019-02-25 CN CN201980016992.8A patent/CN111836859B/en active Active
- 2019-02-26 JP JP2019032594A patent/JP7241566B2/en active Active
- 2019-02-27 TW TW108106773A patent/TWI790354B/en active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012236882A (en) * | 2011-05-10 | 2012-12-06 | Dainippon Printing Co Ltd | Yellow pigment dispersed liquid, yellow photosensitive resin composition for color filter, color filter, liquid crystal display and organic light emitting display device |
CN107586469A (en) * | 2016-07-07 | 2018-01-16 | 住友化学株式会社 | Color compositions, coloured composition and cured composition for color |
Also Published As
Publication number | Publication date |
---|---|
CN111836859A (en) | 2020-10-27 |
JP2019157119A (en) | 2019-09-19 |
KR20200130344A (en) | 2020-11-18 |
TW201938531A (en) | 2019-10-01 |
KR102637673B1 (en) | 2024-02-15 |
CN111836859B (en) | 2022-03-25 |
JP7241566B2 (en) | 2023-03-17 |
WO2019171999A1 (en) | 2019-09-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108983548B (en) | Colored resin composition, color filter and display device | |
TWI790354B (en) | Colorant dispersion, colored curable resin composition, color filter, and display device | |
TWI803668B (en) | Colored curable resin composition, color filter and display device | |
TWI751313B (en) | Colored curable resin composition | |
TWI754733B (en) | Isoindoline dye and method for producing the same | |
JP7067991B2 (en) | Method for manufacturing isoindoline pigment | |
JP7055677B2 (en) | Method for manufacturing isoindoline pigment | |
TWI827836B (en) | Colored resin composition, color filter and display device | |
TW201840738A (en) | Colored resin composition, color filter, and image display device capable of having excellence in contrast and light resistance | |
JP7091104B2 (en) | Isoindoline pigment | |
JP7079127B2 (en) | Color curable resin composition | |
TWI746941B (en) | Compound, colored resin composition, color filter and display device | |
TWI743375B (en) | Colored curable resin composition, color filter and display device | |
TWI738984B (en) | Colored curable resin composition, color filter and display device | |
CN108663903B (en) | Colored resin composition, color filter and display device | |
CN114185247A (en) | Curable coloring composition | |
CN113943494A (en) | Coloring composition |