TW201938531A - Coloring agent dispersion, coloring curable resin composition, color filter and display device - Google Patents
Coloring agent dispersion, coloring curable resin composition, color filter and display device Download PDFInfo
- Publication number
- TW201938531A TW201938531A TW108106773A TW108106773A TW201938531A TW 201938531 A TW201938531 A TW 201938531A TW 108106773 A TW108106773 A TW 108106773A TW 108106773 A TW108106773 A TW 108106773A TW 201938531 A TW201938531 A TW 201938531A
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- ring
- substituent
- hydrocarbon group
- carbon atoms
- 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
-
- 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
-
- 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
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
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 colorant dispersion liquid, a coloring 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 for manufacturing a color filter used in a display device such as a liquid crystal display device, an electroluminescence display device, and a plasma display. A display device using a color filter is required to have 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。
[現有技術文獻]
[專利文獻]In Japanese Patent Application Laid-Open No. 2002-179979 (Patent Document 1), in order to improve the contrast of a display device, a color paste containing a color index (CI) pigment yellow 138 as a yellow pigment is added. It further contains a sulfonated derivative of CI Pigment Yellow 138.
[Prior Art Literature]
[Patent Literature]
[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
[發明所欲解決之課題]
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。[Problems to be Solved by the Invention]
An object of the present invention is to provide a colorant dispersion liquid containing CI Pigment Yellow 138 and capable of forming a color filter exhibiting good contrast, a coloring curable resin composition including the colorant dispersion liquid, and the colorant dispersion liquid. Or a color filter formed of the colored curable resin composition, and a display device including the color filter.
[解決課題之手段]
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。
[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。[Means for solving problems]
The present invention provides a colorant dispersion liquid, a coloring curable resin composition, a color filter, and a display device described below.
[1] A colorant dispersion liquid comprising a co-dispersion of CI Pigment Yellow 138 (A) as a main component and a 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)2
O-
的合計數,且為0~10的任一整數。
a)於a為1~10的任一整數的情況下,
X表示CR8
R9
,
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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
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)2
O-
,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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
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)2
OH。該環可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
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)2
O-
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。
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)2
O-
一起作為-CO2
H及S(O)2
OH而存在。
b表示1~6的任一整數。
m表示Mb+
的個數。
n為滿足n=b×m/a的關係的數。[In formula (I),
a represents the total number of -CO 2 - and -S (O) 2 O - which the compound represented by formula (I) has, and is any integer from 0 to 10.
a) When a is any integer from 1 to 10,
X means CR 8 R 9 ,
R 1 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group or a hydrogen atom which may have a substituent, -CH 2 -contained in the hydrocarbon group, and the heterocyclic group contains- The -CH 2 -at CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
R 2 to R 9 each 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 when the -CH 2 - - (O) 2 O -, -CH the hydrocarbon group contained in 2 - group and the heterocyclic ring containing not constitute -CH 2 may be replaced by -O -, - CO- , -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
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 each carbon The atoms together form a ring which may have a substituent, and the ring contains -CH 2 -when it does not form a ring -CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or- NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The ring may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
R na represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group or a hydrogen atom which may have a substituent, and the hydrocarbon group and the heterocyclic group may have a member selected from -CO 2 - and -S (O) 2 O - at least one of the group. In the case where there are multiple R na , these may be the same or different.
M b + represents a hydrogen ion or a b-valent metal ion. In the case where there are multiple M b + , these may be the same or different. When M b + is a hydrogen positive ion, the hydrogen positive ion together with the -CO 2 - and -S (O) 2 O - exists as -CO 2 H and S (O) 2 OH.
b represents any integer from 1 to 6.
m represents the number of M b + .
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。
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)2
OH。
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)2
OH。
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)2
OH。
R6
表示-CO-ORnb1
、-CO-NH2
、-CO-NH(Rnb1
)、-CO-N(Rnb1
)2
、-CO-H、-CO-Rnb1
或-S(O)2
-Rnb1
。
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。
(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)2
OH。
(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)2
OH。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)2
OH。
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)2
OH。另外,R7
可與R6
及R7
鍵結的碳原子一起形成環。
X表示式(1a)所表示的基團。b) When a is 0,
n represents 1 and m represents 0.
R 1 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group or a hydrogen atom which may have a substituent, -CH 2 -contained in the hydrocarbon group, and the heterocyclic group contains- -CH 2 -in CH 2 -may be substituted with -O-, -CO-, -S (O) 2- , -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
R 2 to R 5 each 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- When CH 2 -and the heterocyclic group include -CH 2 -which does not constitute a ring, the -CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
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 which may have a substituent together with the carbon atoms to which they are bonded, the ring It does not form a ring comprising -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
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 .
However, when R 6 represents -CO-NH (R nb1 ), R 2 to R 5 satisfy at least one of (ib) and (iib).
(Ib) At least one of R 2 to R 5 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom, a cyano group, or a nitro group. -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb - . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
(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, the ring comprising -CH does not form a ring of 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The non-ring-forming ones in R 2 to 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. hydrocarbon contained in the -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - Or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
R 7 represents 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 -and the hetero group contained in the hydrocarbon group cycloalkyl group constituting the ring does not comprise -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . R 7 may form a ring together with the carbon atoms to which R 6 and R 7 are bonded.
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)2
OH。
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)2
OH。
*1表示與異吲哚啉環的結合鍵。]
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。
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)2
OH。於存在多個Rnb1
的情況下,該些可相同亦可不同。
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。][In formula (1a),
R 17b and R 18b each 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 the hydrocarbon group contains- When CH 2 -and the heterocyclic group include -CH 2 -which does not form a ring, the -CH 2 -may be substituted with -O-, -CO-, -S (O) 2- , or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
R 17b and R 18b may be formed with the respective carbon atoms are bonded together ring may have a substituent, which does not form a ring comprising a ring -CH 2 - when the -CH 2 - may be substituted with -O-, -CO-, -S (O) 2 -or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
* 1 represents a bonding bond with an isoindoline ring. ]
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 multiple R nb are present, these may be the same or different.
R nb1 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. The -CH 2 -contained in the hydrocarbon group and the heterocyclic group contains -CH 2 -which does not constitute a ring. The -CH 2 -at this time may be substituted with -O-, -CO- , -S (O) 2 -or -NR nb10- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . When there are multiple R nb1s , these may be the same or different.
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. In the case where a plurality of R nb10 are present, 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 toner dispersion liquid according to [1], wherein the group represented by the formula (1a) is a group represented by the 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)2
OH。
Rnb
表示與前述相同的含義。
*2表示與異吲哚啉環的結合鍵。][In formula (2a),
R 19b and R 20b each independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group or a hydrogen atom which may have a substituent, and -CH 2 -contained in the hydrocarbon group and the heterocyclic group include The -CH 2 -in the case of -CH 2 -which does not constitute a ring may be substituted with -O-, -CO-, -S (O) 2 -or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
R nb has the same meaning as described above.
* 2 represents a bonding bond with an 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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
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)2
OH。該環可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
R6
表示-CO-ORna1
、-CO-NH2
、-CO-NH(Rna1
)、-CO-N(Rna1
)2
、-CO-H、-CO-Rna1
或-S(O)2
-Rna1
。
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。
(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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
(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)2
OH。該環可具有選自由-CO2 -
及-S(O)2
O-
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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
R7
表示氰基。
X表示式(1a-x)所表示的基團。[3] The toner dispersion liquid according to [1] or [2], wherein, in the formula (I),
a) When a is any integer from 1 to 10,
R 2 to R 5 each 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- When CH 2 -and the heterocyclic group include -CH 2 -which does not constitute a ring, the -CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
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 which may have a substituent together with the carbon atoms to which they are bonded, the ring It does not form a ring comprising -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR na -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The ring may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
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 .
However, when R 6 represents -CO-NH (R na1 ), R 2 to R 5 satisfy at least one of (ia) and (iia).
(Ia) At least one of R 2 to R 5 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom, a cyano group, or a nitro group. -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR na - . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
(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, the ring comprising -CH does not form a ring of 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR na -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The ring may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of. The non-ring-forming ones in R 2 to 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. hydrocarbon contained in the -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - Or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
R 7 represents a cyano group.
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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
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)2
OH。該環可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
*1表示與異吲哚啉環的結合鍵。]
Rna
表示與前述相同的含義。
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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
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。
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。
b)於a為0的情況下,
R7
表示氰基。[In formula (1a-x),
R 21 and R 22 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 the hydrocarbon group contains − When CH 2 -and the heterocyclic group include -CH 2 -which does not constitute a ring, the -CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
R 21 and R 22 each may be formed are bonded together with the ring carbon atoms may have a substituent group, which does not form a ring comprising a ring -CH 2 - when the -CH 2 - may be substituted with -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The ring may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
* 1 represents a bonding bond with an isoindoline ring. ]
R na has the same meaning as described above.
R na1 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. The -CH 2 -contained in the hydrocarbon group and the heterocyclic group contains -CH 2- The -CH 2 -at this time may be substituted with -O-, -CO- , -S (O) 2 -or -NR na10- . Among them, -COOH and -S (O) 2 OH are not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of. In the case where there are multiple R na1s , these may be the same or different.
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. When a plurality of R na10 are present, these may be the same or different.
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 toner 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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
Rna
表示與前述相同的含義。
*2表示與異吲哚啉環的結合鍵。][In formula (2a-x),
R 23 and R 24 independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group or a hydrogen atom which may have a substituent, and -CH 2 -contained in the hydrocarbon group and the heterocyclic group include The -CH 2 -in the case of -CH 2 -which does not constitute a ring may be substituted with -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
R na has the same meaning as described above.
* 2 represents a bonding bond with an 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。
[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)。
[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。
[8] 一種顯示裝置,其包含如[7]所述的彩色濾光片。[5] The toner dispersion liquid according to any one of [1] to [4], further comprising a metal salt (C) containing a fat having 1 to 40 carbon atoms having a hydroxyl group Anions of the carboxylic acids of the Group.
[6] A color-setting curable resin composition comprising the colorant dispersion liquid according to any one of [1] to [5], and a resin (D).
[7] A color filter formed of the colorant dispersion liquid according to any one of [1] to [5] or the coloring curable resin composition according to [6].
[8] A display device including the color filter according to [7].
[發明的效果]
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。[Effect of the invention]
According to the coloring agent dispersion liquid and the coloring curable resin composition of the present invention, it is possible to provide a color filter exhibiting good contrast and a display device including the same.
<著色劑分散液>
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。
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。
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)」。
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。< Colorant dispersion liquid >
The coloring agent dispersion liquid of this invention contains the co-dispersion of CI Pigment Yellow 138 (A) and the compound (B) represented by Formula (I).
According to the colorant dispersion liquid, although CI Pigment Yellow 138 (A) is used as a main component, a color filter formed of the colorant dispersion liquid or a coloring curable resin composition containing the colorant dispersion liquid can be used. And the contrast of a display device using the same becomes good.
The colorant dispersion liquid may further include 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 "metal aliphatic carboxylic acid salt (C)".
Hereinafter, the compounds exemplified as each component may be used alone or in combination of a plurality of types unless otherwise specified.
〔1〕C.I.顏料黃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。[1] CI Pigment Yellow 138 (A)
The CI Pigment Yellow 138 (A) contained in the co-dispersion is a yellow pigment classified as a pigment in the Color Index (published by The Society of Dyers and Colourists) .
〔2〕式(I)所表示的化合物(B)
共分散物包含式(I)所表示的化合物(B)。[2] Compound (B) represented by formula (I)
The co-dispersion contains a compound (B) represented by the 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)2
O-
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 - which the compound represented by formula (I) has, and is any integer from 0 to 10.
a)於a為1~10的任一整數的情況下,
X表示CR8
R9
,
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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
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)2
O-
,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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
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)2
OH。該環可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
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)2
O-
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。
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)2
O-
一起作為-CO2
H及S(O)2
OH而存在。
b表示1~6的任一整數。
m表示Mb+
的個數。
n為滿足n=b×m/a的關係的數。a) When a is any integer from 1 to 10,
X means CR 8 R 9 ,
R 1 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group or a hydrogen atom which may have a substituent, -CH 2 -contained in the hydrocarbon group, and the heterocyclic group contains- The -CH 2 -at CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
R 2 to R 9 each 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 when the -CH 2 - - (O) 2 O -, -CH the hydrocarbon group contained in 2 - group and the heterocyclic ring containing not constitute -CH 2 may be replaced by -O -, - CO- , -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
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 each carbon The atoms together form a ring which may have a substituent, and the ring contains -CH 2 -when it does not form a ring -CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or- NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The ring may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
R na represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group or a hydrogen atom which may have a substituent, and the hydrocarbon group and the heterocyclic group may have a member selected from -CO 2 - and -S (O) 2 O - at least one of the group. In the case where there are multiple R na , these may be the same or different.
M b + represents a hydrogen positive ion or a b-valent metal ion. In the case where there are multiple M b + , these may be the same or different. When M b + is a hydrogen positive ion, the hydrogen positive ion together with the -CO 2 - and -S (O) 2 O - exists as -CO 2 H and S (O) 2 OH.
b represents any integer from 1 to 6.
m represents the number of M b + .
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。
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)2
OH。
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)2
OH。
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)2
OH。
R6
表示-CO-ORnb1
、-CO-NH2
、-CO-NH(Rnb1
)、-CO-N(Rnb1
)2
、-CO-H、-CO-Rnb1
或-S(O)2
-Rnb1
。
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。
(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)2
OH。
(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)2
OH。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)2
OH。
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)2
OH。另外,R7
可與R6
及R7
鍵結的碳原子一起形成環。
X表示式(1a)所表示的基團。b) When a is 0,
n represents 1 and m represents 0.
R 1 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group or a hydrogen atom which may have a substituent, -CH 2 -contained in the hydrocarbon group, and the heterocyclic group contains- The -CH 2 -at CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
R 2 to R 5 each 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- When CH 2 -and the heterocyclic group include -CH 2 -which does not constitute a ring, the -CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
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 which may have a substituent together with the carbon atoms to which they are bonded, the ring It does not form a ring comprising -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
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 .
However, when R 6 represents -CO-NH (R nb1 ), R 2 to R 5 satisfy at least one of (ib) and (iib).
(Ib) At least one of R 2 to R 5 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom, a cyano group, or a nitro group. -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb - . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
(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, the ring comprising -CH does not form a ring of 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The non-ring-forming ones in R 2 to 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. hydrocarbon contained in the -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - Or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
R 7 represents 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 -and the hetero group contained in the hydrocarbon group cycloalkyl group constituting the ring does not comprise -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . R 7 may form a ring together with the carbon atoms to which R 6 and R 7 are bonded.
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)2
OH。
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)2
OH。
*1表示與異吲哚啉環的結合鍵。]
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。
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)2
OH。於存在多個Rnb1
的情況下,該些可相同亦可不同。
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。][In formula (1a),
R 17b and R 18b each 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 the hydrocarbon group contains- When CH 2 -and the heterocyclic group include -CH 2 -which does not form a ring, the -CH 2 -may be substituted with -O-, -CO-, -S (O) 2- , or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
R 17b and R 18b may be formed with the respective carbon atoms are bonded together ring may have a substituent, which does not form a ring comprising a ring -CH 2 - when the -CH 2 - may be substituted with -O-, -CO-, -S (O) 2 -or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
* 1 represents a bonding bond with an isoindoline ring. ]
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 multiple R nb are present, these may be the same or different.
R nb1 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. The -CH 2 -contained in the hydrocarbon group and the heterocyclic group contains -CH 2 -which does not constitute a ring. The -CH 2 -at this time may be substituted with -O-, -CO- , -S (O) 2 -or -NR nb10- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . When there are multiple R nb1s , these may be the same or different.
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. In the case where a plurality of R nb10 are present, 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)2
OH。
Rnb
表示與所述相同的含義。
*2表示與異吲哚啉環的結合鍵。][In formula (2a),
R 19b and R 20b each independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group or a hydrogen atom which may have a substituent, and -CH 2 -contained in the hydrocarbon group and the heterocyclic group include The -CH 2 -in the case of -CH 2 -which does not constitute a ring may be substituted with -O-, -CO-, -S (O) 2 -or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
R nb has the same meaning as described above.
* 2 represents a bonding bond with an isoindoline ring. ]
〔2-1〕式(I)所表示的化合物(B)的第1態樣
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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
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)2
OH。該環可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
R6
表示-CO-ORna1
、-CO-NH2
、-CO-NH(Rna1
)、-CO-N(Rna1
)2
、-CO-H、-CO-Rna1
或-S(O)2
-Rna1
。
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。
(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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
(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)2
OH。該環可具有選自由-CO2 -
及-S(O)2
O-
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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
R7
表示氰基。
X表示式(1a-x)所表示的基團。[2-1] The first aspect of the compound (B) represented by the formula (I) is the first aspect of the compound (B) represented by the formula (I),
In formula (I),
a) When a is any integer from 1 to 10,
R 2 to R 5 each 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- When CH 2 -and the heterocyclic group include -CH 2 -which does not constitute a ring, the -CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
At least one of R 2 and R 3 , R 3 and R 4 , and R 4 and R 5 may form a ring which may have a substituent together with the carbon atoms to which they are bonded, and the ring includes a ring that does not form a ring- The -CH 2 -at CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The ring may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
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 .
However, when R 6 represents -CO-NH (R na1 ), R 2 to R 5 satisfy at least one of (ia) and (iia).
(Ia) At least one of R 2 to R 5 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom, a cyano group, or a nitro group. -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR na - . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
(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, the ring comprising -CH does not form a ring of 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR na -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The ring may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of. The non-ring-forming ones in R 2 to 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. hydrocarbon contained in the -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - Or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
R 7 represents a cyano group.
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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
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)2
OH。該環可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
*1表示與異吲哚啉環的結合鍵。]
Rna
表示與前述相同的含義。
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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
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。
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。[In formula (1a-x),
R 21 and R 22 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 the hydrocarbon group contains − When CH 2 -and the heterocyclic group include -CH 2 -which does not constitute a ring, the -CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
R 21 and R 22 each may be formed are bonded together with the ring carbon atoms may have a substituent group, which does not form a ring comprising a ring -CH 2 - when the -CH 2 - may be substituted with -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The ring may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
* 1 represents a bonding bond with an isoindoline ring. ]
R na has the same meaning as described above.
R na1 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. The -CH 2 -contained in the hydrocarbon group and the heterocyclic group contains -CH 2- The -CH 2 -at this time may be substituted with -O-, -CO- , -S (O) 2 -or -NR na10- . Among them, -COOH and -S (O) 2 OH are not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of. In the case where there are multiple R na1s , these may be the same or different.
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. When a plurality of R na10 are present, 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)2
OH。該烴基及該雜環基可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
Rna
表示與前述相同的含義。
*2表示與異吲哚啉環的結合鍵。][In formula (2a-x),
R 23 and R 24 independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group or a hydrogen atom which may have a substituent, and -CH 2 -contained in the hydrocarbon group and the heterocyclic group include The -CH 2 -in the case of -CH 2 -which does not constitute a ring may be substituted with -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The hydrocarbon group and the heterocyclic group may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
R na has the same meaning as described above.
* 2 represents a bonding bond with an isoindoline ring. ]
〔2-2〕式(I)所表示的化合物(B)的第2態樣
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。[2-2] Another preferred aspect of the compound (B) represented by the second aspect pattern (I) of the compound (B) represented by the formula (I) is the second aspect described in the first aspect In aspect, the compound represented by the formula (IIB) in which a is 0.
[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。
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)2
OH。
R16b
表示-CO-ORnb1
、-CO-NH2
、-CO-NH(Rnb1
)、-CO-N(Rnb1
)2
、-CO-H、-CO-Rnb1
或-S(O)2
-Rnb1
。
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。
(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)2
OH。
(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)2
OH。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)2
OH。
X1b
表示式(1a-xb)所表示的基團。[In formula (IIB),
R 11b to R 15b have the same meanings as R 1 to R 5 when a is 0 in Formula (I).
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 which may have a substituent together with the carbon atoms to which they are bonded, the ring It does not form a ring comprising -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
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 .
However, when R 16b represents -CO-NH (R nb1 ), R 12b to R 15b satisfy at least one of (ixb) and (iixb).
(Ixb) At least one of R 12b to R 15b represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom, a cyano group, or a nitro group. -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb - . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
(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 together with the carbon atom to which they are bonded forms a ring which may have a substituent, the ring comprising -CH does not form a ring of 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb -. Among them, -COOH and -S (O) 2 OH are not formed by replacing -CH 2- . The non-ring-forming ones in R 12b to R 15b 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. hydrocarbon contained in the -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - Or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
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。]
Rnb
及Rnb1
表示與前述相同的含義。][In formula (1a-xb),
R 21b , R 22b , and * 1 have the same meanings as R 17b , R 18b, and * 1 in Formula (1a), respectively. ]
R nb and R nb1 have the same meanings as described above. ]
式(IIB)所表示的化合物所具有的-CO2 H及-S(O)2 OH的合計數為0。The total number of -CO 2 H and -S (O) 2 OH contained in the compound represented by formula (IIB) is 0.
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。
Rnb
表示與前述相同的含義。][In formula (2a-xb),
R 23b , R 24b , and * 2 have the same meanings as R 19b , R 20b, and * 2 in Formula (2a), respectively.
R nb has the same meaning as described above. ]
〔2-3〕式(I)所表示的化合物(B)的第3態樣
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)2
O-
的合計數)為1~10的任一整數的式(IA)所表示的化合物。[2-3] Another preferred aspect of the compound (B) represented by the third aspect pattern (I) of the compound (B) represented by formula (I) is the third aspect is represented by formula (I) A (that is, the total number of -CO 2 - and -S (O) 2 O - possessed by the compound represented by formula (I)) is a compound represented by formula (IA) having an integer of 1 to 10 .
[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。
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)2
OH。該環可具有選自由-CO2 -
及-S(O)2
O-
所組成的群組中的至少一種。
Rna
及Mb+
表示與前述相同的含義。
b表示1~6的任一整數。
aa表示式(IA)所表示的化合物所具有的-CO2 -
及-S(O)2
O-
的合計數,且為1~10的任一整數。
ma表示Mb+
的個數。
na為滿足na=b×ma/aa的關係的數。][In formula (IA),
R 1a to R 9a each have the same meaning as R 1 to R 9 when a is any integer from 1 to 10 in formula (I).
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 a substituent, and the ring contains -CH 2 -when it does not form a ring -CH 2 -may be substituted with -O-, -CO-, -S (O) 2 -or- NR na- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The ring may have is selected from -CO 2 - and -S (O) 2 O - at least one of the group consisting of.
R na and M b + have the same meanings as described above.
b represents any integer from 1 to 6.
aa represents the total number of -CO 2 - and -S (O) 2 O - which the compound represented by formula (IA) has, and is any integer from 1 to 10.
ma represents the number of M b + .
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
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。[2-4] Another preferred aspect of the compound (B) represented by the fourth aspect pattern (I) of the compound (B) represented by formula (I) is that the fourth aspect is represented by formula (I) The compound represented by formula (IB) where a 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。
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)2
OH。
R6b
表示-CO-ORnb1
、-CO-NH2
、-CO-NH(Rnb1
)、-CO-N(Rnb1
)2
、-CO-H、-CO-Rnb1
或-S(O)2
-Rnb1
。
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。
(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)2
OH。
(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)2
OH。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)2
OH。
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。
Xb
表示與式(I)中a為0時的X相同的含義。
Rnb
、Rnb1
及Rnb10
表示與前述相同的含義。][In formula (IB),
R 1b to R 5b each have the same meaning as R 1 to R 5 when a is 0 in formula (I).
Selected from the group consisting of R 2b and R 3b, R 3b and R 4b, R 5b, and R 4b and consisting of at least one group may have a substituent may form a ring together with the respective carbon atom bonded to the ring It does not form a ring comprising -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
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 .
However, when R 6b represents -CO-NH (R nb1 ), R 2b to R 5b satisfy at least one of (ibb) and (iibb).
(Ibb) At least one of R 2b to R 5b represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a halogen atom, a cyano group, or a nitro group. -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb - . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
(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 together with the carbon atom to which they are bonded forms a ring which may have a substituent, the ring comprising -CH does not form a ring of 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - or -NR nb -. Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- . The non-ring-forming ones in R 2b to R 5b 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. hydrocarbon contained in the -CH 2 - group and the heterocyclic ring does not form comprises -CH 2 - when the -CH 2 - may be substituted with -O -, - CO -, - S (O) 2 - Or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
R 7b has the same meaning as R 7 when a is 0 in formula (I). R 7b may form a ring together with the carbon atoms to which R 6b and R 7b are bonded.
X b has the same meaning as X when a is 0 in formula (I).
R nb , R nb1 and R nb10 have the same meanings as described above. ]
式(IB)所表示的化合物中所含的-CO2 H及-S(O)2 OH的合計數為0。The total number of -CO 2 H and -S (O) 2 OH contained in the compound represented by formula (IB) is 0.
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。In the compound represented by formula (IB), the group represented by the formula (1a) is preferably a 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。
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。
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)」。In this specification, the carbon number of the hydrocarbon group which has a substituent is the carbon number of the hydrocarbon group before substitution by a substituent.
Hydrocarbon contained -CH 2 - is substituted by -O -, - CO -, - S (O) 2 -, - NR na -, - NR nb -, - NR na10 - or -NR nb10 - like form The carbon number of the group is the carbon number of the hydrocarbon group before the group is substituted.
Or less, -CH be contained in the hydrocarbon by 2 - is substituted by -O -, - CO -, - S (O) 2 -, - NR na -, - NR nb -, - NR na10 - or -NR The group formed by nb10 -is also collectively called "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
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。[2-5] Explanation of the group of the compound (B) represented by the formula (I) and the compounds in the first to fourth aspects thereof
R 1 to R 9 , R 11b to R 16b , R 1a to R 9a , R 1b to R 7b , R na , R nb , R na1 , R nb1 , R na10 , R nb10 , R 17b to 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。
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)2
O-
所組成的群組中的至少一種。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 , and R 21 to R 24 each have a carbon number of 1 A hydrocarbon group of -40 , a hydrocarbon group of 1 to 35 represented by R na1 , R nb1 , R na10 and R nb10 may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated, or may be Chain or alicyclic.
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 member selected from the group consisting of -CO 2 - and -S ( O) 2 O - one kind of the group consisting of at least the.
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。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 R 24 , R na1 , R Examples of the saturated or unsaturated chain hydrocarbon group represented by nb1 , R na10 and R nb10 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, heptyl, octadecyl and icosyl linear alkyl groups, etc .; isopropyl, (2-methyl) propyl, isobutyl, second butyl, Third butyl, (2-ethyl) butyl, isopentyl, neopentyl, third pentyl, (1-methyl) pentyl, (2-methyl) pentyl, (1-ethyl ) Branched chain alkyl groups such as pentyl, (3-ethyl) pentyl, isohexyl, (5-methyl) hexyl, (2-ethyl) hexyl, and (3-ethyl) heptyl; etc .; Vinyl, 1-propenyl, 2-propenyl (allyl), isopropenyl, (1-methyl) vinyl, 2-butenyl, 3-butenyl, 1,3-butadiene Alkenyl, etc., (1- (2-propenyl)) vinyl, (1,2-dimethyl) propenyl, 2-pentenyl, and the like.
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。
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。Saturated or not represented by 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 R 24 The carbon number of the saturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, still more preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 1 to 5. .
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 to 28, more preferably 1 to 18, even more preferably 1 to 13, and even more preferably 1 -8, more preferably 1 to 6, and particularly preferably 1 to 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。
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。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 R 24 , R na1 , R Examples of the saturated or unsaturated alicyclic hydrocarbon group 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 such as octylcyclohexyl and 4-cyclohexylcyclohexyl; cyclohexenyl (such as cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl and cyclooctenyl, etc. Alkenyl; norbornyl, adamantyl, bicyclic [2.2.2 ] Octane and so on.
The carbon number of the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, still more preferably 4 to 20, even more preferably 4 to 15, and even more preferably 5 to 15, Particularly preferred is 5-10, wherein particularly preferred is 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。
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。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 R 24 , R na1 , R nb1 The saturated or unsaturated hydrocarbon group represented by R na10 and R nb10 may be a group obtained by combining the above-mentioned chain hydrocarbon group and alicyclic hydrocarbon group, and examples thereof include cyclopropylmethyl, cyclopropyl Ethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, and cyclohexylethyl are bonded to an alkyl group having one or more alicyclic hydrocarbon groups.
The carbon number of the group obtained by combining a chain hydrocarbon group and an alicyclic hydrocarbon group is preferably 4 to 30, more preferably 4 to 20, and even more preferably 4 to 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。
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。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 R 24 , R na1 , R Examples of the aromatic hydrocarbon group represented by nb1 , R na10 and R nb10 include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, and 2,4-dimethylbenzene. Methyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, o-isopropylphenyl, m Isopropylphenyl, p-isopropylphenyl, o-third butylphenyl, m-third butylphenyl, p-third 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, fluorenyl, phenanthryl and anthracenyl.
The carbon number of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 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。
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。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 R 24 , R na1 , R nb1 The aromatic hydrocarbon group represented by R na10 and R nb10 is not particularly limited as long as it is a hydrocarbon group having an aromatic hydrocarbon ring, and the above-mentioned chain hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group may be used. At least one group combined with the listed aromatic hydrocarbon group includes, for example, benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, phenylethyl, Aralkyl groups such as phenylpropyl and 1-methyl-1-phenylethyl; aryl alkenyl groups such as phenyl ethenyl (phenyl vinyl); phenylacetylene Aryl alkynyl groups such as phenyl; phenyl groups such as biphenyl and tritriphenyl with one or more phenyl groups bonded; cyclohexylmethylphenyl, benzylphenyl, (dimethyl (phenyl) Methyl) phenyl and the like.
The number of carbon atoms of a group obtained 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 to 30, more preferably 7 to 20, and even more preferably 7 to 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 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 R 24 , R na1 , The hydrocarbon group represented by R nb1 , R na10 and R nb10 may have a monovalent substituent or a divalent substituent. The divalent substituent is preferably two substituents that 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-CH2
CH3
、*-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-C6
H5
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。
[所述式中,
*表示與所述烴基的結合鍵。
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)2
OH。
Rnb10
表示與前述相同的含義。
Rnb2
、Rnb3
、Rnb4
的具體例及較佳的例子與Rnb1
相同。]Examples of the monovalent substituent include:
Alkyl sulfanyl with 1 to 10 carbon atoms, such as methylthio, ethylthio, propylthio, and butylthio;
Halogen atoms such as fluorine, chlorine, bromine and iodine;
Nitro; cyano;
Trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, Hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, in which fluorine atoms such as perfluorodecyl, perfluorocyclohexyl, and perfluorophenyl groups are substituted for all hydrogen atoms;
* -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 -A carbonyl group such as -CH 3 bonded to a sulfur atom bonded to an alkyl group (the alkyl group has 1 to 10 carbon atoms);
* -CO-SC 6 H 5 and other carbonyl groups bonded to a sulfur atom bonded to an aryl group (the carbon number of the aryl group is 6 to 20);
* -OP (O) (OR nb2 ) 2 ;
* -Si (R nb2 ) (R nb3 ) (R nb4 ) and the like.
[Wherein,
* Indicates a bonding bond with the hydrocarbon group.
R nb2 , R nb3 , and R nb4 may be the same or different, and each independently represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. When 2- and the heterocyclic group includes -CH 2 -which does not constitute a ring, the -CH 2 -may be substituted with -O-, -CO- , -S (O) 2- , and -N nb10- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
R nb10 has the same meaning as described above.
Specific examples of R nb2, R nb3, R nb4 and preferred examples of the R nb1 same. ]
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。
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。
作為取代有芳基的亞胺基,可列舉C6
H5
-N=等。Examples of the divalent substituent include a thioxo group, an imino group, an imine group substituted with an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and a substituted carbon number 6 to 20 aryl imine groups and the like.
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.
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。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 R 24 , R na1 , R nb1 , a substituent of a hydrocarbon group represented by R na10 and R nb10 ,
Preferred are a halogen atom; a nitro group; a cyano group; a hydrocarbon group having 1 to 20 carbon atoms in which a fluorine atom substitutes all hydrogen atoms; a thiocarbonyl group; * -OP (O) (OR nb2 ) 2 ; * -Si (R nb2 ) (R nb3 ) (R nb4 ), etc.
More preferred are a halogen atom; a nitro group; a cyano group; a hydrocarbon group having 1 to 20 carbon atoms in which a fluorine atom replaces all hydrogen atoms; a thiocarbonyl group, etc.,
Further preferred are a fluorine atom, a chlorine atom, a bromine atom; a nitro group; a cyano group; a hydrocarbon group having 1 to 10 carbon atoms in which a fluorine atom replaces all hydrogen atoms; a thiocarbonyl group and the like.
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)2
OH。
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)2
OH。
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)2
OH。
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)2
OH。When a is any integer from 1 to 10, -CH 2 -contained in the hydrocarbon group 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- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
When a is 0, -CH 2 -may be contained in the hydrocarbon group represented by R 1 to R 5 , R 7 , R 11b to R 15b , R 1b to R 5b , R 7b , R 17b to R 24b Substituted by -O-, -CO-, -S (O) 2 -or -NR nb- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
-CH 2 -contained in the hydrocarbon group represented by R na1 may be substituted with -O-, -CO- , -S (O) 2- , or -NR na10- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
-CH 2 -contained in the hydrocarbon group represented by R nb1 may be substituted with -O-, -CO- , -S (O) 2 -or -NR nb10- . Among them, -COOH or -S (O) 2 OH is not formed by replacing -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1~10、較佳為碳數1~20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。
[所述式中,
*表示結合鍵。
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。]As the hydrocarbon group contained by -CH 2 - is substituted by -O -, - CO -, - S (O) 2 -, - NR na -, - NR nb -, - NR na10 - or -NR nb10 - The groups (Z) formed include:
Methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, third butoxy, pentyloxy, hexyloxy, (2- (Ethyl) hexyloxy, heptyloxy, octyloxy, nonyloxy, phenyloxy, and o-tolyloxy have a carbon number of 1 to 20 on one side, more preferably An oxygen group of a hydrocarbon group having 1 to 10 carbon atoms;
Epoxy
Formamyl
Carbon numbers of ethenyl, propionyl, butylfluorenyl, tertiary butylfluorenyl, pentylfluorenyl, hexamethylene, (2-ethyl) hexyl, heptyl, octyl, nonyl, and benzyl 2 to 22, preferably 2 to 12 fluorenyl groups (preferably alkanoyl);
Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tertiary butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, (2-ethyl) hexyloxycarbonyl, heptyl The alkoxycarbonyl group and octyloxycarbonyl group, nonyloxycarbonyl group, phenyloxycarbonyl group, and o-tolyloxycarbonyl group have a carbon number of 1 to 20, preferably 1 to 10 carbon atoms. Hydrocarbyloxycarbonyl;
Amine
N-methylamino, N, N-dimethylamino, N-ethylamino, N, N-diethylamino, N-propylamino, N, N-dipropylamino , N-isopropylamino, N, N-diisopropylamino, N-butylamino, N, N-dibutylamino, N-isobutylamino, N, N-di Isobutylamino, N-second butylamino, N, N-disecond butylamino, N-third butylamino, N, N-second third butylamino, N- Amylamino, 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) hexylamino, N-heptylamino, N, N-diheptyl Amino, N-octylamino, N, N-dioctylamino, N-nonylamino, N, N-dinonylamino, N-phenylamino, N, N-diphenyl Methylamino, N, N-ethylmethylamino, N, N-propylmethylamino, N, N-isopropylmethylamino, N, N-butylmethylamino, N, N -A tertiary butylmethylamino group, an N, N-phenylmethylamino group and the like, substituted with 1 or 2 carbon atoms having 1 to 10, preferably 1 to 20 hydrocarbon groups;
Sulfamoyl
N-methylaminesulfonyl, N, N-dimethylaminesulfonyl, N-ethylaminesulfonyl, N, N-diethylaminesulfonyl, N-propylaminesulfonyl , N, N-dipropylaminesulfonyl, N-isopropylaminesulfonyl, N, N-diisopropylaminesulfonyl, N-butylaminesulfonyl, N, N-di Butylaminesulfonyl, N-isobutylaminesulfonyl, N, N-diisobutylaminesulfonyl, N-secondbutylaminesulfonyl, N, N-disecondbutyl Aminosulfonyl, N-Third-butylaminosulfonyl, N, N-di-tert-butylaminesulfonyl, N-pentylaminesulfonyl, N, N-dipentylaminesulfonyl , N- (1-ethylpropyl) aminosulfonyl, N, N-bis (1-ethylpropyl) aminesulfonyl, N-hexylaminesulfonyl, N, N-dihexylaminesulfonyl Fluorenyl, N- (2-ethyl) hexylaminesulfonyl, N, N-di (2-ethyl) hexylaminesulfonyl, N-heptylaminesulfonyl, N, N-diheptyl Aminosulfonyl, N-octylaminesulfonyl, N, N-dioctylaminesulfonyl, N, N-octylmethylaminesulfonyl, N-nonylaminesulfonyl, N, N-dinonylaminesulfonyl, N-phenylaminesulfonyl, N, N-diphenylaminesulfonyl, N, N-ethylmethylaminesulfonyl, N, N-propyl Methylaminesulfonyl, N, N-isopropyl One or two of N, N-butylmethylaminesulfonyl, N, N-tert-butylmethylaminesulfonyl, and N, N-phenylmethylaminesulfonyl Hydrocarbyl-substituted aminesulfonyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms;
Formamylamino; ethamylamino, propylamylamino, butylamylamino, 2,2-dimethylpropylamylamino, pentamylamino, hexamylamino, (2- (Ethyl) hexylamino, heptylamino, octylamino, nonylamino, decylamino, undecylamino, dodecylamino, dodecylamino Alkylamino groups having 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms, such as amino groups and benzamidineamino groups;
Hydroxyl
Formamyloxy, ethamyloxy, propylamyloxy, butylamyloxy, 2,2-dimethylpropylamyloxy, pentamyloxy, hexylamyloxy, (2-ethyl Alkyl) Hexamyloxy, heptyloxy, octyloxy, nonyloxy, and benzyloxy, etc. Alkyl groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms Aryloxy
Methanesulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, (2-ethyl) hexylsulfonyl, heptylsulfonyl Substituents such as alkyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, phenylsulfonyl, and p-tolylsulfonyl have 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms. A hydrocarbyl sulfonyl group of 10;
Carbamate
N-methylamine formamyl, N, N-dimethylaminoformamyl, N-ethylamine formamyl, N, N-diethylamine formamyl, N-propylamine formamyl , N, N-dipropylaminoformamyl, N-isopropylamineformamyl, N, N-diisopropylamineformamyl, N-butylaminoformamyl, N, N-diamine Butylamine formamyl, N-isobutylaminoformamyl, N, N-diisobutylamine formamyl, N-second butylaminoformamyl, N, N-disecondyl Carboxamidine, N-Third-butylamine carbamate, N, N-Di-tert-butylamine carbamate, N-Pentylamine carbamate, N, N-Dipentylamine carbamate , N- (1-ethylpropyl) carbamyl, N, N-bis (1-ethylpropyl) carbamyl, N-hexylaminecarbamyl, N, N-dihexylamine Fluorenyl, N- (2-ethyl) hexylamine formamyl, N, N-di (2-ethyl) hexylamine formamyl, N-heptylamine formamyl, N, N-diheptyl Carbamate, N-octylamine carbamate, N, N-dioctylamine carbamate, N-nonylamine carbamate, N, N-dianonylcarbamate, N-benzene Methylaminomethane, N, N-diphenylaminomethane, N, N-ethylmethylaminomethane, N, N-propylmethylaminomethane, N, N-isopropyl Methylmethyl formamidine, N, N-butyl 1 or 2 carbon atoms of 1 to 20 carbon atoms, preferably 1 to 20 carbon atoms, preferably N, N-tertiary butylmethylaminomethyl, and N, N-phenylmethylaminomethylamino, etc. 1 to 10 alkyl substituted carbamoyl groups;
* -COCOR nb2 ;
* -OCON (R nb2 ) 2 ;
* -N (R nb2 ) COOR nb2 and the like.
[Wherein,
* Indicates a bonding key.
In the case where there are multiple R nb2s , the R nb2s may be the same or different, and have the same meaning as the foregoing. ]
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。
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。
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)2
O-
所組成的群組中的至少一種。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 R 24 , R na1 , R nb1 The heterocyclic group represented by Rna10 and Rnb10 may be a single ring or a polycyclic ring, and a heterocyclic ring containing a hetero atom as a constituent element of the ring is preferred. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
The carbon number of the heterocyclic group is preferably from 2 to 30, more preferably from 3 to 22, even more preferably from 3 to 20, still more preferably from 3 to 18, even more preferably from 3 to 15, particularly preferably from 3 to 14.
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 member selected from the group consisting of -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 the heterocyclic ring containing only a nitrogen atom as a heteroatom include monocyclic saturated heterocyclic rings such as aziridine, azetidine, pyrrolidine, piperidine, and piperazine; 2,5-dimethyl Pyrrole such as pyrrole, 2-methylpyrazole and 3-methylpyrazole, and other 5-membered ring systems such as imidazole, 1,2,3-triazole and 1,2,4-triazole Saturated heterocycles; pyrimidines, pyridazines and 6-methylpyrimidines, 6-membered ring system unsaturated rings such as pyrazines, pyrazines, and 1,3,5-triazines, etc. Indolin, indole, indazine, benzimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydro (3-methyl) quinoxaline, 3-methylquinoxaline, etc. Condensed bicyclic heterocyclic rings such as quinoxaline, quinazoline, oxoline, phthalazine, naphthyridine, purine, pyridine, benzopyrazole, and benzopiperidine; carbazole, acridine, and Condensed tricyclic heterocyclic rings such as phenazine; rings and the like represented by the following formula.
[式中,*表示結合鍵。]
[In the formula, * represents a bonding 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。Examples of the heterocyclic ring containing only an oxygen atom as a hetero atom include oxetane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, and Monocyclic saturated heterocyclic rings such as 1-cyclopentyldioxane; 1,4-dioxospiro [4.5] decane, and 1,4-dioxo [4.5] nonane Bicyclic saturated heterocyclic rings; lactone-based heterocyclic rings such as α-acetolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone; 2,3-dimethylfuran, and 5-membered unsaturated ring systems such as 2,5-dimethylfuran and furan; 6-membered unsaturated ring systems such as 2H-pyran and 4H-pyran; 1-benzofuran, and Condensed bicyclic heterocycles such as benzopyrans such as 4-methylbenzopyran, benzodioxole, chromane, and heterochromane; xanthene (Xanthene), and condensed tricyclic heterocyclic rings such as dibenzofuran.
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 the heterocyclic ring containing only a sulfur atom as a heteroatom include a 5-membered ring system saturated heterocyclic ring such as dithiocyclopentane; thiane, 1,3-dithiane, and 2-methyl 6-membered ring saturated rings such as 1,3-dithiane; 3-methylthiophene and 2-carboxythiophene; thiophene; 4H-thiopyran; and benzene such as benzotetrahydrothione 5-membered ring system unsaturated heterocycles such as benzothioan; condensed bicyclic heterocycles such as benzothiophene; etc .; condensed tricyclic heterocycles such as thienhrene 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。Examples of the heterocyclic ring containing a nitrogen atom and an oxygen atom as a hetero atom include morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, and 2-methyl-2- Monocyclic saturated heterocyclic rings such as piperidone; monocyclic unsaturated rings such as oxazole such as 4-methyloxazole, 2-oxisoxazole, and isoxazole such as 3-methylisoxazole Heterocyclic rings; condensed bicyclic heterocyclic rings such as benzoxazole, benzoisoxazole, benzoxazine, benzodioxane, benzimidazoline, etc .; condensed tricyclic heterocyclic rings 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 heterocyclic ring containing a nitrogen atom and a sulfur atom as heteroatoms include a monocyclic heterocyclic ring such as thiazole such as 3-methylthiazole and 2,4-dimethylthiazole; and a condensed two such as benzothiazole. Ring system heterocycles; Condensed tricyclic system heterocycles such as phenothiazine.
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。
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。The heterocyclic group may be a group obtained by combining the listed hydrocarbon groups, and examples thereof include tetrahydrofurylmethyl, methyltetrahydrofuranyl, and the like.
In addition, the bonding position of the heterocyclic ring is a portion where an arbitrary hydrogen atom contained in each ring is detached.
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)2
OH。
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)2
OH。
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)2
OH。
於Rnb1
所表示的包含並未構成環的-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)2
OH。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 includes the group (Z). Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
When a is 0, the heterocyclic groups represented by R 1 to R 5 , R 7 , R 11b to R 15b , R 1b to R 5b , R 7b , and R 17b to R 24b include those which do not form a ring. When -CH 2- , the -CH 2 -may be substituted with -O-, -CO-, -S (O) 2- , or -NR nb- , in which case, the heterocyclic group contains the group ( Z). Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
When the heterocyclic group represented by R na1 contains -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 includes the group (Z). Among them, -COOH or -S (O) 2 OH is not formed by replacing -CH 2- .
When -CH 2 -represented by R nb1 which does not constitute a ring, the -CH 2 -may be substituted with -O-, -CO- , -S (O) 2 -or -NR nb10- , in this case Next, the heterocyclic group contains the group (Z). Among them, -COOH or -S (O) 2 OH is not formed by replacing -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 a constituent element thereof, 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。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 R 24 , R na1 , R Examples of the substituents of the heterocyclic group 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 , 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 substituent.
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。For 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 form a ring together with the carbon atom to which they are bonded, the ring may be a hydrocarbon ring or a heterocyclic ring. Examples of the hydrocarbon ring include an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring.
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。
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。Examples of the aliphatic hydrocarbon ring include a cyclopropane ring, a methylcyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a methylcyclohexane ring, and 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 And other cycloalkane rings; cyclohexene ring, cycloheptene ring, and cyclooctene ring; and other cycloolefin rings; norbornane, adamantane, and bicyclic [2.2.2] octane, etc.
The carbon number of the aliphatic hydrocarbon ring is, for example, 3 to 30, preferably 3 to 20, more preferably 4 to 20, still more preferably 4 to 15, still more preferably 5 to 15, and particularly preferably 5 to 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。
芳香族烴環的碳數例如為6~30,較佳為6~20,更佳為6~15。Examples of the aromatic hydrocarbon ring include benzene, toluene, o-xylene, m-xylene, p-xylene, cumene, third butylbenzene, mesitylene, and 1,5-bis (2-propyl). ) Benzene, naphthalene, 1,2,3,4-tetrahydronaphthalene, fluorene, phenanthrene, and anthracene.
The carbon number of the aromatic hydrocarbon ring is, for example, 6 to 30, preferably 6 to 20, and more preferably 6 to 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。For 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 together form a ring with the carbon atom to which they are bonded, the ring may have a substituent. Examples of the substituent 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 , R nb , R 17b to R 24b , and R 21 to The hydrocarbon group represented by R 24 , R na1 , R nb1 , R na10 and R nb10 may have the same substituent.
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)2 OH。For 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 and the carbon atom to which they are bonded form a ring which may have a substituent, and the ring contains no ring When -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). Among them, -COOH or -S (O) 2 OH is not formed by replacing -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。
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。For 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 atom to which they are bonded, the ring may be a heterocyclic ring.
For 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 atom to which they are bonded, the heterocyclic group and R 2 to R 5 , R The benzene rings bonded to 12b to R 15b , R 2a to R 5a , or R 2b to R 5b all have a ring structure of two or more rings. Examples of the heterocyclic ring having two or more ring structures 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。
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。
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。
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 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.
R 11b ~ R 16b, R 21b and R 22b, at least one, preferably R 16b, R 21b and R 22b, at least one, more preferably R 16b, and R 21b and R 22b of one preferred Is a hydrocarbon group.
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 are preferably a hydrocarbon group.
At least one of R 1b to 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 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 a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, and a hexyl group. Oxycarbonyl, (2-ethyl) hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxy A carbonyl group, a phenyloxycarbonyl group, an eicosyloxycarbonyl group, and the like, an oxycarbonyl group having a hydrocarbon group having 1 to 35 carbon atoms, and more preferably an oxygen group having a hydrocarbon group having 1 to 10 carbon atoms. 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-methylamine formamidine Methyl, N-ethylaminomethylmethyl, N-propylaminomethylmethyl, N-isopropylaminomethylmethyl, N-butylaminomethylmethyl, N-isobutylaminomethylmethyl, N -Second-butylaminomethane, N-third-butylaminomethane, N-pentylaminomethane, N- (1-ethylpropyl) aminomethane, N-hexylamine Fluorenyl, N- (2-ethyl) hexylamine formamyl, N-heptylamine formamyl, N-octylamine formamyl, N-nonylamine formamyl, N-decylamine formamidine Fluorenyl, N-undecylamine formamyl, N-dodecylamine formamyl, N-icosylamine formamyl, and N-phenylamine formamyl, etc., have 1 to 1 carbon number 35 alkyl substituted carbamoyl groups, etc .;
N, N-dimethylaminoformamyl, N, N-ethylmethylaminoformamyl, N, N-diethylamineformamyl, N, N-propylmethylamineformamyl, N, N-dipropylamine formamidine, N, N-isopropylmethylamine formamyl, N, N-diisopropylamine formamidine, N, N-tert-butylmethylamine formamidine Methyl, N, N-diisobutylamine formamyl, N, N-disecond butylaminoformamyl, N, N-di-third butylaminoformamyl, N, N-butylmethylamine Formamyl, N, N-dibutylamine formamyl, N, N-butyloctylamine formamyl, N, N-dipentylamine formamyl, N, N-di (1-ethyl Propyl) aminoformamyl, N, N-dihexylamine formamyl, N, N-bis (2-ethyl) hexylamine formamyl, N, N-diheptylamine formamyl, N , N-octylmethylamine formamyl, N, N-dioctylamine formamyl, N, N-dinonylaminoformamyl, N, N-decylmethylamine formamyl, N , N-undecylmethylamine formamyl, N, N-dodecylmethylamine formamyl, N, N-eicosylmethylamine formamyl, N, N-phenylmethylamine Formamidine and N, N-diphenylaminomethane, and the like are substituted with a hydrocarbyl group having 2 to 1 to 35 carbon atoms. More preferred examples include 1 to 2 or 1 to 2 carbons. 10 alkyl substituted amines Acyl and the like.
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,較佳為可列舉鍵結有為烴基且碳數為1~10的基團的羰基等。
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。
-CO-Rna1
中,於鍵結有烴基的羰基中,該烴基亦可具有-CO2 -
及-S(O)2
O-
等。As -CO-R na1 and -CO-R nb1 , preferred are ethenyl, propionyl, butylfluorenyl , 2,2-dimethylpropanyl, pentamyl, hexyl, and (2-ethyl ) Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, behenyl, benzyl, phenylmethylcarbonyl, phenylethyl A carbonyl group, a phenylpropylcarbonyl group, and the like have a carbonyl group having a hydrocarbon group and a carbon number of 1 to 35. Preferred examples include a carbonyl group having a hydrocarbon group and a 1 to 10 carbon group. .
In the carbonyl groups to which a hydrocarbon group is bonded , namely -CO-R na1 and -CO-R nb1 , the hydrocarbon group may have a halogen atom such as a chlorine atom; an sulfamoyl group; a hydroxyl group; a methoxy group and a single-sided bond An oxy group having a hydrocarbon group having 1 to 10 carbons; an oxycarbonyl group having a hydrocarbon group having 1 to 10 carbons, such as a methoxycarbonyl group;
In -CO-R na1 , the hydrocarbon group may have -CO 2- , -S (O) 2 O - or the like in the carbonyl group to which the hydrocarbon group is bonded.
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。As -S (O) 2 -R na1 and -S (O) 2 -R nb1 , methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, and pentyl are preferred. Sulfonyl, hexylsulfonyl, (2-ethyl) hexylsulfonyl, heptylsulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, undecylsulfonyl Sulfonyl, dodecylsulfonyl, eicosylsulfonyl, phenylsulfonyl, and p-tolylsulfonyl, which are bonded to a hydrocarbon group having 1 to 35 carbon atoms, are more preferred Examples thereof include a sulfonyl group having a hydrocarbon group having 1 to 10 carbon atoms.
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。
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、䓛(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。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 with the carbon atom to which they are respectively bonded is the same as formula (I), formula (IIB), formula (IA ), Or benzene ring condensation of an isoindolino skeleton of formula (IB).
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 The condensed ring structure of the ring that can be formed by 4a and R 5a , R 2b and R 3b , R 3b and R 4b , or R 4b and R 5b together with the carbon atom to which they are bonded, examples include: indene (Indene), naphthalene, biphenylene, indacene, acenaphthylene, pyrene, phenalene, phenanthrene, anthracene, fluoranthene, acephenanthrylene, Aceanthrylene, triphenylene, pyrene, chrysene, N-methylphthalimide, N- (1-phenylethyl) phthalimide And condensed ring structures of hydrocarbons such as tetracene and their partial reductions (for example, 9,10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, etc.); indole, isoindole , Indazole, quinoline, isoquinoline, phthalazine, quinoxaline, quinazoline, oxoline, carbazole, carboline, phenanthridine, acridine, perimidine, morpholine, brown Nitrogen-containing condensed heterocycles and the like Partially reduced form; oxygen-containing condensed heterocycles such as 3-hydrobenzofuran-2-one and partial reduced forms thereof.
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 R 6a and R 7a or R 8a and R 9a can form together with the carbon atom to which they are bonded is an exocyclic methylene (C = CH 2 ) bond with an isoindoleline skeleton of formula (IA) And if the ring is enumerated as a structure including the exo-methylene group (C = CH 2 ), the carbonyl group and the exo-methylene group and carbonyl group in the following group A can be exemplified in this order Structure. ** indicates a bonding bond with an isoindolino skeleton.
[群組A]
[Group 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)2 OH。該烴基及該雜環基可具有選自由-CO2 - 及-S(O)2 O- 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。][Wherein R 25 and R 26 each independently represent 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, and -CH 2 -may be contained in the hydrocarbon group Substituted by -O-, -CO-, -S (O) 2 -or -NR na- . Among them, -COOH and -S (O) 2 OH are not formed by replacing -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 - as a substituent. Specific examples and preferable 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 atom to which they are bonded is bonded to the exocyclic methylene 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 ), a structure in which a carbonyl group, an exocyclic methylene group, and a carbonyl group are arranged in this order as shown in the following group B can be exemplified. ** indicates a bonding bond with an isoindolino skeleton.
[群組B]
[式中,R23
及R24
表示與前述相同的含義。][Group B]
[Where, Rtwenty three
And Rtwenty four
Has the same meaning as described 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 R 17b and R 18b or R 21b and R 22b together with the carbon atom to which they are bonded is an exocyclic methylene (C = CH 2 ) bond with the isoindoline skeleton of formula (IIB) And if the ring is enumerated as a structure including the exo-methylene group (C = CH 2 ), the carbonyl group and the exo-methylene group and carbonyl group in the following group C can be exemplified in this order Structure. ** indicates a bonding bond with an isoindolino skeleton.
[群組C]
[式中,R23b
及R24b
表示與前述相同的含義。][Group C]
[Where, R23b
And R24b
Has the same meaning as described 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 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 atom to which they are each bonded may have a substituent. Examples of the substituent 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 , R nb , R 17b to R 24b , and R 21 to The hydrocarbon group represented by R 24 , R na1 , R nb1 , R na10 and R nb10 may have the same substituent.
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。Halogen atoms 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 Examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom and a bromine atom are preferred.
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。
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+
。
再者,於Mb+
為氫正離子的情況下,該氫正離子與-CO2 -
或-S(O)2
O-
鍵結而作為-COOH或-S(O)2
OH存在。M b + is preferably a hydrogen cation or a monovalent metal ion such as Li + , Na + , K + , or a metal cation having a valence of two or more, more preferably a hydrogen cation or a metal cation having a valence of two or more, and further preferably a hydrogen cation ion.
Examples of the metal cation having a valence of two or more include cations of metals of Groups 2 to 15 of the periodic table of the elements, and preferably Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cd 2+ , 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+, and 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 further Preferred examples include 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 + .
When M b + is a hydrogen positive ion, the hydrogen positive 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, and even more preferably any integer from 0 or 2 to 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。
作為R1
,較佳為氫原子。
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)2
O-
等。
作為R6
,較佳為:-CO-ORna1
、-CO-NH2
、-CO-NH(Rna1
)、-CO-N(Rna1
)2
或-CO-Rna1
。
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)2
O-
,更佳為氰基。該情況下,R6
與R21
較佳為同一基團。
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)2
OH。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。
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。
R21
及R22
亦較佳為並未形成環。
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)2
O-
,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)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。
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。In the first aspect of the compound (B) represented by the formula (I), R 1 to R 6 , R 21 , R 22 , R na1 , R na2 , M b + , and a are preferably as follows.
R 1 is preferably a hydrogen atom.
R 2 to R 5 are preferably: a hydrogen atom; an alkyl group having 1 to 10 carbon atoms such as butyl; an alkoxy group having 1 to 10 carbon atoms such as methoxy; an alkyl group such as trifluoromethyl all of the hydrogen atoms contained in the substituted groups obtained by a fluorine atom; chlorine atom, bromine atom and the like; nitro; -CO 2 -; -S (O ) 2 O - and the like.
R 6 is preferably -CO-OR na1 , -CO-NH 2 , -CO-NH (R na1 ), -CO-N (R na1 ) 2 or -CO-R na1 .
When R 21 and R 22 do not form a ring with the carbon atom 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 , as R 22 , a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have substituent, a hydrogen atom, a halogen atom, cyano, nitro, -CO 2 - or -S (O) 2 O -, more preferably a cyano group. In this case, R 6 and R 21 are preferably the same group.
R na2 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent. The -CH 2 -contained in the hydrocarbon group and the heterocyclic group include -CH 2 which does not form a ring. The -CH 2 -at-may be substituted with -O-, -CO- , -S (O) 2 -or -NR na10- . Among them, -COOH and -S (O) 2 OH are not formed by replacing -CH 2- . Specific examples of R na2 and preferred examples of the R na1 same. In the case where there are multiple R na2 , these may be the same or different.
In the case where R 21 and R 22 form a ring together with the carbon atoms to which they are bonded, the structure of group B is preferred, and the ring represented by formula (2a-x) is more preferred. In formula (2a-x), R 23 and R 24 are preferably a hydrogen atom.
It is also preferable that R 21 and R 22 do not form a ring.
R na1 and R na2 are preferably an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, and butyl, and an aromatic group having 6 to 10 carbon atoms such as phenyl, tolyl, and ethylphenyl. Hydrocarbyl; benzyl (also known as phenylmethyl), 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, phenylethyl, phenylpropyl, etc. in combination with an aromatic hydrocarbon group and formed a group having a carbon number of 7 to 15, the plurality of groups may have a -CO 2 - or -S (O) 2 O -, as a substituent, may have a methoxy Alkoxy groups having 1 to 10 carbons such as alkoxy groups; oxycarbonyl groups having 1 to 10 hydrocarbon groups having carbonyl groups such as methoxycarbonyl groups; sulfamoyl groups; hydroxyl groups; halogen atoms such as chlorine atoms, preferably having -CO 2 -, -S (O) 2 O -.
As M b + , it is preferably selected from the group consisting of hydrogen cations, Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cu 2+ , Fe 2+ , Mn 2+ , Al 3+ , Fe One of the groups consisting of 3+ , Cr3 +, and Mn4 + is more preferably a hydrogen positive ion.
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。
作為R11b
,較佳為氫原子。
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。
作為R16b
,較佳為:-CO-ORnb1
、-CO-NH2
、-CO-NH(Rnb1
)、-CO-N(Rnb1
)2
或-CO-Rnb1
。
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。
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)2
OH。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。
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。
R21b
及R22b
亦較佳為並未形成環。
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。Among the compounds represented by Formula (IIB) in 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.
R 11b is preferably a hydrogen atom.
R 12b to R 15b are preferably: a hydrogen atom; an alkyl group having 1 to 10 carbon atoms such as butyl; an alkoxy group having 1 to 10 carbon atoms such as methoxy; an alkyl group such as trifluoromethyl Groups in which all the hydrogen atoms contained in them are substituted with fluorine atoms; halogen atoms such as chlorine atoms and bromine atoms; nitro groups and the like.
R 16b is preferably -CO-OR nb1 , -CO-NH 2 , -CO-NH (R nb1 ), -CO-N (R nb1 ) 2 or -CO-R nb1 .
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 , as R 22b , 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.
R nb5 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. The -CH 2 -contained in the hydrocarbon group and the heterocyclic group include -CH 2 which does not form a ring The -CH 2 -at-may be substituted with -O-, -CO- , -S (O) 2 -or -NR nb10- . Among them, -COOH and -S (O) 2 OH are not formed by replacing -CH 2- . Specific examples of R nb5 and preferred examples of the R nb1 same. When multiple R nb5s are present, these may be the same or different.
In the case where R 21b and R 22b form a ring together with the carbon atoms to which they are bonded, the structure of group C is preferred, and the ring represented by formula (2a-xb) is more preferred. In formula (2a-xb), R 23b and R 24b are preferably a hydrogen atom.
It is also preferable that R 21b and R 22b do not form a ring.
R nb1 and R nb5 are preferably an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, and butyl, and an aromatic group having 6 to 10 carbon atoms such as phenyl, tolyl, and ethylphenyl. Hydrocarbyl; phenylmethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, phenylethyl, phenylpropyl, etc. Combining a chain hydrocarbon group with an aromatic hydrocarbon group Is a group having 7 to 15 carbon atoms, and these groups may have, as a substituent, an alkoxy group having 1 to 10 carbon atoms such as a methoxy group; a methoxycarbonyl group or the like is bonded to An oxycarbonyl group of a hydrocarbon group having 1 to 10 carbon atoms; an amine sulfonyl group; a hydroxyl group; a halogen atom such as a 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。
作為R1a
,較佳為氫原子。
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)2
O-
等。
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
。
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)2
OH。Rna4
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。
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)2
O-
,更佳為氰基。
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)2
O-
,更佳為氰基。該情況下,R6a
與R8a
較佳為同一基團。
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,較佳為形成式(QQ18)所表示的環。式(QQ18)中,作為R25
及R26
,較佳為氫原子。
R8a
及R9a
亦較佳為並未形成環。
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)2
O-
,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)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。
作為a,較佳為1~5的任一整數。Among the compounds represented by formula (IA) in the third aspect of compound (B) represented by formula (I), R 1a to R 9a , R na4 , M b + , and a are preferably as follows.
R 1a is preferably a hydrogen atom.
R 2a to R 5a are preferably: a hydrogen atom; an alkyl group having 1 to 10 carbon atoms such as butyl; an alkoxy group having 1 to 10 carbon atoms such as methoxy; an alkyl group such as trifluoromethyl all of the hydrogen atoms contained in the substituted groups obtained by a fluorine atom; chlorine atom, bromine atom and the like; nitro; -CO 2 -; -S (O ) 2 O - and the like.
As R 6a, 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 na4 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent. The -CH 2 -contained in the hydrocarbon group and the heterocyclic group include -CH 2 which does not constitute a ring. The -CH 2 -at-may be substituted with -O-, -CO- , -S (O) 2 -or -NR na10- . Among them, -COOH and -S (O) 2 OH are not formed by replacing -CH 2- . Specific examples of R na4 and preferred examples of the R na1 same. In the case where there are multiple R na2 , these may be the same or different.
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 a cyano group.
R 9a is not the case to form a ring together with the respective carbon atom bonded to R 8a and, as 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 , as R 7a , a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group, a hydrogen atom, a halogen atom, cyano, nitro, -CO 2 - or -S (O) 2 O -, more preferably a cyano group. In this case, R 6a and R 8a are preferably the same group.
In the case where R 8a and R 9a form a ring together with the carbon atoms to which they are bonded, it is preferable to form a structure of group A, and it is more preferable to form a ring represented by formula (QQ18). In formula (QQ18), R 25 and R 26 are preferably a hydrogen atom.
R 8a and R 9a also preferably do not form a ring.
R na4 is preferably an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, and butyl; an aromatic hydrocarbon group having 6 to 10 carbon atoms such as phenyl, tolyl, and ethylphenyl; and benzene A group formed by combining a linear hydrocarbon group and an aromatic hydrocarbon group such as methylmethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, phenylethyl, and phenylpropyl. and is a group having a carbon number of 7 to 15, the plurality of groups may have a -CO 2 - or -S (O) 2 O -, as a substituent group, a methoxy group may have a carbon number of such an alkoxy having 1 to 10 group; bond methoxycarbonyl like junctions have butoxycarbonyl hydrocarbon group having 1 to 10 carbon atoms; acyl amine sulfonamide; hydroxyl group; a halogen atom such as chlorine atom, preferably having a -CO 2 -, -S ( O) 2 O -.
As M b + , it is preferably selected from the group consisting of hydrogen cations, Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Zn 2+ , Cu 2+ , Fe 2+ , Mn 2+ , Al 3+ , Fe One of the groups consisting of 3+ , Cr3 +, and Mn4 + is more preferably a hydrogen positive ion.
A is preferably any integer from 1 to 5.
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。
作為R1b
,較佳為氫原子。
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。
作為R6b
,較佳為:-CO-ORnb1
、-CO-NH2
、-CO-NH(Rnb1
)、-CO-N(Rnb1
)2
或-CO-Rnb1
。
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)2
O-
,更佳為氰基。
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。
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)2
OH。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。
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。
R17b
及R18b
亦較佳為並未形成環。
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。Among the compounds represented by formula (IB) in the fourth aspect of compound (B) represented by formula (I), R 1b to R 7b , R 17b to R 18b , R nb1 , and R nb6 are preferably as follows.
R 1b is preferably a hydrogen atom.
R 2b to R 5b are preferably: a hydrogen atom; an alkyl group having 1 to 10 carbon atoms such as butyl; an alkoxy group having 1 to 10 carbon atoms such as methoxy; an alkyl group such as trifluoromethyl Groups in which all the hydrogen atoms contained in them are substituted with fluorine atoms; halogen atoms such as chlorine atoms and bromine atoms; nitro groups and the like.
R 6b is preferably -CO-OR nb1 , -CO-NH 2 , -CO-NH (R nb1 ), -CO-N (R nb1 ) 2 or -CO-R nb1 .
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 a cyano group.
When R 17b and R 18b do not form a ring together with the carbon atom 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 , and 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.
R nb6 represents a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent. The -CH 2 -contained in the hydrocarbon group and the heterocyclic group include -CH 2 which does not form a ring The -CH 2 -at-may be substituted with -O-, -CO- , -S (O) 2 -or -NR nb10- . Among them, -COOH and -S (O) 2 OH are not formed by replacing -CH 2- . Specific examples of R nb6 and preferred examples of the R nb1 same. When there are multiple R nb6s , these may be the same or different.
When R 17b and R 18b form a ring together with the carbon atom to which they are bonded, the structure of group C is preferred, and the ring represented by formula (2a) is more preferred. In formula (2a), R 19b and R 20b are preferably a hydrogen atom.
R 17b and R 18b also preferably have no ring formed.
R nb1 and R nb6 are preferably an alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, and butyl, and an aromatic group having 6 to 10 carbon atoms such as phenyl, tolyl, and ethylphenyl. Hydrocarbyl; phenylmethyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, phenylethyl, phenylpropyl, etc. Combining a chain hydrocarbon group with an aromatic hydrocarbon group Is a group having 7 to 15 carbon atoms, and these groups may have, as a substituent, an alkoxy group having 1 to 10 carbon atoms such as a methoxy group; a bond such as a methoxycarbonyl group An oxycarbonyl group having a hydrocarbon group having 1 to 10 carbon atoms; an amine sulfonyl group; a hydroxyl group; a halogen atom such as a 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。As -CO-OR na1 , -CO-OR na2 , -CO-OR nb1 , -CO-OR nb5 , -CO-OR na4 , -CO-OR nb6 , preferably methoxycarbonyl, ethoxycarbonyl, etc. An alkyloxy group having a carbon number of 1 to 10 (especially an alkyl group) is bonded to.
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、苯基乙基、苯基丙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。
-CO-Rna1
、-CO-Rna2
、-CO-Rna4
的Rna1
、Rna2
、Rna4
可具有-CO2 -
或-S(O)2
O-
,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)2
O-
;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。As -CO-R na1 , -CO-R na2 , -CO-R nb1 , -CO-R nb5 , -CO-R na4 , -CO-R nb6 , preferably, a benzamyl group bond has Carbon rings of 6-10 aromatic rings; carbonyl groups such as ethylcarbonyl and butylcarbonyl groups with 1-10 carbon groups; phenylmethyl, phenylethyl, phenylpropyl, etc. A carbonyl group having 1 to 10 carbon alkyl groups bonded to an aromatic ring having 1 to 10 carbon atoms is bonded.
-CO-R na1, -CO-R na2, -CO-R R na1 na4 a, R na2, R na4 may have a -CO 2 - or -S (O) 2 O -, as a substituent, may have a methoxy Alkoxy groups having 1 to 10 carbons such as alkoxy groups; oxycarbonyl groups having 1 to 10 carbon groups bonded to methoxycarbonyl groups; amine sulfonyl groups; hydroxyl groups; halogen atoms such as chlorine atoms and the like junction carbonyl group of the aromatic ring; the carbonyl group bonded alkyl; bonded to the carbon atom of the carbonyl group such as an alkyl group bonded to the aromatic ring may be bonded with a -CO 2 -; -S (O ) 2 O -; carbon atoms, such as methoxy group having 1 to 10 alkoxy; bond methoxycarbonyl like junctions have butoxycarbonyl hydrocarbon group having 1 to 10 carbon atoms; acyl amine sulfonamide; hydroxyl group; a chlorine atom And other halogen atoms.
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 ) is preferably an aminocarbonyl group such as a methylaminocarbonyl group having an alkyl group having 1 to 10 carbon atoms. Further, -CO 2 - may be bonded to a carbon atom such as an aminocarbonyl group having an alkyl group bonded thereto, or an aminocarbonyl group having an aromatic hydrocarbon ring bonded thereto.
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。-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 And -CO-N (R nb6 ) 2 are preferably an amine carbonyl group having two alkyl groups having 1 to 10 carbon atoms, such as a dimethylamino carbonyl group.
〔2-6〕式(I)所表示的化合物(B)的具體例
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。
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。[2-6] Specific examples of the compound (B) represented by the formula (I) One of the preferable aspects of the compound (B) represented by the formula (I) is the third one described in the above [2-3] Appearance. In the third aspect, it is preferable that 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 hydrogen positive ion, b is 1, ma is 2, and na is 1.
A more preferable example of the compound (B) represented by the formula (I) is a compound represented by the 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。]
作為所述2價烴基,例如可列舉:伸烷基、伸芳基(例如伸苯基)。[In formula (P), L 4 and L 5 each independently represent a divalent hydrocarbon group having 1 to 10 carbon atoms. When the hydrocarbon group contains -CH 2- , the -CH 2 -may be substituted with -NH. -. R P represents a hydrogen atom or a substituent, and p represents any integer of 1 to 4. The wavy line indicates E-body, Z-body, or both. ]
Examples of the divalent hydrocarbon group include an alkylene group and an arylene group (for example, a phenylene group).
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)2 OH基而成的化合物。Another preferred 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
、B1
B2
、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
、B1
B2
、n、m及Mb+
的組合為表5~表6中記載的任一者的化合物。
再者,R31
、R32
、R33
表示式(HH1)~式(HH18)所表示的任一部分結構。B1
B2
表示式(BB1)~式(BB9)所表示的任一部分結構。Specific examples of the compound represented by formula (I), formula (IA), formula (IB), or formula (IIB) include, for example ,:
In the compound represented by the following formula (Ia), a combination of R 31 , L 1 , L 2 , R 32 , B 1 B 2 , n, m, and M b + is any one described in Tables 1 to 4 And a compound represented by the following formula (Ib), wherein the combination of R 33 , L 3 , B 1 B 2 , n, m, and M b + is any one of Tables 5 to 6 .
In addition, R 31 , R 32 , and R 33 each represent a partial structure represented by Formula (HH1) to Formula (HH18). B 1 B 2 represents any one of the structures 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, a wavy line represents an E body, a Z body, or both. ]
[表1]
[Table 1]
[表2]
[Table 2]
[表3]
[table 3]
[表4]
[Table 4]
[表5]
[table 5]
[表6]
[TABLE 6]
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 to 31, 37 to 40, 46 to 49, 55 to 58, 73 to 76, 82 to 85, 91 to 94, 136 to 139, 154 to 157, and 190 are preferable. Compounds of -193, 199-202, 208-211, 244-247, and 298-301.
〔2-7〕式(I)所表示的化合物(B)的製造方法
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。[2-7] Production method of compound (B) represented by formula (I) The compound (B) represented by formula (I) can be produced by formula (pt1) when R 1 is a hydrogen atom. A compound represented by (hereinafter, sometimes referred to as a phthalonitrile compound) is reacted with a compound represented by formula (pt2) (hereinafter, sometimes referred to as an alkoxide compound), and then the compound represented by formula (pt3) is reacted. A compound (hereinafter, sometimes referred to as compound (pt3)) and a compound (hereinafter, sometimes referred to as compound (pt4)) represented by formula (pt4) are 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。
R41
及R42
相互獨立地表示氫原子或碳數1~20的烷基。
M1
及M2
表示鹼金屬原子。
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。
M表示金屬原子。][In formula (pt1) to (pt8) and (1),
R 1 to R 7 , X, M b + , a, m, and n have the same meanings as described above.
R 41 and R 42 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
M 1 and M 2 represent an alkali metal atom.
LG 1 and LG 2 independently represent a halogen atom, a methanesulfonyloxy group, a chloromethylsulfonyloxy group, a tosylsulfonyloxy group, or a trifluoromethanesulfonyloxy group.
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。
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 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. Preferred examples include an alkyl group having 1 to 6 carbon atoms.
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) is usually 0.1 mol or more and 10 mol or less, preferably 0.2 mol, relative to 1 mol of the phthalonitrile compound represented by the formula (pt1). Above and below 5 mol, more preferably between 0.3 and 3 mol, more preferably between 0.4 and 2 mol.
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 the compound (pt3) and the compound (pt4) used is generally 2 mol or more and 20 mol or less, preferably 2 mol, relative to 1 mol of the phthalonitrile compound represented by the formula (pt1). Above and below 10 mol, more preferably between 2 and 6 mol, more preferably between 2 and 4 mol. The compound (pt3) and the 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。
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。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 Carboxylic acids such as citric acid, formic acid, gluconic acid, lactic acid, oxalic acid, and tartaric acid, preferably include hydrochloric acid, hydrobromic acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, The carboxylic acid is more preferably acetic acid.
Relative to 1 mol of phthalonitrile compound, the amount of acid used is usually 1 mol or more and 20 mol or less, preferably 1 mol or more and 10 mol or less, and more preferably 1 mol or more and 8 mols. Molar or less, more preferably 1 Moore or more and 6 Moore or less.
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。
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。
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 reaction of the phthalonitrile compound, alkoxide compound, compound (pt3) and compound (pt4) is usually carried out in the presence of a solvent.
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; 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; N, N-di Phenylamine solvents such as methylformamide and N-methylpyrrolidone; preferred examples of phosphonium solvents such as dimethylsulfine include water, nitrile solvents, alcohol solvents, ether solvents, ketone solvents, Ester solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ammonium solvents, and sulfonium solvents. More preferred examples include 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 dimethylsulfinium, and further preferably For example: water, acetonitrile, methanol, Alcohol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, methylene chloride, chloroform, N, N-dimethylformamide, N, N-dimethylethyl Pyridamine, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, N-methylpyrrolidine Ketones and dimethyl sulfene are particularly preferred. Examples include water, acetonitrile, methanol, ethanol, 2-propanol, N-methylpyrrolidone, and dimethyl sulfene.
The used amount of the solvent is usually 1 part by mass or more and 1,000 parts by mass or less with respect to 1 part by mass of the phthalonitrile compound.
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, alkoxide compound, compound (pt3) and compound (pt4) is usually 0 ° C to 200 ° C, preferably 0 ° C to 100 ° C, and more preferably 0 ° C. Above 50 ° C. The reaction time is usually 0.5 hours to 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, by reacting the compound (pt6), the compound (B) represented by the formula (I) in which R 1 is not a hydrogen atom can be obtained. The amount of the compound (pt6) used is generally 1 mol or more and 10 mol or less, preferably 1 mol or more and 1 mol relative to the compound (B) represented by the formula (I) in which R 1 is a hydrogen atom. 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 the compound (pt6) is reacted, it is preferred that 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 third butoxide, and Metal alkoxides such as potassium tributoxide; organometallic compounds such as butyl lithium, third butyl lithium, and phenyl lithium; 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。The amount of the base to be used is usually 1 mol or more and 10 mol or less, preferably 1 mol or more and 5 mols relative to 1 mol of the compound (B) represented by the formula (I) in which R 1 is a hydrogen atom. Hereinafter, it is more preferably 1 mol or more and 3 mol or less, and still more preferably 1 mol or more and 2 mol or less.
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。The reaction of the compound (pt6) is usually carried out in the presence of a solvent. The solvent 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 to be used is usually 1 part by mass or more and 1,000 parts by mass or less with respect 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, and more preferably 0 ° C to 50 ° C. The reaction time is usually 0.5 hours to 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, the compound (B) represented by the formula (I) can be reacted with a sulfonating agent such as oleum or chlorosulfonic acid to thereby Introduce sulfo.
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 3 used in oleum is generally 1 mol or more and 50 mol or less, preferably 5 mol or more and 40 mols relative to 1 mol of the compound (B) represented by formula (I). Hereinafter, it is more preferably 5 mol or more and 30 mol or less, and still more preferably 5 mol or more and 25 mol or less. The amount of sulfuric acid used in oleum is generally 1 mol or more and 200 mol or less, preferably 10 mol or more and 100 mol or less, relative to 1 mol of the compound (B) represented by formula (I). , More preferably 10 mol or more and 75 mol or less, still more preferably 10 mol or more and 50 mol or less.
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。The amount of chlorosulfonic acid used is usually 1 mol or more and 500 mol or less, preferably 10 mol or more and 300 mol or less, more preferably 1 mol of the compound (B) represented by formula (I). It is 10 mol or more and 200 mol or less, and more preferably 10 mol or more and 150 mol or less.
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 sulfonation reaction temperature is usually -20 ° C to 200 ° C, preferably -10 ° C to 100 ° C, and more preferably 0 ° C to 50 ° C. The reaction time is usually 0.5 hours to 300 hours.
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)。When the compound (B) represented by the formula (I) has a carboxyl group or a sulfo group, the compound (pt7) can be reacted with the compound (pt8) to produce a compound represented by the formula (I) containing a 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 taking out the compound (B) represented by the formula (I) from the reaction mixture is not particularly limited, and it can be taken out by various known methods. For example, after the reaction is completed, the reaction mixture may be filtered to take out the compound (B) represented by the formula (I). Alternatively, the obtained residue may be washed with a solvent after filtration. Alternatively, after filtration, column chromatography, recrystallization, or sublimation purification may be performed.
〔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
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。
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。
所謂著色劑,是指以顏料及染料為代表的色素的總稱。[3] Co-dispersion of CI Pigment Yellow 138 (A) and compound (B) represented by Formula (I), and a colorant dispersion liquid containing the same. The colorant dispersion liquid contains CI Pigment Yellow 138 (A as a main component). ) A co-dispersion with the compound (B) represented by the formula (I). According to the colorant dispersion liquid containing the co-dispersion, for example, a dispersion liquid of CI Pigment Yellow 138 (A) and a dispersion liquid of the compound (B) represented by formula (I) are separately prepared, and the dispersion liquids are mixed. Compared with the toner dispersion, it can significantly improve the contrast.
The main component refers to a component having the highest content rate (quality basis) among the coloring agents contained in the colorant dispersion liquid.
The colorant is a general term for a pigment represented by a pigment and a dye.
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。
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。
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。
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0.2 μm以下左右。The co-dispersion can be prepared by co-dispersing CI Pigment Yellow 138 (A) and the compound (B) represented by formula (I) in the presence of a dispersant, or dispersing in a solvent in the presence of a resin, if necessary. .
Examples of the dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These dispersants may be used alone or in combination of two or more.
Resin can also be selected from resin (D) mentioned later. The solvent may be selected from solvents (G) described later.
The co-dispersion can be prepared, for example, by mixing a part or all of the compound (B) represented by CI Pigment Yellow 138 (A) and Formula (I) with a solvent (G), and coexisting with a dispersant if necessary. If necessary, or in the presence of a part or all of the resin (D), if necessary, they are 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。
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 dispersant is used, its use amount is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 80% by mass or less with respect to the total amount of the colorant. When the usage-amount of a dispersing agent exists in the said range, there exists a tendency for the co-dispersion in a uniform dispersion state to be easily obtained.
When a resin is used, its use amount is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 80% by mass or less with respect to the total amount of the colorant. When the usage-amount of resin exists in the said range, there exists a tendency for the co-dispersion in a uniform dispersion state to be easily obtained.
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。
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。The content of CI Pigment Yellow 138 (A) in the co-dispersion and the colorant dispersion liquid is from the viewpoint of improving the contrast. The amount of 100 parts by mass is preferably 50.1 parts by mass or more and 99.9 parts by mass or less, more preferably 60 parts by mass or more and 99 parts by mass or less, and still more preferably 85 parts by mass or more and 99 parts by mass or less.
The content of the compound (B) represented by the formula (I) in the co-dispersion and the colorant dispersion liquid is higher than that of the compound represented by the formula (I) CI Pigment Yellow 138 (A) and (I) The total amount of B) is preferably 0.1 parts by mass or more and 49.9 parts by mass or less, more preferably 1 part by mass or more and 40 parts by mass or less, and still more preferably 1 part by mass or more and 15 parts by mass or less.
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。
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。
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。The co-dispersion and the colorant dispersion liquid may contain components other than CI Pigment Yellow 138 (A) and the compound (B) represented by Formula (I), respectively.
Examples of the other components include colorants (pigments, dyes), solvents, dispersants, resins, and aliphatic carboxylic acid metal salts other than CI Pigment Yellow 138 (A) and the compound (B) represented by formula (I). (C) and so on. The aliphatic carboxylic acid metal salt (C) will be described later.
The co-dispersion and the colorant dispersion may each contain only one other component, or may include two or more.
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。
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。Other pigments are not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments in the Dye Index (published by The Society of Dyers and Colourists).
Examples of the pigment include:
CI 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;
CI Pigment Orange (Pigment Orange) 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
CI 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 And other red pigments;
CI Pigment Blue (Pigment Blue) 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments;
CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments;
CI Pigment Green (Pigment Green) 7, 36, 58, 59 and other green pigments;
CI Pigment Brown (Pigment Brown) 23, 25 and other brown pigments;
CI Pigment Black (Pigment Black) 1, 7 and other black pigments.
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 with CI Pigment Yellow 138 (A) and compound (B) represented by Formula (I) in a co-dispersion, or can be added to include CI Pigment Yellow 138 (A) and Formula (I) The co-dispersion of the compound (B) is included in a 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。CI Pigment Yellow 138 (A), the compound (B) represented by formula (I), and other pigments may be optionally subjected to rosin treatment, surface treatment using pigment derivatives into which acidic or basic groups are introduced, and the like. Grafting of pigment surfaces by polymer compounds, micronization by sulfuric acid micronization, etc., or cleaning treatment with organic solvents or water to remove impurities, ion exchange with ionic impurities Removal process, 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。
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。
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。
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 is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes.
Examples of the dye include known dyes described in the dye index (published by The Society of Dyers and Colourists) and dyeing notes (Shikisensha).
In addition, according to the chemical structure, dyes can be exemplified by azo dyes, cyanine dyes, triphenylmethane dyes, xanthene xanthene dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, and quinoneimines 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.
The dye may be contained in the co-dispersion, or may be added to the co-dispersion and contained 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。Resin can also be selected from resin (D) mentioned later. The solvent may 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 CI Pigment Yellow 138 (A) and the compound (B) represented by the formula (I) is preferably 5 parts by mass or more out of 100 parts by mass of the coloring agent contained in the co-dispersion or the colorant dispersion liquid. It is preferably 10 parts by mass or more, more preferably 30 parts by mass or more, even more preferably 50 parts by mass or more, even more preferably 80 parts by mass or more, and most preferably 90 parts by mass or more. The total content may be 100 parts by mass of 100 parts by mass of the coloring agent contained in the co-dispersion or the 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。
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。The total content of CI Pigment Yellow 138 (A) and the compound (B) represented by the formula (I) is preferably 10 parts by mass out of 100 parts by mass of the total amount of solid components contained in the co-dispersion or the colorant dispersion liquid. The amount is more than 90 parts by mass, more preferably 15 parts by mass or more and 80 parts by mass or less, and still more preferably 20 parts by mass or more and 70 parts by mass or less.
In this specification, the "total amount of solid content" contained in a co-dispersion, a colorant dispersion, or a colored curable resin composition means a self-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 the solid component and the content of each component relative thereto can be measured by a known analysis means such as liquid chromatography or gas chromatography.
〔4〕脂肪族羧酸金屬鹽(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。
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。[4] Aliphatic carboxylic acid metal salt (C)
The colorant dispersion liquid may include an aliphatic metal carboxylic acid salt (C) as the other component. Furthermore, the inclusion of an aliphatic carboxylic acid metal salt (C) is advantageous for improving contrast.
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)」。
本說明書中所謂「脂肪族羧酸」,是指不具有芳香環的羧酸。
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 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. Hereinafter, the aliphatic carboxylic acid having 1 to 40 carbon atoms having a hydroxyl group is also referred to as "aliphatic carboxylic acid (X)".
The "aliphatic carboxylic acid" as used in this specification means the carboxylic acid which does not have an aromatic ring.
The colored curable resin composition of the present invention may contain only one type of the 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。
脂肪族羧酸(X)亦可包含不飽和鍵。The aliphatic carboxylic acid (X) has a carbon number of 1 to 40 including carbons containing a carboxyl group, and may be linear, branched, or cyclic, or selected from linear A combination of two or more structures in a group consisting of a chain structure, a branched chain structure, and a cyclic structure.
The aliphatic carboxylic acid (X) may contain an unsaturated bond.
脂肪族羧酸(X)於分子內具有一個以上的羥基。
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 hydroxyl groups in the molecule.
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。From the viewpoint of improving the contrast, the carbon number of the aliphatic carboxylic acid (X) is 1 to 40, preferably 10 to 36, and more preferably 12 to 24.
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。
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。
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。
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。The aliphatic carboxylic acid metal salt (C) may have at least one anion of the aliphatic carboxylic acid (X). When 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 kinds of anions of the aliphatic carboxylic acid (X), It may have an anion other than the anion of the aliphatic carboxylic acid (X) and the anion of the aliphatic carboxylic acid (X).
The other anion is not particularly limited, and may be a halogen ion, a nitrate ion, a sulfate ion, or the like, and an anion of an aliphatic carboxylic acid other than the aliphatic carboxylic acid (X) is preferred.
The aliphatic carboxylic acid other than the aliphatic carboxylic acid (X) means an aliphatic carboxylic acid which does not have a hydroxyl group, and examples thereof include those having the same structure as the aliphatic carboxylic acid (X) except that it does not have a hydroxyl group.
The anion possessed by the aliphatic carboxylic acid metal salt (C) is preferably an anion containing only the 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。
金屬陽離子
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+
。
脂肪族羧酸金屬鹽(A)亦可具有兩種以上的金屬陽離子。From the viewpoint of improving the contrast, the metal cation of the aliphatic carboxylic acid metal salt (C) is preferably a metal cation having a valence of 2 or more and 10 or less. Examples of the divalent or higher metal cation include cations of metals belonging to Groups 2 to 15 of the periodic table. The metal cation is preferably a metal cation having a divalent value or more and a hexavalent value or less.
The metal cations are 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 Divalent metal cations such as 2+ , Pb 2+, and Mn 2+ ; trivalent metal cations such as Al 3+ , Fe 3+ , Co 3+, and Cr 3+ ; Sn 4+ and Mn 4+, etc. 4-valent metal cation,
Furthermore, 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 preferred are 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+ ,
Further preferred are Fe 2+ , Co 2+ , Fe 3+ and Co 3+ .
The aliphatic carboxylic acid metal salt (A) 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) can be specifically a compound represented by the following formula (Aa).
[式(Aa)中,
D表示具有羥基的脂肪族烴。
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。
D的碳數+a為1~40的任一整數。
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。
Jk -
表示『[D]-(CO2 -
)a
』以外的陰離子。
k表示1~10的任一整數,較佳為1~6的任一整數。
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。
Ac+
表示c價的金屬陽離子,具體例如上所述。
c表示2~10的任一整數,較佳為2~6的任一整數。
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。
其中,
及
的合計價數與
的價數相等。][In formula (Aa),
D represents an aliphatic hydrocarbon having a hydroxyl group.
a represents any integer from 1 to 10, and preferably any integer from 1 to 3. When there are multiple a's, these may be the same as or different from each other.
The carbon number + a of D is any integer from 1 to 40.
b represents any integer of 1 or more. When b represents any integer of 2 or more, [[D]-(CO2 -
)a
It can be the same as or different from each other.
Jk -
Means "[D]-(CO2 -
)a
』Other anions.
k represents any integer from 1 to 10, and preferably any integer from 1 to 6.
m represents any integer of 0 or more. When m represents any integer of 2 or more, "Jk -
It can be the same as or different from each other.
Ac +
The c-valent metal cation is as described above.
c represents any integer from 2 to 10, and preferably any integer from 2 to 6.
d represents any integer of 1 or more. When d represents any integer of 2 or more, "Ac +
It can be the same as or different from each other.
among them,
and
The total price and
The valences are equal. ]
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 an aliphatic carboxylic acid (X) in an alkaline aqueous solution and then adding a salt (for example, a halide or the like) having a metal cation. The obtained aliphatic metal carboxylic acid salt (C) can also be used for purification treatment such as washing, if necessary.
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。
MpLq (AA)Specific examples of the aliphatic carboxylic acid metal salt (C) include the compounds represented by the following [Table A] and the compounds of [Table A] in the following formula (AA): M, L, p, and q, respectively. In AA1 to AA22, M is Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Cd 2+ , Ni 2+ , Zn 2+ , Cu 2+ , Hg 2+ , Co 2 instead of Fe 2+ . + , Sn 2+ , Pb 2+ , or Mn 2+ compounds, compounds shown in [Table B], and compounds AA23 to AA44 of [Table B] M is Al 3+ instead of Fe 3+ and Co 3 + Or Cr 3+ compounds, and compounds represented by [Table C].
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。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 a salt represented by the following formula.
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。
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。When the co-dispersion or colorant dispersion liquid contains an aliphatic carboxylic acid metal salt (C), the content of the aliphatic carboxylic acid metal salt (C) in the solid component contained in the co-dispersion or colorant dispersion liquid The total amount of 100 parts by mass is preferably 0.01 parts by mass or more and 25 parts by mass or less, more preferably 0.1 parts by mass or more and 20 parts by mass or less, still more preferably 0.2 parts by mass or more and 15 parts by mass or less, particularly preferably 0.3 parts by mass. It is at least 10 parts by mass. If the content of the aliphatic carboxylic acid metal salt (C) is within the above range, the contrast can be significantly improved.
The content of the aliphatic carboxylic acid metal salt (C) is preferably 0.1 part by mass or more and 20 parts by mass with respect to 100 parts by mass of the total amount of the compound (B) represented by CI Pigment Yellow 138 (A) and Formula (I) It is more preferably 0.3 parts by mass or more and 15 parts by mass or less, and still more preferably 0.5 parts by mass or more and 13 parts by mass or less.
<著色硬化性樹脂組成物>
著色硬化性樹脂組成物包含所述著色劑分散液與樹脂(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)。
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)。
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。
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。<Colored curable resin composition>
The colored curable resin composition includes the colorant dispersion liquid and a resin (D).
The colored curable resin composition preferably further contains a polymerizable compound (E) and a polymerization initiator (F), and more preferably further contains a polymerizable compound (E), a polymerization initiator (F), and a solvent (G). .
The colored curable resin composition may further contain a polymerization initiator (F1) and / or a leveling agent (H).
According to the colored curable resin composition, the contrast of the color filter formed by the color filter and the display device using the color filter can be improved.
Hereinafter, the compounds exemplified as each component may be used alone or in combination of a plurality of types unless otherwise specified.
〔1〕著色硬化性樹脂組成物中的著色劑分散液的含量
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。[1] Content of colorant dispersion liquid in colored curable resin composition From the viewpoint of brightness, the colorant dispersion liquid is the content of colorant (or CI Pigment Yellow 138 (A) and formula ( The total content of the compound (B) represented by I) is preferably 0.1 parts by mass or more and 90 parts by mass or less, and more preferably 0.5 parts by mass, based on 100 parts by mass of the total solid content of the colored curable resin composition. It is contained in the coloring curable resin composition so that it is 80 mass parts or more and more preferably 1 mass part or more and 70 mass parts or less.
〔2〕樹脂(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。
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。〔2〕 Resin (D)
The resin (D) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably has at least one (a) derived from a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride (hereinafter sometimes referred to as Resin as the structural unit of "(a)").
The resin (D) further preferably has at least one structural unit selected from the group consisting of a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (b ) (Hereinafter sometimes referred to as "(b)"), a structural unit derived from a singular body (c) that can be copolymerized with (a) (wherein it is different from (a) and (b)) (hereinafter sometimes referred to 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 anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, and succinic acid mono [2- (methyl) Acrylic fluorenyloxyethyl] ester and the like are preferably acrylic acid, methacrylic acid, and 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。
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。
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。(B) A cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxetane ring, an oxetane ring, and a tetrahydrofuran ring) and (A ) A singular body of acrylfluorenyloxy.
The "(meth) acrylic acid" in this specification means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth) acrylfluorenyl" and "(meth) acrylate" also have the same meaning.
Examples of (b) include glycidyl (meth) acrylate, vinyl benzyl glycidyl ether, 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl ester (meth) acrylate, 3-ethyl-3- (meth) acrylfluorenyloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate, etc., preferably glycidyl (meth) acrylate, (methyl) ) 3,4-epoxytricyclo [5.2.1.0 2,6 ] decyl acrylate, 3-ethyl-3- (meth) acrylfluorenyloxymethyloxetane.
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, and (methyl) ) 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, vinyltoluene, etc., preferably styrene, vinyltoluene, 2-hydroxyethyl (meth) acrylate, N -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, etc. are preferred.
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。The resin having a structural unit having an ethylenically unsaturated bond in the side chain can be obtained by adding (b) to the copolymer of (a) and (c), or adding (a) to (b) and (c). ) Copolymers. This resin may be a resin obtained by adding (a) to the 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。
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 polystyrene equivalent weight average molecular weight of the resin (D) is preferably 3,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, and even more preferably 5,000 or more and 30,000 or less.
The dispersion [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (D) is preferably 1.1 or more and 6 or less, and more preferably 1.2 or more and 4 or less.
樹脂(D)的酸價以固體成分換算計較佳為20 mg-KOH/g以上且170 mg-KOH/g以下,更佳為30 mg-KOH/g以上且150 mg-KOH/g以下,進而佳為40 mg-KOH/g以上且135 mg-KOH/g以下。
酸價是作為中和樹脂(D)1 g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 of the resin (D) in terms of solid content is preferably 20 mg-KOH / g or more and 170 mg-KOH / g or less, more preferably 30 mg-KOH / g or more and 150 mg-KOH / g or less, and furthermore It is preferably above 40 mg-KOH / g and below 135 mg-KOH / g.
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 by, for example, 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 7 parts by mass or more and 65 parts by mass or less, more preferably 13 parts by mass or more and 60 parts by mass or less in 100 parts by mass of the total solid content of the colored curable resin composition. It is more preferably 17 parts by mass or more and 55 parts by mass or less.
〔3〕聚合性化合物(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。[3] Polymerizable compound (E)
The polymerizable compound (E) is a compound that can be polymerized by living radicals and / or acids generated from the polymerization initiator (F), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond. 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) acrylic acid. Esters, dipentaerythritol hexa (meth) acrylate, and the like.
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 150 or more and 2900 or less, and more preferably 250 or more and 1500 or less.
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 7 parts by mass or more and 65 parts by mass or less, and more preferably 13 parts by mass or more and 60 parts by mass or less in 100 parts by mass of the total solid content of the colored curable resin composition. It is more preferably 15 parts by mass or more and 55 parts by mass or less.
〔4〕聚合起始劑(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。[4] Polymerization initiator (F)
The polymerization initiator (F) is not particularly limited as long as it is a compound that can generate active radicals, acids, and the like by the action of light or heat and starts polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates living radicals include N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine and N-benzene Formamyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl)- 3-cyclopentylpropane-1-one-2-imine, 2-methyl-2-morpholinyl-1- (4-methylthiophenyl) propane-1-one, 2-dimethylamine 1- (4-morpholinylphenyl) -2-benzylbutane-1-one, 1-hydroxycyclohexylphenyl ketone, 2,4-bis (trichloromethyl) -6-piperyl -1,3,5-triazine, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 2,2'-bis (2-chlorophenyl) -4,4'5, 5'-tetraphenylbiimidazole and the like.
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 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more, based on 100 parts by mass of the total amount of the resin (D) and the polymerizable compound (E). 20 parts by mass or less. When the content of the polymerization initiator (F) is within the above range, the sensitivity tends to increase and the exposure time tends to decrease. Therefore, the productivity of the color filter is improved.
〔5〕聚合起始助劑(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。
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。[5] Polymerization initiation aid (F1)
The polymerization initiation aid (F1) is a compound or a sensitizer for promoting the polymerization of the polymerizable compound (E) that has been polymerized by the polymerization initiator (F). When a polymerization initiator (F1) is included, it is usually used in combination with a polymerization initiator (F).
Examples of the polymerization initiation aid (F1) include 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (bis Ethylamino) benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone, N-phenylglycine and the like.
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 the polymerization initiation aid (F1), the content is preferably 0.1 to 30 parts by mass, and more preferably 100 parts by mass relative to the total amount of the resin (D) and the polymerizable compound (F). 1 to 20 parts by mass. When the amount of the polymerization initiation aid (F1) is within this range, a colored pattern can be further formed with high sensitivity, and the productivity of the color filter tends to be improved.
〔6〕溶劑(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。[6] Solvent (G)
The solvent (G) is not particularly limited, and solvents commonly used in this field can be used. Examples include: ester solvents (solvents containing -COO- but not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether ester solvents (in the molecule Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (containing OH in the molecule and not containing -O-, -CO -And -COO- solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene 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。
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。Examples of the solvent (G) include:
Ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, ethyl acetate, cyclohexanol acetate, and Ester solvents such as γ-butyrolactone (solvents containing -COO- but not -O- in the molecule);
Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methyl ether (Solvent containing -O- and not -COO- in the molecule);
Methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethyl Ether ester solvents such as glycol monoethyl ether acetate (solvents containing -COO- and -O- in the molecule);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone, heptanone, 4-methyl-2-pentanone, cyclohexanone (solvents containing -CO- in the molecule and not containing -COO- );
Alcohol solvents such as butanol, cyclohexanol, propylene glycol (solvents containing OH in the molecule and excluding -O-, -CO- and -COO-);
Solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
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。
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 solvent (G) is contained, the content of the solvent (G) is preferably 70 parts by mass or more and 95 parts by mass or less, and more preferably 75 parts by mass, based on 100 parts by mass of the total amount of the coloring curable resin composition. Above 92 parts by mass. In other words, the total solid content of the colored curable resin composition is preferably 5 parts by mass or more and 30 parts by mass or less, more preferably 8 parts by mass or more, and 100 parts by mass of the total amount of the colored curable resin composition. 25 parts by mass or less.
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 color density will not be insufficient when forming a color filter, so that the display characteristics will be good.
〔7〕調平劑(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。
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。〔7〕 Leveling agent (H)
Examples of the leveling agent (H) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in a side chain.
Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (Trade name: Toray Dow Corning) )); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (Momentive Performance Materials Japan), 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 a surfactant having a fluorocarbon chain in the molecule. Specific examples include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M), 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 Electronics Corporation), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass) (Stock) manufacturing) and E5844 (Daikin Fine Chemicals Research Institute (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. Specifically, it can be listed as: Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477 and Megafac F443 (Diegison (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(F)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 (F) is preferably 0.001 part by mass or more and 0.2 part by mass or less, more preferably 100 parts by mass of the total amount of the coloring curable resin composition. It is 0.002 mass parts or more and 0.1 mass parts or less. Moreover, the content does not include the content of the dispersant. When the content of the leveling agent (H) is within the above range, the flatness of the color filter can be made good.
〔8〕其他成分
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。
該添加劑亦可包含於所述著色劑分散液或共分散物中。[8] Other components The colored curable resin composition may contain additives known in the technical field, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as necessary.
The additive may also be contained in the colorant dispersion or co-dispersion.
〔9〕著色硬化性樹脂組成物的製造方法
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。[9] Method for producing colored curable resin composition The colored curable resin composition can be obtained by dispersing a colorant dispersion liquid and a resin (D), and optionally using a polymerizable compound (E) and a polymerization initiator (F ), Solvent (G), polymerization initiation aid (F1), leveling agent (H) and other ingredients.
<彩色濾光片的製造方法>
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。< Manufacturing method of color filter >
Examples of a method for producing a colored pattern from a colorant dispersion liquid or a colored curable resin composition include a photolithography method, an inkjet method, and a printing method. 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。
[實施例]When the colorant dispersion liquid or the coloring curable resin composition contains the co-dispersion, a color filter having excellent contrast can be produced. This color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state imaging element.
[Example]
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 through examples. "%" And "part" in the examples are mass% and mass parts unless otherwise specified.
<合成例1:化合物(I)的製備>
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%)。<Synthesis Example 1: Preparation of Compound (I)>
3 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed with 300 parts of methanol. While maintaining the temperature of the obtained mixture at 5 ° C or lower, 2.71 parts of a 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 maintaining the temperature of the obtained mixture to 5 ° C or lower, 14 parts of acetic acid was added. 14 parts of 4- (2-cyanoacetamido) benzoic acid (synthesized according to the method described in US2680731) were added to the obtained mixture, and the mixture was stirred at 45 ° C 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 a compound (I) represented by the following formula (yield: 83%).
[化合物(I)的鑑定]
(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[Identification of Compound (I)]
(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>
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)。<Synthesis Example 2: Preparation of Compound (II)>
7.02 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with 61.6 parts of methanol. While maintaining the temperature of the obtained mixture at 2 ° C, 8.20 parts of a 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 the temperature of the obtained mixture was kept at 4 ° C or lower, 10.7 parts of acetic acid was added. 17.6 parts of benzamidine acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the obtained mixture, and the mixture was 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]
(質量分析)離子化模式=ESI+:m/z=[M+H]+
402
精確質量(Exact Mass):401[Identification of Compound (IIa)]
(Mass analysis) Ionization mode = ESI +: m / z = [M + H] + 402
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, while stirring 7.6 parts of oleum (25%) (manufactured by Wako Pure Chemical Industries, Ltd.) at 3 ° C, 0.513 parts of the compound (IIa) obtained above was added while stirring. To the obtained mixture, 3.8 parts of oleum (25%) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. While stirring the obtained mixture, it took 3 hours and 30 minutes to raise to 15 ° C. 139 parts of ice water was added to the obtained mixture, and 38.2 parts of sodium chloride was further added. The obtained mixture was filtered, and the obtained residue was washed with 64 parts of a 21.5% sodium chloride aqueous solution. The obtained residue was dried under reduced pressure at 60 ° C to obtain 1.02 parts of a compound (II) represented by the following formula (a compound obtained by bonding two sulfo groups to the compound (IIa)).
[化合物(II)的鑑定]
(質量分析)離子化模式=ESI-:m/z=[M-H]-
560
精確質量(Exact Mass):561[Identification of Compound (II)]
(Mass spectrometry) ionization mode = ESI-: m / z = [ MH] - 560
Exact Mass: 561
<合成例3:樹脂(D)的製備>
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77 mg-KOH/g。樹脂(D)具有下述結構單元。<Synthesis Example 3: Preparation of Resin (D)>
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to create a nitrogen atmosphere. 280 parts of propylene glycol monomethyl ether acetate was placed, and heated to 80 ° C while stirring. Next, 38 parts of acrylic acid, acrylic acid 3,4-epoxytricyclo [5.2.1.0 2,6 ] decane-8-yl ester, and acrylic acid 3,4 were added dropwise to the flask using a dropping pump for about 5 hours. -A solution in which 289 parts of a mixture of epoxy tricyclo [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, it took about 6 hours using another dropping pump to dropwise add 33 parts of a polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) into propylene glycol monomethyl ether ethyl. A solution of 235 parts of the acid ester. After the completion of the dropwise addition, the temperature was maintained at this temperature 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 9,200, 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。
裝置:K2479(島津製作所(股)製造)
管柱:島津(SHIMADZU)Shim-pack GPC-80M
管柱溫度:40℃
溶媒:四氫呋喃(tetrahydrofuran,THF)
流速:1.0 mL/min
檢測器: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)The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured using the GPC method under the following conditions.
Installation: K2479 (manufactured by Shimadzu Corporation)
Column: Shimadzu Shim-pack GPC-80M
Column temperature: 40 ℃
Solvent: tetrahydrofuran (THF)
Flow rate: 1.0 mL / min
Detector: RI
Calibration reference materials: TSK Standard Polystyrene (STANDARD POLYSTYRENE) F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh)
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 set 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>
(脂肪族羧酸金屬鹽(C)的合成)
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。
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)。<Synthesis Example 4: Preparation of Aliphatic Carboxylic Acid Metal Salt (C) Dispersion Liquid (Dispersion Liquid (C))>
(Synthesis of aliphatic carboxylic acid metal salt (C))
In a beaker, 100 parts of pure water and 5 parts of 12-hydroxystearic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed. To this mixture was added 65 parts of a 1% sodium hydroxide aqueous solution at 70 ° 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 while maintaining it at 70 ° C to 75 ° C for about 2 hours and 30 minutes. The mixture was stirred while maintaining the temperature at 70 ° C to 75 ° C for about 1 hour. The mixture was cooled to 35 ° C and filtered.
The obtained residue was washed three times with 245 parts of water, and dried under reduced pressure at 60 ° C. to obtain an iron (III) carboxylate salt containing 12-hydroxystearic acid anion as an anion component (the following formula (c) Indicated salt). Hereinafter, this salt is referred to as an aliphatic carboxylic acid metal salt (C).
(分散液(C)的製備)
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)。
調配成分的詳細情況如下。
〔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)
〔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)
〔3〕PGMEA:丙二醇單甲醚乙酸酯
〔4〕DAA:二丙酮醇(4-羥基-4-甲基-2-戊酮)(Preparation of dispersion (C))
2.50 parts of aliphatic carboxylic acid metal salt (C);
Dispersant 1 4.00 parts;
Solvent (G): 68.50 parts of PGMEA;
And solvent (G): 25.00 parts of DAA were mixed and the aliphatic carboxylic acid metal salt (C) was dispersed, thereby obtaining a dispersion liquid (C).
The details of the prepared ingredients are as follows.
[1] Aliphatic carboxylic acid metal salt (C): Aliphatic carboxylic acid metal salt (C) obtained in Synthesis Example 4
[2] Dispersant 1: Dispersant (DISPERBYK-111; manufactured by BYK-chemie Japan)
[3] PGMEA: propylene glycol monomethyl ether acetate [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>
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。
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)。
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。<Example 1 to Example 7, Comparative Example 1 to Comparative Example 5: Preparation of colorant dispersion liquid>
The coloring agent, dispersant 2 and resin (D) solution obtained in Synthesis Example 3, the dispersion liquid (C) obtained in Synthesis Example 4 (with unused examples), and The solvents (G) were mixed, and each colorant dispersion liquid was obtained using a bead mill.
The toner dispersion liquids of Example 1, Example 4, Example 6, and Comparative Example 2 include a co-dispersion of two kinds of toners. The toner dispersion liquids of Example 2, Example 3, Example 5, Example 7, Comparative Example 3, and Comparative Example 4 include a co-dispersion of the two toners and a dispersion liquid (C) (aliphatic carboxylic acid metal salt) (C) Dispersion).
The composition of the toner dispersion liquid obtained in each Example and a comparative example is shown in Table 7. The unit of the numerical value of Table 7 is a mass part. The solvent (G) in Table 7 includes the solvent in the resin (D) solution and the dispersion (C).
[表7]
著色劑分散液中所含的調配成分的詳細情況如下。
〔1〕Y138:C.I.顏料黃138
〔2〕Y185:C.I.顏料黃185
〔3〕化合物(I):合成例1中獲得的化合物(I)
〔4〕化合物(II):合成例2中獲得的化合物(II)
〔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)
〔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)
〔7〕樹脂(D):合成例3中獲得的樹脂(D)溶液中所含的樹脂(D)
〔8〕PGMEA:丙二醇單甲醚乙酸酯
〔9〕DAA:二丙酮醇(4-羥基-4-甲基-2-戊酮)The detail of the preparation component contained in a colorant dispersion liquid is as follows.
[1] Y138: CI Pigment Yellow 138
[2] Y185: CI Pigment Yellow 185
[3] Compound (I): Compound (I) obtained in Synthesis Example 1
[4] Compound (II): Compound (II) obtained in Synthesis Example 2
[5] Aliphatic carboxylic acid metal salt (C): Aliphatic carboxylic acid metal salt (C) obtained in Synthesis Example 4
[6] Dispersant 2: Dispersant (BYK-LP N 6919; manufactured by BYK-chemie Japan)
[7] Resin (D): Resin (D) contained in the resin (D) solution obtained in Synthesis Example 3
[8] PGMEA: propylene glycol monomethyl ether acetate [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>
(1)著色硬化性樹脂組成物的製備
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。
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。
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)。
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。<Example 8 to Example 16, Comparative Example 6 to Comparative Example 10>
(1) Preparation of colored curable resin composition In Examples 8 to 14 and Comparative Examples 6 to 10, the toners of Examples 1 to 7 and Comparative Examples 1 to 5 were dispersed, respectively. It is mixed with a resin (D) solution, a polymerizable compound (E), a polymerization initiator (F), and a leveling agent (H) to obtain a colored curable resin composition.
In Examples 15 and 16, the toner dispersion liquid of Example 1 and the dispersion liquid (C) obtained in Synthesis Example 4 and the resin (D) solution, the polymerizable compound (E), and the polymerization initiation were used. The agent (F) and the leveling agent (H) are mixed to obtain a colored curable resin composition.
When the colored curable resin composition is prepared, propylene glycol monomethyl ether acetate (PGMEA) is added so that the solid content of the colored curable resin composition becomes 20% by mass.
Table 8 and Table 9 show the composition except the solvent (G) in the coloring agent dispersion liquid used in each Example and the comparative example, and the coloring curable resin composition obtained in each Example and Comparative Example. The unit of the amount of each component in Table 8 and Table 9 is a mass part.
[表8]
[表9]
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。
〔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)
〔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)
〔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)The details of the polymerizable compound (E), the polymerization initiator (F), and the leveling agent (H) are as follows.
[1] Polymerizable compound (E): dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
[2] Polymerization initiator (F): N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure ( (Registered trademark) OXE-01; manufactured by BASF Japan)
[3] Leveling agent (H): polyether modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning)
(2)著色塗膜的製作
於5 cm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150 mJ/cm2
的曝光量(365 nm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。(2) Preparation of colored coating film A 5 cm square glass substrate (eagle 2000; manufactured by Corning) was coated with a colored hardening resin composition by a spin coating method, and then at 100 ° C. Pre-bake for 3 minutes to form a colored composition layer. After leaving to cool, light exposure was performed using an exposure machine (TME-150RSK; manufactured by Topcon (Stock)) at an exposure of 150 mJ / cm 2 (365 nm standard) in the atmospheric environment. The coloring composition layer after light irradiation was immersed and developed at 24 ° C for 10 seconds in an aqueous developing solution containing non-ionic surfactant 0.12% and potassium hydroxide 0.04%. After washing, it was washed in an oven at 230 ° C. After 30 minutes of post-baking, a colored coating film was obtained.
(3)膜厚測定
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。
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。(3) Film thickness measurement The film thickness measurement device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) was used to measure the film thickness of the colored coating film obtained in the above (2).
The film thickness of the obtained colored coating film was 2.0 μm in each of the Examples and Comparative Examples.
(4)色度評價
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。(4) Colorimetric Evaluation For the colored coating film obtained in the above (2), spectrometry was measured using a colorimeter (OSP-SP-200; manufactured by Olympus) and characteristics of a C light source were used. Function to determine the XY chromaticity coordinates (x, y) in the XYZ color system of the Commission Internationale de I'Eclairage (CIE). The results are shown in Tables 8 and 9.
(5)對比度評價
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。
[產業上之可利用性](5) Contrast evaluation For the colored coating film obtained in the above (2), a contrast meter (CT-1: manufactured by Kesaka Electric Co., Ltd., a colorimeter BM-5A: manufactured by Topcon Corporation, and a light source: F were used. -10. Polarizing film: manufactured by Kesaka Electric Co., Ltd.) and set the blank value to 30,000 to measure the contrast. The results are shown in Tables 8 and 9. It can be said that if the contrast in the colored coating film is high, the same is also true in the colored pattern.
[Industrial availability]
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.
無no
無no
Claims (8)
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 true TW201938531A (en) | 2019-10-01 |
TWI790354B 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 |
Family Cites Families (9)
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 |
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 |
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 |
TWI729161B (en) * | 2016-07-07 | 2021-06-01 | 日商住友化學股份有限公司 | Pigment composition, colored composition and colored curable 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
Also Published As
Publication number | Publication date |
---|---|
CN111836859A (en) | 2020-10-27 |
JP2019157119A (en) | 2019-09-19 |
KR20200130344A (en) | 2020-11-18 |
TWI790354B (en) | 2023-01-21 |
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 |
---|---|---|
KR102392406B1 (en) | Colored resin composition, colored filter and display device | |
TWI790354B (en) | Colorant dispersion, colored curable resin composition, color filter, and display device | |
TWI751313B (en) | Colored curable resin composition | |
KR102389352B1 (en) | Colored resin composition, colored filter and display device | |
TWI754733B (en) | Isoindoline dye and method for producing the same | |
JP7067991B2 (en) | Method for manufacturing isoindoline pigment | |
JP7055677B2 (en) | Method for manufacturing isoindoline pigment | |
JP7079127B2 (en) | Color curable resin composition | |
JP7091104B2 (en) | Isoindoline pigment | |
TWI738984B (en) | Colored curable resin composition, color filter and display device | |
TWI827836B (en) | Colored resin composition, color filter and display device | |
TWI746941B (en) | Compound, colored resin composition, color filter and display device | |
TWI743375B (en) | Colored curable resin composition, color filter and display device | |
CN108663903B (en) | Colored resin composition, color filter and display device | |
CN113943494A (en) | Coloring composition | |
TW202102617A (en) | Colored curable resin composition | |
TW202033674A (en) | Cyan-colored curable composition |