TWI778975B - Coloring composition - Google Patents
Coloring composition Download PDFInfo
- Publication number
- TWI778975B TWI778975B TW106129973A TW106129973A TWI778975B TW I778975 B TWI778975 B TW I778975B TW 106129973 A TW106129973 A TW 106129973A TW 106129973 A TW106129973 A TW 106129973A TW I778975 B TWI778975 B TW I778975B
- Authority
- TW
- Taiwan
- Prior art keywords
- group
- substituent
- formula
- hydrocarbon group
- compound
- Prior art date
Links
Classifications
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/02—Coumarine dyes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Organic Chemistry (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Liquid Crystal (AREA)
- Cosmetics (AREA)
Abstract
Description
本發明係有關於一種作為著色劑而言有用的化合物及著色組成物。 The present invention relates to a compound and a coloring composition useful as a colorant.
染料係在例如纖維材料、液晶顯示裝置、噴墨等領域中為了利用反射光或透射光來顯示顏色而使用。作為此種染料者,已知下述式表示之香豆素6(日本特開2006-154740號公報)。 Dyes are used, for example, in the fields of fiber materials, liquid crystal display devices, inkjet, etc. to express colors by reflected light or transmitted light. As such a dye, coumarin 6 represented by the following formula is known (JP-A-2006-154740).
本發明係包含以下發明。 The present invention includes the following inventions.
[1]一種著色組成物,係含有式(I)表示之化合物及樹脂。 [1] A coloring composition comprising a compound represented by formula (I) and a resin.
[式(I)中,RN1及RN2係互相獨立地表示可具有取代基之碳數1至40的脂肪族烴基,RN3係表示可具有取代基之碳數1至40的烴基或可具有取代基之雜環基,R1至R8係互相獨立地表示氫原子、-CO-R102、-COO-R101、-OCO-R102、-COCO-R102、-O-R102、-SO2-R101、-SO2N(R102)2、-CON(R102)2、-N(R102)2、-NHCO-R102、-NHCO-N(R102)2、-NHCOOR102、-OCON(R102)2、鹵素原子、氰基、硝基、-SO3M、-CO2M、可具有取代基之碳數1至40的烴基或可具有取代基之雜環基,R101係表示可具有取代基之碳數1至40的烴基或可具有取代基之雜環基,R102係表示氫原子、可具有取代基之碳數1至40的烴基或可具有取代基之雜環基,M係表示氫原子或鹼金屬原子,R101、R102及M存在複數個時,該等可相同,亦可不同,Ag-係表示g價的陰離子,g係表示1至14的整數]。 [In the formula (I), R N1 and R N2 independently represent an aliphatic hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, and R N3 represents a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent or an aliphatic hydrocarbon group that may have a substituent For heterocyclic groups with substituents, R 1 to R 8 independently represent hydrogen atoms, -CO-R 102 , -COO-R 101 , -OCO-R 102 , -COCO-R 102 , -OR 102 , - SO 2 -R 101 , -SO 2 N(R 102 ) 2 , -CON(R 102 ) 2 , -N(R 102 ) 2 , -NHCO-R 102 , -NHCO-N(R 102 ) 2 , -NHCOOR 102 , -OCON(R 102 ) 2 , a halogen atom, a cyano group, a nitro group, -SO 3 M, -CO 2 M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent , R 101 represents a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent or a heterocyclic group that may have a substituent, R 102 represents a hydrogen atom, a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, or a hydrocarbon group that may have a substituent The heterocyclic group of the group, M represents a hydrogen atom or an alkali metal atom, and when there are multiple R 101 , R 102 and M, they may be the same or different. A g- represents an anion with a valence of g, and g represents an integer from 1 to 14].
[2]如[1]所述之著色組成物,其中,Ag-為將選自由鎢、鉬、矽、及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之陰離子、或含氟陰離子。 [2] The coloring composition according to [1], wherein Ag- is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen as essential elements. , or fluorine-containing anions.
[3]如[1]或[2]所述之著色組成物,其中,Ag-為將選自由鎢及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之陰離子、或含氟陰離子。 [3] The coloring composition according to [1] or [2], wherein Ag- is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements, or fluoride-containing anions.
[4]如[1]至[3]中任一項所述之著色組成物,其中,Ag 為將選自由鎢及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之陰離子。 [4] The coloring composition according to any one of [1] to [3], wherein Ag contains at least one element selected from the group consisting of tungsten and phosphorus, and oxygen as essential elements. The anion.
[5]如[1]至[4]中任一項所述之著色組成物,其中,RN1及RN2互相獨立地為可具有取代基之碳數1至10的烷基。 [5] The coloring composition according to any one of [1] to [4], wherein R N1 and R N2 are independently an alkyl group having 1 to 10 carbon atoms which may have a substituent.
[6]如[1]至[5]中任一項所述之著色組成物,係進一步含有溶劑。 [6] The coloring composition according to any one of [1] to [5], which further contains a solvent.
[7]如[1]至[6]中任一項所述之著色組成物,係進一步含有黃色著色劑、橙色著色劑或紅色著色劑。 [7] The colored composition according to any one of [1] to [6], which further contains a yellow colorant, an orange colorant or a red colorant.
[8]一種著色硬化性組成物,係含有如[1]至[7]中任一項所述之著色組成物、及聚合性化合物。 [8] A colored curable composition comprising the colored composition according to any one of [1] to [7], and a polymerizable compound.
[9]如[8]所述之著色硬化性組成物,係進一步含有聚合起始劑。 [9] The colored curable composition as described in [8], further comprising a polymerization initiator.
[10]一種彩色濾光片,係由如[1]至[7]中任一項所述之著色組成物或是如[8]或[9]所述之著色硬化性組成物所形成。 [10] A color filter formed of the colored composition described in any one of [1] to [7] or the colored curable composition described in [8] or [9].
[11]一種液晶顯示裝置,係包含如[10]所述之彩色濾光片。 [11] A liquid crystal display device comprising the color filter described in [10].
[12]一種化合物,係以式(I-B)表示者。 [12] A compound represented by the formula (I-B).
[式(I-B)中,RN1及RN2係互相獨立地表示可具有取代基之碳數1至40的脂肪族烴基, RN3係表示可具有取代基之碳數1至40的烴基或可具有取代基之雜環基,R1至R8係互相獨立地表示氫原子、-CO-R102、-COO-R101、-OCO-R102、-COCO-R102、-O-R102、-SO2-R101、-SO2N(R102)2、-CON(R102)2、-N(R102)2、-NHCO-R102、-NHCO-N(R102)2、-NHCOOR102、-OCON(R102)2、鹵素原子、氰基、硝基、-SO3M、-CO2M、可具有取代基之碳數1至40的烴基或可具有取代基之雜環基,R101係表示可具有取代基之碳數1至40的烴基或可具有取代基之雜環基,R102係表示氫原子、可具有取代基之碳數1至40的烴基或可具有取代基之雜環基,M係表示氫原子或鹼金屬原子,R101、R102及M存在複數個時,該等可相同,亦可不同,Bh-係表示將選自由鎢、鉬、矽、及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之h價的陰離子,h係表示1至14的整數]。 [In the formula (IB), R N1 and R N2 independently represent an aliphatic hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, and R N3 represents a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent or an aliphatic hydrocarbon group that may have a substituent For heterocyclic groups with substituents, R 1 to R 8 independently represent hydrogen atoms, -CO-R 102 , -COO-R 101 , -OCO-R 102 , -COCO-R 102 , -OR 102 , - SO 2 -R 101 , -SO 2 N(R 102 ) 2 , -CON(R 102 ) 2 , -N(R 102 ) 2 , -NHCO-R 102 , -NHCO-N(R 102 ) 2 , -NHCOOR 102 , -OCON(R 102 ) 2 , a halogen atom, a cyano group, a nitro group, -SO 3 M, -CO 2 M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent , R 101 represents a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent or a heterocyclic group that may have a substituent, R 102 represents a hydrogen atom, a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, or a hydrocarbon group that may have a substituent The heterocyclic group of the group, M represents a hydrogen atom or an alkali metal atom, and when there are multiple R 101 , R 102 and M, these may be the same or different, and B h- represents a group selected from tungsten, molybdenum, silicon , and at least one element of the group consisting of phosphorus, and an anion of h valence containing oxygen as an essential element, h represents an integer of 1 to 14].
[13]如[12]所述之化合物,其中,Bh-為將選自由鎢及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之陰離子。 [13] The compound according to [12], wherein B h- is an anion containing at least one element selected from the group consisting of tungsten and phosphorus, and oxygen as essential elements.
[14]如[12]或[13]所述之化合物,其中,RN1及RN2互相獨立地表示可具有取代基之碳數1至10的烷基。 [14] The compound according to [12] or [13], wherein R N1 and R N2 independently represent an optionally substituted alkyl group having 1 to 10 carbon atoms.
本發明的著色組成物係含有式(I)表示之化合物(以下,有稱為化合物(I)之情形)及樹脂(以下,有稱為樹脂(B)之情形)。 The coloring composition of the present invention contains a compound represented by formula (I) (hereinafter referred to as compound (I)) and a resin (hereinafter referred to as resin (B)).
化合物(I)包括其互變異構物、該等的鹽。 Compound (I) includes its tautomers, salts thereof.
化合物(I)係能夠使用作為著色劑。 Compound (I) can be used as a colorant.
本發明的著色組成物可含有1種或2種以上的化合物(I)。 The coloring composition of the present invention may contain 1 type or 2 or more types of compounds (I).
本發明的著色組成物可含有溶劑(以下,有稱為溶劑(E)之情形)。 The coloring composition of the present invention may contain a solvent (hereinafter, sometimes referred to as a solvent (E)).
又,化合物(I)係以分散在溶劑(E)中為佳。 Also, compound (I) is preferably dispersed in solvent (E).
本發明的著色組成物,可含有化合物(I)以外的著色劑(以下,有稱為著色劑(A1)之情形。而且,以下有將化合物(I)及著色劑(A1)總稱為「著色劑(A)」之情形。 The coloring composition of the present invention may contain a coloring agent other than compound (I) (hereinafter referred to as coloring agent (A1). In addition, compound (I) and coloring agent (A1) are collectively referred to as "coloring agent (A1) below." agent (A)".
著色劑(A1)可含有1種或2種以上的著色劑。 The coloring agent (A1) may contain 1 type or 2 or more types of coloring agents.
著色劑(A1)係以含有黃色著色劑、橙色著色劑或紅色著色劑為佳。 The coloring agent (A1) preferably contains a yellow coloring agent, an orange coloring agent or a red coloring agent.
又,本發明的著色硬化性組成物,係含有化合物(I)、樹脂(B)及溶劑(E)兩者中的至少一者、以及聚合性化合物(C)。 Furthermore, the curable colored composition of the present invention contains the compound (I), at least one of the resin (B) and the solvent (E), and a polymerizable compound (C).
本發明的著色硬化性組成物可含有聚合起始劑(D)。 The curable colored composition of the present invention may contain a polymerization initiator (D).
本發明的著色硬化性組成物可含有聚合起始助劑(D1)。 The colored curable composition of the present invention may contain a polymerization initiation aid (D1).
本發明的著色組成物可進一步含有調平劑(F)及抗氧 化劑。 The coloring composition of the present invention may further contain a leveling agent (F) and an antioxidant.
化合物(I)係以式(I)表示之化合物。 Compound (I) is a compound represented by formula (I).
[式(I)中,RN1及RN2係互相獨立地表示可具有取代基之碳數1至40的脂肪族烴基。 [In formula (I), R N1 and R N2 independently represent an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have substituents.
RN3係表示可具有取代基之碳數1至40的烴基或可具有取代基之雜環基。 R N3 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.
R1至R8係互相獨立地表示氫原子、-CO-R102、-COO-R101、-OCO-R102、-COCO-R102、-O-R102、-SO2-R101、-SO2N(R102)2、-CON(R102)2、-N(R102)2、-NHCO-R102、-NHCO-N(R102)2、-NHCOOR102、-OCON(R102)2、鹵素原子、氰基、硝基、-SO3M、-CO2M、可具有取代基之碳數1至40的烴基或可具有取代基之雜環基。 R 1 to R 8 independently represent a hydrogen atom, -CO-R 102 , -COO-R 101 , -OCO-R 102 , -COCO-R 102 , -OR 102 , -SO 2 -R 101 , -SO 2 N(R 102 ) 2 , -CON(R 102 ) 2 , -N(R 102 ) 2 , -NHCO-R 102 , -NHCO-N(R 102 ) 2 , -NHCOOR 102 , -OCON(R 102 ) 2. A halogen atom, a cyano group, a nitro group, -SO 3 M, -CO 2 M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
R101係表示可具有取代基之碳數1至40的烴基或可具有取代基之雜環基。 R 101 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.
R102係表示氫原子、可具有取代基之碳數1至40的烴基或可具有取代基之雜環基。 R 102 represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
M係表示氫原子或鹼金屬原子。 The M system represents a hydrogen atom or an alkali metal atom.
R101、R102及M存在複數個時,該等可相同,亦可不同。 When there are plural R 101 , R 102 and M, these may be the same or different.
Ag-係表示g價的陰離子。 The A g- series represents an anion of g valency.
g係表示1至14的整數]。 g represents an integer from 1 to 14].
以RN1及RN2表示之脂肪族烴基的碳數為1至40,以1至30為佳,較佳為1至20,更佳為1至15,特佳為1至10。 The carbon number of the aliphatic hydrocarbon group represented by R N1 and R N2 is 1-40, preferably 1-30, more preferably 1-20, more preferably 1-15, particularly preferably 1-10.
以RN1及RN2表示之脂肪族烴基,可為飽和或不飽和,可為鏈狀或脂環。 The aliphatic hydrocarbon groups represented by R N1 and R N2 may be saturated or unsaturated, chain or alicyclic.
RN1及RN2表示之飽和或不飽和鏈狀脂肪族烴基,可舉出甲基、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、及二十基等直鏈狀烷基等;異丙基、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)庚基等分枝鏈狀烷基等;乙烯基、1-丙烯基、2-丙烯基(烯丙基)、(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-戊烯基等烯基等。飽和或不飽和鏈狀烴基的碳數係以1至30為佳,較佳為1至20,更佳為1至15,特佳為1至10,進一步更佳為1至8。進一步特佳為1至5。其中以碳數1至10、較佳是碳數1至8的直鏈或分枝鏈的烷基為尤佳,以甲基或乙基為特佳。 The saturated or unsaturated chain aliphatic hydrocarbon groups represented by R N1 and R N2 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, deca One base, dodecyl, heptadecyl, octadecyl, and eicosyl and other linear alkyl groups; isopropyl, isobutyl, second butyl, third butyl, (2-ethyl ) butyl, isopentyl, neopentyl, third pentyl, (1-methyl) pentyl, (2-methyl) pentyl, (1-ethyl) pentyl, (3-ethyl) Pentyl, isohexyl, (5-methyl)hexyl, (2-ethyl)hexyl and (3-ethyl)heptyl and other branched chain alkyl groups; vinyl, 1-propenyl, 2-propene (allyl), (1-methyl) vinyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, (1-(2-propenyl)) vinyl, Alkenyl groups such as (1,2-dimethyl)propenyl and 2-pentenyl, etc. The carbon number of the saturated or unsaturated chain hydrocarbon group is preferably 1-30, more preferably 1-20, more preferably 1-15, particularly preferably 1-10, and even more preferably 1-8. More preferably, it is 1-5. Among them, a linear or branched alkyl group having 1 to 10 carbons, preferably 1 to 8 carbons is particularly preferred, and methyl or ethyl is particularly preferred.
以RN1及RN2表示之飽和或不飽和脂環式烴基,可舉出環丙基、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、4-環己基環己基等環烷基;環己烯基(例如環己-2-烯、環己-3-烯)、環庚烯基、環辛烯基等環烯基;降莰基、金剛烷基、雙環[2.2.2]辛烷等。飽和或不飽和的脂環式烴基的碳數係以3至30為佳,較佳為3至20,更佳為4至20,進一步較佳為4至15,進一步特佳為5至15,最佳為5至10。其中以環戊基、環己基、環庚基、環辛基為特佳。 Saturated or unsaturated alicyclic hydrocarbon groups represented by R N1 and R N2 include cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methyl Cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-di Methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-di Methylcyclohexyl, 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-octyl Cycloalkyl groups such as cyclohexyl and 4-cyclohexylcyclohexyl; cyclohexenyl (such as cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, cyclooctenyl and other cycloalkenyl groups; nor Camphenyl, adamantyl, bicyclo[2.2.2]octane, etc. The carbon number of the saturated or unsaturated alicyclic hydrocarbon group is preferably from 3 to 30, preferably from 3 to 20, more preferably from 4 to 20, further preferably from 4 to 15, and even more preferably from 5 to 15, Optimal is 5 to 10. Among them, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl are particularly preferred.
以RN1及RN2表示之脂肪族烴基,亦可為將上述舉出的脂肪族烴基與碳數1至40的芳香族烴基(例如鏈狀烴基及脂環式烴基的至少1個、與芳香族烴基)組合而成之基。 The aliphatic hydrocarbon group represented by R N1 and R N2 may be a combination of the above-mentioned aliphatic hydrocarbon group and an aromatic hydrocarbon group having 1 to 40 carbon atoms (for example, at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group, and an aromatic hydrocarbon group). A group of hydrocarbon groups) combined base.
此種芳香族烴基,可舉出苯基、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、4-乙烯基苯基、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、2,4,6-三甲苯基(mesityl)、4-乙基苯基、4-丁基苯基、 4-戊基苯基、2,6-雙(2-丙基)苯基、4-環己基苯基、2,4,6-三甲基苯基、4-辛基苯基、4-乙烯基苯基、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、蒽基、芘基等芳香族烴基等。前述芳香族烴基的碳數係以6至30為佳,較佳為6至20,更佳為6至15。 Such aromatic hydrocarbon groups include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, phenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 4-vinylphenyl, o-isopropylphenyl, m-isopropylphenyl Propylphenyl, p-isopropylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl, 2,4,6-trimethylphenyl (mesityl), 4 -Ethylphenyl, 4-butylphenyl, 4-pentylphenyl, 2,6-bis(2-propyl)phenyl, 4-cyclohexylphenyl, 2,4,6-trimethyl Phenyl, 4-octylphenyl, 4-vinylphenyl, 1-naphthyl, 2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, 5,6,7,8 - Aromatic hydrocarbon groups such as tetrahydro-2-naphthyl, fenyl, phenanthrenyl, anthracenyl, pyrenyl, etc. The carbon number of the aforementioned aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, more preferably 6-15.
就將上述舉出的脂肪族烴基與碳數1至40的芳香族烴基(例如鏈狀烴基及脂環式烴基的至少1個、與芳香族烴基)組合而成之基而言,可舉出苯甲基、苯乙基、1-甲基-1-苯乙基等芳烷基;苯基乙烯基等芳烯基;苯基乙炔基等芳炔基;聯苯基、聯三苯基等鍵結有1個以上的苯基之苯基;環己基甲基苯基、苯甲基苯基、(二甲基(苯基)甲基)苯基等。以RN1、RN2表示之基,就將上述舉出的烴基(例如鏈狀烴基與脂環式烴基)組合而成之基而言,例如可為環丙基甲基、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、2-甲基環己基甲基、環己基乙基、金剛烷基甲基等鍵結有1個以上的脂環式烴基之烷基。 In terms of the group formed by combining the above-mentioned aliphatic hydrocarbon group and an aromatic hydrocarbon group having 1 to 40 carbon atoms (for example, at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group, and an aromatic hydrocarbon group), there are listed Aralkyl groups such as benzyl, phenethyl, and 1-methyl-1-phenethyl; aralkenyl groups such as phenylvinyl; aralkynyl groups such as phenylethynyl; biphenyl, terphenyl, etc. Phenyl with one or more phenyl groups bonded; cyclohexylmethylphenyl, benzylphenyl, (dimethyl(phenyl)methyl)phenyl, etc. The group represented by R N1 and R N2 is a combination of the above-mentioned hydrocarbon groups (such as chain hydrocarbon groups and alicyclic hydrocarbon groups), such as cyclopropylmethyl, cyclopropylethyl , cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, 2-methylcyclohexylmethyl, cyclohexylethyl, adamantylmethyl, etc. An alkyl group having one or more alicyclic hydrocarbon groups.
前述烴之碳數係以4至30為佳,較佳為6至30,進一步較佳為6至20,又進一步較佳為4至20,更佳為4至15,特佳為6至15。 The carbon number of the aforementioned hydrocarbons is preferably from 4 to 30, preferably from 6 to 30, more preferably from 6 to 20, still more preferably from 4 to 20, more preferably from 4 to 15, especially preferably from 6 to 15 .
以RN3、R1至R8、R101及R102表示之烴基的碳數為1至40,以1至30為佳,較佳為1至20,更佳為1至15,特佳為1至10。 The carbon number of the hydrocarbon group represented by R N3 , R 1 to R 8 , R 101 and R 102 is 1 to 40, preferably 1 to 30, more preferably 1 to 20, more preferably 1 to 15, especially preferably 1 to 10.
以RN3、R1至R8、R101及R102表示之碳數1至40的烴基,可為脂肪族烴基及芳香族烴基,該脂肪族烴基 可為飽和或不飽和,可為鏈狀或脂環。 The hydrocarbon groups with 1 to 40 carbons represented by R N3 , R 1 to R 8 , R 101 and R 102 can be aliphatic hydrocarbon groups and aromatic hydrocarbon groups, and the aliphatic hydrocarbon groups can be saturated or unsaturated, and can be chain or alicyclic.
以RN3、R1至R8、R101及R102表示之飽和或不飽和鏈狀烴基,可舉出甲基、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、及二十基等直鏈狀烷基等;異丙基、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)庚基等分枝鏈狀烷基等;乙烯基、1-丙烯基、2-丙烯基(烯丙基)、(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-戊烯基等烯基等。前述飽和或不飽和鏈狀烴基的碳數係以1至30為佳,較佳為1至20,更佳為1至15,特佳為1至10,進一步更佳為1至8。其中以碳數1至10,較佳為碳數1至8的直鏈或分枝鏈的烷基為特佳,以甲基或乙基為特佳。 Saturated or unsaturated chain hydrocarbon groups represented by R N3 , R 1 to R 8 , R 101 and R 102 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl , nonyl, decyl, undecyl, dodecyl, heptadecyl, octadecyl, and eicosyl and other linear alkyl groups; isopropyl, isobutyl, second butyl, third Butyl, (2-ethyl)butyl, isopentyl, neopentyl, third pentyl, (1-methyl)pentyl, (2-methyl)pentyl, (1-ethyl)pentyl Base, (3-ethyl)pentyl, isohexyl, (5-methyl)hexyl, (2-ethyl)hexyl and (3-ethyl)heptyl and other branched chain alkyl groups; vinyl, 1-propenyl, 2-propenyl (allyl), (1-methyl) vinyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, (1-(2 Alkenyl groups such as -propenyl))vinyl, (1,2-dimethyl)propenyl, and 2-pentenyl, etc. The carbon number of the aforementioned saturated or unsaturated chain hydrocarbon group is preferably 1-30, preferably 1-20, more preferably 1-15, particularly preferably 1-10, and even more preferably 1-8. Among them, a linear or branched alkyl group with 1 to 10 carbons, preferably 1 to 8 carbons is particularly preferred, and methyl or ethyl is particularly preferred.
以RN3、R1至R8、R101及R102表示之飽和或不飽和脂環式烴基,可舉出環丙基、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、4-環己基環己基等環烷基;環己烯基(例如環己-2-烯、環己-3-烯)、環庚烯基、環辛烯基等環烯基;降莰基、金剛烷基、雙環[2.2.2]辛烷等。前述飽和或不飽和的脂環式烴基的碳數係以3至30為佳,較佳為3至20,更佳為4至20,進一步較佳為4至15,進一步特佳為5至15,最佳為5至10。其中以環戊基、環己基、環庚基、環辛基為特佳。 The saturated or unsaturated alicyclic hydrocarbon groups represented by R N3 , R 1 to R 8 , R 101 and R 102 include cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclo Hexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethyl Cyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl Cyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3,3-dimethylcyclohexyl, 4,4-dimethylcyclohexyl Cyclohexyl, cyclooctyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl, 4- Cycloalkyl such as pentylcyclohexyl, 4-octylcyclohexyl, 4-cyclohexylcyclohexyl; cyclohexenyl (such as cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, cyclohexyl Cycloalkenyl such as octenyl; norbornyl, adamantyl, bicyclo[2.2.2]octane, etc. The carbon number of the aforementioned saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 30, preferably 3 to 20, more preferably 4 to 20, further preferably 4 to 15, and even more preferably 5 to 15 , preferably 5 to 10. Among them, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl are particularly preferred.
以RN3、R1至R8、R101及R102表示之芳香族烴基,可舉出苯基、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、4-乙烯基苯基、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、2,4,6-三甲苯基、4-乙基苯基、4-丁基苯基、4-戊基苯基、2,6-雙(2-丙基)苯基、4-環己基苯基、2,4,6-三甲基苯基、4-辛基苯基、4-乙烯基苯基、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、蒽基、芘基等芳香族烴基等。前述芳香族烴基的碳數係以6至30為佳,較佳為6至20,更佳為6至15。 The aromatic hydrocarbon groups represented by R N3 , R 1 to R 8 , R 101 and R 102 include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2 ,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 4 -Vinylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, p-tert-butylphenyl , 2,4,6-trimethylphenyl, 4-ethylphenyl, 4-butylphenyl, 4-pentylphenyl, 2,6-bis(2-propyl)phenyl, 4-cyclohexyl Phenyl, 2,4,6-trimethylphenyl, 4-octylphenyl, 4-vinylphenyl, 1-naphthyl, 2-naphthyl, 5,6,7,8-tetrahydro- Aromatic hydrocarbon groups such as 1-naphthyl, 5,6,7,8-tetrahydro-2-naphthyl, fenyl, phenanthrenyl, anthracenyl, pyrenyl, etc. The carbon number of the aforementioned aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, more preferably 6-15.
以RN3、R1至R8、R101及R102表示之烴基,可為將上述舉出的烴基(例如芳香族烴基、與鏈狀烴基及脂環式烴基的至少1個)組合而成之基,可舉出苯甲基、苯乙基、1-甲基-1-苯乙基等芳烷基;苯基乙烯基等芳烯基;苯 基乙炔基等芳炔基;聯苯基、聯三苯基等鍵結有1個以上的苯基之苯基;環己基甲基苯基、苯甲基苯基、(二甲基(苯基)甲基)苯基等。 The hydrocarbon group represented by R N3 , R 1 to R 8 , R 101 and R 102 may be a combination of the above-mentioned hydrocarbon groups (such as aromatic hydrocarbon groups, at least one of chain hydrocarbon groups and alicyclic hydrocarbon groups) The bases include aralkyl groups such as benzyl, phenethyl, and 1-methyl-1-phenethyl; aralkenyl groups such as phenylvinyl; aralkynyl groups such as phenylethynyl; biphenyl , terphenyl, and other phenyl groups bonded to one or more phenyl groups; cyclohexylmethylphenyl, benzylphenyl, (dimethyl(phenyl)methyl)phenyl, etc.
以RN3、R1至R8、R101及R102表示之基,就將上述舉出的烴基(例如鏈狀烴基與脂環式烴基)組合而成之基而言,例如可為環丙基甲基、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、2-甲基環己基甲基、環己基乙基、金剛烷基甲基等鍵結有1個以上的脂環式烴基之烷基。 The group represented by R N3 , R 1 to R 8 , R 101 and R 102 may be, for example, cyclopropyl Cyclopropylmethyl, Cyclopropylethyl, Cyclobutylmethyl, Cyclobutylethyl, Cyclopentylmethyl, Cyclopentylethyl, Cyclohexylmethyl, 2-Methylcyclohexylmethyl, Cyclohexylethyl An alkyl group to which one or more alicyclic hydrocarbon groups are bonded, such as , adamantylmethyl, etc.
前述烴的碳數係以4至30為佳,較佳為6至30,進一步較佳為6至20,又較佳為4至20,更佳為4至15,特佳為6至15。 The carbon number of the aforementioned hydrocarbons is preferably 4-30, more preferably 6-30, further preferably 6-20, still more preferably 4-20, more preferably 4-15, particularly preferably 6-15.
以RN1及RN2表示之脂肪族烴基、以RN3、R1至R8、R101及R102表示之烴基可具有取代基。取代基可為一價亦可為二價。二價的取代基之2個連結鍵係以鍵結在相同碳原子而形成雙鍵為佳。 The aliphatic hydrocarbon groups represented by R N1 and R N2 , and the hydrocarbon groups represented by R N3 , R 1 to R 8 , R 101 and R 102 may have substituents. The substituent may be monovalent or divalent. The two linkages of the divalent substituent are preferably bonded to the same carbon atom to form a double bond.
該一價的取代基,可舉出甲氧基、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、戊氧基、己氧基、(2-乙基)己氧基、庚氧基、辛氧基、壬氧基、癸氧基、十一基氧基、十二基氧基、(2-乙基)己氧基、二十基氧基、1-苯基乙氧基、1-甲基-1-苯基乙氧基、苯氧基、鄰甲苯基氧基、2,3-二甲基苯氧基、2,4-二甲基苯氧基、2,5-二甲基苯氧基、2,6-二甲基苯氧基、3,4-二甲基苯氧基、3,5-二甲基苯氧基、2,2-二氰基苯氧基、2,3-二氰 基苯氧基、2,4-二氰基苯氧基、2,5-二氰基苯氧基、2,6-二氰基苯氧基、3,4-二氰基苯氧基、3,5-二氰基苯氧基、4-甲氧基苯氧基、2-甲氧基苯氧基、3-甲氧基苯氧基、4-乙氧基苯氧基、2-乙氧基苯氧基、3-乙氧基苯氧基等,及下述式表示之基等在一側鍵結有碳數1至20(較佳為碳數1至10)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之氧基;
甲硫基、乙硫基、丙硫基、丁硫基、第三丁硫基、戊硫基、己硫基、(2-乙基)己硫基、庚硫基、辛硫基、壬硫基、癸硫基、十一基硫基、十二基硫基、二十基硫基、苯硫基及鄰甲苯基硫基等鍵結有碳數1至20(較佳為碳數1至10)的烴基之硫基; 環氧基、氧雜環丁烷基、四氫呋喃基、四氫吡喃基;甲醯基;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、苯甲醯基等,及下述式表示之基等鍵結有碳數為1至20(較佳為碳數為1至11)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之羰基(將該羰基設為烷醯基之情況,碳數較佳為2至12);
甲氧羰基、乙氧羰基、丙氧羰基、丁氧羰基、第三丁氧羰基、戊氧羰基、己氧羰基、(2-乙基)己氧羰基、庚氧 羰基、辛氧羰基、壬氧羰基、癸氧羰基、十一基氧基羰基、十二基氧基羰基、二十基氧基羰基、苯氧羰基、鄰甲苯基氧羰基等,及下述式表示之基等鍵結有碳數1至20(較佳為碳數1至10)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之氧羰基;
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-癸基胺基、N,N-癸基甲基胺基、N-十一基胺基、N,N-十一基甲基胺基、N-十二基胺基、N,N-十二基甲基胺基、N-二十基胺基、N,N-二十基甲基胺基、N,N-第三丁基甲基胺基、N,N-苯基甲基胺基等,及下述式表示之基等被1個或2個碳數1至20(較佳為碳數1至10)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)取代之胺基;
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-癸基胺磺醯基、N,N-癸基甲基胺磺醯基、N-十一基胺磺醯基、N,N-十一基甲基胺磺醯基、N-十二基胺磺醯基、N,N-十二基甲基胺磺醯基、N-二十基胺磺醯基、N,N-二十基甲基胺磺醯基、N,N-第三丁基甲基胺磺醯基、N,N-苯基甲基胺磺醯基等,及下述式表示之基等被1個或2個碳數1至20(較佳為碳數1至10)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)取代之胺磺醯基;
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、苯甲醯基胺基等,及下述式表示之基等被鍵結有碳數1至20(較佳為碳數1至12)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之羰基取代之胺基(將該羰基胺基設為烷醯基胺基的情況,碳數係較佳為1至12);
羥基;氟原子、氯原子、溴原子及碘原子等鹵素原子;羧基、-CO2M2(M2為鹼金屬,較佳為鋰、鈉、鉀);磺酸基、-SO3M2(M2為鹼金屬,較佳為鋰、鈉、鉀);硝基;氰基;甲醯氧基;乙醯氧基、丙醯氧基、丁醯氧基、2,2-二甲基丙醯氧基、戊醯氧基、己醯氧基、(2-乙基)己醯氧基、庚醯氧基、辛醯氧基、壬醯氧基、癸醯氧基、十一醯氧基、十二醯氧基、二十一醯氧基、苯甲醯基氧基等,及下述式表示之基等鍵結有碳數1至20(較佳為碳數1至10) 的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之羰氧基(將該羰氧基設為烷醯氧基的情況,碳數較佳為1至10);
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、對甲苯基磺醯基等,及下述式表示之基等鍵結有碳數1至20(較佳為碳數1至10)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之磺醯基;
胺基甲醯基;N-甲基胺基甲醯基、N,N-二甲基胺基甲醯基、N-乙基胺基甲醯基、N,N-二乙基胺基甲醯基、N-丙基胺基甲醯基、N,N-二丙基胺基甲醯基、N-異丙基胺基甲醯基、N,N-二異丙基胺基甲醯基、N-丁基胺基甲醯基、N,N-二丁基胺基甲醯基、N-異丁基胺基甲醯基、N,N-二異丁基胺基甲醯基、N-第二丁基胺基甲醯基、N,N-二第二丁基胺基甲醯基、N-第三丁基胺基甲醯基、N,N-二第三丁基胺基甲醯基、N-戊基胺基甲醯基、N,N-二戊基胺基甲醯基、N-(1-乙基丙基)胺基甲醯基、N,N-二(1-乙基丙基)胺基甲醯基、N-己基胺基甲醯基、N,N-二己基胺基甲醯基、N-(2-乙基)己基胺基甲醯基、N,N-二(2-乙基)己基胺基甲醯基、N-庚基胺基甲醯基、N,N-二庚基胺基甲醯基、N-辛基胺基甲醯基、N,N-二辛基胺基甲醯基、N-壬基胺基甲醯基、N,N-辛基甲 基胺基甲醯基、N,N-辛基丁基胺基甲醯基、N,N-二壬基胺基甲醯基、N-苯基胺基甲醯基、N,N-二苯基胺基甲醯基、N,N-乙基甲基胺基甲醯基、N,N-丙基甲基胺基甲醯基、N,N-異丙基甲基胺基甲醯基、N,N-丁基甲基胺基甲醯基、N-癸基胺基甲醯基、N,N-癸基甲基胺基甲醯基、N-十一基胺基甲醯基、N,N-十一基甲基胺基甲醯基、N-十二基胺基甲醯基、N,N-十二基甲基胺基甲醯基、N-二十基胺基甲醯基、N,N-二十基甲基胺基甲醯基、N,N-第三丁基甲基胺基甲醯基、N,N-苯基甲基胺基甲醯基等,及下述式表示之基等被1個或2個碳數1至20(較佳為碳數1至10)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)取代之胺基甲醯基;
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、全氟十一基、全氟十二基、全氟二十基、全氟環己基、全氟苯基等全部的氫原子經氟原子取代之碳數1至20的烴基;全氟乙基甲基、全氟丙基甲基、全氟異丙基甲基、全氟丁基甲基、全氟戊基甲基、全氟己基甲基、全氟庚基甲基、全氟辛基甲基、全氟壬基甲基、全氟癸基甲基、全氟十一基甲基、全氟十二基甲基、全氟二十基甲基等被全部的氫原子經氟原子取代之碳數1至20的直鏈或分枝鏈的烷基所取代之碳數1至20的烴基;2-氟苯基、3-氟苯基、4-氟苯基及2,4,6-三氟苯基等一部分的氫原子經氟原子取代之碳數1至20(較佳為碳數1至10)的烴基;-CO-SH、-CO-S-CH3、-CO-S-CH2CH3、-CO-S-CH2-CH2-CH3、-CO-S-CH2-CH2-CH2-CH3等已與碳數1至20(較佳為碳數2至10)的烷基鍵結之硫羰基,-CO-S-C6H5等已與碳數6至20的芳基鍵結之硫羰基;如下式表示的*-COCO-R(式中,R為氫原子、碳數1至20的烴基(例如上述舉出的烴基之中滿足碳數1至20者)、或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基))之基;
如下式表示的*-NRCONR2(式中,R為氫原子、碳數1至20的烴基(例如上述舉出的烴基之中滿足碳數1至20者)、或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基),該R可互相相同亦可不同,亦可互相鍵結而形成環)之基;
如下式表示的*-OCONR2(式中,R為氫原子、碳數1至20的烴基(例如上述舉出的烴基之中滿足碳數1至20者)、或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基),該R可互相相同亦可不同,亦可互相鍵結而形成環)之基;
如下式表示的*-NRCOOR(式中,R為氫原子、碳數1至20的烴基(例如上述舉出的烴基之中滿足碳數1至20者)、或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基),該R可互相相同亦可不同,亦可互相鍵結而形成環)之基;
*-OP(O)(OCH3)2等*-OP(O)(OR)2(式中,R為氫原子、碳數1至20的烴基(例如上述舉出的烴基之中滿足碳數1至 20者)、或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基),該R可互相相同亦可不同,亦可互相鍵結而形成環)之基;*-Si(CH3)3、*-Si(CH2CH3)3、*-Si(C6H5)3及*-Si(CH(CH3)2)3等*-SiR3(式中,R為氫原子、碳數1至20的烴基(例如上述舉出的烴基之中滿足碳數1至20者)、或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基),該R可互相相同亦可不同,亦可互相鍵結而形成環)之基等。 *-OP(O)(OCH 3 ) 2 etc. *-OP(O)(OR) 2 (wherein, R is a hydrogen atom, a hydrocarbon group with 1 to 20 carbons (for example, among the hydrocarbon groups listed above, the carbon number 1 to 20), or its derivatized group (such as carboxyl group, sulfonic acid group, nitro group, hydroxyl group, halogen (preferably chlorine atom), alkylsulfamoyl group with carbon number 1 to 10 (preferably octylsulfamoyl) and other derivatized groups), the R can be the same or different, and can also be bonded to each other to form a ring); *-Si(CH 3 ) 3 , *-Si( CH 2 CH 3 ) 3 , *-Si(C 6 H 5 ) 3 and *-Si(CH(CH 3 ) 2 ) 3 etc. *-SiR 3 (wherein, R is a hydrogen atom, carbon number 1 to 20 Hydrocarbyl (for example, among the above-mentioned hydrocarbon groups satisfying the carbon number of 1 to 20), or its derivatized group (such as carboxyl, sulfonic acid group, nitro, hydroxyl, halogen (preferably chlorine atom), carbon number 1 10 to 10 alkyl sulfamoyl (preferably octyl sulfamoyl) and other derivatized groups), the R may be the same or different from each other, and may be bonded to each other to form a ring), etc. .
二價的取代基,可舉出側氧基、硫酮基(thioxo)、亞胺基、被碳數1至20(較佳為碳數1至10)的烷基取代之亞胺基、被碳數6至20的芳基取代之亞胺基等。被烷基取代之亞胺基,可舉出CH3-N=、CH3-CH2-N=、CH3-(CH2)2-N=、CH3-(CH2)3-N=等。被芳基取代之亞胺基,可舉出C6H5-N=等。 Divalent substituents include side oxy groups, thioxo groups, imino groups, imino groups substituted by alkyl groups with 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), An imino group substituted with an aryl group having 6 to 20 carbon atoms, etc. The imino group substituted by an alkyl group includes 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.
碳數1至40的烴基之取代基,較佳可舉出群s1的取代基。以下揭示的衍生化基,係以被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基為佳。 The substituent of the hydrocarbon group having 1 to 40 carbon atoms preferably includes a substituent of Group s1. The derivatization group disclosed below is based on a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group with a carbon number of 1 to 10 (preferably an octylsulfamate group) Derivatized bases such as acyl groups) are preferred.
[群s1] [group s1]
在一側鍵結有碳數1至20的烴基或其衍生化基之氧基; 鍵結有碳數1至20的烴基或其衍生化基之羰基;鍵結有碳數1至20的烴基或其衍生化基之氧羰基;胺基;被1個或2個碳數1至20的烴基或其衍生化基取代之胺基;胺磺醯基;被1個或2個碳數1至20的烴基或其衍生化基取代之胺磺醯基;鍵結有碳數1至20的烴基或其衍生化基之羰胺基;羥基;鹵素原子;-CO2M(較佳為羧基)(M係表示氫原子或鹼金屬原子,較佳是表示氫原子);-SO3M(較佳為磺酸基)(M係表示氫原子或鹼金屬原子,較佳是表示氫原子);硝基;氰基;鍵結有碳數1至20的烴基或其衍生化基之羰氧基;鍵結有碳數1至20的烴基或其衍生化基之磺醯基;胺基甲醯基;被1個或2個碳數1至20的烴基或其衍生化基取代之胺基甲醯基;全部的氫原子經氟原子取代之碳數1至20的烴基;被全部的氫原子經氟原子取代之碳數1至20的直鏈或分枝鏈的烷基所取代之碳數1至20的烴基;一部分的氫原子經氟取代之碳數1至20的烴基;側氧基。 Oxygen group bonded with a hydrocarbon group with 1 to 20 carbons or its derivatives on one side; carbonyl bonded with a hydrocarbon group with 1 to 20 carbons or its derivatives; bonded with a hydrocarbon group with 1 to 20 carbons Oxycarbonyl or its derivatized group; amino group; amine group substituted by 1 or 2 hydrocarbon groups with 1 to 20 carbons or its derivatized groups; sulfamoyl group; A sulfamoyl group substituted with a hydrocarbon group of 20 or a derivative thereof; a carbonylamino group bonded to a hydrocarbon group of 1 to 20 carbons or a derivative thereof; a hydroxyl group; a halogen atom; -CO 2 M (preferably a carboxyl group) (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom); -SO 3 M (preferably a sulfonic acid group) (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom); Nitro; cyano; carbonyloxy bonded to a hydrocarbon group with 1 to 20 carbons or a derivative thereof; sulfonyl bonded to a hydrocarbon group with 1 to 20 carbons or a derivative thereof; carbamoyl Aminoformyl group substituted by 1 or 2 hydrocarbon groups with 1 to 20 carbons or derivatives thereof; hydrocarbon groups with 1 to 20 carbons replaced by all hydrogen atoms by fluorine atoms; all hydrogen atoms A hydrocarbon group with 1 to 20 carbons substituted by a linear or branched chain alkyl group with 1 to 20 carbons substituted by fluorine atoms; a hydrocarbon group with 1 to 20 carbons substituted by fluorine for a part of the hydrogen atoms; side oxygen group .
碳數1至40的烴基的取代基,較佳可舉出群s2的取代基。 The substituent of the hydrocarbon group having 1 to 40 carbon atoms preferably includes a substituent of the group s2.
[群s2] [group s2]
在一側鍵結有碳數1至10的烴基或其衍生化基之氧基;鍵結有碳數1至10的烴基或其衍生化基之羰基;鍵結有碳數1至10的烴基或其衍生化基之氧羰基; 胺基;被1個或2個碳數1至10的烴基取代之胺基;胺磺醯基;被1個或2個碳數1至10的烴基或其衍生化基取代之胺磺醯基;鍵結有碳數1至10的烴基或其衍生化基之羰胺基;羥基;氟原子、氯原子、溴原子;-CO2M(較佳為羧基)(M係表示氫原子或鹼金屬原子、較佳是表示氫原子);-SO3M(較佳為磺酸基)(M係表示氫原子或鹼金屬原子,較佳是表示氫原子);硝基;氰基;鍵結有碳數1至10的烴基或其衍生化基之羰氧基;鍵結有碳數1至10的烴基或其衍生化基之磺醯基;胺基甲醯基;被1個或2個碳數1至10的烴基或其衍生化基取代之胺基甲醯基;全部的氫原子經氟原子取代之碳數1至10的烴基;被全部的氫原子經氟原子取代之碳數1至10的直鏈或分枝鏈的烷基所取代之碳數1至10的烴基;一部分的氫原子經氟取代之碳數1至10的烴基;側氧基。 Oxygen group bonded with a hydrocarbon group with 1 to 10 carbons or its derivatives on one side; carbonyl bonded with a hydrocarbon group with 1 to 10 carbons or its derivatives; bonded with a hydrocarbon group with 1 to 10 carbons Oxycarbonyl or its derivatized group; amino group; amino group substituted by 1 or 2 hydrocarbon groups with 1 to 10 carbons; sulfamoyl group; substituted by 1 or 2 hydrocarbon groups with 1 to 10 carbons or A sulfamoyl group substituted with a derivatizing group; a carbonylamino group bonded to a hydrocarbon group with 1 to 10 carbons or a derivatizing group thereof; hydroxyl; a fluorine atom, a chlorine atom, a bromine atom; -CO 2 M (preferably a carboxyl group ) (M represents a hydrogen atom or an alkali metal atom, preferably represents a hydrogen atom); -SO 3 M (preferably a sulfonic acid group) (M represents a hydrogen atom or an alkali metal atom, preferably represents a hydrogen atom) ; nitro; cyano; carbonyloxy bonded to a hydrocarbon group with 1 to 10 carbons or a derivative thereof; sulfonyl bonded to a hydrocarbon group with 1 to 10 carbons or a derivative thereof; aminomethyl Acyl group; aminoformyl group substituted by 1 or 2 hydrocarbon groups with 1 to 10 carbons or derivatives thereof; hydrocarbon groups with 1 to 10 carbons replaced by fluorine atoms; all hydrogen Hydrocarbon groups with 1 to 10 carbons substituted by linear or branched chain alkyl groups with 1 to 10 carbon atoms replaced by fluorine atoms; hydrocarbon groups with 1 to 10 carbon atoms replaced by fluorine atoms; side oxygen base.
以RN3、R1至R8、R101及R102表示的具有取代基之碳數1至40的烴基,可舉出具有一價或二價的取代基之碳數1至40的烴基,較佳可舉出:具有一價或是二價的取代基之碳數1至30的飽和或是不飽和鏈狀烴基、具有一價或是二價的取代基之碳數3至30的飽和或是不飽和脂環式烴基、具有一價或是二價的取代基之碳數6至30的芳香族烴基或將烴基組合而成之基,且具有一價或是二價的取代基之碳數1至30的基,更佳可舉出:具有群s1的取代基之碳數1至20的飽和或是不飽和鏈狀烴基、具有群s1的取代基之碳數3至 20的飽和或是不飽和脂環式烴基、具有群s1的取代基之碳數6至20的芳香族烴基或將烴基組合而成之基,且具有群s1的取代基之碳數1至20的基,特佳可舉出:具有群s2的取代基之碳數1至15的飽和或是不飽和鏈狀烴基、具有群s2的取代基之碳數3至15的飽和或是不飽和脂環式烴基、具有群s2的取代基之碳數6至15的芳香族烴基或將烴基組合而成之基,且具有群s2的取代基之碳數1至15的基。 The hydrocarbon groups having 1 to 40 carbon atoms having substituents represented by R N3 , R 1 to R 8 , R 101 and R 102 include hydrocarbon groups having 1 to 40 carbon atoms having monovalent or divalent substituents, Preferable examples include: a saturated or unsaturated chain hydrocarbon group having a monovalent or divalent substituent having 1 to 30 carbon atoms, a saturated hydrocarbon group having a monovalent or divalent substituent having a carbon number of 3 to 30 Or an unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group with 6 to 30 carbon atoms having a monovalent or divalent substituent, or a combination of hydrocarbon groups with a monovalent or divalent substituent The group having 1 to 30 carbon atoms is more preferably a saturated or unsaturated chain hydrocarbon group having 1 to 20 carbon atoms having a substituent of group s1, and a saturated or unsaturated chain hydrocarbon group having 3 to 20 carbon atoms having a substituent of group s1. or an unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbon atoms in the substituent of group s1, or a combination of hydrocarbon groups, and a group having 1 to 20 carbon atoms in the substituent of group s1, Particularly preferred examples include: a saturated or unsaturated chain hydrocarbon group having 1 to 15 carbons in a substituent of group s2, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 15 carbons in a substituent of group s2 . An aromatic hydrocarbon group having 6 to 15 carbon atoms in the substituent of group s2 or a combination of hydrocarbon groups, and a group having 1 to 15 carbon atoms in the substituent of group s2.
以RN3、R1至R8、R101及R102表示之雜環基,可為單環亦可為多環,較佳是含有雜原子作為環的構成要素之雜環。作為雜原子者,可舉出氮原子、氧原子及硫原子等。 The heterocyclic group represented by R N3 , R 1 to R 8 , R 101 and R 102 may be monocyclic or polycyclic, and is preferably a heterocyclic ring containing a heteroatom as a constituent element of the ring. A nitrogen atom, an oxygen atom, a sulfur atom, etc. are mentioned as a hetero atom.
雜環基的碳數係以3至30為佳,較佳為3至22,更佳為3至20,更佳為3至18,更佳為3至15,特佳為3至14。 The carbon number of the heterocyclic group is preferably 3-30, more preferably 3-22, more preferably 3-20, more preferably 3-18, more preferably 3-15, particularly preferably 3-14.
含有氮原子之雜環,可舉出:吖環丙烷、氮雜環丁烷(azetidine)、吡咯啶(pyrrolidine)、哌啶、哌等單環系飽和雜環;2,5-二甲基吡咯等吡咯、2-甲基吡唑、3-甲基吡唑等吡唑、咪唑、1,2,3-***、1,2,4-***等5員環系不飽和雜環;吡啶、嗒、6-甲基嘧啶等嘧啶、吡、1,3,5-三等6員環系不飽和雜環;吲唑、吲哚啉、異吲哚啉、吲哚、吲哚、苯并咪唑、喹啉、異喹啉、5,6,7,8-四氫(3-甲基)喹啉、3-甲基喹 啉等喹啉、喹唑啉、啉(cinnoline)、呔、啶、嘌呤、喋啶(pteridine)、苯并吡唑、苯并哌啶等縮合二環系雜環;咔唑、吖啶、啡等縮合三環系雜環等。 Heterocycles containing a nitrogen atom include: aziridine, azetidine, pyrrolidine, piperidine, piperidine Monocyclic saturated heterocyclic rings; 2,5-dimethylpyrrole and other pyrroles, 2-methylpyrazole, 3-methylpyrazole and other pyrazoles, imidazoles, 1,2,3-triazoles, 1,2 , 5-membered unsaturated heterocyclic rings such as 4-triazole; pyridine, palladium , 6-methylpyrimidine and other pyrimidines, pyrimidines , 1,3,5-three 6-membered ring system unsaturated heterocycle; indazole, indoline, isoindoline, indole, indole , benzimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydro(3-methyl)quinoline phylloline, 3-methylquinone quinoline phylloline, quinazoline, Cinnoline, Tie , Pyridine, purine, pteridine, benzopyrazole, benzopiperidine and other condensed bicyclic heterocycles; carbazole, acridine, phenanthrene Condensation tricyclic heterocyclic rings etc.
含有氧原子之雜環,可舉出:環氧乙烷、氧雜環丁烷、四氫呋喃、四氫吡喃、1,3-二烷、1,4-二烷、1-環戊基二氧雜戊環等單環系飽和雜環;1,4-二氧雜螺[4.5]癸烷、1,4-二氧雜螺[4.5]壬烷等二環系飽和雜環;α-乙內酯、β-丙內酯、γ-丁內酯、γ-戊內酯、δ-戊內酯等內酯系雜環;2,3-二甲基呋喃、2,5-二甲基呋喃等呋喃等5員環系不飽和雜環;2H-吡喃、4H-吡喃等6員環系不飽和雜環;1-苯并呋喃、4-甲基苯并吡喃等苯并吡喃、苯并二呃(benzodioxole)、唍(chroman)、異烷等縮合二環系雜環;二苯并哌喃(xanthene)、二苯并呋喃等縮合三環系雜環等。 Heterocyclic rings containing oxygen atoms include: oxirane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-bis Alkane, 1,4-bis Monocyclic saturated heterocycles such as alkane and 1-cyclopentyldioxolane; bicyclic rings such as 1,4-dioxaspiro[4.5]decane and 1,4-dioxaspiro[4.5]nonane It is a saturated heterocyclic ring; α-hydantoin, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone and other lactone heterocyclic rings; 2,3-dimethylfuran, 5-membered unsaturated heterocycles such as 2,5-dimethylfuran and furan; 6-membered unsaturated heterocycles such as 2H-pyran and 4H-pyran; 1-benzofuran, 4-methylbenzene Benzopyran such as pyran, benzodi Er (benzodioxole), 唍 (chroman), different Alkanes and other condensed bicyclic heterocycles; dibenzopyran (xanthene), dibenzofuran and other condensed tricyclic heterocycles, etc.
含有硫原子之雜環,可舉出:二硫雜環戊烷等5員環系飽和雜環;硫雜環己烷(thiane)、1,3-二硫雜環己烷、2-甲基1,3-二硫雜環己烷等6員環系飽和雜環;3-甲基噻吩、2-羧基噻吩等噻吩、4H-噻喃、苯并四氫噻喃等苯并噻喃等5員環系不飽和雜環;苯并噻吩等縮合二環系雜環等;噻蒽、二苯并噻吩等縮合三環系雜環等。 Heterocyclic rings containing a sulfur atom include: 5-membered saturated heterocyclic rings such as dithiolane; thiane, 1,3-dithiane, 2-methyl 6-membered saturated heterocyclic rings such as 1,3-dithiacyclohexane; 3-methylthiophene, 2-carboxythiophene and other thiophenes, 4H-thiopyran, benzothiopyran and other benzothiopyrans, etc. 5 Unsaturated heterocycles with member rings; condensed bicyclic heterocycles such as benzothiophene, etc.; condensed tricyclic heterocycles such as thianthracene and dibenzothiophene, etc.
含有氮原子及氧原子之雜環,可舉出:嗎啉、2-吡咯啶酮、2-甲基-2-吡咯啶酮、2-哌啶酮、2-甲基-2-哌 啶酮等單環系飽和雜環;4-甲基唑等唑、2-甲基異唑、3-甲基異唑等異唑等單環系不飽和雜環;苯并唑、苯并異唑、苯并、苯并二烷、苯并咪唑啉等縮合二環系雜環;啡(phenoxazine)等縮合三環系雜環等。 Heterocycles containing nitrogen and oxygen atoms include: morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, 2-methyl-2-piperidone Monocyclic saturated heterocycle; 4-methyl Azole etc. Azole, 2-methyliso Azole, 3-Methyliso Azole isoiso Monocyclic unsaturated heterocyclic rings such as azoles; benzo azoles, benziso Azole, benzo , Benzodi Condensed bicyclic heterocycles such as alkanes and benzimidazolins; (phenoxazine) and other condensed tricyclic heterocycles, etc.
含有氮原子及硫原子之雜環,可舉出:3-甲基噻唑、2,4-二甲基噻唑等噻唑等單環系雜環;苯并噻唑等縮合二環系雜環;啡噻等縮合三環系雜環等。 Heterocycles containing nitrogen atoms and sulfur atoms include monocyclic heterocycles such as thiazoles such as 3-methylthiazole and 2,4-dimethylthiazole; condensed bicyclic heterocycles such as benzothiazole; Condensation tricyclic heterocyclic rings etc.
上述雜環,可為組合上述舉出的烴基而成之基,例如可舉出四氫呋喃基甲基等。 The above-mentioned heterocyclic ring may be a combination of the above-mentioned hydrocarbon groups, for example, tetrahydrofurylmethyl group and the like are mentioned.
而且上述雜環,亦可為下述式所示者。 Furthermore, the aforementioned heterocycle may be represented by the following formulae.
上述雜環基亦可為2個以上的R1至R3、R5至R8鍵結而形成之雜環基。如此的雜環基,係連同R1至R3、R5至R8鍵結之苯環而具有2環以上的環結構。該2環以上的環結構,例如可舉出下述式之結構。 The aforementioned heterocyclic group may also be a heterocyclic group formed by bonding two or more R 1 to R 3 , and R 5 to R 8 . Such a heterocyclic group has a ring structure of two or more rings together with the benzene ring to which R 1 to R 3 and R 5 to R 8 are bonded. The ring structure having two or more rings includes, for example, a structure of the following formula.
又,上述的雜環之鍵結位置,係各環所含有的任意氫原子脫離後的部分。 In addition, the above-mentioned bonding position of the heterocyclic ring is a part from which any hydrogen atom contained in each ring is removed.
以RN3、R1至R8、R101及R102表示之雜環基,可具有取代基。作為該取代基者,可舉出以RN1及RN2表示之脂肪族烴基、以RN3、R1至R8、R101及R102表示之烴基可具有的取代基相同者。又,前述雜環係含有氮原子作為其構成元素時,該氮原子可鍵結上述舉出的烴基作為取代基。 The heterocyclic group represented by R N3 , R 1 to R 8 , R 101 and R 102 may have a substituent. Examples of such substituents include those that may have the same substituents that the aliphatic hydrocarbon groups represented by R N1 and R N2 and the hydrocarbon groups represented by R N3 , R 1 to R 8 , R 101 and R 102 may have. Also, when the aforementioned heterocyclic ring system contains a nitrogen atom as its constituent element, the nitrogen atom may be bonded to the aforementioned hydrocarbon group as a substituent.
該取代基的較佳者,可舉出與以RN1及RN2表示之脂肪族烴基、以RN3、R1至R8、R101及R102表示之烴基可具有的取代基之較佳者相同者。 Preferable examples of this substituent include preferred substituents that may be present with aliphatic hydrocarbon groups represented by R N1 and R N2 , and hydrocarbon groups represented by R N3 , R 1 to R 8 , R 101 , and R 102 who are the same.
以RN3、R1至R8、R101及R102表示之具有取代基的雜環基,可舉出具有一價或二價的取代基之雜環基,較佳可舉出具有群s1的取代基之雜環基,更佳可舉出具有群s2的取代基之雜環基。 The heterocyclic group having a substituent represented by R N3 , R 1 to R 8 , R 101 and R 102 includes a heterocyclic group having a monovalent or divalent substituent, preferably a heterocyclic group having a group s1 The heterocyclic group having a substituent of the group s2 is more preferably a heterocyclic group having a substituent of the group s2.
上述烴基或雜環基可具有的取代基(第一取代基),可為1個或2個以上,2個以上的取代基係互相獨立且可相同亦可不同。而且,前述第一取代基可在其一部分所含有的烴基鍵結另外的取代基(第二取代基)。第二取代基係能夠選自與第一取代基同樣的基。 The substituents (first substituents) that the hydrocarbon group or heterocyclic group may have may be one or more, and the two or more substituents are independent from each other and may be the same or different. Furthermore, another substituent (second substituent) may be bonded to the hydrocarbon group contained in the aforementioned first substituent. The second substituent can be selected from the same groups as the first substituent.
以下,說明R1至R8的-CO-R102、-COO-R101、-OCO-R102、-COCO-R102、-O-R102、-SO2-R101、-SO2N(R102)2、-CON(R102)2、-N(R102)2、-NHCO-R102、-NHCO-N(R102)2、-NHCOOR102、-OCON(R102)2、鹵素原子、-SO3M、-CO2M。 In the following, -CO - R 102 , -COO-R 101 , -OCO-R 102 , -COCO-R 102 , -OR 102 , -SO 2 -R 101 , -SO 2 N(R 102 ) 2 , -CON(R 102 ) 2 , -N(R 102 ) 2 , -NHCO-R 102 , -NHCO-N(R 102 ) 2 , -NHCOOR 102 , -OCON(R 102 ) 2 , halogen atom , -SO 3 M, -CO 2 M.
作為-CO-R102者,可舉出甲醯基;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、苯甲醯基等,及上述式表示之基等鍵結有碳數1至40(較佳為碳數1至20)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之羰基,較佳是鍵結有碳數為1至10的烴基之羰基(將該羰基設為醯基之情況,碳數為2至41)等。較佳可舉出鍵結有碳數1至11(更佳是碳數為1至10)的烴基或其衍生化基之羰基(將該羰基設為烷醯基之情況,碳數係較佳為2至12)等。 Examples of -CO-R 102 include formyl; acetyl, propionyl, butyryl, 2,2-dimethylacryl, pentyl, hexyl, (2-ethyl) Hexyl, heptyl, octyl, nonyl, decanyl, undecyl, dodecyl, hexacyl, benzoyl, etc., and the groups represented by the above formulas are A hydrocarbon group with 1 to 40 carbons (preferably 1 to 20 carbons) or a derivative thereof (such as a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), a carbon number 1 to 10 A carbonyl group derived from an alkylsulfamoyl group (preferably an octylsulfamoyl group), etc.), preferably a carbonyl group bonded to a hydrocarbon group with a carbon number of 1 to 10 (the carbonyl group is set as In the case of an acyl group, the carbon number is 2 to 41), etc. Preferably, a carbonyl group bonded to a hydrocarbon group with a carbon number of 1 to 11 (more preferably a carbon number of 1 to 10) or a derivative thereof (when the carbonyl group is an alkyl group, the carbon number is preferred) 2 to 12) etc.
作為-COO-R101者,可舉出甲氧羰基、乙氧羰基、丙氧羰基、第三丁氧羰基、丁氧羰基、戊氧羰基、己氧羰基、(2-乙基)己氧羰基、庚氧羰基、辛氧羰基、壬氧羰基、癸氧羰基、十一基氧基羰基、十二基氧基羰基、苯氧羰基、二十基氧基羰基等,及上述式表示之基等鍵結有碳數1至40(較佳為碳數1至20)的烴基之氧羰基,較佳可舉出鍵結有碳數1至10的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之氧羰基等。 Examples of -COO-R 101 include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tertiary butoxycarbonyl, butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, (2-ethyl)hexyloxycarbonyl , heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, phenoxycarbonyl, eicosyloxycarbonyl, etc., and the groups represented by the above formula, etc. The oxycarbonyl group bonded with a hydrocarbon group having 1 to 40 carbons (preferably 1 to 20 carbons), preferably a hydrocarbon group bonded with 1 to 10 carbons or a derivative thereof (such as carboxyl, sulfo Oxygen of acid group, nitro group, hydroxyl group, halogen (preferably chlorine atom), alkylsulfamoyl group with 1 to 10 carbons (preferably octylsulfamoyl group), etc.) Carbonyl etc.
較佳可舉出鍵結有碳數1至10的烴基或其衍生化基之氧羰基等。 Preferable examples include an oxycarbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivative thereof is bonded.
作為-OCO-R102者,可舉出甲醯氧基;乙醯氧基、丙醯氧基、丁醯氧基、2,2-二甲基丙醯氧基、戊醯氧基、己醯氧基、(2-乙基)己醯氧基、庚醯氧基、辛醯氧基、 壬醯氧基、癸醯氧基、十一醯氧基、十二醯氧基、二十一醯氧基、苯甲醯基氧基等,及上述式表示之基等鍵結有已鍵結碳數1至40(較佳是碳數1至20)的烴基之羰基之氧基,較佳可舉出鍵結有碳數1至10的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化之基)之羰氧基(將該羰氧基設為醯氧基時、碳數為2至41)等,較佳可舉出鍵結有碳數1至11(更佳是碳數1至10)的烴基或其衍生化基之羰氧基(將該羰氧基設為醯氧基的情況,碳數較佳為2至12)等。 Examples of -OCO-R 102 include formyloxy; acetyloxy, propionyloxy, butyryloxy, 2,2-dimethylacryloxy, pentyloxy, hexyloxy Oxygen, (2-Ethyl)hexyloxy, Heptyloxy, Octyloxy, Nonyloxy, Decyloxy, Undecyloxy, Dodecyloxy, Eicosyloxy Oxygen group, benzoyloxyl group, etc., and the group represented by the above formula, etc., are bonded to the carbonyl group of the hydrocarbon group with 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms). Examples include hydrocarbon groups with carbon numbers from 1 to 10 or derivatives thereof (such as carboxyl, sulfonic acid, nitro, hydroxyl, halogen (preferably chlorine), alkylsulfamoyl (preferably (octylsulfamoyl) and other derivatized groups) carbonyloxy group (when the carbonyloxy group is an acyloxy group, the number of carbon atoms is 2 to 41), etc., preferably bonded with 1 carbon number A carbonyloxy group of a hydrocarbon group having 1 to 11 carbon atoms (more preferably 1 to 10 carbon atoms) or a derivative thereof (when the carbonyloxy group is an acyloxy group, the carbon number is preferably 2 to 12 carbon atoms), etc.
作為-COCO-R102者,可舉出甲基草醯基、乙基草醯基、丙基草醯基、丁基草醯基、戊基草醯基、己基草醯基、(2-乙基)己基草醯基、庚基草醯基、辛基草醯基、壬基草醯基、癸基草醯基、十一基草醯基、十二基草醯基、二十基草醯基、環戊基草醯基、環己基草醯基、苯基草醯基、對甲苯基草醯基等,及上述式表示之基等鍵結有碳數1至40(較佳為碳數1至20)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之草醯基等。 As -COCO-R 102 , methyl oxalyl, ethyl oxalyl, propyl oxalyl, butyl oxalyl, pentyl oxalyl, hexyl oxalyl, (2-ethyl oxalyl) Base) hexyl oxalyl, heptyl oxalyl, octyl oxalyl, nonyl oxalyl, decyl oxalyl, undecyl oxalyl, dodecyl oxalyl, eicosyl oxalyl oxalyl group, cyclopentyl oxalyl group, cyclohexyl oxalyl group, phenyl oxalyl group, p-tolyl oxalyl group, etc., and the groups represented by the above formulas have a carbon number of 1 to 40 (preferably carbon number 1 to 20) hydrocarbon group or its derivation group (such as carboxyl group, sulfonic acid group, nitro group, hydroxyl group, halogen (preferably chlorine atom), alkylsulfamoyl group with carbon number 1 to 10 (preferably Octylsulfamoyl) and other derivatives such as oxalyl, etc.
作為-O-R102者,可舉出羥基;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、戊氧基、己氧基、庚氧基、辛氧基、壬氧基、癸氧基、十一基氧基、十二基氧基、(2-乙基)己氧基、二十基 氧基、1-苯基乙氧基、1-甲基-1-苯基乙氧基、苯氧基、2,3-二甲基苯氧基、2,4-二甲基苯氧基、2,5-二甲基苯氧基、2,6-二甲基苯氧基、3,4-二甲基苯氧基、3,5-二甲基苯氧基、2,2-二氰基苯氧基、2,3-二氰基苯氧基、2,4-二氰基苯氧基、2,5-二氰基苯氧基、2,6-二氰基苯氧基、3,4-二氰基苯氧基、3,5-二氰基苯氧基、4-甲氧基苯氧基、2-甲氧基苯氧基、3-甲氧基苯氧基、4-乙氧基苯氧基、2-乙氧基苯氧基、3-乙氧基苯氧基等,及上述式表示之基等鍵結有碳數1至40(較佳為碳數1至20)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之氧基,較佳可舉出鍵結有碳數1至10的烴基之氧基等。 As -OR 102 , hydroxyl can be mentioned; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, third butoxy, pentyloxy Oxy, Hexyloxy, Heptyloxy, Octyloxy, Nonyloxy, Decyloxy, Undecyloxy, Dodecyloxy, (2-Ethyl)hexyloxy, Eicosyloxy , 1-phenylethoxy, 1-methyl-1-phenylethoxy, phenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2, 5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,2-dicyanobenzene Oxygen, 2,3-dicyanophenoxy, 2,4-dicyanophenoxy, 2,5-dicyanophenoxy, 2,6-dicyanophenoxy, 3,4 -Dicyanophenoxy, 3,5-dicyanophenoxy, 4-methoxyphenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, 4-ethoxy phenoxy, 2-ethoxyphenoxy, 3-ethoxyphenoxy, etc., and the groups represented by the above formulas are bonded with 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) Hydrocarbyl or its derivation group (such as carboxyl group, sulfonic acid group, nitro group, hydroxyl group, halogen (preferably chlorine atom), carbon number 1 to 10 alkyl sulfamoyl group (preferably octyl sulfamoyl group) The oxy group of the group) derivatized by (group) etc., Preferably, the oxy group etc. which bonded the hydrocarbon group of 1-10 carbons are mentioned.
較佳可舉出鍵結有碳數1至10的烴基或其衍生化基之氧基等。 Preferable examples include an oxy group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivative thereof is bonded.
作為-SO2-R101者,可舉出甲基磺醯基、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、對甲苯基磺醯基等,及上述式表示之基等鍵結有碳數1至40(較佳為碳數1至20)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之磺醯基等,較佳可舉出鍵結有碳數1至10的烴基或其衍生化基之磺醯基等。 Examples of -SO 2 -R 101 include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, (2- Ethyl) Hexylsulfonyl, Heptylsulfonyl, Octylsulfonyl, Nonylsulfonyl, Decylsulfonyl, Undecylsulfonyl, Dodecylsulfonyl, Eicosylsulfonyl Acyl group, phenylsulfonyl group, p-tolylsulfonyl group, etc., and the groups represented by the above formulas are bonded with hydrocarbon groups with 1 to 40 carbons (preferably 1 to 20 carbons) or derivatives thereof ( For example, it is derivatized by carboxyl, sulfonic acid, nitro, hydroxyl, halogen (preferably chlorine atom), alkyl sulfamoyl group with 1 to 10 carbons (preferably octyl sulfamoyl group), etc. A sulfonyl group, etc., preferably a sulfonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or a derivative thereof is bonded.
作為-SO2N(R102)2者,可舉出胺磺醯基;N-甲基胺磺醯基、N-乙基胺磺醯基、N-丙基胺磺醯基、N-異丙基胺磺醯基、N-丁基胺磺醯基、N-異丁基胺磺醯基、N-第二丁基胺磺醯基、N-第三丁基胺磺醯基、N-戊基胺磺醯基、N-(1-乙基丙基)胺磺醯基、N-己基胺磺醯基、N-(2-乙基)己基胺磺醯基、N-庚基胺磺醯基、N-辛基胺磺醯基、N-壬基胺磺醯基、N-癸基胺磺醯基、N-十一基胺磺醯基、N-十二基胺磺醯基、N-二十基胺磺醯基、N-苯基胺磺醯基等,及上述式表示之基等被1個碳數1至40(較佳為碳數1至20)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)取代之胺磺醯基等;N,N-二甲基胺磺醯基、N,N-乙基甲基胺磺醯基、N,N-二乙基胺磺醯基、N,N-丙基甲基胺磺醯基、N,N-二丙基胺磺醯基、N,N-異丙基甲基胺磺醯基、N,N-二異丙基胺磺醯基、N,N-第三丁基甲基胺磺醯基、N,N-二異丁基胺磺醯基、N,N-二第二丁基胺磺醯基、N,N-二第三丁基胺磺醯基、N,N-丁基甲基胺磺醯基、N,N-二丁基胺磺醯基、N,N-二戊基胺磺醯基、N,N-二(1-乙基丙基)胺磺醯基、N,N-二己基胺磺醯基、N,N-二(2-乙基)己基胺磺醯基、N,N-二庚基胺磺醯基、N,N-辛基甲基胺磺醯基、N,N-二辛基胺磺醯基、N,N-二壬基胺磺醯基、N,N-癸基甲基胺磺醯基、N,N-十一基甲基胺磺醯基、N,N-十二基甲基胺磺醯基、N,N-二十基甲基胺磺 醯基、N,N-苯基甲基胺磺醯基及、N,N-二苯基胺磺醯基等,及上述式表示之基等被2個碳數1至40(較佳為碳數1至20)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)取代之胺磺醯基等,較佳可舉出被1個或2個碳數1至10的烴基或其衍生化基取代之胺磺醯基等。 Examples of -SO 2 N(R 102 ) 2 include sulfamoyl; N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-iso Propyl sulfamoyl, N-butyl sulfamoyl, N-isobutyl sulfamoyl, N-second butyl sulfamoyl, N- tertiary butyl sulfamoyl, N- Amylsulfamoyl, N-(1-ethylpropyl)sulfamoyl, N-hexylsulfamoyl, N-(2-ethyl)hexylsulfamoyl, N-heptylsulfamoyl Acyl group, N-octyl sulfamoyl group, N-nonyl sulfamoyl group, N-decyl sulfamoyl group, N-undecyl sulfamoyl group, N-dodecyl sulfamoyl group, N-eicosylsulfamoyl group, N-phenylsulfamoyl group, etc., and the group represented by the above formula, etc. are derived by a hydrocarbon group with 1 to 40 carbons (preferably 1 to 20 carbons) or derivatives thereof Cyl group (for example by carboxyl group, sulfonic acid group, nitro group, hydroxyl group, halogen (preferably chlorine atom), carbon number 1 to 10 alkyl sulfamoyl group (preferably octyl sulfamoyl group) etc. Chemical base) substituted sulfamoyl group, etc.; N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group , N,N-propylmethylsulfamoyl, N,N-dipropylsulfamoyl, N,N-isopropylmethylsulfamoyl, N,N-diisopropylsulfamoyl Acyl group, N,N-tert-butylmethylsulfamoyl group, N,N-diisobutylsulfamoyl group, N,N-disecond-butylsulfamoyl group, N,N-di-tertiary Butylsulfamoyl, N,N-butylmethylsulfamoyl, N,N-dibutylsulfamoyl, N,N-dipentylsulfamoyl, N,N-di(1- Ethylpropyl)sulfamoyl, N,N-dihexylsulfamoyl, N,N-di(2-ethyl)hexylsulfamoyl, N,N-diheptylsulfamoyl, N,N-octylmethylsulfamoyl, N,N-dioctylsulfamoyl, N,N-dinonylsulfamoyl, N,N-decylmethylsulfamoyl, N,N-undecylmethylsulfamoyl, N,N-dodecylmethylsulfamoyl, N,N-eicosylmethylsulfamoyl, N,N-phenylmethyl Aminosulfonyl group, N,N-diphenylsulfamoyl group, etc., and the group represented by the above formula are derivatized by two hydrocarbon groups with 1 to 40 carbons (preferably 1 to 20 carbons) group (for example, derivatized by carboxyl group, sulfonic acid group, nitro group, hydroxyl group, halogen (preferably chlorine atom), alkylsulfamoyl group with 1 to 10 carbons (preferably octylsulfamoyl group), etc. A sulfamoyl group substituted with a sulfamoyl group etc., preferably a sulfamoyl group substituted with one or two hydrocarbon groups having 1 to 10 carbons or derivatives thereof.
作為-CON(R102)2者,可舉出胺基甲醯基;N-甲基胺基甲醯基、N-乙基胺基甲醯基、N-丙基胺基甲醯基、N-異丙基胺基甲醯基、N-丁基胺基甲醯基、N-異丁基胺基甲醯基、N-第二丁基胺基甲醯基、N-第三丁基胺基甲醯基、N-戊基胺基甲醯基、N-(1-乙基丙基)胺基甲醯基、N-己基胺基甲醯基、N-(2-乙基)己基胺基甲醯基、N-庚基胺基甲醯基、N-辛基胺基甲醯基、N-壬基胺基甲醯基、N-癸基胺基甲醯基、N-十一基胺基甲醯基、N-十二基胺基甲醯基、N-二十基胺基甲醯基、N-苯基胺基甲醯基等,及上述式表示之基等被1個碳數1至40(較佳為碳數1至20)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)取代之胺基甲醯基等;N,N-二甲基胺基甲醯基、N,N-乙基甲基胺基甲醯基、N,N-二乙基胺基甲醯基、N,N-丙基甲基胺基甲醯基、N,N-二丙基胺基甲醯基、N,N-異丙基甲基胺基甲醯基、N,N-二 異丙基胺基甲醯基、N,N-第三丁基甲基胺基甲醯基、N,N-二異丁基胺基甲醯基、N,N-二第二丁基胺基甲醯基、N,N-二第三丁基胺基甲醯基、N,N-丁基甲基胺基甲醯基、N,N-二丁基胺基甲醯基、N,N-丁基辛基胺基甲醯基、N,N-二戊基胺基甲醯基、N,N-二(1-乙基丙基)胺基甲醯基、N,N-二己基胺基甲醯基、N,N-二(2-乙基)己基胺基甲醯基、N,N-二庚基胺基甲醯基、N,N-辛基甲基胺基甲醯基、N,N-二辛基胺基甲醯基、N,N-二壬基胺基甲醯基、N,N-癸基甲基胺基甲醯基、N,N-十一基甲基胺基甲醯基、N,N-十二基甲基胺基甲醯基、N,N-二十基甲基胺基甲醯基、N,N-苯基甲基胺基甲醯基、N,N-二苯基胺基甲醯基等,及上述式表示之基等被2個碳數1至40(較佳為碳數1至20)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)取代之胺基甲醯基等,較佳可舉出被1個或2個碳數1至10的烴基或其衍生化基取代之胺基甲醯基等。 Examples of -CON(R 102 ) 2 include carbamoyl; N-methyl carbamoyl, N-ethyl carbamoyl, N-propyl carbamoyl, N -Isopropylaminoformyl, N-butylaminoformyl, N-isobutylaminoformyl, N-second butylaminoformyl, N-tert-butylamine Aminoformyl, N-pentylaminoformyl, N-(1-ethylpropyl)aminoformyl, N-hexylaminoformyl, N-(2-ethyl)hexylamine Aminoformyl, N-heptylaminoformyl, N-octylaminoformyl, N-nonylaminoformyl, N-decylaminoformyl, N-undecyl Aminoformyl group, N-dodecylaminoformyl group, N-eicosylaminoformyl group, N-phenylaminoformyl group, etc., and the groups represented by the above formulas are replaced by 1 carbon A hydrocarbon group with a number of 1 to 40 (preferably a carbon number of 1 to 20) or a derivative thereof (such as a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), a carbon number of 1 to 10 Alkylaminosulfonyl (preferably octylaminosulfonyl) and other derivatives) substituted aminoformyl, etc.; N,N-dimethylaminoformyl, N,N -Ethylmethylaminoformyl, N,N-Diethylaminoformyl, N,N-Propylmethylaminoformyl, N,N-Dipropylaminoformyl , N,N-isopropylmethylaminoformyl, N,N-diisopropylaminoformyl, N,N-tert-butylmethylaminoformyl, N,N-diiso Butylaminoformyl, N,N-disecond-butylaminoformyl, N,N-di-tert-butylaminoformyl, N,N-butylmethylaminoformyl, N,N-dibutylaminoformyl, N,N-butyloctylaminoformyl, N,N-dipentylaminoformyl, N,N-di(1-ethyl Propyl)aminoformyl, N,N-dihexylaminoformyl, N,N-di(2-ethyl)hexylaminoformyl, N,N-diheptylaminoformyl N,N-octylaminoformyl, N,N-dioctylaminoformyl, N,N-dinonylaminoformyl, N,N-decylaminoformyl Aminoformyl, N,N-undecylmethylaminoformyl, N,N-dodecylmethylaminoformyl, N,N-eicosylmethylaminoformyl , N,N-phenylmethylaminoformyl, N,N-diphenylaminoformyl, etc., and the group represented by the above formula is replaced by 2 carbon numbers of 1 to 40 (preferably carbon number 1 to 20) hydrocarbon group or its derivation group (such as carboxyl group, sulfonic acid group, nitro group, hydroxyl group, halogen (preferably chlorine atom), alkylsulfamoyl group with carbon number 1 to 10 (preferably octylsulfamoyl) and other derivatives) substituted carbamoyl, etc., preferably amines substituted by one or two hydrocarbon groups with 1 to 10 carbons or derivatives thereof methacryl, etc.
作為-N(R102)2者,可舉出胺基;N-甲基胺基、N-乙基胺基、N-丙基胺基、N-異丙基胺基、N-丁基胺基、N-異丁基胺基、N-第二丁基胺基、N-第三丁基胺基、N-戊基胺基、N-己基胺基、N-(2-乙基)己基胺基、N-庚基胺基、N-辛基胺基、N-壬基胺基、N-癸基胺基、N-十一基胺基、N-十二基胺基、N-二十基胺基、N-苯基胺基等,及上述式表示之基等被1個碳數1至40(較佳為碳數1至20)的烴基或其衍 生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)取代之胺基等;N,N-二甲基胺基、N,N-乙基甲基胺基、N,N-二乙基胺基、N,N-丙基甲基胺基、N,N-二丙基胺基、N,N-異丙基甲基胺基、N,N-二異丙基胺基、N,N-第三丁基甲基胺基、N,N-二異丁基胺基、N,N-二第二丁基胺基、N,N-二第三丁基胺基、N,N-丁基甲基胺基、N,N-二丁基胺基、N,N-二戊基胺基、N,N-二(1-乙基丙基)胺基、N,N-二己基胺基、N,N-二(2-乙基)己基胺基、N,N-二庚基胺基、N,N-二辛基胺基、N,N-二壬基胺基、N,N-癸基甲基胺基、N,N-十一基甲基胺基、N,N-十二基甲基胺基、N,N-二十基甲基胺基、N,N-苯基甲基胺基、N,N-二苯基胺基等,及上述式表示之基等被2個碳數1至40(較佳為碳數1至20)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)取代之胺基等;較佳可舉出被1個或2個碳數1至10的烴基或其衍生化基取代之胺基等。 Examples of -N(R 102 ) 2 include amino groups; N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamine Base, N-isobutylamino group, N-second butylamino group, N-tertiary butylamino group, N-pentylamino group, N-hexylamino group, N-(2-ethyl)hexyl Amino, N-heptylamino, N-octylamino, N-nonylamino, N-decylamino, N-undecylamino, N-dodecylamino, N-two Decylamino group, N-phenylamino group, etc., and the groups represented by the above formulas are replaced by a hydrocarbon group with 1 to 40 carbons (preferably 1 to 20 carbons) or a derivative thereof (for example, by carboxyl, Sulfonic acid group, nitro group, hydroxyl group, halogen (preferably chlorine atom), alkyl sulfamoyl group with 1 to 10 carbons (preferably octyl sulfamoyl group) and other derivatized groups) Amino groups, etc.; N,N-dimethylamino, N,N-ethylmethylamino, N,N-diethylamino, N,N-propylmethylamino, N,N -Dipropylamino, N,N-isopropylmethylamino, N,N-diisopropylamino, N,N-tert-butylmethylamino, N,N-diisobutylamine group, N,N-disecond butylamino group, N,N-ditertiary butylamino group, N,N-butylmethylamino group, N,N-dibutylamino group, N,N-dibutylamino group Amylamino, N,N-di(1-ethylpropyl)amino, N,N-dihexylamino, N,N-di(2-ethyl)hexylamino, N,N-di Heptylamino, N,N-dioctylamino, N,N-dinonylamino, N,N-decylmethylamino, N,N-undecylmethylamino, N, N-dodecylmethylamino group, N,N-eicosylmethylamino group, N,N-phenylmethylamino group, N,N-diphenylamino group, etc., and groups represented by the above formula etc. by two hydrocarbon groups with 1 to 40 carbons (preferably 1 to 20 carbons) or their derivatives (such as carboxyl, sulfonic acid, nitro, hydroxyl, halogen (preferably chlorine), carbon 1 to 10 alkyl sulfamoyl group (preferably octyl sulfamoyl group) and other derivatives) substituted amino groups, etc.; preferably 1 or 2 carbon number 1 Hydrocarbyl to 10 or amino groups substituted by derivatized groups, etc.
作為-NHCO-R102者,可舉出甲醯基胺基;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、苯甲醯基胺基等,及上 述式表示之基等鍵結有碳數1至40(較佳為碳數1至20)的烴基或其衍生化基(例如被羧基、磺酸基、硝基、羥基、鹵素(較佳為氯原子)、碳數1至10的烷基胺磺醯基(較佳為辛基胺磺醯基)等衍生化而成之基)之羰胺基(將該羰胺基設為醯胺基的情況,碳數為1至40)等,較佳可舉出鍵結有碳數1至10的烴基或其衍生化基之羰胺基(將該羰胺基設為烷醯基胺基的情況,碳數較佳為1至10)等。 Examples of -NHCO-R 102 include formylamine; acetylamino, propionylamine, butyrylamine, 2,2-dimethylacrylamine, pentylamine Base, Caproylamine, (2-Ethyl)caproylamine, Heptylamino, Octylamino, Nonylamine, Decacylamino, Undecylamino, Decacylamino Diacylamino group, eicosylamino group, benzoylamino group, etc., and groups represented by the above formulas are bonded to hydrocarbon groups with 1 to 40 carbons (preferably 1 to 20 carbons) or Its derivatization group (such as carboxyl group, sulfonic acid group, nitro group, hydroxyl group, halogen (preferably chlorine atom), carbon number 1 to 10 alkyl sulfamoyl group (preferably octyl sulfamoyl group) Derivatized groups such as) carbonylamino group (when the carbonylamino group is an amido group, the carbon number is 1 to 40), etc., preferably a hydrocarbon group with 1 to 10 carbon atoms bonded A carbonylamino group or a derivative thereof (when the carbonylamino group is an alkylamino group, the number of carbon atoms is preferably 1 to 10), etc.
作為-NHCON(R102)2者,可舉出上述舉出的基等。 Examples of -NHCON(R 102 ) 2 include the groups mentioned above and the like.
作為-NHCOOR102者,可舉出上述舉出的基等。 Examples of -NHCOOR 102 include the groups mentioned above and the like.
作為-OCON(R102)2者,可舉出上述舉出的基等。 Examples of -OCON(R 102 ) 2 include the above-mentioned groups and the like.
鹵素原子,係以氟原子、氯原子、溴原子及碘原子等為佳。 The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
-SO3M及-CO2M的M,可舉出氫原子;鋰原子、鈉原子及鉀原子等鹼金屬原子,較佳可舉出氫原子、鈉原子、鉀原子。 M of -SO 3 M and -CO 2 M includes a hydrogen atom; an alkali metal atom such as a lithium atom, a sodium atom, and a potassium atom preferably includes a hydrogen atom, a sodium atom, and a potassium atom.
上述-CO-R102、-COO-R102、-OCO-R102、-COCO-R102、-O-R102、-SO2-R102、-SO2N(R102)2、-CON(R102)2、-N(R102)2、-NHCO-R102、-NHCON(R102)2、-NHCOOR102、-OCON(R102)2所含有的取代基(第一取代基)可為1個或2個以上,2個以上的取代基係互相獨立且可相同亦可不同。 The above-CO-R 102 , -COO-R 102 , -OCO-R 102 , -COCO-R 102 , -OR 102 , -SO 2 -R 102 , -SO 2 N(R 102 ) 2 , -CON(R 102 ) 2 , -N(R 102 ) 2 , -NHCO-R 102 , -NHCON(R 102 ) 2 , -NHCOOR 102 , -OCON(R 102 ) 2 (first substituent) may be One or two or more substituents are independent of each other and may be the same or different.
而且,前述第一取代基可在其一部分所含有的烴基鍵結有另外的取代基(第二取代基)。第二取代基係能夠選自與第一取代基同樣的基。 In addition, another substituent (second substituent) may be bonded to the hydrocarbon group contained in the first substituent described above. The second substituent can be selected from the same groups as the first substituent.
式(I)表示之化合物係除了上述的基以外,亦可具有以下顯示的部分構造。 The compound represented by formula (I) may have a partial structure shown below in addition to the above-mentioned groups.
RN1及RN2係以脂肪族烴基、芳烷基、(環烷基)烷基、被羥基取代之脂肪族烴基、被在一側鍵結有碳數1至20的烴基之氧基取代之脂肪族烴基為佳,以直鏈狀或分枝鏈狀烷基、直鏈狀或分枝鏈狀烯基、環烷基、芳烷基、(環烷基)烷基、被羥基取代之直鏈狀或分枝鏈狀烷基、被烷氧基取代之直鏈狀或分枝鏈狀烷基為較佳。 R N1 and R N2 are aliphatic hydrocarbon groups, aralkyl groups, (cycloalkyl) alkyl groups, aliphatic hydrocarbon groups substituted by hydroxyl groups, and oxy groups substituted by hydrocarbon groups with 1 to 20 carbon atoms bonded to one side Aliphatic hydrocarbon group is preferably straight chain or branched chain alkyl, straight chain or branched chain alkenyl, cycloalkyl, aralkyl, (cycloalkyl) alkyl, straight chain substituted by hydroxyl A chain or branched chain alkyl group, and a straight chain or branched chain alkyl group substituted with an alkoxy group are preferred.
RN1及RN2可相同亦可不同。 R N1 and R N2 may be the same or different.
RN3係以脂肪族烴基為佳,以直鏈狀或分枝鏈狀烷基為較佳,以直鏈狀烷基為更佳。 R N3 is preferably an aliphatic hydrocarbon group, preferably a straight-chain or branched-chain alkyl group, and more preferably a straight-chain alkyl group.
R4係以氫原子為佳,R1至R8係以氫原子為較佳。 R 4 is preferably a hydrogen atom, and R 1 to R 8 are preferably a hydrogen atom.
在式(I)表示之化合物中之Ag-係表示g價的陰離子。g係表示1至14的整數,以表示1至10的整數為 佳,較佳是表示1至8的整數,更佳是表示1至6的整數,特佳是表示1至4的整數。 Ag- in the compound represented by the formula (I) represents an anion having a g valency. g represents an integer of 1 to 14, preferably represents an integer of 1 to 10, more preferably represents an integer of 1 to 8, more preferably represents an integer of 1 to 6, particularly preferably represents an integer of 1 to 4.
作為Ag-者,可舉出眾所周知的陰離子。作為Ag-者,具體而言可舉出:氟化物離子、氯化物離子、溴化物離子、碘化物離子等鹵化物離子;OH-;CN-;NO3 -;NO2 -;ClO-;ClO2 -;ClO3-;ClO4-;MnO4 -;CH3CO2-、C6H5CO2 -;甲苯磺酸根陰離子;HCO3 -;H2PO4 -;HSO4 -;HS-;SCN-;H(COO)2 -;[Al(OH)4]-、[Al(OH)4(H2O)2]-;[Ag(CN)2]-;[Cr(OH)4]-;[AuCl4]-;O2-;S2-;O2 2-;SO4 2-、HSO4 -;SO3 2-;S2O3 2-;CO3 2-;CrO4 2-;Cr2O7 2-;(COO)2 2-;HPO4 2-;[Zn(OH)4]2-;[Zn(CN)4]2-;[CuCl4]2-;PO4 3-;[Fe(CN)6]3-;[Ag(S2O3)2]3-;[Fe(CN)6]4-;CH3O-、CH3CH2O-、(CH3)3CO-等碳數1至20的烷氧基離子、C6H5O-等碳數6至20的芳氧基離子;含氟陰離子;將選自由鎢、鉬、矽及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之陰離子等。 Well-known anions are mentioned as Ag- . Specific examples of Ag- include halide ions such as fluoride ions, chloride ions, bromide ions, and iodide ions; OH - ; CN - ; NO 3 - ; NO 2 - ; ClO - ; ClO 2 - ; ClO3 - ; ClO4 - ; MnO 4 - ; CH 3 CO 2 - , C 6 H 5 CO 2 - ; SCN - ; H(COO) 2 - ; [Al(OH) 4 ] - , [Al(OH) 4 (H 2 O) 2 ] - ; [Ag(CN) 2 ] - ; [Cr(OH) 4 ] - ; [ AuCl 4 ] - ; O 2- ; S 2- ; O 2 2- ; SO 4 2- , HSO 4 - ; SO 3 2- ; - ; Cr 2 O 7 2- ; (COO) 2 2- ; HPO 4 2- ; [Zn(OH) 4 ] 2- ; [Zn(CN ) 4 ] 2- ; 3- ; [Fe(CN) 6 ] 3- ; [Ag(S 2 O 3 ) 2 ] 3- ; [Fe(CN) 6 ] 4- ; CH 3 O - , CH 3 CH 2 O-, (CH 3 ) 3 CO - an alkoxyl ion with a carbon number of 1 to 20, C 6 H 5 O - an aryloxyl ion with a carbon number of 6 to 20; fluorine-containing anions; will be selected from tungsten, molybdenum, silicon and phosphorus At least one element constituting the group, an anion containing oxygen as an essential element, and the like.
就耐熱性提升和昇華性減低而言,Ag-係以含氟陰離子、或將選自由鎢、鉬、矽及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之陰離子為佳,以將選自由鎢及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之陰離子、或含氟陰離子為較佳,以將選自由鎢及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之陰離子為更佳。 In terms of heat resistance improvement and sublimation reduction, Ag- is an anion containing fluorine-containing anions, or at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen as essential elements Preferably, at least one element selected from the group consisting of tungsten and phosphorus, and an anion containing oxygen as an essential element, or an anion containing fluorine is preferably selected from the group consisting of tungsten and phosphorus An anion containing at least one element and oxygen as an essential element is more preferable.
作為含氟陰離子者,例如可舉出CF3CO2 -及下述式(III)、(IV)、(V)、(VI)表示之基。 Examples of fluorine-containing anions include CF 3 CO 2 - and groups represented by the following formulas (III), (IV), (V), and (VI).
[式(III)中,W3及W4係互相獨立地表示氟原子或是碳數1至4的氟化烷基,或者W3與W4一起而表示碳數1至4的氟化烷二基],
[式(IV)中,W5至W7係互相獨立地表示氟原子或是碳數1至4的氟化烷基],
[式(V)中,Y1係表示碳數1至4的氟化烷二基],
[式(VI)中,Y2係表示碳數1至4的氟化烷基]。 [In the formula (VI), Y 2 represents a fluorinated alkyl group having 1 to 4 carbon atoms].
在式(III)、(IV)、及(VI)中,碳數1至4的氟化烷基,係以全氟烷基為佳。作為該全氟烷基者,可舉出-CF3、-CF2CF3、-CF2CF2CF3、-CF(CF3)2、-CF2CF2CF2CF3、-CF2CF(CF3)2、-C(CF3)3等。 In formulas (III), (IV) and (VI), the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include -CF 3 , -CF 2 CF 3 , -CF 2 CF 2 CF 3 , -CF(CF 3 ) 2 , -CF 2 CF 2 CF 2 CF 3 , -CF 2 CF(CF 3 ) 2 , -C(CF 3 ) 3 , etc.
在式(III)及(V)中,碳數1至4的氟化烷二基,係以全氟烷二基為佳,可舉出-CF2-、-CF2CF2-、 -CF2CF2CF2-、-C(CF3)2-、-CF2CF2CF2CF2-等。 In formulas (III) and (V), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, such as -CF 2 -, -CF 2 CF 2 -, -CF 2 CF 2 CF 2 -, -C(CF 3 ) 2 -, -CF 2 CF 2 CF 2 CF 2 -, etc.
式(III)表示之陰離子(以下,有稱為「陰離子(III)」之情形),可舉出各自以式(III-1)至式(III-6)表示之陰離子(以下,有稱為「陰離子(III-1)」至「陰離子(III-6)」之情形)。 The anion represented by formula (III) (hereinafter referred to as "anion (III)") includes anions represented by formula (III-1) to formula (III-6) respectively (hereinafter referred to as "anion (III)"). In the case of "anion (III-1)" to "anion (III-6)").
式(IV)表示之陰離子(以下,有稱為「陰離子(IV)」之情形),可舉出以式(IV-1)表示之陰離子(IV-1)。 Examples of the anion represented by formula (IV) (hereinafter, sometimes referred to as "anion (IV)") include anion (IV-1) represented by formula (IV-1).
式(V)表示之陰離子(以下,有稱為「陰離子(V)」之情形),可舉出各自以式(V-1)至式(V-4)表示之陰離子(以下,有稱為「陰離子(V-1)」至「陰離子(V-4)」之情形)。 The anion represented by formula (V) (hereinafter referred to as "anion (V)") may include anions represented by formula (V-1) to formula (V-4) (hereinafter referred to as "Anion (V-1)" to "Anion (V-4)").
式(VI)表示之陰離子(以下,有稱為「陰離子(VI)」之情形),可舉出各自以式(VI-1)至式(VI-4)表示之陰離子(以下,有稱為「陰離子(VI-1)」至「陰離子(VI-4)」之情形)。 The anion represented by formula (VI) (hereinafter referred to as "anion (VI)") may include anions represented by formula (VI-1) to formula (VI-4) (hereinafter referred to as "Anion (VI-1)" to "Anion (VI-4)").
含氟陰離子可為選自由CF3CO2 -、陰離子(III)、陰離子(IV)、陰離子(V)及陰離子(VI)所組成群組之至少1個陰離子。其中,以CF3CO2 -、陰離子(III-1)、陰離子(III-2)、陰離子(III-6)、陰離子(IV-1)、陰離子(V-1)、陰離子(VI-1)、陰離子(VI-2)、陰離子(VI-3)為佳,以CF3CO2 -、陰離子(III-2)、陰離子(IV-1)、陰離子(VI-1)為較佳。 The fluorine-containing anion may be at least one anion selected from the group consisting of CF 3 CO 2 - , anion (III), anion (IV), anion (V) and anion (VI). Among them, with CF 3 CO 2 - , anion (III-1), anion (III-2), anion (III-6), anion (IV-1), anion (V-1), anion (VI-1) , anion (VI-2) and anion (VI-3) are preferred, and CF 3 CO 2 - , anion (III-2), anion (IV-1) and anion (VI-1) are preferred.
作為陰離子者,可舉出將選自由鎢、鉬、矽及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之陰離子。以將鎢作為必要元素而含有之異性聚合酸或同素聚合酸的陰離子為佳,以磷鎢酸、矽鎢酸及鎢系同素聚合酸的陰離子為較佳。此種陰離子係例如使用在具有含氟陰離子(較佳為陰離子(VI-1))之式(I)表示之著色化合物中且進行陰離子交換時,有助於提升耐熱性。 Examples of the anion include anions containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen as essential elements. The anion of heteropolymeric acid or homopolymeric acid containing tungsten as an essential element is preferable, and the anion of phosphotungstic acid, silicotungstic acid, and tungsten homopolymeric acid is more preferable. Such anions contribute to improvement of heat resistance when used, for example, in a coloring compound represented by formula (I) having a fluorine-containing anion (preferably anion (VI-1)) and performing anion exchange.
此種將鎢作為必要元素而含有之異性聚合酸(heteropoly acid)或同素聚合酸(isopoly acid)的陰離子,例如科金型(Keggin type)磷鎢酸離子α-[PW12O40]3-、道森型(Dawson type)磷鎢酸離子α-[P2W18O62]6-、β-[P2W18O62]6-、科金型矽鎢酸離子α-[SiW12O40]4-、β-[SiW12O40]4-、γ-[SiW12O40]4-,而且作為其它例子者,可舉出[P2W17O61]10-、[P2W15O56]12-、[H2P2W12O48]12-、[NaP5W30O110]14-、α -[SiW9O34]10-、γ-[SiW10O36]8-、α-[SiW11O39]8-、β-[SiW11O39]8-、[W6O19]2-、[W10O32]4-、WO4 2-等。其中,以科金型磷鎢酸離子α-[PW12O40]3-為較佳。 This kind of anion of heteropoly acid or isopoly acid containing tungsten as an essential element, such as Keggin type (Keggin type) phosphotungstic acid ion α-[PW 12 O 40 ] 3 - , Dawson type (Dawson type) phosphotungstic acid ion α-[P 2 W 18 O 62 ] 6- , β-[P 2 W 18 O 62 ] 6- , Cojin type silicotungstic acid ion α-[SiW 12 O 40 ] 4- , β-[SiW 12 O 40 ] 4- , γ-[SiW 12 O 40 ] 4- , and other examples include [P 2 W 17 O 61 ] 10- , [ P 2 W 15 O 56 ] 12- , [H 2 P 2 W 12 O 48 ] 12- , [NaP 5 W 30 O 110 ] 14- , α -[SiW 9 O 34 ] 10- , γ-[SiW 10 O 36 ] 8- , α-[SiW1 1 O 39 ] 8- , β-[SiW 11 O 39 ] 8- , [W 6 O 19 ] 2 -, [W 10 O 32 ] 4- , WO 4 2- Wait. Among them, the Kojin-type phosphotungstic acid ion α-[PW 12 O 40 ] 3- is preferred.
化合物(I)係以式(I-B)表示之化合物(以下,有稱為化合物(I-B)之情形)為佳。化合物(I)為化合物(I-B)時,具有優異的耐熱性。 Compound (I) is preferably a compound represented by formula (I-B) (hereinafter, sometimes referred to as compound (I-B)). When the compound (I) is the compound (I-B), it has excellent heat resistance.
[式(I-B)中,RN1、RN2、RN3、R1至R8、R101、R102及M係表示與前述相同意思。 [In formula (IB), R N1 , R N2 , R N3 , R 1 to R 8 , R 101 , R 102 and M represent the same meanings as above.
Bh-係表示將選自由鎢、鉬、矽、及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之h價的陰離子。 B h- represents an h-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen as essential elements.
h係表示1至14的整數] h represents an integer from 1 to 14]
式(I-B)中,作為Bh-者,可舉出與式(I)中已舉出作為Ag-之具有鎢、鉬等之g價的陰離子相同者。 In formula (IB), examples of B h- include the same anions having a g-valence of tungsten, molybdenum, or the like already mentioned as A g- in formula (I).
式(I-B)中,較佳的Bh-,可舉出與式(I)中已舉出作為Ag-之將選自由鎢、鉬、矽、及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之g價的陰離子中的較佳者相同者。 In formula (IB), preferred B h- can be mentioned as Ag- in formula (I) and at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus , and g-valent anions containing oxygen as an essential element are preferably the same.
作為化合物(I)者,可舉出表1至10顯示之化 合物或其鹼金屬鹽。 Examples of the compound (I) include the compounds shown in Tables 1 to 10 or alkali metal salts thereof.
又,表1至10中,「Me」係表示甲基,「Et」係表示乙基,「Bu」係表示丁基,「TBu」係表示第三丁基,「Hex」係表示己基,「Oct」係表示辛基,「2EH」係表示2-乙基己基,「CHM」係表示環己基甲基,「CH」係表示環己基,「PH」係表示苯基,「BZ」係表示苯甲基,「NPR」係表示丙基,「IPR」係表示異丙基,「IBu」係表示異丁基,「EOE」係表示-CH2CH2OCH2CH3,「ALL」係表示烯丙基,「HYE」係表示2-羥乙基,「COM」係表示-CO-CH3,「COE」係表示-COO-CH2CH3,「OCM」係表示-OCO-CH3,「OME」係表示-O-CH3,「SOT」係表示甲苯磺醯基,「SNH」係表示-SO2NH-CH2CH(CH2CH3)((CH2)3CH3),「SN2」係表示-SO2N(CH3)((CH2)7CH3),「CNM」係表示-CONHCH3,「CN2」係表示-CON(CH3)C6H5,「NPH」係表示-NHC6H5,「NOT」係表示-N((CH2)7CH3)2,「NCO」係表示-NHCO((CH2)4CH3),「F」係表示氟原子,「Cl」係表示氯原子,「Br」係表示溴原子,「CN」係表示氰基,「NO2」係表示硝基,「SUA」係表示-SO3H,「CBA」係表示-CO2H,「CHO」係表示-CHO,「OCH」係表示-OCOH,「OH」係表示-OH,「SFM」係表示-SO2NH2,「CBM」係表示-CONH2,「NH2」係表示-NH2,「NCH」係表示-NHCOH,「III-1」至「III-6」係表示陰離子(III-1)至陰離子(III-6), 「IV-1」係表示陰離子(IV-1),「V-1」至「V-4」係表示陰離子(V-1)至陰離子(V-4),「VI-1」至「VI-4」係表示陰離子(VI-1)至陰離子(VI-4)。 Also, in Tables 1 to 10, "Me" means a methyl group, "Et" means an ethyl group, "Bu" means a butyl group, "TBu" means a tertiary butyl group, "Hex" means a hexyl group, "Oct" means octyl, "2EH" means 2-ethylhexyl, "CHM" means cyclohexylmethyl, "CH" means cyclohexyl, "PH" means phenyl, "BZ" means benzene Methyl, "NPR" means propyl, "IPR" means isopropyl, "IBu" means isobutyl, "EOE" means -CH 2 CH 2 OCH 2 CH 3 , "ALL" means ene Propyl, "HYE" means 2-hydroxyethyl, "COM" means -CO-CH 3 , "COE" means -COO-CH 2 CH 3 , "OCM" means -OCO-CH 3 , "OME" stands for -O-CH 3 , "SOT" stands for tosyl, "SNH" stands for -SO 2 NH-CH 2 CH(CH 2 CH 3 )((CH 2 ) 3 CH 3 ), "SN2" means -SO 2 N(CH 3 )((CH 2 ) 7 CH 3 ), "CNM" means -CONHCH 3 , "CN2" means -CON(CH 3 ) C 6 H 5 , "NPH""NOT" means -N((CH 2 ) 7 CH 3 ) 2 , " NCO " means -NHCO((CH 2 ) 4 CH 3 ), "F" means fluorine atom , "Cl" means chlorine atom, "Br" means bromine atom, "CN" means cyano group, "NO2" means nitro group, "SUA" means -SO 3 H, "CBA" means -CO 2 H, "CHO" means -CHO, "OCH" means -OCOH, "OH" means -OH, "SFM" means -SO 2 NH 2 , "CBM" means -CONH 2 , "NH2" means -NH 2 , "NCH" means -NHCOH, "III-1" to "III-6" means anion (III-1) to anion (III-6), "IV-1" means anion ( IV-1), "V-1" to "V-4" means anion (V-1) to anion (V-4), "VI-1" to "VI-4" means anion (VI-1 ) to the anion (VI-4).
化合物(I-1)係例如式(I-1)表示之化合物。 Compound (I-1) is, for example, a compound represented by formula (I-1).
從容易合成的觀點而言,係以化合物(I-1)至化合物(I-312)為佳,以化合物(I-1)至化合物(I-156)為較佳,以化合物(I-1)至化合物(I-24)為更佳,以化合物(I-13)至化合物(I-24)為尤佳。 From the viewpoint of easy synthesis, compounds (I-1) to compounds (I-312) are preferred, compounds (I-1) to compounds (I-156) are preferred, compounds (I-1 ) to compound (I-24) are more preferable, and compound (I-13) to compound (I-24) are especially preferable.
其中,本發明的化合物(I)係以化合物(I-14)為特佳。 Among them, compound (I) of the present invention is particularly preferably compound (I-14).
本發明的化合物(I)可藉由使式(II)表示之化合物(以下,有稱為化合物(II)之情形)、與式(II-1)表示之化合物(以下,有稱為化合物(II-1)之情形)反應而得到,而且,亦可藉由使將選自由鎢、矽、及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之化合物對所得到的化合物進一步進行反應來得到。 Compound (I) of the present invention can be obtained by making a compound represented by formula (II) (hereinafter referred to as compound (II)), and a compound represented by formula (II-1) (hereinafter referred to as compound ( The case of II-1)) can be obtained by reacting, and can also be obtained by pairing a compound containing at least one element selected from the group consisting of tungsten, silicon, and phosphorus, and oxygen as an essential element. The compound is further reacted to obtain.
[式(II)及式(II-1)中,R1至R8、RN1、RN2、RN3及g係表示與上述相同意思,A’係表示對上述Ag-供給g個電子者] [In formula (II) and formula (II-1), R 1 to R 8 , R N1 , R N2 , R N3 and g represent the same meanings as above, and A' represents that g electrons are donated to the above-mentioned A g- By]
式(II-1)表示之化合物,可舉出烷基化劑。作為烷基化劑者,可舉出:較佳為碳數1至10、更佳為碳數1至3的鹵化烷基等鹵化烷基(氯化甲烷、溴化甲烷或碘化甲烷等);較佳為碳數2至10、更佳為碳數2至6、又更佳為碳數2至4的碳酸二烷基酯(碳酸二甲酯或碳酸二乙酯等);較佳為碳數1至10、更佳為碳數1至6、又更佳為碳數1至4等的二烷基硫酸(二甲基硫酸或二乙基硫酸等);較佳為碳數2至10、更佳為碳數2至6、又更佳為碳數2至4的烷磺酸烷酯(甲磺酸甲酯、乙磺酸乙酯、甲磺酸乙酯、乙磺酸甲酯、三氟甲磺酸甲酯、三氟甲磺酸乙酯等)。 The compound represented by formula (II-1) includes an alkylating agent. Examples of the alkylating agent include: preferably a halogenated alkyl group having 1 to 10 carbon atoms, more preferably a halogenated alkyl group having 1 to 3 carbon atoms (methane chloride, methyl bromide, or methyl iodide, etc.) ; preferably carbon number 2 to 10, more preferably carbon number 2 to 6, and more preferably carbon number 2 to 4 dialkyl carbonate (dimethyl carbonate or diethyl carbonate, etc.); preferably Dialkyl sulfuric acid (dimethyl sulfuric acid or diethyl sulfuric acid, etc.) with 1 to 10 carbons, more preferably 1 to 6 carbons, and more preferably 1 to 4 carbons; preferably 2 to 2 carbons 10. Alkanesulfonate alkyl esters (methyl methanesulfonate, ethyl ethanesulfonate, ethyl methanesulfonate, methyl ethanesulfonate, more preferably carbon number 2 to 6, more preferably carbon number 2 to 4) , methyl triflate, ethyl triflate, etc.).
前述烷基化劑係以甲基化劑、乙基化劑、丙基化劑、丁 基化劑等為佳,較佳為甲基化劑。 The aforementioned alkylating agent is preferably a methylating agent, an ethylating agent, a propylating agent, a butylating agent, etc., and is preferably a methylating agent.
相對於化合物(II)1莫耳,烷基化劑的使用量係以1莫耳以上且20莫耳以下為佳,較佳為1莫耳以上且10莫耳以下。 The amount of the alkylating agent to be used is preferably not less than 1 mol and not more than 20 mol, more preferably not less than 1 mol and not more than 10 mol, relative to 1 mol of compound (II).
反應溫度係以0至150℃為佳,以10至100℃為較佳。為了使式(I)表示之著色化合物前驅物的溶解性成為充分者,亦可在70至100℃左右預先混合預定有機溶劑。反應時間係以10分鐘至24小時為佳,以1小時至12小時為較佳。 The reaction temperature is preferably from 0 to 150°C, more preferably from 10 to 100°C. In order to make the coloring compound precursor represented by the formula (I) sufficiently soluble, a predetermined organic solvent may be mixed in advance at about 70 to 100°C. The reaction time is preferably from 10 minutes to 24 hours, more preferably from 1 hour to 12 hours.
就產率而言,反應係以在有機溶劑中進行為佳。作為有機溶劑者,可舉出甲苯、二甲苯等芳香族烴溶劑;己烷等脂肪族烴溶劑;氯苯、二氯苯、二氯甲烷、氯仿等鹵化烴溶劑;甲醇、乙醇、異丙醇、丁醇等醇溶劑;硝基苯等硝基烴溶劑;丙酮、甲基異丁基酮等酮溶劑;乙酸乙酯等酯溶劑;二***、四氫呋喃等醚溶劑;乙腈等腈溶劑;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、1-甲基-2-吡咯啶酮等醯胺溶劑等,以芳香族烴溶劑為佳,以甲苯及二甲苯為較佳。相對於化合物(II)1質量份,有機溶劑的使用量係以1質量份以上且300質量份以下為佳,較佳為1質量份以上且100質量份以下。 In terms of yield, the reaction is preferably carried out in an organic solvent. Examples of organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, methylene chloride, and chloroform; methanol, ethanol, and isopropanol nitrobenzene and other nitro hydrocarbon solvents; acetone, methyl isobutyl ketone and other ketone solvents; ethyl acetate and other ester solvents; diethyl ether and tetrahydrofuran and other ether solvents; acetonitrile and other nitrile solvents; N, Amide solvents such as N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, etc., preferably aromatic hydrocarbon solvents, toluene and xylene better. The usage-amount of an organic solvent is 1 mass part or more and 300 mass parts or less with respect to 1 mass part of compound (II), Preferably it is 1 mass part or more and 100 mass parts or less.
從反應混合物取得化合物之方法係沒有特別限定,能夠採用眾所周知的各種手法。例如能夠舉出:將反應混合物過濾,使用例如甲苯等芳香族烴溶劑等溶劑洗淨且將所得到的殘渣乾燥之方法。必要時亦可藉由進一步 使用溶劑而進行再結晶之方法或使用矽凝膠管柱層析法進行精製。所得到的化合物係例如成為式(I)表示之化合物。 The method for obtaining the compound from the reaction mixture is not particularly limited, and various well-known methods can be employed. For example, a method of filtering the reaction mixture, washing with a solvent such as an aromatic hydrocarbon solvent such as toluene, and drying the obtained residue can be mentioned. Purification can also be carried out by a method of further using a solvent to perform recrystallization or using silica gel column chromatography if necessary. The obtained compound is, for example, a compound represented by formula (I).
其次,亦可採用將式(I)表示之化合物的陰離子進行交換之方法,作為該方法者,可舉出添加將選自由鎢、矽、及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之化合物等之方法等。 Next, a method of exchanging the anion of the compound represented by the formula (I) can also be used. As this method, adding at least one element selected from the group consisting of tungsten, silicon, and phosphorus, and oxygen A method, etc., of a compound or the like contained as an essential element.
將選自由鎢、矽、及磷所組成群組之至少1個元素、以及氧作為必要元素而含有之化合物(在本說明書中,以下亦稱為陰離子交換劑),係能夠使用眾所周知慣用的方法來製造,但是亦可直接使用市售品。如此的化合物,例如可舉出對應之異性聚合酸鹽、同素聚合酸鹽、或矽酸鹽、磷酸鹽等,亦可為磷鎢酸、矽鎢酸、磷鉬酸及矽鉬酸等。 A compound containing at least one element selected from the group consisting of tungsten, silicon, and phosphorus, and oxygen as an essential element (in this specification, hereinafter also referred to as an anion exchanger) can be obtained by a well-known and commonly used method. to manufacture, but commercially available products can also be used as they are. Such compounds include, for example, corresponding heterotropic polymeric acid salts, homotropic polymeric acid salts, or silicates, phosphates, etc., and can also be phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, and silicomolybdic acid.
相對於式(I)表示之化合物1莫耳,陰離子交換劑的使用量係以0.01莫耳以上且5莫耳以下為佳,較佳為0.01莫耳以上且1莫耳以下。 The amount of the anion exchanger used is preferably 0.01 mol to 5 mol, more preferably 0.01 mol to 1 mol, relative to 1 mol of the compound represented by formula (I).
反應溫度係以0至150℃為佳,以10至100℃為較佳。反應時間係以10分鐘至36小時為佳,以10分鐘至24小時為較佳。 The reaction temperature is preferably from 0 to 150°C, more preferably from 10 to 100°C. The reaction time is preferably 10 minutes to 36 hours, more preferably 10 minutes to 24 hours.
就產率而言,該反應係以在水、有機溶劑或該等的混合物中進行為佳。作為有機溶劑者,可舉出甲苯、二甲苯等芳香族烴溶劑;己烷等脂肪族烴溶劑;氯苯、二氯苯、二氯甲烷、氯仿等鹵化烴溶劑;甲醇、乙醇、異丙醇、丁醇等醇溶劑;硝基苯等硝基烴溶劑;丙酮、甲基異 丁基酮等酮溶劑;乙酸乙酯等酯溶劑;二***、四氫呋喃等醚溶劑;乙腈等腈溶劑;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、1-甲基-2-吡咯啶酮等醯胺溶劑等。前述反應能夠進行之溶劑,可舉出水、醇溶劑、酮溶劑、醚溶劑、腈溶劑、醯胺溶劑或該等的混合物,較佳可舉出水、醇溶劑、酮溶劑、腈溶劑、醯胺溶劑或該等的混合物,更佳可舉出水、醇溶劑或該等的混合物,特佳可舉出水、甲醇或該等的混合物。 In terms of yield, the reaction is preferably carried out in water, an organic solvent or a mixture thereof. Examples of organic solvents include aromatic hydrocarbon solvents such as toluene and xylene; aliphatic hydrocarbon solvents such as hexane; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, methylene chloride, and chloroform; methanol, ethanol, and isopropanol nitrobenzene and other nitro hydrocarbon solvents; acetone, methyl isobutyl ketone and other ketone solvents; ethyl acetate and other ester solvents; diethyl ether and tetrahydrofuran and other ether solvents; acetonitrile and other nitrile solvents; N, Amide solvents such as N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone, etc. The solvents in which the aforementioned reaction can be carried out include water, alcohol solvents, ketone solvents, ether solvents, nitrile solvents, amide solvents, or mixtures thereof, preferably water, alcohol solvents, ketone solvents, nitrile solvents, and amide solvents. An amine solvent or a mixture thereof, more preferably water, an alcohol solvent or a mixture thereof, particularly preferably water, methanol or a mixture thereof.
相對於式(I)表示之化合物1質量份,有機溶劑的使用量係以1質量份以上且1000質量份以下為佳,較佳為10質量份以上且500質量份以下。 The amount of the organic solvent used is preferably from 1 part by mass to 1000 parts by mass, more preferably from 10 parts by mass to 500 parts by mass, relative to 1 part by mass of the compound represented by formula (I).
採用此種方法時,式(I)表示之化合物的陰離子進行交換時,能夠成為適合耐熱性提升和昇華性減低之化合物。 According to this method, when the anion of the compound represented by the formula (I) is exchanged, it can become a compound suitable for improving the heat resistance and reducing the sublimation property.
化合物(II)係能夠藉由使式(VII)表示之化合物(以下,有稱為化合物(VII)之情形)及式(VIII)表示之化合物(以下,有稱為化合物(VIII)之情形)在鹼的存在下反應來製造。 Compound (II) can be obtained by making a compound represented by formula (VII) (hereinafter referred to as compound (VII)) and a compound represented by formula (VIII) (hereinafter referred to as compound (VIII)) It is produced by reacting in the presence of a base.
[式(VII)及式(VIII)中,R1至R3、R5至R8、RN1及RN2係表示與上述相同意思,R9係表示碳數1至20的烷基] [In formula (VII) and formula (VIII), R 1 to R 3 , R 5 to R 8 , R N1 and R N2 represent the same meaning as above, and R 9 represents an alkyl group with 1 to 20 carbons]
以R9表示之碳數1至20的烷基,可舉出甲 基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基等,較佳可舉出碳數1至6的烷基。 The alkyl group with 1 to 20 carbons represented by R9 can include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, etc., preferably Examples thereof include alkyl groups having 1 to 6 carbon atoms.
作為鹼者,可舉出三乙胺、哌啶等有機鹼,相對於化合物(VII)1莫耳,其使用量通常為0.05至20莫耳。 Examples of the base include organic bases such as triethylamine and piperidine, and the amount used is usually 0.05 to 20 moles relative to 1 mole of compound (VII).
相對於化合物(II)1莫耳,化合物(VIII)的使用量通常為1至10莫耳,較佳為1至4莫耳。 Compound (VIII) is usually used in an amount of 1 to 10 mol, preferably 1 to 4 mol, relative to 1 mol of compound (II).
化合物(VII)與化合物(VIII)之反應,通常在溶劑的存在下實施,作為該溶劑者,可舉出乙腈等腈溶劑,甲醇、乙醇、2-丙醇、1-丁醇、1-戊醇、1-辛醇等醇溶劑,四氫呋喃等醚溶劑,丙酮等酮溶劑,乙酸乙酯等酯溶劑,己烷等脂肪族烴溶劑,甲苯等芳香族烴溶劑,二氯甲烷、氯仿等鹵化烴溶劑,及N,N-二甲基甲醛、N-甲基吡咯啶酮等醯胺溶劑,較佳為腈溶劑、醇溶劑及芳香族烴溶劑,較佳可舉出乙腈、甲醇及甲苯。相對於化合物(VII)1質量份,其使用量通常為1至100質量份。 The reaction between compound (VII) and compound (VIII) is usually carried out in the presence of a solvent, and examples of the solvent include nitrile solvents such as acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, etc. Alcohol solvents such as alcohol and 1-octanol, ether solvents such as tetrahydrofuran, ketone solvents such as acetone, ester solvents such as ethyl acetate, aliphatic hydrocarbon solvents such as hexane, aromatic hydrocarbon solvents such as toluene, halogenated hydrocarbons such as methylene chloride and chloroform The solvent, and amide solvents such as N,N-dimethylformaldehyde and N-methylpyrrolidone, are preferably nitrile solvents, alcohol solvents, and aromatic hydrocarbon solvents, and preferably include acetonitrile, methanol, and toluene. The amount used is usually 1 to 100 parts by mass relative to 1 part by mass of compound (VII).
反應溫度通常為0至200℃,較佳為0至150℃。反應時間通常為0.5至36小時。 The reaction temperature is usually 0 to 200°C, preferably 0 to 150°C. The reaction time is usually 0.5 to 36 hours.
反應結束後,係例如藉由將化合物(II)不容易溶解的溶劑與所得到的反應混合物進行混合且過濾,而能夠將化合物(II)取出。必要時亦可進一步使用溶劑而進行再結晶之方法或使用矽凝膠管柱層析法來進行精製。 After completion of the reaction, the compound (II) can be taken out, for example, by mixing the obtained reaction mixture with a solvent in which the compound (II) is not easily soluble, and filtering. If necessary, the method of recrystallization using a solvent or the purification using silica gel column chromatography may also be used.
化合物(VII),能夠藉由使式(IX)表示之化合物(以下,有稱為化合物(IX)之情形)與式(X)表示之化合物(以下,有稱為化合物(X)之情形)在溶劑中反應來製造。 Compound (VII) can be obtained by making a compound represented by formula (IX) (hereinafter referred to as compound (IX)) and a compound represented by formula (X) (hereinafter referred to as compound (X)) React in a solvent to manufacture.
[式(IX)及式(X)中,R5至R9係表示與上述相同意思,R10係表示碳數1至4的烷基] [In formula (IX) and formula (X), R 5 to R 9 represent the same meaning as above, and R 10 represents an alkyl group with 1 to 4 carbons]
以R10表示之碳數1至4的烷基,可舉出甲基、乙基、丙基及丁基。 The alkyl group having 1 to 4 carbon atoms represented by R 10 includes methyl group, ethyl group, propyl group and butyl group.
相對於化合物(IX)1莫耳,化合物(X)的使用量通常為1至5莫耳,較佳為1至3莫耳。 Compound (X) is usually used in an amount of 1 to 5 mol, preferably 1 to 3 mol, relative to 1 mol of compound (IX).
作為溶劑者,可舉出甲醇等醇溶劑,相對於化合物(IX)1質量份,其使用量通常為1至200質量份。 As a solvent, alcohol solvents, such as methanol, are mentioned, and the usage-amount is 1-200 mass parts normally with respect to 1 mass part of compound (IX).
反應溫度通常為-20至100℃,反應時間通常為1至72小時。 The reaction temperature is usually -20 to 100°C, and the reaction time is usually 1 to 72 hours.
反應結束後,例如能夠視需要而將反應混合物與水或甲醇混合之後,藉由過濾而將化合物(VII)取出。又,反應結束後,例如亦能夠視需要而將反應混合物與水混合之後,藉由使用乙酸乙酯等不溶於水的有機溶劑進行萃取且將得到的有機層進行濃縮,而將化合物(VII)取出。必要時亦可進一步使用溶劑而進行再結晶之方法或使用矽凝膠管柱層析法而進行精製。 After completion of the reaction, the compound (VII) can be taken out by filtration, for example, after mixing the reaction mixture with water or methanol if necessary. In addition, after the reaction is completed, for example, the reaction mixture can be mixed with water if necessary, and the compound (VII) can be extracted by using a water-insoluble organic solvent such as ethyl acetate and concentrating the obtained organic layer. take out. If necessary, it may further be purified by recrystallization using a solvent or by silica gel column chromatography.
化合物(X),例如能夠依據J.Med.Chem.2012,55,3398-3413記載的方法等眾所周知的方法而製造。 Compound (X) can be produced according to known methods such as the method described in J. Med. Chem. 2012, 55, 3398-3413, for example.
本發明的著色組成物亦可含有2種以上的化 合物(I)。化合物(I)能夠視需要而與化合物(I)以外的染料或顏料(著色劑A1)同時使用來作為著色劑(A)。 The coloring composition of the present invention may contain two or more compounds (I). The compound (I) can be used as a coloring agent (A) together with dyes or pigments (coloring agent A1) other than a compound (I) as needed.
本發明的著色組成物,係含有前述化合物(1)、以及樹脂(B)及溶劑(E)的至少一方,以含有前述化合物(1)、以及樹脂(B)及溶劑(E)之雙方為佳。 The coloring composition of the present invention contains at least one of the aforementioned compound (1), resin (B) and solvent (E), or contains both of the aforementioned compound (1), resin (B) and solvent (E). good.
樹脂(B)係以鹼可溶性樹脂為佳,以具有源自選自由不飽和羧酸及不飽和羧酸酐所組成群組之至少1種單體(a)(以下有稱為「(a)」之情形)的結構單元之聚合物為較佳。 The resin (B) is preferably an alkali-soluble resin having at least one monomer (a) (hereinafter referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. case) polymers of structural units are preferred.
樹脂(B)係以具有源自具有碳數2至4的環狀醚結構與乙烯性不飽和鍵之單體(b)(以下有稱為「(b)」之情形)之結構單元、及其它結構單元之共聚物為佳。 The resin (B) is composed of a structural unit derived from a monomer (b) (hereinafter referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and Copolymers of other structural units are preferred.
作為其它結構單元者,可舉出源自能夠與單體(a)共聚合的單體(c)(但是與單體(a)及單體(b)為不同。以下有稱為「(c)」之情形)之結構單元、具有乙烯性不飽和鍵之結構單元等。 As other structural units, monomers (c) derived from monomers (a) copolymerizable (but different from monomers (a) and monomers (b). Hereinafter referred to as "(c) )" in the case of), a structural unit having an ethylenically unsaturated bond, etc.
作為(a)者,例如可舉出丙烯酸、甲基丙烯酸、巴豆酸及鄰-、間-、對-乙烯基苯甲酸等不飽和單羧酸;順丁烯二酸、反丁烯二酸、檸康酸、中康酸、伊康酸、3-乙烯基鄰苯二甲酸、4-乙烯基鄰苯二甲酸、3,4,5,6-四氫鄰苯二甲酸、1,2,3,6-四氫鄰苯二甲酸、二甲基四氫鄰苯二甲酸及1,4-環己烯二羧酸等不飽和二羧酸;甲基-5-降莰烯-2,3-二羧酸、5-羧基雙環[2.2.1]庚-2- 烯、5,6-二羧基雙環[2.2.1]庚-2-烯、5-羧甲基雙環[2.2.1]庚-2-烯及5-羧乙基雙環[2.2.1]庚-2-烯等含有羧基之雙環不飽和化合物;將反丁烯二酸及中康酸除外之上述不飽和二羧酸的酐等羧酸酐;琥珀酸單[2-(甲基)丙烯醯氧基乙基]及鄰苯二甲酸單[2-(甲基)丙烯醯氧基乙基]等二元以上的多元羧酸的不飽和單[(甲基)丙烯醯氧基烷基]酯類;如α-(羥甲基)丙烯酸等在相同分子中含有羥基及羧基之不飽和丙烯酸酯類等。 Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, ortho-, meta-, and p-vinylbenzoic acid; maleic acid, fumaric acid, Citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3 , unsaturated dicarboxylic acids such as 6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3- Dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxymethylbicyclo[2.2.1]hept-2-ene Bicyclic unsaturated compounds containing carboxyl groups, such as 2-ene and 5-carboxyethylbicyclo[2.2.1]hept-2-ene; anhydrides of the above-mentioned unsaturated dicarboxylic acids, excluding fumaric acid and mesaconic acid, etc. Carboxylic acid anhydrides; polycarboxylic acids with more than two valences, such as succinic acid mono[2-(meth)acryloxyethyl] and phthalic acid mono[2-(meth)acryloxyethyl], etc. Saturated mono[(meth)acryloxyalkyl] esters; unsaturated acrylates such as α-(hydroxymethyl)acrylic acid containing hydroxyl and carboxyl groups in the same molecule, etc.
該等之中,就共聚合反應性之點、所得到的樹脂對鹼水溶液的溶解性之點而言,係以丙烯酸、甲基丙烯酸及順丁烯二酸酐等為佳。 Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable in terms of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution.
(b)係指具有碳數2至4的環狀醚結構(例如,選自由環氧乙烷環、氧雜環丁烷環及四氫呋喃環所組成群組之至少1種)及乙烯性不飽和鍵之聚合性化合物。(b)係以具有碳數2至4的環狀醚及(甲基)丙烯醯基氧基之單體為佳。 (b) refers to a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and ethylenically unsaturated bonded polymeric compounds. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.
作為(b)者,例如可舉出具有環氧乙烷基及乙烯性不飽和鍵之單體(b1)(以下有稱為「(b1)」之情形)、具有氧雜環丁烷基及乙烯性不飽和鍵之單體(b2)(以下有稱為「(b2)」之情形)、以及具有四氫呋喃基及乙烯性不飽和鍵之單體(b3)(以下有稱為「(b3)」之情形)等。 Examples of (b) include monomers (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter referred to as "(b1)"), monomers having an oxetane group and Monomer (b2) having an ethylenically unsaturated bond (hereinafter referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "(b3) ” situation) and so on.
作為(b1)者,例如可舉出具有直鏈狀或分枝 鏈狀脂肪族不飽和烴被環氧化而成的構造之單體(b1-1)(以下有稱為「(b1-1)」之情形)、及具有脂環式不飽和烴被環氧化而成的構造之單體(b1-2)(以下有稱為「(b1-2)」之情形)。 Examples of (b1) include monomers (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(b1-1) "), and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "(b1-2)").
作為(b1-1)者,係以具有環氧丙基及乙烯性不飽和鍵之單體為佳。作為(b1-1)者,具體而言,可舉出(甲基)丙烯酸環氧丙基酯、(甲基)丙烯酸β-甲基環氧丙基酯、(甲基)丙烯酸β-乙基環氧丙基酯、環氧丙基乙烯醚、乙烯基苯甲基環氧丙基醚、α-甲基乙烯基苯甲基環氧丙基醚、2,3-雙(環氧丙氧基甲基)苯乙烯、2,4-雙(環氧丙氧基甲基)苯乙烯、2,5-雙(環氧丙氧基甲基)苯乙烯、2,6-雙(環氧丙氧基甲基)苯乙烯、2,3,4-參(環氧丙氧基甲基)苯乙烯、2,3,5-參(環氧丙氧基甲基)苯乙烯、2,3,6-參(環氧丙氧基甲基)苯乙烯、3,4,5-參(環氧丙氧基甲基)苯乙烯及2,4,6-參(環氧丙氧基甲基)苯乙烯等。 (b1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. Examples of (b1-1) specifically include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethyl (meth)acrylate Glycidyl ester, glycidyl vinyl ether, vinylbenzyl glycidyl ether, α-methylvinylbenzyl glycidyl ether, 2,3-bis(glycidoxypropoxy Methyl)styrene, 2,4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxypropoxy methyl) styrene, 2,3,4-paraffin (glycidoxymethyl) styrene, 2,3,5-paraffin (glycidoxymethyl) styrene, 2,3,6 -Phenol(glycidoxymethyl)styrene, 3,4,5-paraffin(glycidoxymethyl)styrene and 2,4,6-paraffin(glycidoxymethyl)benzene vinyl etc.
作為(b1-2)者,可舉出乙烯基環己烯單氧化物、1,2-環氧基-4-乙烯基環己烷(例如,CELLOXIDE(註冊商標)2000;Daicel(股)製)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如,CYCLOMER(註冊商標)A400;Daicel(股)製)、(甲基)丙烯酸3,4-環氧基環己基甲酯(例如,CYCLOMER(註冊商標)M100;Daicel(股)製)、式(BI)表示之化合物及式(BII)表示之化合物等。 Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE (registered trademark) 2000; manufactured by Daicel Co., Ltd. ), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMER (registered trademark) A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate Esters (eg, CYCLOMER (registered trademark) M100; manufactured by Daicel Co., Ltd.), compounds represented by formula (BI), compounds represented by formula (BII), and the like.
[式(BI)及式(BII)中,Ra及Rb係互相獨立地表示氫原子、或碳數1至4的烷基,該烷基所含有的氫原子可被羥基取代。 [In the formulas (BI) and (BII), R a and R b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted by a hydroxyl group.
Xa及Xb係互相獨立地表示單鍵、*-Rc-、*-Rc-O-、*-Rc-S-或*-Rc-NH-。 X a and X b independently represent a single bond, *-R c -, *-R c -O-, *-R c -S- or *-R c -NH-.
Rc係表示碳數1至6的烷二基。 R c represents an alkanediyl group having 1 to 6 carbon atoms.
*係表示與O的連結鍵]。 * represents the connection key with O].
式(BI)表示之化合物,可舉出式(BI-1)至式(BI-15)的任一者所表示之化合物等,較佳可舉出式(BI-1)、式(BI-3)、式(BI-5)、式(BI-7)、式(BI-9)及式(BI-11)至式(BI-15)表示之化合物,更佳可舉出式(BI-1)、式(BI-7)、式(BI-9)及式(BI-15)表示之化合物。 The compound represented by formula (BI) can include compounds represented by any one of formula (BI-1) to formula (BI-15), preferably formula (BI-1), formula (BI- 3), the compound represented by formula (BI-5), formula (BI-7), formula (BI-9) and formula (BI-11) to formula (BI-15), more preferably formula (BI- 1), compounds represented by formula (BI-7), formula (BI-9) and formula (BI-15).
式(BII)表示之化合物,可舉出式(BII-1)至式(BII-15)的任一者表示之化合物等,較佳可舉出式(BII-1)、式(BII-3)、式(BII-5)、式(BII-7)、式(BII-9)及式(BII-11)至式(BII-15)表示之化合物,更佳可舉出式(BII-1)、式(BII-7)、式(BII-9)及式(BII-15)表示之化合物。 The compound represented by formula (BII) may include compounds represented by any one of formula (BII-1) to formula (BII-15), preferably formula (BII-1), formula (BII-3 ), formula (BII-5), formula (BII-7), formula (BII-9) and formula (BII-11) to the compound represented by formula (BII-15), more preferably formula (BII-1 ), compounds represented by formula (BII-7), formula (BII-9) and formula (BII-15).
式(BI)表示之化合物及式(BII)表示之化合物係可各自單獨使用,亦可併用式(BI)表示之化合物及式(BII)表示之化合物。併用該等時,式(BI)表示之化合物及式(BII)表示之化合物的含有比率就莫耳基準而言係以5:95至95:5為佳,較佳為10:90至90:10,更佳為20:80至80:20。 The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone, or the compound represented by the formula (BI) and the compound represented by the formula (BII) may be used in combination. When these are used together, the content ratio of the compound represented by formula (BI) and the compound represented by formula (BII) is preferably 5:95 to 95:5 on a molar basis, preferably 10:90 to 90: 10, preferably 20:80 to 80:20.
作為(c)者,例如可舉出(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸第二丁酯、(甲基)丙烯酸第三丁酯、(甲基)丙烯酸2-乙基己酯、(甲基)丙烯酸十二酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸 硬脂酯、(甲基)丙烯酸環戊酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-8-基酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-9-基酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-基酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-9-基酯、(甲基)丙烯酸二環戊基氧基乙酯、(甲基)丙烯酸異莰酯、(甲基)丙烯酸金剛烷酯、(甲基)丙烯酸烯丙酯、(甲基)丙烯酸炔丙酯、(甲基)丙烯酸苯酯、(甲基)丙烯酸萘酯及(甲基)丙烯酸苯甲酯等(甲基)丙烯酸酯;(甲基)丙烯酸2-羥基乙酯及(甲基)丙烯酸2-羥基丙酯等含羥基之(甲基)丙烯酸酯;順丁烯二酸二乙酯、反丁烯二酸二乙酯及伊康酸二乙酯等二羧酸二酯;雙環[2.2.1]庚-2-烯、5-甲基雙環[2.2.1]庚-2-烯、5-乙基雙環[2.2.1]庚-2-烯、5-羥基雙環[2.2.1]庚-2-烯、5-羥甲基雙環[2.2.1]庚-2-烯、5-(2’-羥乙基)雙環[2.2.1]庚-2-烯、5-甲氧基雙環[2.2.1]庚-2-烯、5-乙氧基雙環[2.2.1]庚-2-烯、5,6-二羥基雙環[2.2.1]庚-2-烯、5,6-二(羥甲基)雙環[2.2.1]庚-2-烯、5,6-二(2’-羥乙基)雙環[2.2.1]庚-2-烯、5,6-二甲氧基雙環[2.2.1]庚-2-烯、5,6-二乙氧基雙環[2.2.1]庚-2-烯、5-羥基-5-甲基雙環[2.2.1]庚-2-烯、5-羥基-5-乙基雙環[2.2.1]庚-2-烯、5-羥甲基-5-甲基雙環[2.2.1]庚-2-烯、5-第三丁氧羰基雙環[2.2.1]庚-2-烯、5-環己氧羰基雙環[2.2.1]庚-2-烯、5-苯氧羰基雙環[2.2.1]庚-2-烯、5,6-雙(第三丁氧羰基)雙環[2.2.1]庚-2-烯及5,6-雙(環己氧羰基)雙環[2.2.1]庚-2-烯等雙環不飽和化合物; N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯甲基順丁烯二醯亞胺、N-琥珀醯亞胺基-3-順丁烯二醯亞胺苯甲酸酯、N-琥珀醯亞胺基-4-順丁烯二醯亞胺丁酸酯、N-琥珀醯亞胺基-6-順丁烯二醯亞胺己酸酯、N-琥珀醯亞胺基-3-順丁烯二醯亞胺丙酸酯及N-(9-吖啶基)順丁烯二醯亞胺等二羰基醯亞胺衍生物;苯乙烯、α-甲基苯乙烯、乙烯基甲苯及對甲氧基苯乙烯等含乙烯基的芳香族化合物;(甲基)丙烯腈等含乙烯基的腈;氯乙烯及偏二氯乙烯等鹵化烴;(甲基)丙烯醯胺等含乙烯基的醯胺;乙酸乙烯酯等酯;1,3-丁二烯、異戊二烯及2,3-二甲基-1,3-丁二烯等二烯等。 Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second-butyl (meth)acrylate, (meth)acrylic acid Tertiary butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate Tricyclo[5.2.1.0 2,6 ]decane-8-yl (meth)acrylate, Tricyclo[5.2.1.0 2,6 ]decane-9-yl (meth)acrylate, (meth)acrylate base) tricyclo[5.2.1.0 2,6 ]decen-8-yl acrylate, tricyclo[5.2.1.0 2,6 ]decen-9-yl (meth)acrylate, di(meth)acrylate Cyclopentyloxyethyl ester, Isocamphoryl (meth)acrylate, Adamantyl (meth)acrylate, Allyl (meth)acrylate, Propargyl (meth)acrylate, Benzene (meth)acrylate (meth)acrylic acid esters such as naphthyl (meth)acrylate and benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate containing hydroxyl groups (meth)acrylic esters; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; bicyclo[2.2.1]hept-2-ene , 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5- Hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept- 2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo [2.2.1] Hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1] Hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy- 5-Ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1 ]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(third Butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylbutadiene Diene imide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzine Ester, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-cis-butyl Dicarbonyl amides such as olefinic imide caproate, N-succinimidyl-3-maleimide propionate, and N-(9-acridyl)maleimide Imine derivatives; vinyl-containing aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl-containing nitriles such as (meth)acrylonitrile; vinyl chloride and Halogenated hydrocarbons such as vinylidene chloride; vinyl-containing amides such as (meth)acrylamide; esters such as vinyl acetate; 1,3-butadiene, isoprene and 2,3-dimethyl- Dienes such as 1,3-butadiene, etc.
該等之中,就共聚合反應性及耐熱性之點而言,係以苯乙烯、乙烯基甲苯、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-8-基酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烷-9-基酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-8-基酯、(甲基)丙烯酸三環[5.2.1.02,6]癸烯-9-基酯、N-苯基順丁烯二醯亞胺、N-環己基順丁烯二醯亞胺、N-苯甲基順丁烯二醯亞胺、雙環[2.2.1]庚-2-烯及(甲基)丙烯酸苯甲酯等為佳。 Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyl toluene, tricyclo[5.2.1.0 2,6 ]decane-8-yl (meth)acrylate, Tricyclo[5.2.1.0 2,6 ]decane-9-yl (meth)acrylate, Tricyclo[5.2.1.0 2,6 ]decen-8-yl (meth)acrylate, (methyl) Tricyclo[5.2.1.0 2,6 ]decen-9-yl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide Preferred are alkene imide, bicyclo[2.2.1]hept-2-ene, and benzyl (meth)acrylate.
具有乙烯性不飽和鍵之結構單元,較佳是具有(甲基)丙烯醯基之結構單元。具有此種結構單元之樹脂,係能夠藉由使在能夠與(a)、(b)所具有的基反應之基具有乙烯性不飽和鍵的單體,附加在具有源自(a)、(b)的結構單元之聚合物而得到。 The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth)acryloyl group. The resin having such a structural unit can be added to a monomer having an ethylenically unsaturated bond in a group derived from (a), ( The polymer of the structural unit of b) is obtained.
作為此種結構單元者,可舉出:使(甲基)丙烯酸環氧 丙酯附加在(甲基)丙烯酸單元而成之結構單元、使(甲基)丙烯酸2-羥基乙酯附加在順丁烯二酸酐單元而成之結構單元、及使(甲基)丙烯酸附加在(甲基)丙烯酸環氧丙酯單元而成之結構單元等。又,該等結構單元具有羥基時,亦可舉出進一步附加羧酸酐而成之結構單元作為具有乙烯性不飽和鍵之結構單元。 Examples of such structural units include: a structural unit in which glycidyl (meth)acrylate is added to a (meth)acrylic acid unit; 2-hydroxyethyl (meth)acrylate is added to cis-butyl Structural units formed by alkene anhydride units, and structural units formed by adding (meth)acrylic acid to glycidyl (meth)acrylate units, etc. Moreover, when these structural units have a hydroxyl group, the structural unit which further added carboxylic anhydride can also be mentioned as a structural unit which has an ethylenically unsaturated bond.
具有源自(a)的結構單元之聚合物,例如能夠藉由在聚合起始劑的存在下,將構成聚合物的結構單元之單體在溶劑中進行聚合來製造。聚合起始劑及溶劑等係沒有特別限定,能夠使用在該領域通常被使用之物。例如,作為聚合起始劑者,可舉出偶氮化合物(2,2’-偶氮雙異丁腈、2,2’-偶氮雙(2,4-二甲基戊腈)等)、有機過氧化物(過氧化苯甲醯等),作為溶劑者,只要係將各單體溶解者即可。 The polymer having the structural unit derived from (a) can be produced, for example, by polymerizing monomers constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, solvent, and the like are not particularly limited, and those commonly used in this field can be used. For example, examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), The organic peroxide (benzoyl peroxide, etc.) may be used as a solvent as long as it dissolves each monomer.
又,所得到的聚合物,可直接使用反應後的溶液,亦可使用濃縮或稀釋後的溶液,亦可使用藉由再沈澱等方法而以固體(粉體)的形式取出之物。 In addition, the obtained polymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be taken out as a solid (powder) by reprecipitation or the like.
亦可視需要而使用羧酸或羧酸酐及環狀醚的反應觸媒(例如參(二甲基胺甲基)苯酚等)及聚合抑制劑(例如氫醌等)等。 Reaction catalysts (for example, ginseng(dimethylaminomethyl)phenol, etc.), polymerization inhibitors (for example, hydroquinone, etc.) and the like of carboxylic acids, carboxylic acid anhydrides, and cyclic ethers can also be used as needed.
作為羧酸酐者,可舉出順丁烯二酸酐、檸康酸酐、伊康酸酐、3-乙烯基鄰苯二甲酸酐、4-乙烯基鄰苯二甲酸酐、3,4,5,6-四氫鄰苯二甲酸酐、1,2,3,6-四氫鄰苯二甲酸酐、二甲基四氫鄰苯二甲酸酐及5,6-二羧基雙環[2.2.1]庚-2-烯酐等。 Examples of carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6- Tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2 -Alkenic anhydride, etc.
作為樹脂(B)者,具體而言可舉出(甲基)丙烯酸3,4-環氧基環己基甲酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸環氧丙酯/(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸環氧丙酯/苯乙烯/(甲基)丙烯酸共聚物、(甲基)丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/(甲基)丙烯酸/N-環己基順丁烯二醯亞胺共聚物、(甲基)丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/(甲基)丙烯酸/N-環己基順丁烯二醯亞胺/(甲基)丙烯酸2-羥基乙酯共聚物、(甲基)丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/(甲基)丙烯酸/乙烯基甲苯共聚物、(甲基)丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/(甲基)丙烯酸/(甲基)丙烯酸2-乙基己酯共聚物、(甲基)丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/(甲基)丙烯酸三環[5.2.1.02,6]癸烯酯/(甲基)丙烯酸/N-環己基順丁烯二醯亞胺共聚物、3-甲基-3-(甲基)丙烯醯氧基甲基氧雜環丁烷/(甲基)丙烯酸/苯乙烯共聚物、(甲基)丙烯酸苯甲酯/(甲基)丙烯酸共聚物、苯乙烯/(甲基)丙烯酸共聚物以及日本特開平9-106071號公報、日本特開2004-29518號公報及日本特開2004-361455號公報的各公報記載之樹脂等。 Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxy (meth)acrylate Tricyclo[5.2.1.0 2,6 ]decyl ester/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (meth)acrylic acid copolymer, base) glycidyl acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate/(meth)acrylic acid/ N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylcis Butenediimide/2-Hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate/(meth)acrylate /vinyl toluene copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate/(meth)acrylic acid/2-ethylhexyl (meth)acrylate copolymer 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate/tricyclo[5.2.1.0 2,6 ]decenyl (meth)acrylate/(methyl) Acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3-(meth)acryloxymethyloxetane/(meth)acrylic acid/styrene copolymer, Benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, Japanese Patent Application Laid-Open No. 9-106071, Japanese Patent Application Laid-Open No. 2004-29518 and Japanese Patent Application Laid-Open No. 2004 - Resins, etc., described in the publications of Publication No. 361455.
其中,樹脂(B)係以含有源自(a)的結構單元及源自(b)的結構單元之共聚物為佳。 Among them, the resin (B) is preferably a copolymer containing a structural unit derived from (a) and a structural unit derived from (b).
樹脂(B)亦可組合2種以上,此時,樹脂(B)係以至少含有選自由(甲基)丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/(甲基)丙烯酸共聚物、(甲基)丙烯酸3,4-環氧基三環 [5.2.1.02,6]癸酯/(甲基)丙烯酸/N-環己基順丁烯二醯亞胺/(甲基)丙烯酸2-羥基乙酯共聚物、(甲基)丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/(甲基)丙烯酸/乙烯基甲苯共聚物、及(甲基)丙烯酸3,4-環氧基三環[5.2.1.02,6]癸酯/(甲基)丙烯酸/(甲基)丙烯酸2-乙基己酯共聚物之1種以上為佳。 Resin (B) can also combine two or more types. At this time, resin (B) is based on at least containing (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl ester/( Meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexylmaleimide/ 2-Hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate/(meth)acrylic acid/vinyltoluene copolymer, And one or more of 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl (meth)acrylate/(meth)acrylic acid/2-ethylhexyl (meth)acrylate copolymer is good.
樹脂(B)的聚苯乙烯換算之重量平均分子量(Mw),係以3,000至100,000為佳,較佳為5,000至50,000,更佳為5,000至30,000。樹脂(B)的分散度[重量平均分子量(Mw)/數量平均分子量(Mn)]係以1.1至6為佳,較佳為1.2至4。 The polystyrene-equivalent weight average molecular weight (Mw) of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, more preferably 5,000 to 30,000. The dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.
樹脂(B)的酸價(固體成分換算值),係以10至300mg-KOH/g為佳,較佳為20至250mg-KOH/g,更佳為30至200mg-KOH/g。在此,酸價係作為將樹脂(B)1g中和所需要的氫氧化鉀之量(mg)而測定之值,例如能夠藉由使用氫氧化鉀水溶液進行滴定來求取。 The acid value (solid content conversion value) of the resin (B) is preferably 10 to 300 mg-KOH/g, more preferably 20 to 250 mg-KOH/g, more preferably 30 to 200 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.
著色組成物中,相對於固體成分的總量,樹脂(B)的含有率係以3至99質量%為佳,較佳為5至99質量%,更佳為7至95質量%。 In the coloring composition, the content of the resin (B) is preferably 3 to 99% by mass, more preferably 5 to 99% by mass, more preferably 7 to 95% by mass, based on the total amount of solid content.
溶劑(E),例如可舉出酯溶劑(在分子內含有-COO-且不含有-O-之溶劑)、醚溶劑(在分子內含有-O-且不含有-COO-之溶劑)、醚酯溶劑(在分子內含有-COO-及-O-之溶劑)、酮溶劑(在分子內含有-CO-且不含有-COO-之溶劑)、醇溶劑 (在分子內含有OH且不含有-O-、-CO-及-COO-之溶劑)、芳香族烴溶劑、醯胺溶劑及二甲基亞碸等。 Examples of the solvent (E) include ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecule), ether solvents Ester solvents (solvents that contain -COO- and -O- in the molecule), ketone solvents (solvents that contain -CO- and do not contain -COO- in the molecule), alcohol solvents (solvents that contain OH in the molecule and do not contain - O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfide, etc.
作為酯溶劑者,可舉出乳酸甲酯、乳酸乙酯、乳酸丁酯、2-羥基異丁酸甲酯、乙酸乙酯、乙酸正丁基、乙酸異丁酯、甲酸戊酯、甲酸異戊酯、丙酸丁酯、丁酸異丙基、丁酸乙酯、丁酸丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸丙酯、乙醯乙酸甲酯、乙醯乙酸乙酯、環己醇乙酸酯及γ-丁內酯等。 Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isopentyl formate ester, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetyl acetate, ethyl acetyl acetate, Cyclohexanol acetate and γ-butyrolactone, etc.
作為醚溶劑者,可舉出乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丁醚、丙二醇單甲醚、丙二醇單***、丙二醇單丙醚、丙二醇單丁醚、3-甲氧基-1-丁醇、3-甲氧基-3-甲基丁醇、四氫呋喃、四氫吡喃、1,4-二烷、二乙二醇二甲醚、二乙二醇二***、二乙二醇甲基乙基醚、二乙二醇二丙醚、二乙二醇二丁醚、苯甲醚、苯***及甲基苯甲醚等。 Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol , tetrahydrofuran, tetrahydropyran, 1,4-two alkanes, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl anisole etc.
作為醚酯溶劑溶劑者,可舉出甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-甲氧基-2-甲基丙酸甲酯、2-乙氧基-2-甲基丙酸乙酯、乙酸3-甲氧基丁酯、乙酸3-甲基-3-甲氧基丁酯、丙二醇單甲醚乙酸酯、丙二醇單***乙酸 酯、丙二醇單丙醚乙酸酯、乙二醇單甲醚乙酸酯、乙二醇單***乙酸酯、二乙二醇單***乙酸酯、二乙二醇單丁醚乙酸酯及二丙二醇甲醚乙酸酯等。 Examples of ether ester solvents include methyl methoxy acetate, ethyl methoxy acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, Propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Methyl 2-methoxy-2-methylpropionate, 2-Ethoxy-2-methyl propionate ethyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Ester, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate And dipropylene glycol methyl ether acetate, etc.
作為酮溶劑者,可舉出4-羥基-4-甲基-2-戊酮、丙酮、2-丁酮、2-庚酮、3-庚酮、4-庚酮、4-甲基-2-戊酮、環戊酮、環己酮及異佛爾酮等。 Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2 -Pentanone, cyclopentanone, cyclohexanone, isophorone, etc.
作為醇溶劑者,可舉出甲醇、乙醇、丙醇、丁醇、己醇、環己醇、乙二醇、丙二醇及甘油等。 Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.
作為芳香族烴溶劑者,可舉出苯、甲苯、二甲苯及均三甲苯(mesitylene)等。 Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.
作為醯胺溶劑者,可舉出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。 Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.
該等溶劑亦可併用2種以上。 These solvents may use 2 or more types together.
相對於著色組成物的總量,溶劑(E)的含有率係以40至99質量%為佳,較佳為50至95質量%。 The content of the solvent (E) is preferably 40 to 99% by mass, more preferably 50 to 95% by mass relative to the total amount of the coloring composition.
在本發明的著色組成物中,化合物(I)係以分散在溶劑(E)為佳。 In the coloring composition of the present invention, compound (I) is preferably dispersed in solvent (E).
化合物(I)可視需要而施行松香(rosin)處理、使用導入有酸性基或鹼性基的衍生物等之表面處理、使用高分子化合物等而對化合物(I)表面進行之接枝處理、使用硫酸微粒化法等而進行之微粒化處理、為了將不純物除去而使用有機溶劑、水等而進行之洗淨處理、使用離子性不純物的離子交換法等而進行之除去處理等。化合物(I)的粒徑係以大略均一為佳。化合物(I)係藉由使其含有分散劑進 行分散處理,化合物(I)能夠成為在分散液之中均勻地分散之狀態。 Compound (I) may be subjected to rosin treatment, surface treatment using a derivative having an acidic group or a basic group, etc., grafting treatment on the surface of Compound (I) using a polymer compound, etc. Micronization treatment by sulfuric acid micronization method, etc., cleaning treatment using organic solvent, water, etc. to remove impurities, removal treatment by ion exchange method using ionic impurities, etc. The particle size of the compound (I) is preferably approximately uniform. The compound (I) is dispersed by adding a dispersant, and the compound (I) can be uniformly dispersed in the dispersion liquid.
作為分散劑者,可舉出界面活性劑等,可為陽離子系、陰離子系、非離子系及兩性的任一種界面活性劑。具體而言,可舉出聚酯系、多元胺系及丙烯酸系等的界面活性劑等。該等分散劑係可單獨使用或將二種以上組合而使用。作為分散劑者,以商品名表示時,能夠舉出KP(信越化學工業(股)製)、FLOWLEN(共榮社化學(股)製)、SOLSPERSE(註冊商標)(ZENECA(股)製)、EFKA(註冊商標)(BASF(股)製)、AJISPER(註冊商標)(Ajinomoto Fine-Techno(股)製)、Disperbyk(註冊商標)(BYK-Chemie(股)製)、BYK(註冊商標)(BYK-Chemie(股)製)等。 Examples of the dispersant include surfactants and the like, and any of cationic, anionic, nonionic, and amphoteric surfactants may be used. Specifically, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants are exemplified. These dispersants may be used alone or in combination of two or more. As a dispersant, when expressed by a trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (registered trademark) (manufactured by ZENECA Co., Ltd.), EFKA (registered trademark) (BASF Co., Ltd.), AJISPER (registered trademark) (Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (BYK-Chemie Co., Ltd.), BYK (registered trademark) ( BYK-Chemie (stock) system), etc.
使用分散劑時,相對於化合物(I)100質量份,分散劑(固體成分)的使用量係以300質量份以下為佳,較佳為5質量份以上且100質量份以下。分散劑的使用量為前述範圍時,有能夠得到較均勻的分散狀態的著色組成物之傾向。 When using a dispersant, the usage-amount of a dispersant (solid content) is 300 mass parts or less with respect to 100 mass parts of compound (I), Preferably it is 5 mass parts or more and 100 mass parts or less. When the usage-amount of a dispersing agent is the said range, it exists in the tendency for the coloring composition in a relatively uniform dispersion state to be obtained.
著色組成物中的化合物(I)的含有率,在著色組成物的總量中,通常為0.1至60質量%,以0.5至50質量%為佳,較佳為1至40質量%。 The content of the compound (I) in the coloring composition is usually 0.1 to 60% by mass, preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on the total amount of the coloring composition.
著色組成物中,相對於著色組成物的固體成分的總量,化合物(I)的含有率通常為1質量%以上且90質量%以下,以1質量%以上且80質量%以下為佳,較佳為2質量%以上且75質量%以下。 In the coloring composition, the content of the compound (I) is usually 1% by mass to 90% by mass, preferably 1% by mass to 80% by mass, with respect to the total amount of solids in the coloring composition, preferably Preferably, it is not less than 2% by mass and not more than 75% by mass.
本發明的著色組成物,亦可含有化合物(I)以外的著色劑(以下,有稱為著色劑(A1)之情形)。著色劑(A1)可含有1種或2種以上的著色劑。著色劑(A1)係以含有黃色著色劑、橙色著色劑或紅色著色劑為佳。 The coloring composition of the present invention may contain coloring agents other than the compound (I) (hereinafter, sometimes referred to as coloring agent (A1)). The coloring agent (A1) may contain 1 type or 2 or more types of coloring agents. The coloring agent (A1) preferably contains a yellow coloring agent, an orange coloring agent or a red coloring agent.
著色劑(A1)可為染料亦可為顏料。作為染料者,能夠使用眾所周知的染料,可舉出色指數(The Society of Dyers and Colourists出版)及染色筆記(色染社)所記載的染料。依照化學結構時,可舉出偶氮染料、蒽醌染料、三苯基甲烷染料、二苯并哌喃染料及酞花青染料等。該等染料可單獨使用、或組合2種以上而使用。 The coloring agent (A1) may be a dye or a pigment. As the dye, well-known dyes can be used, and dyes described in Color Index (published by The Society of Dyers and Colourists) and Dyeing Notes (Yorsensha) are exemplified. In terms of chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran dyes, phthalocyanine dyes, and the like can be mentioned. These dyes can be used individually or in combination of 2 or more types.
具體而言,可舉出如以下的色指數(C.I.)號碼的染料。C.I.溶劑黃14、15、23、24、25、38、62、63、68、79、81、82、83、89、94、98、99、162;C.I.酸性黃1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251;C.I.反應性黃2、76、116;C.I.直接黃2、4、28、33、34、35、38、39、43、44、 47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、132、136、138、141;C.I.分散黃51、54、76;C.I.溶劑橙2、7、11、15、26、41、54、56、99;C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、149、162、169、173;C.I.反應性橙16;C.I.直接橙26、34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107;C.I.溶劑紅24、49、90、91、111、118、119、122、124、125、127、130、132、143、145、146、150、151、155、160、168、169、172、175、181、207、218、222、227、230、245、247;C.I.酸性紅52、73、80、91、92、97、138、151、211、274、289;C.I.酸性紫34、102;C.I.分散紫26、27;C.I.溶劑紫11、13、14、26、31、36、37、38、45、47、48、51、59、60;C.I.溶劑藍14、18、35、36、45、58、59、59:1、63、68、69、78、79、83、94、97、98、100、101、102、104、105、111、112、122、128、132、136、139;C.I.酸性藍25、27、40、45、78、80、112; C.I.直接藍40;C.I.分散藍1、14、56、60;C.I.溶劑綠1、3、5、28、29、32、33;C.I.酸性綠3、5、9、25、27、28、41;C.I.鹼性綠1;C.I.還原綠(vat green)1等。 Specifically, dyes with the following color index (C.I.) numbers are exemplified. C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Reactive Yellow 2, 76, 116; , 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109 , 129, 132, 136, 138, 141; C.I. Disperse Yellow 51, 54, 76; C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99; C.I. Acid Orange 6, 7, 8, 10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,149,162,169,173; C.I. Reactive Orange 16; C.I. Direct Orange 26 , 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; C.I. Acid Red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289; C.I. Acid Violet 34, 102; C.I. Disperse Violet 26, 27; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78 , 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Acid Blue 25, 27, 40, 45, 78, 80, 112; C.I. Direct Blue 40; C.I. Disperse Blue 1, 14, 56, 60; C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33; C.I. acid green 3, 5, 9, 25, 27, 28, 41; C.I. basic green 1; C.I. vat green 1, etc.
作為顏料者,能夠使用眾所周知的顏料,例如可舉出在色指數(The Society of Dyers and Colourists出版)中被分類為顏料之顏料。能夠將該等單獨使用、或組合2種以上而使用。 As the pigment, well-known pigments can be used, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists). These can be used individually or in combination of 2 or more types.
具體而言,可舉出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、129、137、138、139、147、148、150、153、154、166、173、185、194、214等黃色顏料;C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橙色顏料;C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、179、180、192、209、215、216、224、242、254、255、264、265、266、268、269、273等紅色顏料;C.I.顏料藍15、15:3、15:4、15:6、60等青色顏料;C.I.顏料紫1、19、23、29、32、36、38等紫色顏料;C.I.顏料綠7、36、58、59等綠色顏料。 Specifically, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273 and other red pigments; C.I. pigment blue 15, 15:3, 15:4, 15:6, 60 and other cyan pigments ; C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C.I. Pigment Green 7, 36, 58, 59 and other green pigments.
著色劑(A1)係以含有選自黃色著色劑、橙色著色劑及紅色著色劑之1種以上的著色劑為佳。 The coloring agent (A1) preferably contains at least one coloring agent selected from a yellow coloring agent, an orange coloring agent, and a red coloring agent.
黃色著色劑可選自下列之中:上述的C.I.溶劑黃14、15、23、24、25、38、62、63、68、79、81、82、83、89、94、98、99、162;C.I.酸性黃1、3、7、9、11、17、23、25、29、34、36、38、40、42、54、65、72、73、76、79、98、99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、212、214、220、221、228、230、232、235、238、240、242、243、251;C.I.反應性黃2、76、116;C.I.直接黃2、4、28、33、34、35、38、39、43、44、47、50、54、58、68、69、70、71、86、93、94、95、98、102、108、109、129、132、136、138、141;C.I.分散黃51、54、76等黃色染料;及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、129、137、138、139、147、148、150、153、154、166、173、185、194、214等黃色顏料。 The yellow colorant may be selected from among the following: C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162 mentioned above ; 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Reaction Sexual Yellow 2, 76, 116; C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93 , 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; C.I. Disperse Yellow 51, 54, 76 and other yellow dyes; and C.I. Pigment Yellow 1, 3, 12, 13, 14, 15 ,16,17,20,24,31,53,83,86,93,94,109,110,117,125,128,129,137,138,139,147,148,150,153,154,166 , 173, 185, 194, 214 and other yellow pigments.
黃色著色劑,係以黃色染料及黃色顏料為佳,以黃色顏料為較佳,以喹啉黃(quinophthalone)黃色顏料、含金屬的黃色顏料及異吲哚啉黃色顏料為更佳,以C.I.顏料黃129、138、139、150、185為特佳。 The yellow coloring agent is preferably yellow dye and yellow pigment, preferably yellow pigment, more preferably quinophthalone yellow pigment, metal-containing yellow pigment and isoindoline yellow pigment, and C.I. pigment Yellow 129, 138, 139, 150, 185 are especially good.
橙色著色劑可選自下列之中:上述的C.I.溶劑橙2、7、11、15、26、41、54、56、99; C.I.酸性橙6、7、8、10、12、26、50、51、52、56、62、63、64、74、75、94、95、107、108、149、162、169、173;C.I.反應性橙16;C.I.直接橙26、34、39、41、46、50、52、56、57、61、64、65、68、70、96、97、106、107等橙色染料;及C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73等橙色顏料。 The orange colorant may be selected from among the following: C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99 mentioned above; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; C.I. Reactive Orange 16; C.I. Direct Orange 26, 34, 39, 41, 46 , 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107 and other orange dyes; and C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments.
橙色著色劑,係以橙色染料及橙色顏料為佳,以橙色顏料為較佳,以C.I.顏料橙13、31、36、38、40、42、43、51、55、59、61、64、65、71、73為更佳。 Orange colorant, orange dye and orange pigment are preferred, orange pigment is preferred, C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 , 71, 73 are better.
紅色著色劑可選自下列之中:上述的C.I.溶劑紅24、49、90、91、111、118、119、122、124、125、127、130、132、143、145、146、150、151、155、160、168、169、172、175、181、207、218、222、227、230、245、247;C.I.酸性紅52、73、80、91、92、97、138、151、211、274、289等紅色染料;及C.I.顏料紅9、97、105、122、123、144、149、166、168、176、177、179、180、192、209、215、216、224、242、254、255、264、265、266、268、269、273等紅色顏料。 The red colorant may be selected from among the following: C.I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151 , 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; C.I. Acid Red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289 and other red dyes; and C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209, 215, 216, 224, 242, 254 , 255, 264, 265, 266, 268, 269, 273 and other red pigments.
紅色著色劑,係以紅色染料及紅色顏料為佳,以偶氮染料、蒽醌染料、三苯基甲烷染料、二苯并哌喃染料、苝染料、偶氮顏料、二酮吡咯并吡咯顏料、蒽醌顏料、二苯并哌喃顏料、苝顏料為較佳,以C.I.酸性紅52、C.I.顏料 紅144、177、179、242、254、269為更佳。 The red coloring agent is preferably red dyes and red pigments, such as azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopyran dyes, perylene dyes, azo pigments, diketopyrrolopyrrole pigments, Anthraquinone pigments, dibenzopyran pigments, and perylene pigments are preferred, and C.I. Acid Red 52, C.I. Pigment Red 144, 177, 179, 242, 254, and 269 are more preferred.
又,作為黃色著色劑、橙色著色劑或紅色著色劑,亦可使用日本特開2013-235257號公報所記載的二苯并哌喃化合物等。 Moreover, the dibenzopyran compound etc. which are described in Unexamined-Japanese-Patent No. 2013-235257 can also be used as a yellow coloring agent, an orange coloring agent, or a red coloring agent.
本發明的著色組成物含有著色劑(A1)及溶劑(E)時,可預先調製含有著色劑(A1)及溶劑(E)之著色劑(A1)含有液之後,使用該著色劑(A1)含有液而調製著色組成物。著色劑(A1)不溶解在溶劑(E)時,著色劑(A1)含有液能夠藉由使著色劑(A1)分散在溶劑(E)並混合而調製。著色劑(A1)含有液可含有著色組成物所含有的溶劑(E)的一部分或全部。 When the coloring composition of the present invention contains the coloring agent (A1) and the solvent (E), the coloring agent (A1) can be used after preparing a coloring agent (A1) containing liquid containing the coloring agent (A1) and the solvent (E) in advance. A coloring composition is prepared by containing a liquid. When the coloring agent (A1) is not dissolved in the solvent (E), the coloring agent (A1)-containing liquid can be prepared by dispersing and mixing the coloring agent (A1) in the solvent (E). The liquid containing the coloring agent (A1) may contain part or all of the solvent (E) contained in the coloring composition.
本發明的著色組成物,係以藉由將式(I)表示之化合物、樹脂、溶劑(E)、含有著色劑(A1)及溶劑(E)之著色劑(A1)含有液進行混合來製造為佳。前述製造方法,係以使用珠磨機等將式(I)表示之化合物、樹脂、溶劑(E)進行混合而調製著色組成物,而且將所得到的著色組成物與含有著色劑(A1)及溶劑(E)之著色劑(A1)含有液進行混合之方法為佳。 The coloring composition of the present invention is produced by mixing a compound represented by formula (I), a resin, a solvent (E), a coloring agent (A1) containing liquid containing a coloring agent (A1) and a solvent (E) better. The aforementioned production method is to prepare a colored composition by mixing a compound represented by formula (I), a resin, and a solvent (E) using a bead mill, etc., and mix the obtained colored composition with a colorant (A1) and The method of mixing the coloring agent (A1) containing solution of the solvent (E) is preferable.
著色劑(A1)亦可視需要而施行松香處理、使用導入有酸性基或鹼性基之著色劑衍生物等之表面處理、使用高分子化合物等而對著色劑(A1)表面進行之接枝處理、使用硫酸微粒化法等而進行之微粒化處理、為了將不純物除去而使用有機溶劑、水等而進行之洗淨處理、使用離子性不純物的離子交換法等而進行之除去處理等。著色 劑(A1)的粒徑係以大略均一為佳。著色劑(A1)係能夠藉由含有分散劑進行分散處理,著色劑(A1)成為均勻地分散在著色劑(A1)含有液之中之狀態。著色劑(A1)可各自單獨進行分散處理,亦可將複數種混合而進行分散處理。 The colorant (A1) may also be subjected to rosin treatment, surface treatment using a colorant derivative having an acidic or basic group introduced therein, or grafting treatment on the surface of the colorant (A1) using a polymer compound, etc. , Micronization treatment using sulfuric acid micronization method, etc., cleaning treatment using organic solvents, water, etc. to remove impurities, removal treatment using ion exchange method, etc. for ionic impurities, etc. The particle size of the coloring agent (A1) is preferably roughly uniform. The colorant (A1) can be dispersed by containing a dispersant, and the colorant (A1) is in a state of being uniformly dispersed in the colorant (A1)-containing liquid. The coloring agent (A1) may be dispersed individually, or may be mixed and dispersed in plural.
作為分散劑者,可舉出界面活性劑等,且可為陽離子系、陰離子系、非離子系及兩性的任一種界面活性劑。具體而言,可舉出聚酯系、多元胺系及丙烯酸系等的界面活性劑等。該等分散劑可單獨使用或組合二種以上而使用。作為分散劑者,以商品名表示時,可舉出KP(信越化學工業(股)製)、FLOWLEN(共榮社化學(股)製)、SOLSPERSE(註冊商標)(ZENECA(股)製)、EFKA(註冊商標)(BASF(股)製)、AJISPER(註冊商標)(Ajinomoto Fine-Techno(股)製)、Disperbyk(註冊商標)(BYK-Chemie(股)製)、BYK(註冊商標)(BYK-Chemie(股)製)等。 Examples of the dispersant include surfactants and the like, and may be any of cationic, anionic, nonionic, and amphoteric surfactants. Specifically, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants are exemplified. These dispersants can be used individually or in combination of 2 or more types. As dispersants, when expressed by trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLOWLEN (manufactured by Kyoeisha Chemical Co., Ltd.), SOLSPERSE (registered trademark) (manufactured by ZENECA Co., Ltd.), EFKA (registered trademark) (BASF Co., Ltd.), AJISPER (registered trademark) (Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (BYK-Chemie Co., Ltd.), BYK (registered trademark) ( BYK-Chemie (stock) system), etc.
為了調製前述著色劑(A1)含有液而使用分散劑時,相對於著色劑(A1)100質量份,該分散劑(固體成分)的使用量係以300質量份以下為佳,較佳為5質量份以上且100質量份以下。該分散劑的使用量為前述範圍時,有能夠得到較均勻的分散狀態的著色劑(A1)含有液之傾向。 When a dispersant is used to prepare the liquid containing the colorant (A1), the amount of the dispersant (solid content) used is preferably 300 parts by mass or less, preferably 5 parts by mass, per 100 parts by mass of the colorant (A1). More than 100 parts by mass and less than or equal to 100 parts by mass. When the usage-amount of this dispersing agent is the said range, there exists a tendency for the coloring agent (A1) containing liquid in a relatively uniform dispersion state to be obtained.
著色劑(A1)含有液中的著色劑(A1)之含有率,在著色劑(A1)含有液的總量中,通常為0.1至60質量%,以0.5至50質量%為佳,較佳為1至40質量%。 The content of the coloring agent (A1) in the coloring agent (A1) containing liquid is usually 0.1 to 60% by mass, preferably 0.5 to 50% by mass in the total amount of the coloring agent (A1) containing liquid, more preferably 1 to 40% by mass.
著色劑(A1)含有液中,相對於固體成分的總量,著色劑(A1)的含有率通常為1質量%以上且90質量% 以下,以1質量%以上且80質量%以下為佳,較佳為2質量%以上且75質量%以下。 In the liquid containing the coloring agent (A1), the content of the coloring agent (A1) is usually 1% by mass to 90% by mass, preferably 1% by mass to 80% by mass, based on the total amount of solid content. Preferably it is 2 mass % or more and 75 mass % or less.
預先調製含有著色劑(A1)及溶劑(E)之著色劑(A1)含有液之後,使用該著色劑(A1)含有液而調製本發明的著色組成物時,著色劑(A1)含有液可預先含有著色組成物所含有的樹脂(B)的一部分或全部,較佳為一部分。藉由預先含有樹脂(B),能夠進一步改善著色劑(A1)含有液的分散安定性。 When preparing the coloring agent (A1)-containing liquid containing the coloring agent (A1) and the solvent (E) in advance, and then using the coloring agent (A1)-containing liquid to prepare the coloring composition of the present invention, the coloring agent (A1)-containing liquid may be A part or all of the resin (B) contained in a coloring composition is contained beforehand, Preferably it is a part. By containing the resin (B) in advance, the dispersion stability of the colorant (A1)-containing liquid can be further improved.
相對於著色劑(A1)100質量份,著色劑(A1)含有液中的樹脂(B)含量係例如1至500質量份,以5至200質量份為佳,較佳為10至100質量份。 The content of the resin (B) in the colorant (A1)-containing liquid is, for example, 1 to 500 parts by mass, preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass relative to 100 parts by mass of the colorant (A1). .
著色組成物中,相對於固體成分的總量,將化合物(I)及著色劑(A1)合在一起之著色劑(A)的含有率,通常為1質量%以上且90質量%以下,以1質量%以上且80質量%以下為佳,較佳為2質量%以上且75質量%以下。 In the coloring composition, the content rate of the coloring agent (A) that combines the compound (I) and the coloring agent (A1) with respect to the total amount of solid content is usually 1% by mass or more and 90% by mass or less. It is preferably at least 1% by mass and at most 80% by mass, more preferably at least 2% by mass and at most 75% by mass.
在著色劑(A)的總量中,化合物(I)的含有率通常為0.001質量%以上,以0.003質量%以上為佳,較佳為0.005質量%以上,上限為100質量%以下,以99.999質量%以下為佳,較佳為99.997質量%以下。 The content of the compound (I) in the total amount of the colorant (A) is usually at least 0.001% by mass, preferably at least 0.003% by mass, more preferably at least 0.005% by mass, and the upper limit is 100% by mass or less, preferably 99.999% by mass. It is preferably at most mass %, more preferably at most 99.997 mass %.
含有著色劑(A1)時,相對於化合物(I)100質量份,著色劑(A1)的含量係以0.1質量份以上為佳,以0.5質量份以上為較佳,以1質量份以上為更佳,以10000質量份以下為佳,以5000質量份以下為較佳。 When the colorant (A1) is contained, the content of the colorant (A1) is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, and more preferably at least 1 part by mass, relative to 100 parts by mass of the compound (I). Better, preferably less than 10,000 parts by mass, more preferably less than 5,000 parts by mass.
本發明的著色硬化性組成物係含有化合物 (I)、樹脂(B)及溶劑(E)兩者中的至少一者以及聚合性化合物(C)。 The colored curable composition of the present invention contains a compound (I), at least one of a resin (B) and a solvent (E), and a polymerizable compound (C).
聚合性化合物(C)係能夠藉由從聚合起始劑(D)所產生的活性自由基及/或酸而聚合的化合物,例如聚合性之具有乙烯性不飽和鍵的化合物等,較佳為(甲基)丙烯酸酯化合物。 The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D), such as a polymerizable compound having an ethylenically unsaturated bond, etc., preferably (meth)acrylate compounds.
具有1個乙烯性不飽和鍵之聚合性化合物,例如可舉出壬基苯基卡必醇丙烯酸酯、丙烯酸2-羥基-3-苯氧基丙酯、2-乙基己基卡必醇丙烯酸酯、丙烯酸2-羥基乙酯、N-乙烯基吡咯啶酮等,以及上述的單體(a)、單體(b)及單體(c)。 Polymerizable compounds having one ethylenically unsaturated bond, for example, nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate , 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., and the above-mentioned monomer (a), monomer (b) and monomer (c).
具有2個乙烯性不飽和鍵之聚合性化合物,例如可舉出1,6-己二醇二(甲基)丙烯酸酯、乙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三乙二醇二(甲基)丙烯酸酯、雙酚A的雙(丙烯醯氧基乙基)醚及3-甲基戊二醇二(甲基)丙烯酸酯等。 Polymerizable compounds having two ethylenically unsaturated bonds, for example, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, base) acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A and 3-methylpentanediol di(meth)acrylate, etc.
其中,聚合性化合物(C)係以具有3個以上的乙烯性不飽和鍵之聚合性化合物為佳。此種聚合性化合物,例如可舉出三羥甲基丙烷三(甲基)丙烯酸酯、新戊四醇三(甲基)丙烯酸酯、新戊四醇四(甲基)丙烯酸酯、二新戊四醇五(甲基)丙烯酸酯、二新戊四醇六(甲基)丙烯酸酯、三新戊四醇八(甲基)丙烯酸酯、三新戊四醇七(甲基)丙烯酸 酯、四新戊四醇十(甲基)丙烯酸酯、四新戊四醇九(甲基)丙烯酸酯、參(2-(甲基)丙烯醯氧基乙基)異三聚氰酸酯、乙二醇改性新戊四醇四(甲基)丙烯酸酯、乙二醇改性二新戊四醇六(甲基)丙烯酸酯、丙二醇改性新戊四醇四(甲基)丙烯酸酯、丙二醇改性二新戊四醇六(甲基)丙烯酸酯、己內酯改性新戊四醇四(甲基)丙烯酸酯及己內酯改性二新戊四醇六(甲基)丙烯酸酯等,較佳可舉出二新戊四醇五(甲基)丙烯酸酯及二新戊四醇六(甲基)丙烯酸酯。 Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Such polymerizable compounds include, for example, trimethylolpropane tri(meth)acrylate, neopentylthritol tri(meth)acrylate, neopentylthritol tetra(meth)acrylate, dipentyl Tetrol Penta(meth)acrylate, Di-Neopentylthritol Hexa(Meth)acrylate, Tri-Neopentylthritol Octa(Meth)acrylate, Tri-Neopentylthritol Hepta(Meth)acrylate, Four Neopentylthritol deca(meth)acrylate, tetraneopentylthritol nona(meth)acrylate, ginseng(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol Modified Neopentylthritol Tetra(Meth)acrylate, Ethylene Glycol Modified Di-Neopentylthritol Hexa(Meth)acrylate, Propylene Glycol Modified Neopentylthritol Tetra(Meth)acrylate, Propylene Glycol Modified Dineopentaerythritol hexa(meth)acrylate, caprolactone-modified neopentylthritol tetra(meth)acrylate and caprolactone-modified dipenteoerythritol hexa(meth)acrylate, etc., compared with Preferable examples include diperythritol penta(meth)acrylate and dipenteoerythritol hexa(meth)acrylate.
聚合性化合物(C)的重量平均分子量係以150以上且2,900以下為佳,較佳為250以上且1,500以下。 The weight average molecular weight of the polymerizable compound (C) is preferably not less than 150 and not more than 2,900, more preferably not less than 250 and not more than 1,500.
在著色硬化性組成物中,相對於固體成分的總量,聚合性化合物(C)的含有率係以1至65質量%為佳,以3至60質量%為較佳,以5至55質量%為更佳。 In the colored curable composition, the content of the polymerizable compound (C) is preferably 1 to 65% by mass, more preferably 3 to 60% by mass, and 5 to 55% by mass relative to the total amount of solid content. % is better.
本發明的著色硬化性組成物亦可含有聚合起始劑(D)。 The curable colored composition of the present invention may also contain a polymerization initiator (D).
聚合起始劑(D),只要為能夠藉由光、熱的作用而產生活性自由基、酸等且使聚合開始之化合物,就沒有特別限定,能夠使用眾所周知的聚合起始劑。 The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc. by the action of light or heat to initiate polymerization, and well-known polymerization initiators can be used.
作為聚合起始劑(D)者,可舉出O-醯基肟化合物、烷基苯酮(alkylphenone)化合物、雙咪唑(biimidazole)化合物、三化合物及醯基氧化膦化合物等。 Examples of the polymerization initiator (D) include O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, three Compounds and acyl phosphine oxide compounds, etc.
作為O-醯基肟化合物者,例如可舉出N-苯甲 醯氧基-1-(4-苯硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯硫基苯基)辛烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-(4-苯硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-(4-苯硫基苯基)-3-環己基丙烷-1-酮-2-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-{2-甲基-4-(3,3-二甲基-2,4-二氧雜環戊基甲氧基)苯甲醯基}-9H-咔唑-3-基]乙烷-1-亞胺、N-乙醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-亞胺及N-苯甲醯氧基-1-[9-乙基-6-(2-甲基苯甲醯基)-9H-咔唑-3-基]-3-環戊基丙烷-1-酮-2-亞胺等。又,作為O-醯基肟化合物者,亦可使用IRGACURE OXE01、OXE02(以上,BASF(股)製)及N-1919(ADEKA(股)公司製)等市售品。其中,O-醯基肟化合物,係以選自由N-苯甲醯氧基-1-(4-苯硫基苯基)丁烷-1-酮-2-亞胺、N-苯甲醯氧基-1-(4-苯硫基苯基)辛烷-1-酮-2-亞胺及N-苯甲醯氧基-1-(4-苯硫基苯基)-3-環戊基丙烷-1-酮-2-亞胺所組成群組之至少1種為佳,以N-苯甲醯氧基-1-(4-苯硫基苯基)辛烷-1-酮-2-亞胺為較佳。 Examples of O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzoyloxy Base-1-(4-phenylthiophenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentyl Propan-1-one-2-imine, N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetyl Oxy-1-(4-phenylthiophenyl)-3-cyclohexylpropane-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2- Methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4- (3,3-Dimethyl-2,4-dioxolylmethoxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyl Oxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine and N-benzyl Acyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine Wait. Moreover, as an O-acyl oxime compound, commercial items, such as IRGACURE OXE01 and OXE02 (above, manufactured by BASF Co., Ltd.), and N-1919 (made by ADEKA Co., Ltd.) can also be used. Among them, the O-acyl oxime compound is selected from N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy 1-(4-phenylthiophenyl)octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentyl Preferably at least one of the group consisting of propan-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2- Imines are preferred.
作為烷基苯酮化合物者,可舉出2-甲基-2-嗎啉基-1-(4-甲基硫基苯基)丙烷-1-酮、2-二甲胺基-1-(4-嗎啉基苯基)-2-苯甲基丁烷-1-酮及2-(二甲胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-嗎啉基)苯基]丁烷-1-酮等。作為烷基苯酮化合物者,亦可使用IRGACURE 369、907、379(以上, BASF公司製)等市售品。 As the alkylphenone compound, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-( 4-morpholinophenyl)-2-benzylbutan-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4- (4-morpholinyl)phenyl]butan-1-one, etc. As the alkylphenone compound, commercial items such as IRGACURE 369, 907, and 379 (the above, manufactured by BASF Corporation) can also be used.
作為烷基苯酮化合物者,亦可舉出2-羥基-2-甲基-1-苯基丙烷-1-酮、2-羥基-2-甲基-1-[4-(2-羥乙氧基)苯基]丙烷-1-酮、1-羥基環己基苯基酮、2-羥基-2-甲基-1-(4-異丙烯基苯基)丙烷-1-酮的寡聚物、α,α-二乙氧基苯乙酮及苯甲基二甲縮酮。 As the alkyl phenone compound, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethyl Oligomers of oxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one , α,α-diethoxyacetophenone and benzyl dimethyl ketal.
作為雙咪唑化合物者,例如可舉出2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2,3-二氯苯基)-4,4’,5,5’-四苯基雙咪唑(例如,參照日本特開平6-75372號公報、日本特開平6-75373號公報等)、2,2’-雙(2-氯苯基)-4,4’,5,5’-四苯基雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(烷氧基苯基)雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(二烷氧基苯基)雙咪唑、2,2’-雙(2-氯苯基)-4,4’,5,5’-四(三烷氧基苯基)雙咪唑(例如,參照日本特公昭48-38403號公報、日本特開昭62-174204號公報等)及4,4’,5,5’-位置的苯基被烷氧羰基(carboalkoxy)取代之咪唑化合物(例如,參照日本特開平7-10913號公報等)等。 Examples of bisimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2,3 -dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to JP-A-6-75372, JP-A-6-75373, etc.), 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'- Tetrakis(alkoxyphenyl)bisimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)bisimidazole, 2,2 '-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62 -174204, etc.) and imidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted by carboalkoxy (for example, refer to JP-A-7-10913, etc.), etc.
作為三化合物者,可舉出2,4-雙(三氯甲基)-6-(4-甲氧基苯基)-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(5-甲基呋喃-2-基)乙烯基]-1,3,5-三、2,4-雙(三氯甲基)-6-[2-(呋喃-2-基)乙烯基]-13,5-三、2,4-雙(三氯甲基)-6-[2-(4-二乙胺基-2-甲基 苯基)乙烯基]-1,3,5-三及2,4-雙(三氯甲基)-6-[2-(3,4-二甲氧基苯基)乙烯基]-1,3,5-三等。 as three Compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-tri , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-13,5-tri , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-tri And 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-tri Wait.
作為醯基氧化膦化合物者,可舉出2,4,6-三甲基苯甲醯基二苯基氧化膦等。 Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like.
而且作為聚合起始劑(D)者,可舉出苯偶姻、苯偶姻甲醚、苯偶姻***、苯偶姻異丙基醚、苯偶姻異丁醚等苯偶姻化合物;二苯基酮、鄰苯甲醯基苯甲酸甲酯、4-苯基二苯基酮、4-苯甲醯基-4’-甲基二苯基硫醚、3,3’,4,4’-四(第三丁基過氧羰基)二苯基酮及2,4,6-三甲基二苯基酮等二苯基酮化合物;9,10-菲醌、2-乙基蒽醌及樟腦醌等醌化合物;10-丁基-2-氯吖啶酮、二苯基乙二酮(benzil)、苯基乙醛酸甲酯及二茂鈦化合物等。 And as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether can be enumerated; Phenyl ketone, methyl o-benzoyl benzoate, 4-phenyl diphenyl ketone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4' - Diphenyl ketone compounds such as tetrakis(tert-butylperoxycarbonyl) diphenyl ketone and 2,4,6-trimethyl diphenyl ketone; 9,10-phenanthrenequinone, 2-ethylanthraquinone and Quinone compounds such as camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate and titanocene compounds, etc.
該等係以與後述的聚合起始助劑(D1)(特別是胺類)組合而使用為佳。 These are preferably used in combination with a polymerization initiation aid (D1) (especially amines) described later.
聚合起始劑(D)較佳是含有選自由烷基苯酮化合物、三化合物、醯基氧化膦化合物、O-醯基肟化合物及雙咪唑化合物所組成群組的至少一種之聚合起始劑,較佳是含有O-醯基肟化合物之聚合起始劑。 The polymerization initiator (D) preferably contains a compound selected from the group consisting of alkyl phenone compounds, three The polymerization initiator is at least one kind of compound, an acyl phosphine oxide compound, an O-acyl oxime compound, and a bisimidazole compound, preferably a polymerization initiator containing an O-acyl oxime compound.
著色硬化性組成物中的固體成分之總量中,聚合起始劑(D)的含有率係以0.001至40質量%為佳,較佳為0.01至30質量%。 The content of the polymerization initiator (D) is preferably from 0.001 to 40% by mass, more preferably from 0.01 to 30% by mass, in the total amount of solids in the colored curable composition.
本發明的著色硬化性組成物亦可含有聚合起始助劑(D1)。 The colored curable composition of the present invention may also contain a polymerization initiation aid (D1).
聚合起始助劑(D1),係為了促進藉由聚合起始劑而使聚合開始之聚合性化合物的聚合而使用之化合物、或敏化劑。含有聚合起始助劑(D1)時,通常係與聚合起始劑(D)組合而使用。 The polymerization initiation aid (D1) is a compound or a sensitizer used to accelerate the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator. When a polymerization start aid (D1) is contained, it is usually used in combination with a polymerization start agent (D).
作為聚合起始助劑(D1)者,可舉出胺化合物、烷氧基蒽化合物、硫雜蒽酮(thioxanthone)化合物及羧酸化合物等。 Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone (thioxanthone) compounds, and carboxylic acid compounds.
作為胺化合物者,可舉出三乙醇胺、甲基二乙醇胺、三異丙醇胺、4-二甲基胺基苯甲酸甲酯、4-二甲基胺基苯甲酸乙酯、4-二甲基胺基苯甲酸異戊酯、苯甲酸2-二甲基胺基乙酯、4-二甲基胺基苯甲酸2-乙基己酯、N,N-二甲基對甲苯胺、4,4’-雙(二甲基胺基)二苯基酮(通稱米其勒酮)、4,4’-雙(二乙基胺基)二苯基酮及4,4’-雙(乙基甲基胺基)二苯基酮等,較佳為4,4’-雙(二乙基胺基)二苯基酮。又,作為胺化合物者,亦可使用EAB-F(保土谷化學工業(股)製)等市售品。 Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)diphenyl ketone (commonly known as Michelle's ketone), 4,4'-bis(diethylamino)diphenyl ketone and 4,4'-bis(ethyl methylamino) diphenyl ketone, etc., preferably 4,4'-bis(diethylamino) diphenyl ketone. Moreover, as an amine compound, a commercial item, such as EAB-F (made by Hodogaya Chemical Industry Co., Ltd.), can also be used.
作為烷氧基蒽化合物者,可舉出9,10-二甲氧基蒽、2-乙基-9,10-二甲氧基蒽、9,10-二乙氧基蒽、2-乙基-9,10-二乙氧基蒽、9,10-二丁氧基蒽及2-乙基-9,10-二丁氧基蒽等。 Examples of alkoxyanthracene compounds include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene, etc.
作為硫雜蒽酮化合物者,可舉出2-異丙基硫雜蒽酮、4-異丙基硫雜蒽酮、2,4-二乙基硫雜蒽酮、2,4-二氯硫雜蒽酮及1-氯-4-丙氧基硫雜蒽酮等。 Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, Xanthone and 1-chloro-4-propoxythioxanthone, etc.
作為羧酸化合物者,可舉出苯硫基乙酸、甲 基苯硫基乙酸、乙基苯硫基乙酸、甲基乙基苯硫基乙酸、二甲基苯硫基乙酸、甲氧基苯硫基乙酸、二甲氧基苯硫基乙酸、氯苯硫基乙酸、二氯苯硫基乙酸、N-苯基甘胺酸、苯氧基乙酸、萘基硫乙酸、N-萘基甘胺酸及萘氧基乙酸等。 Examples of carboxylic acid compounds include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, and Glycolic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine And naphthyloxyacetic acid, etc.
使用該等聚合起始助劑(D1)時,著色硬化性組成物中的固體成分之總量中,聚合起始助劑(D1)的含有率係以0.001至30質量%為佳,較佳為0.01至20質量%。 When these polymerization initiation aids (D1) are used, the content of the polymerization initiation aid (D1) in the total amount of solids in the colored curable composition is preferably 0.001 to 30% by mass, more preferably 0.01 to 20% by mass.
本發明的著色組成物亦可進一步含有調平劑(F)及抗氧化劑。 The coloring composition of the present invention may further contain a leveling agent (F) and an antioxidant.
調平劑(F),可舉出矽酮系界面活性劑、氟系界面活性劑及具有氟原子的矽酮系界面活性劑等。該等亦可在側鏈具有聚合性基。 The leveling agent (F) includes silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having fluorine atoms, and the like. These may have a polymeric group in a side chain.
作為矽酮系界面活性劑者,可舉出在分子內具有矽氧烷鍵之界面活性劑等。具體而言,可舉出Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH8400(TORAY.DOW CORNING(股)製),KP321、KP322、KP323、KP324、KP326、KP340、KP341(信越化學工業(股)製),TSF400、TSF401、TSF410、TSF4300、TSF4440、TSF4445、TSF4446、TSF4452及TSF4460(Momentive Performance Materials Japan合同公司製)等。 Examples of the silicone-based surfactant include those having a siloxane bond in the molecule, and the like. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by TORAY DOW CORNING Co., Ltd.), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan contract company), etc.
作為氟系界面活性劑者,可舉出在分子內具有氟碳鏈之界面活性劑等。具體而言,可舉出FLUORAD(註冊商標)FC430、FLUORAD FC431(住友3M(股)製),MEGAFAC(註冊商標)F142D、MEGAFAC F171、MEGAFAC F172、MEGAFAC F173、MEGAFAC F177、MEGAFAC F183、MEGAFAC F554、MEGAFAC R30、MEGAFAC RS-718-K(DIC(股)製),EFTOP(註冊商標)EF301、EFTOP EF303、EFTOP EF351、EFTOP EF352(三菱MATERIAL電子化成(股)製),SURFLON(註冊商標)S381、SURFLON S382、SURFLON SC101、SURFLON SC105(旭硝子(股)製),及E5844(DAIKIN FINECHEMICAL研究所(股)製)等。 Examples of the fluorine-based surfactant include those having a fluorocarbon chain in the molecule, and the like. Specifically, FLUORAD (registered trademark) FC430, FLUORAD FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (manufactured by DIC Co., Ltd.), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (manufactured by Mitsubishi Material Electron Chemicals Co., Ltd.), SURFLON (registered trademark) S381, SURFLON S382, SURFLON SC101, SURFLON SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by DAIKIN FINECHEMICAL Research Institute Co., Ltd.), etc.
作為具有氟原子之矽酮系界面活性劑者,可舉出在分子內具有矽氧烷鍵及氟碳鏈之界面活性劑等。具體而言,可舉出MEGAFAC(註冊商標)R08、MEGAFAC BL20、MEGAFAC F475、MEGAFAC F477及MEGAFAC F443(DIC(股)製)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, MEGAFAC (registered trademark) R08, MEGAFAC BL20, MEGAFAC F475, MEGAFAC F477, MEGAFAC F443 (manufactured by DIC Co., Ltd.) etc. are mentioned.
含有調平劑(F)時,相對於著色組成物的總量,其含有率通常為0.0005質量%以上且1質量%以下,以0.001質量%以上且0.5質量%以下為佳,較佳為0.001質量%以上且0.2質量%以下,更佳為0.002質量%以上且0.1質量%以下,特佳為0.005質量%以上且0.1質量%以下。調平劑(F)的含有率為前述範圍內時,能夠使彩色濾光片的平坦性成為良好。 When the leveling agent (F) is contained, its content is usually 0.0005% by mass to 1% by mass, preferably 0.001% by mass to 0.5% by mass, more preferably 0.001% by mass, based on the total amount of the coloring composition. It is more than mass % and 0.2 mass %, More preferably, it is 0.002 mass % or more and 0.1 mass % or less, Most preferably, it is 0.005 mass % or more and 0.1 mass % or less. When the content rate of a leveling agent (F) exists in the said range, the flatness of a color filter can be made favorable.
從使著色劑的耐熱性及耐光性提升之觀點而言,以將抗氧化劑單獨使用或組合2種以上而使用為佳。作為抗氧化劑者,只要為在工業上通常被使用的抗氧化劑,就沒有特別限定,能夠使用酚系抗氧化劑、磷系抗氧化劑及硫系抗氧化劑等。 From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use the antioxidant alone or in combination of two or more. The antioxidant is not particularly limited as long as it is an antioxidant commonly used industrially, and phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like can be used.
作為前述酚系抗氧化劑者,例如可舉出IRGANOX1010(Irganox 1010:新戊四醇肆[3-(3,5-二-第三丁基-4-羥苯基)丙酸酯]、BASF(股)製)、IRGANOX1076(Irganox 1076:十八基-3-(3,5-二-第三丁基-4-羥苯基)丙酸酯、BASF(股)製)、IRGANOX1330(Irganox 1330:3,3’,3”,5,5’,5”-六-第三丁基-a,a’,a”-(均三甲苯-2,4,6-三基)三-對甲酚、BASF(股)製)、IRGANOX3114(Irganox 3114:1,3,5-參(3,5-二-第三丁基-4-羥苯甲基)-1,3,5-三-2,4,6(1H,3H,5H)-三酮、BASF(股)製)、IRGANOX3790(Irganox 3790:1,3,5-參((4-第三丁基-3-羥基-2,6-二甲苯基)甲基)-1,3,5-三-2,4,6(1H,3H,5H)-三酮、BASF(股)製)、IRGANOX1035(Irganox 1035:硫二伸乙基雙[3-(3,5-二-第三丁基-4-羥苯基)丙酸酯]、BASF(股)製)、IRGANOX1135(Irganox 1135:苯丙酸、3,5-雙(1,1-二甲基乙基)-4-羥基、C7-C9側鏈烷酯、BASF(股)製)、IRGANOX1520L(Irganox 1520L:4,6-雙(辛硫基甲基)-鄰甲酚、BASF(股)製)、IRGANOX3125(Irganox 3125、BASF(股)製)、IRGANOX565(Irganox 565:2,4-雙(正辛硫基)-6-(4-羥 基3’、5’-二-第三丁基苯胺基)-1,3,5-三、BASF(股)製)、Adekastab AO-80(Adekastab AO-80:3,9-雙(2-(3-(3-第三丁基-4-羥基-5-甲基苯基)丙醯氧基)-1,1-二甲基乙基)-2,4,8,10-四氧雜螺(5,5)十一烷、ADEKA(股)製)、Sumilizer BHT(Sumilizer BHT、住友化學(股)製)、Sumilizer GA-80(Sumilizer GA-80、住友化學(股)製)、Sumilizer GS(Sumilizer GS、住友化學(股)製)、Cyanox1790(Cyanox 1790、CYTEC(股)製)及VITAMIN E(EISAI(股)製)等。 Examples of the aforementioned phenolic antioxidants include IRGANOX 1010 (Irganox 1010: Neopentylthritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], BASF ( Co., Ltd.), IRGANOX1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, BASF Co., Ltd.), IRGANOX1330 (Irganox 1330: 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol , BASF Co., Ltd.), IRGANOX3114 (Irganox 3114: 1,3,5-ginseng (3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tri -2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), IRGANOX3790 (Irganox 3790: 1,3,5-ginseng ((4-tert-butyl-3-hydroxy-2 ,6-xylyl)methyl)-1,3,5-tri -2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), IRGANOX1035 (Irganox 1035: thiobisethylenebis[3-(3,5-di-tert-butyl- 4-Hydroxyphenyl)propionate], manufactured by BASF Co., Ltd.), IRGANOX 1135 (Irganox 1135: phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxyl, C7- C9 side chain alkyl ester, manufactured by BASF Co., Ltd.), IRGANOX1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Co., Ltd.), IRGANOX3125 (Irganox 3125, BASF Co., Ltd. )), IRGANOX565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxyl 3', 5'-di-tert-butylanilino)-1,3,5-tri , BASF Co., Ltd.), Adekastab AO-80 (Adekastab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyl Oxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, manufactured by ADEKA Co., Ltd.), Sumilizer BHT (Sumilizer BHT, Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, Sumitomo Chemical Co., Ltd.), Cyanox1790 (Cyanox 1790, CYTEC Co., Ltd.) And VITAMIN E (EISAI (stock) system), etc.
作為前述磷系抗氧化劑者,例如可舉出IRGAFOS 168(Irgafos 168:亞磷酸參(2,4-二-第三丁基苯基)酯、BASF(股)製)、IRGAFOS 12(Irgafos 12:參[2-[[2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二氧雜膦-6-基]氧基]乙基]胺、BASF(股)製)、IRGAFOS 38(Irgafos 38:雙(2,4-雙(1,1-二甲基乙基)-6-甲基苯基)乙基酯亞磷酸、BASF(股)製)、Adekastab 329K(ADEKA(股)製)、Adekastab PEP36(ADEKA(股)製)、Adekastab PEP-8(ADEKA(股)製)、Sandstab P-EPQ(CLARIANT公司製)、Weston 618(Weston 618、GE公司製)、Weston 619G(Weston 619G、GE公司製)、Ultranox 626(Ultranox 626、GE公司製)及Sumilizer GP(Sumilizer GP:6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四-第三丁基二苯并[d,f][1.3.2]二氧雜磷雜環庚烷)(住友化學(股)製)等。 Examples of the phosphorus-based antioxidant include IRGAFOS 168 (Irgafos 168: ginseng (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Co., Ltd.), IRGAFOS 12 (Irgafos 12: Reference [2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl] Amine, manufactured by BASF Co., Ltd.), IRGAFOS 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl) ethyl phosphorous acid, BASF Co., Ltd. )), Adekastab 329K (manufactured by ADEKA), Adekastab PEP36 (manufactured by ADEKA), Adekastab PEP-8 (manufactured by ADEKA), Sandstab P-EPQ (manufactured by CLARIANT), Weston 618 (manufactured by Weston 618, produced by GE), Weston 619G (Weston 619G, produced by GE), Ultranox 626 (Ultranox 626, produced by GE) and Sumilizer GP (Sumilizer GP: 6-[3-(3-tertiary butyl-4- Hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]dioxaphosphopane) (Sumitomo Chemical Co., Ltd.), etc.
作為前述硫系抗氧化劑者,例如可舉出硫代二丙酸二月桂酯、二肉豆蔻酯及二硬脂酯等硫代二丙酸二 烷基酯化合物以及肆[亞甲基(3-十二基硫基)丙酸酯]甲烷等多元醇的β-烷基巰基丙酸酯化合物等。 Examples of the aforementioned sulfur-based antioxidants include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, and distearyl ester, and tetrakis[methylene(3- β-alkylmercaptopropionate compounds of polyalcohols such as dodecylthio)propionate]methane, and the like.
本發明的著色組成物,亦可視需要而含有填充劑、其它高分子化合物、密著促進劑、光安定劑、鏈轉移劑等在該技術領域眾所周知的添加劑。 The coloring composition of the present invention may optionally contain fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and other well-known additives in this technical field.
作為密著促進劑者,例如可舉出乙烯基三甲氧基矽烷、乙烯基三乙氧基矽烷、乙烯基參(2-甲氧基乙氧基)矽烷、3-環氧丙氧基丙基三甲氧基矽烷、3-環氧丙氧基丙基甲基二甲氧基矽烷、3-環氧丙氧基丙基甲基二乙氧基矽烷、2-(3,4-環氧基環己基)乙基三甲氧基矽烷、3-氯丙基甲基二甲氧基矽烷、3-氯丙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、3-氫硫基丙基三甲氧基矽烷、3-異氰酸酯基丙基三乙氧基矽烷、N-2-(胺乙基)-3-胺丙基甲基二甲氧基矽烷、N-2-(胺乙基)-3-胺丙基甲基二乙氧基矽烷、N-2-(胺乙基)-3-胺丙基三甲氧基矽烷、3-胺丙基三甲氧基矽烷、3-胺丙基三乙氧基矽烷、N-苯基-3-胺丙基三甲氧基矽烷及N-苯基-3-胺丙基三乙氧基矽烷等。 Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinylginseng (2-methoxyethoxy)silane, 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclo Hexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto Propyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethylsilane Oxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-amine Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltriethoxysilane, etc.
能夠從本發明的著色組成物或著色硬化性組成物形成彩色濾光片。形成著色圖案之方法,可舉出微影術法、 噴墨法、印刷法等,較佳可舉出微影術法。微影術法,係將前述著色硬化性組成物塗佈在基板且使其乾燥而形成著色硬化性組成物層,而且隔著光罩而將該著色硬化性組成物層進行曝光且顯影之方法。在微影術法中,著色硬化性組成物係以含有聚合起始劑(D)為佳。在微影術法中,藉由在曝光時不使用光罩、及/或不顯影,而能夠形成上述著色硬化性組成物層的硬化物之著色塗膜。能夠將如此形成的著色圖案、著色塗膜作為本發明之彩色濾光片。 A color filter can be formed from the colored composition or colored curable composition of the present invention. The method for forming a colored pattern includes lithography, inkjet method, printing method, etc., preferably lithography. Lithography is a method in which the aforementioned colored curable composition is coated on a substrate and dried to form a colored curable composition layer, and the colored curable composition layer is exposed and developed through a photomask . In the lithography method, the colored curable composition preferably contains a polymerization initiator (D). In the lithography method, a colored coating film of a cured product of the above-mentioned colored curable composition layer can be formed by not using a photomask and/or without developing during exposure. The colored pattern and colored coating film formed in this way can be used as the color filter of this invention.
所製造的彩色濾光片之膜厚係沒有特別限定,能夠按照目的、用途等而適當地調整,例如0.1至30μm,以0.1至20μm為佳,較佳為0.5至6μm。 The film thickness of the manufactured color filter is not particularly limited, and can be appropriately adjusted according to the purpose, application, etc., for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0.5 to 6 μm.
作為基板者,能夠使用玻璃板、樹脂板、矽、在前述基板上形成有鋁、銀、銀/銅/鈀合金薄膜等者。在該等基板上,亦可形成另外的彩色濾光片層、樹脂層、電晶體及電路等。 As the substrate, a glass plate, a resin plate, silicon, or a substrate on which a thin film of aluminum, silver, or silver/copper/palladium alloy is formed can be used. On these substrates, additional color filter layers, resin layers, transistors, circuits, etc. can also be formed.
藉由微影術法而形成各色像素,係能夠在眾所周知或慣用的裝置和條件下進行。例如能夠如下述方式進行而製造。 The formation of pixels of various colors by lithography can be carried out under well-known or conventional devices and conditions. For example, it can manufacture as follows.
首先,將著色硬化性組成物塗佈在基板上,藉由加熱乾燥(預烘烤)及/或減壓乾燥而將溶劑等揮發成分除去且使其乾燥,來得到平滑的著色硬化性組成物層。 First, the colored curable composition is coated on the substrate, and the volatile components such as solvents are removed and dried by heat drying (pre-baking) and/or reduced pressure drying to obtain a smooth colored curable composition Floor.
作為塗佈方法者,可舉出旋轉塗佈法、狹縫塗佈法、以及狹縫及旋轉塗佈法等。 Examples of the coating method include a spin coat method, a slit coat method, a slit and spin coat method, and the like.
其次,著色硬化性組成物層,係隔著用以形 成目的著色圖案之光罩而進行曝光。為了能夠對曝光面全體均勻地照射平行光線、將光罩與形成有著色硬化性組成物層之基板進行正確的位置對準,係以使用光罩對準曝光機(mask aligner)及步進器等曝光裝置為佳。 Next, the colored curable composition layer is exposed through a photomask for forming the desired colored pattern. A mask aligner and a stepper are used to uniformly irradiate the entire exposure surface with parallel light and to align the mask and the substrate on which the colored curable composition layer is formed. It is better to wait for the exposure device.
藉由使曝光後的著色硬化性組成物層接觸顯影液而顯影,能夠在基板上形成著色圖案。藉由顯影而能夠將著色硬化性組成物層的未曝光部溶解在顯影液而除去。 A colored pattern can be formed on a substrate by contacting the exposed colored curable composition layer with a developer and developing it. By development, the unexposed portion of the colored curable composition layer can be dissolved in a developing solution and removed.
作為顯影液者,例如以氫氧化鉀、碳酸氫鈉、碳酸鈉及氫氧化四甲基銨等鹼性化合物的水溶液為佳。 As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferable.
顯影方法可為浸置(puddle)法、浸漬法及噴霧法等任一種。而且在顯影時亦可將基板以任意角度傾斜。 The image development method may be any one of a dipping method, a dipping method, a spraying method, and the like. In addition, the substrate can be tilted at any angle during development.
顯影後的基板,係以被水洗為佳。 The developed substrate is preferably washed with water.
而且,以對所得到的著色圖案進行後烘烤為佳。 Furthermore, it is preferable to post-bak the obtained colored pattern.
前述彩色濾光片,係有用於作為被使用在顯示裝置(例如液晶顯示裝置、有機EL裝置、電子紙等)及固體攝像元件之彩色濾光片,尤其有用於作為被使用在液晶顯示裝置之彩色濾光片。 The aforementioned color filter is useful as a color filter used in display devices (such as liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements, and is especially useful as a color filter used in liquid crystal display devices. color filter.
以下,舉出實施例而更具體地說明本發明,但是本發明當然不被下述的實施例限制,在能夠適合前/後述的宗旨之範圍可施行適當地變更而實施亦是自不待言,該等係任一者均被包含在本發明的技術範圍。 Hereinafter, examples are given to illustrate the present invention more specifically, but the present invention is of course not limited by the following examples, and it goes without saying that it can be implemented with appropriate changes within the range that can be adapted to the purpose described above/later. Any of these are included in the technical scope of the present invention.
例中的「%」及「份」,只要未特別記載,則 係表示質量%及質量份。 "%" and "parts" in the examples mean % by mass and parts by mass unless otherwise specified.
在以下的合成例中,化合物的構造係藉由NMR(JMM-ECA-500;日本電子(股)製)或質量分析(LC;Agilent製1200型、MASS;Agilent製LC/MSD6130型)而確認 In the following synthesis examples, the structures of the compounds were confirmed by NMR (JMM-ECA-500; manufactured by JEOL Ltd.) or mass analysis (LC; Model 1200 manufactured by Agilent, MASS; Model LC/MSD6130 manufactured by Agilent)
樹脂的聚苯乙烯換算的重量平均分子量(Mw)及數量平均分子量(Mn)之測定,係使用GPC法且在以下的條件下進行。 The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polystyrene conversion of resin was performed on the following conditions using the GPC method.
裝置:HLC-8120GPC(TOSOH(股)製) Device: HLC-8120GPC (manufactured by TOSOH Co., Ltd.)
管柱:TSK-GELG2000HXL Column: TSK-GELG2000HXL
管柱溫度:40℃ Column temperature: 40°C
溶劑:四氫呋喃 Solvent: THF
流速:1.0mL/分鐘 Flow rate: 1.0mL/min
分析試料的固體成分濃度:0.001至0.01質量% Solid content concentration of analysis sample: 0.001 to 0.01% by mass
注入量:50μL Injection volume: 50μL
檢測器:RI Detector: RI
校正用標準物質:TSK STANDARD POLYSTYRENE F-40、F-4、F-288、A-2500、A-500(TOSOH(股)製) Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH Co., Ltd.)
將上述所得到的聚苯乙烯換算的重量平均分子量(Mw)及數量平均分子量(Mn)之比(Mw/Mn)設為分散度。 The ratio (Mw/Mn) of the polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) obtained above was made into the degree of dispersion.
將香豆素6(東京化成工業(股)製)14.4份及甲苯737份混合且於87℃進行攪拌。在該混合物中添加三氟甲磺酸甲 酯10.1份。將該混合物在87℃攪拌3小時。將該混合物在10℃攪拌。將該混合物過濾且使用甲苯433份將所得到的殘渣洗淨6次。將該殘渣在60℃進行減壓乾燥而得到式(I-2)表示之化合物20.8份。 14.4 parts of coumarin 6 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 737 parts of toluene were mixed and stirred at 87°C. To this mixture was added 10.1 parts of methyl triflate. The mixture was stirred at 87°C for 3 hours. The mixture was stirred at 10°C. This mixture was filtered, and the obtained residue was washed 6 times with 433 parts of toluene. The residue was dried under reduced pressure at 60° C. to obtain 20.8 parts of the compound represented by the formula (I-2).
(質量分析)離子化模式=ESI+:m/z=365[M-CF3SO3]+ (mass analysis) ionization mode = ESI+: m/z = 365 [M-CF 3 SO 3 ] +
Exact Mass:514 Exact Mass: 514
將式(I-2)表示之化合物5.00份及甲醇1500份混合。在該混合物中添加磷鎢酸水合物(Sigma-Aldrich Japan(股)製)10.4份及甲醇104份的混合物。將該混合物過濾且使用甲醇500份將所得到的殘渣洗淨。將該殘渣在60℃進行減壓乾燥而得到式(I-14)表示之化合物12.4份。 5.00 parts of the compound represented by formula (I-2) and 1500 parts of methanol were mixed. A mixture of 10.4 parts of phosphotungstic acid hydrate (manufactured by Sigma-Aldrich Japan Co., Ltd.) and 104 parts of methanol was added to this mixture. This mixture was filtered, and the obtained residue was wash|cleaned using 500 parts of methanol. The residue was dried under reduced pressure at 60° C. to obtain 12.4 parts of the compound represented by the formula (I-14).
(質量分析)離子化模式=ESI+:m/z=365[(M-PW12O40)/3]+ (mass analysis) ionization mode = ESI+: m/z = 365 [(M-PW 12 O 40 )/3] +
Exact MaSS:3974 Exact Mass: 3974
使用差示熱熱重量同時測定裝置(SII Nano Technology製TG/DTA6200),進行實施例1所得到的化合物的差示掃描熱量測定。一次的測定所使用的試料量為5mg。測定溫度係首先從45℃開始,以每分鐘5℃的速度升溫且測定至550℃為止。在氮氣環境下求取重量減少率成為5%之溫度T5(氮下)。將結果顯示在表11。 The differential scanning calorimetry of the compound obtained in Example 1 was performed using a differential thermogravimetric simultaneous measurement device (TG/DTA6200 manufactured by SII Nano Technology). The sample amount used for one measurement was 5 mg. The measurement temperature starts from 45°C, increases the temperature at a rate of 5°C per minute, and measures to 550°C. The temperature T 5 (under nitrogen) at which the weight loss rate becomes 5% was determined in a nitrogen atmosphere. The results are shown in Table 11.
從表11的結果,得知本發明的化合物係耐熱性高。 From the results in Table 11, it can be seen that the compound system of the present invention has high heat resistance.
在具備回流冷卻器、滴液漏斗及攪拌機之燒瓶內,使氮氣適量地流動且取代成為氮氣環境,添加丙二醇單甲醚乙酸酯280份,邊攪拌邊加熱至80℃為止。其次,將丙烯酸38份、丙烯酸3,4-環氧基三環[5.2.1.02,6]癸烷-8-基酯及丙烯酸3,4-環氧基三環[5.2.1.02,6]癸烷-9-基酯的混合物289份、丙二醇單甲醚乙酸酯125份的混合溶液花費5小時滴下。另一方面,將使2,2-偶氮雙(2,4-二甲基戊腈)33份溶解在丙二醇單甲醚乙酸酯235份而成的混合溶液,花費6小 時滴下。滴下結束後,在同溫度保持4小時後,冷卻至室溫而得到固體成分35.0%的共聚物(樹脂B1)溶液。所得到的樹脂B1的重量平均分子量(Mw)為8800,分散度為2.1,溶液酸價為28mg-KOH/g。 In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, an appropriate amount of nitrogen gas was flowed to replace the nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and it was heated to 80° C. while stirring. Secondly, 38 parts of acrylic acid, 3,4-epoxy tricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate and 3,4-epoxy tricyclo[5.2.1.0 2,6 A mixed solution of 289 parts of a mixture of ]decane-9-yl ester and 125 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. On the other hand, a mixed solution obtained by dissolving 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was dropped over 6 hours. After completion|finish of dripping, after maintaining at the same temperature for 4 hours, it cooled to room temperature and obtained the copolymer (resin B1) solution of 35.0% of solid content. The weight average molecular weight (Mw) of the obtained resin B1 was 8800, the degree of dispersion was 2.1, and the acid value of the solution was 28 mg-KOH/g.
在具備回流冷卻器、滴液漏斗及攪拌機之燒瓶內,使氮氣適量地流動且取代成為氮氣環境,添加乳酸乙酯257份,邊攪拌邊加熱至75℃為止。其次,將甲基丙烯酸81份、丙烯酸3,4-環氧基三環[5.2.1.02,6]癸烷-8-基酯及丙烯酸3,4-環氧基三環[5.2.1.02,6]癸烷-9-基酯的混合物369份、乳酸乙酯25份的混合溶液花費5小時滴下。另一方面,將使2,2-偶氮雙(2,4-二甲基戊腈)11份溶解在乳酸乙酯162份而成的混合溶液,花費5小時滴下。滴下結束後,在同溫度保持5小時後,添加乳酸乙酯95份且冷卻至室溫而得到固體成分47.7%的共聚物(樹脂B2)溶液。所得到的樹脂B2的重量平均分子量(Mw)為8100,分散度為1.9,溶液酸價為53mg-KOH/g。 In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, an appropriate amount of nitrogen gas was flowed to replace the atmosphere with nitrogen gas, 257 parts of ethyl lactate was added, and the mixture was heated to 75° C. while stirring. Secondly, 81 parts of methacrylic acid, 3,4-epoxy tricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate and 3,4-epoxy tricyclo[5.2.1.0 2 ,6 ] A mixed solution of 369 parts of a mixture of decane-9-yl ester and 25 parts of ethyl lactate was dropped over 5 hours. On the other hand, a mixed solution obtained by dissolving 11 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 162 parts of ethyl lactate was dropped over 5 hours. After completion|finish of dripping, after maintaining at the same temperature for 5 hours, 95 parts of ethyl lactates were added, and it cooled to room temperature, and obtained the copolymer (resin B2) solution of 47.7% of solid content. The weight average molecular weight (Mw) of the obtained resin B2 was 8100, the degree of dispersion was 1.9, and the acid value of the solution was 53 mg-KOH/g.
在具備回流冷卻器、滴液漏斗及攪拌機之燒瓶內,使氮氣適量地流動且取代成為氮氣環境,添加丙二醇單甲醚乙酸酯371份,邊攪拌邊加熱至85℃為止。其次,將丙烯酸54份、丙烯酸3,4-環氧基三環[5.2.1.02,6]癸烷-8-基酯及 丙烯酸3,4-環氧基三環[5.2.1.02,6]癸烷-9-基酯的混合物225份、乙烯基甲苯(異構物混合物)81份、丙二醇單甲醚乙酸酯80份的混合溶液花費4小時滴下。另一方面,將使聚合起始劑2,2-偶氮雙(2,4-二甲基戊腈)30份溶解在丙二醇單甲醚乙酸酯160份而成之溶液,花費5小時滴下。起始劑溶液的滴下結束後,在同溫度保持4小時後,冷卻至室溫而得到固體成分37.5%的共聚物(樹脂B3)溶液。所得到的樹脂B3的重量平均分子量(Mw)為10600,分散度為2.01,溶液酸價為43mg-KOH/g。 In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, an appropriate amount of nitrogen gas was flowed to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was added, and heated to 85° C. while stirring. Secondly, 54 parts of acrylic acid, 3,4-epoxy tricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate and 3,4-epoxy tricyclo[5.2.1.0 2,6 A mixed solution of 225 parts of a mixture of ]decane-9-yl ester, 81 parts of vinyl toluene (isomer mixture), and 80 parts of propylene glycol monomethyl ether acetate was dropped over 4 hours. On the other hand, a solution obtained by dissolving 30 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. . After completion|finish of dripping of an initiator solution, after maintaining at the same temperature for 4 hours, it cooled to room temperature and obtained the copolymer (resin B3) solution of 37.5% of solid content. The weight average molecular weight (Mw) of the obtained resin B3 was 10600, the degree of dispersion was 2.01, and the acid value of the solution was 43 mg-KOH/g.
在具備回流冷卻器、滴液漏斗及攪拌機之燒瓶內,使氮氣適量地流動且取代成為氮氣環境,添加乳酸乙酯54份、丙二醇單甲醚乙酸酯141份,邊攪拌邊加熱至85℃為止。其次,將丙烯酸35份、丙烯酸3,4-環氧基三環[5.2.1.02,6]癸烷-8-基酯及丙烯酸3,4-環氧基三環[5.2.1.02,6]癸烷-9-基酯的混合物23份、環己基順丁烯二醯亞胺161份、甲基丙烯酸2-羥基乙酯12份、丙二醇單甲醚乙酸酯493份的混合溶液花費5小時滴下。另一方面,將使2,2-偶氮雙(2,4-二甲基戊腈)3份溶解在丙二醇單甲醚乙酸酯78份而成之溶液,花費6小時滴下。滴下結束後,在同溫度保持4小時後,冷卻至室溫而得到固體成分24.4%的共聚物(樹脂B4)溶液。所得到的樹脂B4的重量平均分子量(Mw)為8400,分散度為2.1,溶液酸價為26mg-KOH/g。 In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, flow an appropriate amount of nitrogen gas and replace it with a nitrogen atmosphere, add 54 parts of ethyl lactate and 141 parts of propylene glycol monomethyl ether acetate, and heat to 85°C while stirring until. Secondly, 35 parts of acrylic acid, 3,4-epoxy tricyclo[5.2.1.0 2,6 ]decane-8-yl acrylate and 3,4-epoxy tricyclo[5.2.1.0 2,6 ] The mixed solution of 23 parts of the mixture of decane-9-yl ester, 161 parts of cyclohexylmaleimide, 12 parts of 2-hydroxyethyl methacrylate, and 493 parts of propylene glycol monomethyl ether acetate costs 5 Hours drip. On the other hand, a solution obtained by dissolving 3 parts of 2,2-azobis(2,4-dimethylvaleronitrile) in 78 parts of propylene glycol monomethyl ether acetate was dropped over 6 hours. After completion|finish of dripping, after maintaining at the same temperature for 4 hours, it cooled to room temperature and obtained the copolymer (resin B4) solution of 24.4% of solid content. The weight average molecular weight (Mw) of the obtained resin B4 was 8400, the degree of dispersion was 2.1, and the acid value of the solution was 26 mg-KOH/g.
膜厚係使用DEKTAK3(日本真空技術(股)製)而測定。 The film thickness was measured using DEKTAK3 (manufactured by Nippon Vacuum Technology Co., Ltd.).
將樹脂:甲基丙烯酸/甲基丙烯酸苯甲酯(莫耳比:30/70)共聚物(田岡化學工業(股)製、重量平均分子量 Resin: methacrylic acid/benzyl methacrylate (molar ratio: 30/70) copolymer (manufactured by Tagoka Chemical Industry Co., Ltd., weight average molecular weight
(Mw)10700、酸價70-mgKOH/g)33.8%丙二醇單甲醚乙酸酯溶液40份;聚合性化合物:二新戊四醇六丙烯酸酯(KAYARAD(註冊商標)DPHA;日本化藥(股)製)5.8份;聚合起始劑:N-苯甲醯氧基-1-(4-苯硫基苯基)辛烷-1-酮-2-亞胺(IRGACURE(註冊商標)OXE01;BASF Japan公司製)0.58份;調平劑:聚醚改性矽酮油(Toray Silicone SH8400;TORAY.DOW CORNING(股)製)0.010份;溶劑:丙二醇單甲醚47份;溶劑:丙二醇單甲醚乙酸酯6.8份混合而得到昇華性試驗用樹脂組成物(SJS)。 (Mw) 10700, acid value 70-mgKOH/g) 40 parts of 33.8% propylene glycol monomethyl ether acetate solution; stock)) 5.8 parts; polymerization initiator: N-benzoyloxy-1-(4-phenylthiophenyl) octane-1-one-2-imine (IRGACURE (registered trademark) OXE01; BASF Japan company) 0.58 parts; leveling agent: polyether modified silicone oil (Toray Silicone SH8400; TORAY.DOW CORNING (stock)) 0.010 parts; solvent: propylene glycol monomethyl ether 47 parts; solvent: propylene glycol monomethyl 6.8 parts of ether acetates were mixed to obtain a resin composition (SJS) for a sublimation test.
將上述所得到的昇華性試驗用樹脂組成物(SJS)使用旋轉塗佈法塗佈在2英吋見方的玻璃基板(EAGLE XG;Corning公司製)上,且在100℃ 3分鐘的條件下使揮發成分揮發。冷卻後,使用曝光機(TME-150RSK;TOPCON(股)製), 在大氣環境下以150mJ/cm2的曝光量(365nm基準)照射光。在烘箱中於220℃加熱2小時而形成昇華性試驗用樹脂塗佈膜(SJSM)(膜厚2.2μm)。 The above-obtained resin composition for sublimation test (SJS) was coated on a 2-inch square glass substrate (EAGLE XG; manufactured by Corning Co., Ltd.) by a spin coating method, and allowed to dry at 100° C. for 3 minutes. Volatile components evaporate. After cooling, using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.), light was irradiated with an exposure amount of 150 mJ/cm 2 (365 nm reference) in an air environment. It heated at 220 degreeC in oven for 2 hours, and formed the resin coating film (SJSM) (film thickness 2.2 micrometers) for sublimation test.
將著色劑(A):式(I-2)表示之化合物14份;樹脂(B):樹脂B1溶液480份;溶劑(E):丙二醇單甲醚乙酸酯6.2份;溶劑(E):N-甲基-2-吡咯啶酮500份;以及界面活性劑:聚醚改性矽酮油(Toray Silicone SH8400;TORAY.DOW CORNING(股)製)0.063份混合而得到著色組成物1。 Colorant (A): 14 parts of compounds represented by formula (I-2); Resin (B): 480 parts of resin B1 solution; Solvent (E): 6.2 parts of propylene glycol monomethyl ether acetate; Solvent (E): Coloring composition 1 was obtained by mixing 500 parts of N-methyl-2-pyrrolidone and 0.063 parts of surfactant: polyether-modified silicone oil (Toray Silicone SH8400; manufactured by TORAY.DOW CORNING Co., Ltd.).
將著色劑(A):式(I-14)表示之化合物36份;樹脂(B):樹脂B1溶液410份;溶劑(E):丙二醇單甲醚乙酸酯6.2份;溶劑(E):N-甲基-2-吡咯啶酮540份;以及界面活性劑:聚醚改性矽酮油(Toray Silicone SH8400;TORAY.DOW CORNING(股)製)0.063份混合而得到著色組成物2。 Colorant (A): 36 parts of compounds represented by formula (I-14); Resin (B): 410 parts of resin B1 solution; Solvent (E): 6.2 parts of propylene glycol monomethyl ether acetate; Solvent (E): Coloring composition 2 was obtained by mixing 540 parts of N-methyl-2-pyrrolidone and 0.063 parts of surfactant: polyether-modified silicone oil (Toray Silicone SH8400; manufactured by TORAY.DOW CORNING Co., Ltd.).
將著色劑(A):式(I-14)表示之化合物10份; 樹脂(B):樹脂B2溶液97份;溶劑(E):N-甲基-2-吡咯啶酮180份;溶劑(E):4-羥基-4-甲基-2-戊酮26份;溶劑(E):丙二醇單甲醚乙酸酯2.0份;以及界面活性劑:聚醚改性矽酮油(Toray Silicone SH8400;TORAY.DOW CORNING(股)製)0.020份混合而得到著色組成物3。 Coloring agent (A): 10 parts of compounds represented by formula (I-14); Resin (B): 97 parts of resin B2 solution; Solvent (E): 180 parts of N-methyl-2-pyrrolidone; Solvent ( E): 26 parts of 4-hydroxy-4-methyl-2-pentanone; solvent (E): 2.0 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether modified silicone oil (Toray Silicone SH8400 ; TORAY-DOW CORNING Co., Ltd.) 0.020 parts were mixed to obtain coloring composition 3.
將使著色劑(A):式(I-14)表示之化合物10份、分散劑(BYK-LPN21324;BYK-Chemie.Japan股份有限公司製)10份、樹脂(B):樹脂B1溶液11份、及溶劑(E):丙二醇單甲醚乙酸酯160份 混合且使用珠磨機使式(I-14)表示之化合物分散而成的著色組成物之中100份;樹脂(B):樹脂B1溶液55份;溶劑(E):丙二醇單甲醚乙酸酯3.6份;以及界面活性劑:聚醚改性矽酮油(Toray Silicone SH8400;TORAY.DOW CORNING(股)製)0.010份混合而得到著色組成物4。 Colorant (A): 10 parts of compound represented by formula (I-14), 10 parts of dispersant (BYK-LPN21324; manufactured by BYK-Chemie.Japan Co., Ltd.), resin (B): 11 parts of resin B1 solution , and solvent (E): 100 parts of the coloring composition obtained by mixing 160 parts of propylene glycol monomethyl ether acetate and dispersing the compound represented by formula (I-14) using a bead mill; resin (B): resin 55 parts of B1 solution; solvent (E): 3.6 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether modified silicone oil (Toray Silicone SH8400; TORAY.DOW CORNING (stock)) 0.010 parts mixed and Coloring composition 4 was obtained.
將著色劑(A):香豆素611份; 樹脂(B):樹脂B2溶液350份;溶劑(E):丙二醇單甲醚乙酸酯6.2份;溶劑(E):N,N-二甲基甲醯胺630份;以及界面活性劑:聚醚改性矽酮油(Toray Silicone SH8400;TORAY.DOW CORNING(股)製)0.063份混合而得到著色組成物5。 Colorant (A): 611 parts of coumarin; Resin (B): 350 parts of resin B2 solution; Solvent (E): 6.2 parts of propylene glycol monomethyl ether acetate; Solvent (E): N,N-dimethyl Coloring composition 5 was obtained by mixing 630 parts of methamide; and 0.063 parts of surfactant: polyether-modified silicone oil (Toray Silicone SH8400; manufactured by TORAY-DOW CORNING Co., Ltd.).
將著色組成物1使用旋轉塗佈法塗佈在2英吋見方的玻璃基板(EAGLE XG;Corning公司製)上之後,在100℃預烘烤3分鐘而形成著色組成物層。使用DEKTAK3(日本真空技術(股)製)而測定膜厚。使該著色塗佈膜與上述所得到的昇華性試驗用樹脂塗佈膜(SJSM),在空出70μm的間隔之狀態下相向且在220℃進行後烘烤40分鐘。使用測色機(OSP-SP-200;OLYMPUS公司製)測定昇華性試驗用樹脂塗佈膜(SJSM)之加熱前後的色差(△Eab*)。色差(△Eab*)為5.0以上時,係表示著色劑具有昇華性。將結果顯示在表12。在表12中,○係表示著色劑不具有昇華性,×係表示著色劑具有昇華性。 Coloring composition 1 was coated on a 2-inch square glass substrate (EAGLE XG; manufactured by Corning) by spin coating, and then prebaked at 100° C. for 3 minutes to form a coloring composition layer. The film thickness was measured using DEKTAK3 (manufactured by Nippon Vacuum Technology Co., Ltd.). This colored coating film and the resin coating film (SJSM) for a sublimation test obtained above were made to face each other with the space|interval of 70 micrometers open, and they post-baked at 220 degreeC for 40 minutes. The color difference (ΔEab*) before and after heating of the resin coating film (SJSM) for a sublimation test was measured using the colorimeter (OSP-SP-200; OLYMPUS company make). When the color difference (ΔEab*) is 5.0 or more, it means that the colorant has sublimation properties. The results are shown in Table 12. In Table 12, ◯ indicates that the colorant does not have sublimation property, and the × system indicates that the colorant has sublimation property.
除了將著色組成物1變更成為著色組成物2以外,係與實施例6同樣地操作而進行昇華性評估。將結果顯示在 表12。 Except having changed the coloring composition 1 into the coloring composition 2, it carried out similarly to Example 6, and performed sublimation evaluation. The results are shown in Table 12.
除了將著色組成物1變更成為著色組成物3以外,係與實施例6同樣地操作而進行昇華性評估。將結果顯示在表12。 Except having changed the coloring composition 1 into the coloring composition 3, it carried out similarly to Example 6, and performed sublimation evaluation. The results are shown in Table 12.
除了將著色組成物1變更成為著色組成物4以外,係與實施例6同樣地操作而進行昇華性評估。將結果顯示在表12。 Except having changed the coloring composition 1 into the coloring composition 4, it carried out similarly to Example 6, and performed sublimation evaluation. The results are shown in Table 12.
除了將著色組成物1變更成為著色組成物5以外,係與實施例6同樣地操作而進行昇華性評估。將結果顯示在表12。 Except having changed the coloring composition 1 into the coloring composition 5, it carried out similarly to Example 6, and performed sublimation evaluation. The results are shown in Table 12.
從上述的結果,得知含有本發明的化合物之著色組成物,係能夠減低著色劑的昇華。 From the above results, it is known that the coloring composition containing the compound of the present invention can reduce the sublimation of the coloring agent.
將使著色劑(A):式(I-14)表示之化合物100份、分散劑(BYK-LPN21324;BYK-Chemie.Japan(股)製)130份、樹脂(B):樹脂B4溶液170份、及溶劑(E):丙二醇單甲醚乙酸酯610份混合且使用珠磨機使式(I-14)表示之化合物分散而成之著色組成物之中380份;將著色劑(A):C.I.顏料黃138(顏料)18份、分散劑7.6份、樹脂7.6份、及溶劑(E):丙二醇單甲醚乙酸酯120份混合且使用珠磨機使顏料分散而成之顏料分散液的總量;著色劑(A):下述式表示之化合物(使用日本特開2013-235257號公報所記載的方法製造)4.2份;
樹脂(B):樹脂B3溶液21份; 聚合性化合物(C):聚合性化合物(A9550;新中村化學工業(股)製)25份;聚合起始劑(D):下述式表示之化合物(常州強力電子新材料股份有限公司製)6.6份;
溶劑(E):4-羥基-4-甲基-2-戊酮170份;溶劑(E):丙二醇單甲醚乙酸酯250份;以及界面活性劑:聚醚改性矽酮油(Toray Silicone SH8400;TORAY.DOW CORNING(股)製)0.075份混合而得到著色硬化性組成物1。 Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone; Solvent (E): 250 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether modified silicone oil (Toray Colored curable composition 1 was obtained by mixing 0.075 parts of Silicone SH8400; manufactured by TORAY-DOW CORNING Co., Ltd.
將著色硬化性組成物1使用旋轉塗佈法塗佈在2英吋見方的玻璃基板(EAGLE XG;Corning公司製)上之後,在100℃預烘烤3分鐘而形成著色硬化性組成物層。冷卻後,將形成有著色硬化性組成物層之基板與石英玻璃製光罩之間隔設為200μm,使用曝光機(TME-150RSK;TOPCON(股)製),在大氣環境下,以80mJ/cm2的曝光量(365nm基準)進行曝光。又,作為光罩者,係使用形成有100μm的線與間隙圖案者。使曝光後的著色硬化性組成物層,於25℃浸漬在含有非離子系界面活性劑0.12%及氫氧化鉀0.04%之水溶液中70秒鐘而顯影,且進行水洗。藉由將該著色塗佈 膜於230℃進行後烘烤30分鐘來得到著色圖案。 The colored curable composition 1 was coated on a 2-inch square glass substrate (EAGLE XG; manufactured by Corning) by spin coating, and then prebaked at 100° C. for 3 minutes to form a colored curable composition layer. After cooling, set the distance between the substrate with the colored curable composition layer and the quartz glass photomask at 200 μm, and use an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) at 80 mJ/cm Exposure was performed at an exposure amount (365nm reference) of 2 . In addition, as a photomask, the thing in which the line-and-space pattern of 100 micrometers was formed was used. The colored curable composition layer after exposure was immersed in an aqueous solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 70 seconds to develop, and washed with water. A colored pattern was obtained by post-baking the colored coating film at 230° C. for 30 minutes.
將著色硬化性組成物1使用旋轉塗佈法塗佈在2英吋見方的玻璃基板(EAGLE XG;Corning公司製)上之後,在100℃預烘烤3分鐘而形成著色硬化性組成物層。冷卻後,將形成有著色硬化性組成物層之基板,使用曝光機(TME-150RSK;TOPCON(股)製),在大氣環境下,以80mJ/cm2的曝光量(365nm基準)進行曝光。使曝光後的著色硬化性組成物層,於25℃浸漬在含有非離子系界面活性劑0.12%及氫氧化鉀0.04%之水溶液70秒鐘而顯影,且進行水洗。使用DEKTAK3(日本真空技術(股)製)而測定膜厚。 The colored curable composition 1 was coated on a 2-inch square glass substrate (EAGLE XG; manufactured by Corning) by spin coating, and then prebaked at 100° C. for 3 minutes to form a colored curable composition layer. After cooling, the substrate on which the colored curable composition layer was formed was exposed using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) at an exposure dose of 80 mJ/cm 2 (based on 365 nm) in an air environment. The colored curable composition layer after exposure was immersed in an aqueous solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 25°C for 70 seconds to develop, and washed with water. The film thickness was measured using DEKTAK3 (manufactured by Nippon Vacuum Technology Co., Ltd.).
使該著色塗佈膜與上述所得到的昇華性試驗用樹脂塗佈膜(SJSM),在空出70μm的間隔之狀態下相向且在220℃進行後烘烤40分鐘。 This colored coating film and the resin coating film (SJSM) for a sublimation test obtained above were made to face each other with the space|interval of 70 micrometers open, and they post-baked at 220 degreeC for 40 minutes.
使用測色機(OSP-SP-200;OLYMPUS公司製)測定昇華性試驗用樹脂塗佈膜(SJSM)之加熱前後的色差(△Eab*)。色差(△Eab*)為5.0以上時,係表示著色劑具有昇華性。將結果顯示在表13。在表13中,○係表示著色劑不具有昇華性,×係表示著色劑具有昇華性。 The color difference (ΔEab*) before and after heating of the resin coating film (SJSM) for a sublimation test was measured using the colorimeter (OSP-SP-200; OLYMPUS company make). When the color difference (ΔEab*) is 5.0 or more, it means that the colorant has sublimation properties. The results are shown in Table 13. In Table 13, ◯ means that the colorant does not have sublimation property, and × means that the colorant has sublimation property.
將使著色劑(A):式(I-14)表示之化合物100份、分散劑(BYK-LPN21324;BYK-Chemie.Japan(股)製)130 份、樹脂(B):樹脂B4溶液170份、及溶劑(E):丙二醇單甲醚乙酸酯610份混合且使用珠磨機使式(I-14)表示之化合物分散而成之著色組成物之中340份;將著色劑(A):C.I.顏料黃138(顏料)18份、分散劑7.6份、樹脂7.6份、及溶劑(E):丙二醇單甲醚乙酸酯120份混合且使用珠磨機使顏料分散而成之顏料分散液的總量;著色劑(A):下述式表示之化合物(使用日本特開2013-235257號公報所述之方法製成)7.8份;
樹脂(B):樹脂B3溶液27份;聚合性化合物(C):聚合性化合物(A9550;新中村化學工業(股)製)26份;聚合起始劑(D):下述式表示之化合物(常州強力電子新材料股份有限公司製)6.8份;
溶劑(E):4-羥基-4-甲基-2-戊酮170份;溶劑(E):丙二醇單甲醚乙酸酯270份;以及界面活性劑:聚醚改性矽酮油(Toray Silicone SH8400;TORAY.DOW CORNING(股)製)0.075份混合而得到著色硬化性組成物2。 Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone; Solvent (E): 270 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether modified silicone oil (Toray Silicone SH8400; manufactured by TORAY-DOW CORNING Co., Ltd.) was mixed in 0.075 parts to obtain Colored Curable Composition 2.
除了將著色硬化性組成物1變更成為著色硬化性組成物2以外,係與實施例10同樣地實施而進行著色圖案的製造及昇華性評估。將昇華性評估結果顯示在表13。 Except having changed the colored curable composition 1 into the colored curable composition 2, it carried out similarly to Example 10, and performed manufacture of the colored pattern and sublimation property evaluation. Table 13 shows the sublimation evaluation results.
將使著色劑(A):式(I-14)表示之化合物100份、分散劑(BYK-LPN21324;BYK-Chemie.Japan(股)製)130份、樹脂(B):樹脂B4溶液170份、及溶劑(E):丙二醇單甲醚乙酸酯610份 混合且使用珠磨機使式(I-14)表示之化合物分散而成之著色組成物之中290份;將著色劑(A):C.I.顏料黃138(顏料)23份、分散劑9.6份、樹脂9.6份、及溶劑(E):丙二醇單甲醚乙酸酯150份混合且使用珠磨機使顏料分散而成之顏料分散液的總量;著色劑(A):下述式表示之化合物(使用日本特開2013-235257號公報所述之方法製成)5.1份;
樹脂(B):樹脂B3溶液31份;聚合性化合物(C):聚合性化合物(A9550;新中村化學工業(股)製)27份;聚合起始劑(D):下述式表示之化合物(常州強力電子新材料股份有限公司製)7.2份;
溶劑(E):4-羥基-4-甲基-2-戊酮170份;溶劑(E):丙二醇單甲醚乙酸酯280份;以及界面活性劑:聚醚改性矽酮油(Toray Silicone SH8400;TORAY.DOW CORNING(股)製)0.075份混合而得到著色硬化性組成物3。 Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone; Solvent (E): 280 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether modified silicone oil (Toray Silicone SH8400; manufactured by TORAY-DOW CORNING Co., Ltd.) was mixed in 0.075 parts to obtain colored curable composition 3.
除了將著色硬化性組成物1變更成為著色硬化性組成物3以外,係與實施例10同樣地實施而進行著色圖案的製造及昇華性評估。將昇華性評估結果顯示在表13。 Except having changed the colored curable composition 1 into the colored curable composition 3, it carried out similarly to Example 10, and performed manufacture of the colored pattern and sublimation property evaluation. Table 13 shows the sublimation evaluation results.
將使著色劑(A):式(I-14)表示之化合物100份、分散劑(BYK-LPN21324;BYK-Chemie.Japan(股)製)130 份、樹脂(B):樹脂B4溶液170份、及溶劑(E):丙二醇單甲醚乙酸酯610份 混合且使用珠磨機使式(I-14)表示之化合物分散而成之著色組成物之中270份;將著色劑(A):C.I.顏料黃138(顏料)23份、分散劑9.6份、樹脂9.6份、及溶劑(E):丙二醇單甲醚乙酸酯150份混合且使用珠磨機使顏料分散而成之顏料分散液的總量;著色劑(A):下述式表示之化合物(使用日本特開2013-235257號公報所述之方法製成)7.4份;
樹脂(B):樹脂B3溶液35份;聚合性化合物(C):聚合性化合物(A9550;新中村化學工業(股)製)27份;聚合起始劑(D):下述式表示之化合物(常州強力電子新材料股份有限公司製)7.3份;
溶劑(E):4-羥基-4-甲基-2-戊酮170份;溶劑(E):丙二醇單甲醚乙酸酯290份;以及界面活性劑:聚醚改性矽酮油(Toray Silicone SH8400;TORAY.DOW CORNING(股)製)0.075份混合而得到著色硬化性組成物4。 Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone; Solvent (E): 290 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether modified silicone oil (Toray Silicone SH8400; manufactured by TORAY-DOW CORNING Co., Ltd.) was mixed in 0.075 parts to obtain Colored Curable Composition 4.
除了將著色硬化性組成物1變更成為著色硬化性組成物4以外,係與實施例10同樣地實施而進行著色圖案的製造及昇華性評估。將昇華性評估結果顯示在表13。 Except changing the coloring curable composition 1 into the coloring curable composition 4, it carried out similarly to Example 10, and performed manufacture of the coloring pattern and sublimation property evaluation. Table 13 shows the sublimation evaluation results.
除了將式(I-14)表示之化合物變更成為式(I-2)表示之化合物以外,係與實施例10同樣地實施而得到著色硬化性組成物5且進行著色圖案的製造及昇華性評估。將昇華性評估結果顯示在表13。 Except changing the compound represented by the formula (I-14) to the compound represented by the formula (I-2), it was carried out in the same manner as in Example 10 to obtain a colored curable composition 5, and to produce a colored pattern and evaluate its sublimation property. . Table 13 shows the sublimation evaluation results.
除了將式(I-14)表示之化合物變更成為式(I-2)表示之化合物以外,係與實施例13同樣地實施而得到著色硬化性組成物6且進行著色圖案的製造及昇華性評估。將昇華性評估結果顯示在表13。 Except changing the compound represented by the formula (I-14) to the compound represented by the formula (I-2), it was carried out in the same manner as in Example 13 to obtain a colored curable composition 6, and to produce a colored pattern and evaluate its sublimation property. . Table 13 shows the sublimation evaluation results.
除了將式(I-14)表示之化合物變更成為香豆素6以外,係與實施例10同樣地實施而得到著色硬化性組成物7 且進行著色圖案的製造及昇華性評估。將昇華性評估結果顯示在表13。 Except having changed the compound represented by formula (I-14) into coumarin 6, it carried out similarly to Example 10, and obtained the coloring curable composition 7, and performed manufacture of the coloring pattern, and sublimation property evaluation. Table 13 shows the sublimation evaluation results.
除了將式(I-14)表示之化合物變更成為香豆素6以外,係與實施例13同樣地實施而得到著色硬化性組成物8且進行著色圖案的製造及昇華性評估。將昇華性評估結果顯示在表13。 Except changing the compound represented by formula (I-14) into coumarin 6, it carried out similarly to Example 13, and obtained the coloring curable composition 8, and performed manufacture of the coloring pattern, and sublimation evaluation. Table 13 shows the sublimation evaluation results.
從上述的結果,得知含有本發明的化合物之著色硬化性組成物,減低著色劑的昇華。 From the above results, it was found that the colored curable composition containing the compound of the present invention reduces the sublimation of the colorant.
本發明的著色組成物和著色硬化性組成物係 能夠減低著色劑的昇華性,而適合用在彩色濾光片、液晶顯示裝置等顯示裝置。 The coloring composition and coloring curable composition of the present invention can reduce the sublimation property of the colorant, and are suitable for use in display devices such as color filters and liquid crystal display devices.
Claims (10)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016174117 | 2016-09-06 | ||
JP2016-174117 | 2016-09-06 |
Publications (2)
Publication Number | Publication Date |
---|---|
TW201815983A TW201815983A (en) | 2018-05-01 |
TWI778975B true TWI778975B (en) | 2022-10-01 |
Family
ID=61531706
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW106129973A TWI778975B (en) | 2016-09-06 | 2017-09-01 | Coloring composition |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6974081B2 (en) |
KR (1) | KR102450273B1 (en) |
CN (1) | CN107797382B (en) |
TW (1) | TWI778975B (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107793407B (en) * | 2016-09-06 | 2022-07-08 | 住友化学株式会社 | Compounds useful as colorants |
TWI670354B (en) * | 2017-02-03 | 2019-09-01 | 南韓商東友精細化工有限公司 | Self emission type photosensitive resin composition, color filter and image display device using the same |
JP2019167488A (en) * | 2018-03-26 | 2019-10-03 | 保土谷化学工業株式会社 | Salt-forming compound, and coloring composition and color filter colorant containing the same |
CN109651889A (en) * | 2018-12-21 | 2019-04-19 | 天津环球磁卡股份有限公司 | A kind of temperature becomes Antiforge fluorescent ink and preparation method thereof |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105051620A (en) * | 2013-01-25 | 2015-11-11 | 拜耳材料科技股份有限公司 | Security element having volume hologram and printed feature |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH390250A (en) * | 1958-06-19 | 1965-07-30 | Geigy Ag J R | Process for the production of fluorescent dyes |
CH487231A (en) | 1967-10-03 | 1970-03-15 | Geigy Ag J R | Concentrated solution of cyclammonium color salts |
LU78311A1 (en) | 1977-10-13 | 1979-06-01 | Ciba Geigy Ag | NEW CUMARIN DYES, THEIR PRODUCTION AND USE |
DE19509043A1 (en) * | 1995-03-03 | 1996-09-05 | Bayer Ag | Cyanation of double bond systems |
ATE471513T1 (en) * | 2003-07-30 | 2010-07-15 | Hoffmann La Roche | NEW CHEMILUMINESCENCE COMPOUNDS AND THEIR USE |
KR102105617B1 (en) * | 2012-08-24 | 2020-04-29 | 스미또모 가가꾸 가부시키가이샤 | Compound for dye |
KR20140100264A (en) * | 2013-02-06 | 2014-08-14 | 동우 화인켐 주식회사 | Colored photosensitive resin composition |
CN104513498B (en) * | 2013-10-03 | 2020-01-17 | 东友精细化工有限公司 | Dye dispersion liquid |
JP6340871B2 (en) * | 2014-03-31 | 2018-06-13 | 東洋インキScホールディングス株式会社 | Coloring composition for color filter, and color filter |
JP6749242B2 (en) * | 2014-09-12 | 2020-09-02 | 住友化学株式会社 | Compound and colored curable resin composition containing the compound |
JP6056844B2 (en) * | 2014-12-26 | 2017-01-11 | 大日本印刷株式会社 | Color material dispersion for color filter, colored resin composition for color filter, color material, color filter, liquid crystal display device and light emitting display device |
JP6440494B2 (en) * | 2014-12-26 | 2018-12-19 | 住友化学株式会社 | Compound |
JP6699999B2 (en) * | 2015-02-26 | 2020-05-27 | 東友ファインケム株式会社Dongwoo Fine−Chem Co., Ltd. | Colored curable resin composition, color filter and display device |
-
2017
- 2017-09-01 CN CN201710780670.3A patent/CN107797382B/en active Active
- 2017-09-01 TW TW106129973A patent/TWI778975B/en active
- 2017-09-04 KR KR1020170112679A patent/KR102450273B1/en active IP Right Grant
- 2017-09-06 JP JP2017171514A patent/JP6974081B2/en active Active
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105051620A (en) * | 2013-01-25 | 2015-11-11 | 拜耳材料科技股份有限公司 | Security element having volume hologram and printed feature |
Also Published As
Publication number | Publication date |
---|---|
CN107797382A (en) | 2018-03-13 |
KR20180027371A (en) | 2018-03-14 |
TW201815983A (en) | 2018-05-01 |
JP6974081B2 (en) | 2021-12-01 |
CN107797382B (en) | 2022-02-22 |
KR102450273B1 (en) | 2022-10-04 |
JP2018040001A (en) | 2018-03-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR102561742B1 (en) | Colored composition and compound | |
TWI733945B (en) | Colored curable resin composition, color filter formed from the colored curable resin composition and display device including the color filter | |
TWI476517B (en) | Coloring the photosensitive resin composition | |
TWI738797B (en) | Compound, colored curable resin composition, color filter and display device | |
TWI778975B (en) | Coloring composition | |
TWI712654B (en) | Compound and coloring composition | |
TWI775913B (en) | Colored curable resin composition, color filter, and display device | |
JP6943558B2 (en) | Color curable resin composition, color filter, and display device | |
TWI515268B (en) | Colored photosensitive resin composition and compound | |
JP6672725B2 (en) | Colored curable resin composition | |
TW202030264A (en) | Colored composition, colored curable resin composition, color filter, and display device | |
TWI763706B (en) | Compound useful as colorant | |
TWI746612B (en) | Compound, coloring composition, fiber material, color filter and display device | |
JP2020083982A (en) | Colored curable resin composition, color filter, display device, and compound | |
JP7324045B2 (en) | Colored curable resin composition | |
TW202222987A (en) | Compound, colored curable resin composition, color filter and display device excellent in the drainage treatment property of a developer | |
TW202212485A (en) | Colored curable resin composition, color filter, display device capable of forming a dark-colored curable film with a thin film thickness | |
TW202239878A (en) | Colored resin composition, compound, color filter and display device wherein the colored resin composition includes a colorant, a resin, a polymerizable compound and a polymerization initiator | |
TW202012393A (en) | Coloring composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
GD4A | Issue of patent certificate for granted invention patent |