CN107015435B - Photosensitive resin composition, color filter and manufacturing method and application thereof - Google Patents

Photosensitive resin composition, color filter and manufacturing method and application thereof Download PDF

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CN107015435B
CN107015435B CN201610961814.0A CN201610961814A CN107015435B CN 107015435 B CN107015435 B CN 107015435B CN 201610961814 A CN201610961814 A CN 201610961814A CN 107015435 B CN107015435 B CN 107015435B
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carbon atoms
alkyl group
carbon number
substituted
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CN107015435A (en
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何维凱
许荣宾
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Chi Mei Corp
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Chi Mei Corp
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    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

Abstract

The invention provides a photosensitive resin composition, which comprises a pigment (A), a dye (B), an alkali-soluble resin (C), a compound (D) containing an ethylene unsaturated group, a photoinitiator (E), a benzophenone compound (F) containing an unsaturated group and a solvent (G). The invention also provides a color filter and a manufacturing method and application thereof. The photosensitive resin composition can be used for preparing a color filter with good chemical resistance and contrast.

Description

Photosensitive resin composition, color filter and manufacturing method and application thereof
Technical Field
The present invention relates to a photosensitive resin composition, a color filter, a method for manufacturing the same, and an application of the same, and more particularly, to a photosensitive resin composition, a color filter, a method for manufacturing the same, and an application of the same having good chemical resistance and contrast.
Background
At present, color filters are widely used in the fields of office equipment such as color liquid crystal displays, color facsimile machines, and color cameras. With the increasing market demand, the manufacturing technology of color filters tends to be diversified, and the manufacturing methods such as dyeing method, printing method, electroplating method, and dispersion method have been developed, wherein the dispersion method is the main process.
the process of the dispersion method is to disperse the coloring pigment in the photosensitive resin, then coat the photosensitive resin on the glass substrate, and then the specific pattern can be obtained by the steps of exposure, development, etc. After repeating the operation three times, patterns of pixel coloring layers of red (R), green (G) and blue (B) can be prepared, and then a protective film can be applied on the patterns of the pixel coloring layers as required.
The photosensitive resin used in the dispersion process is, for example, an alkali-soluble resin which is a copolymer obtained by polymerizing (meth) acrylic acid as a monomer component, as disclosed in Japanese patent application laid-open Nos. 6-95211 and 8-183819.
However, in the manufacturing process of the color filter, it is necessary to perform a plurality of heat treatment steps, such as a post-baking (post-baking) step after patterning the pixel coloring layer such as red (R), green (G), and blue (B), and a forming step of the transparent conductive film (ITO film), which are generally performed at a high temperature of 200 ℃ or higher, but if the above-mentioned conventional photosensitive resin is heated at 180 ℃ for about 1 hour, pigment aggregated particles (generally having a particle diameter of 1 μm to 10 μm) are easily generated in the pixel coloring layer, and the heat resistance of the pixel coloring layer is also not good.
In order to solve the above problems, jp 2001-075273 a discloses a photosensitive resin composition comprising a polymer obtained by polymerizing a carboxylic acid group-containing unsaturated monomer and a glycidyl group-containing monomer, and using the polymer as an alkali-soluble resin of a photosensitive resin. However, the color filter prepared by using the photosensitive resin composition of the prior art has the problems of poor chemical resistance and contrast.
Therefore, how to overcome the problems of poor chemical resistance and contrast simultaneously to meet the requirements of the present industry is an objective of the present invention.
Disclosure of Invention
Therefore, an object of the present invention is to provide a photosensitive resin composition which can provide good chemical resistance and contrast for subsequent applications.
another object of the present invention is to provide a method for manufacturing a color filter, which uses the photosensitive resin composition to form a pixel layer on a substrate.
Another objective of the present invention is to provide a color filter, which is manufactured by the above method.
Another objective of the present invention is to provide a liquid crystal display device, which includes the color filter.
Photosensitive resin composition
In accordance with the above object of the present invention, a photosensitive resin composition is provided. In one embodiment, the photosensitive resin composition comprises a pigment (A), a dye (B), an alkali-soluble resin (C), an ethylenically unsaturated group-containing compound (D), a photoinitiator (E), an unsaturated group-containing benzophenone compound (F), and a solvent (G). These are described in detail below.
Pigment (A)
The pigment (A) of the present invention may be an inorganic pigment, an organic pigment or a combination of the above.
The inorganic pigment may be a metal compound such as a metal oxide or a metal complex, and may be selected from oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, antimony, and composite oxides of the above metals.
The organic pigment is selected from c.1 pigment yellow 1,3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; c.i. pigment orange, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64, 71, 73; c.i. pigment red, 2,3, 4,5, 6,7, 8, 9,10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: l, 48: 2. 48: 3. 48: 4. 49: l, 49: 2. 50: 1. 52: l, 53: l, 57: l, 57: 2. 58: 2. 58: 4. 60: l, 63: l, 63: 2. 64: l, 81: l, 83, 88, 90: l, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; c.i. pigment violet, 14, 19, 23, 29, 32, 33, 36, 37, 38, 39, 40, 50; c.i. pigment blue l, 2, 15: 1. 15: 2. 15: 3. 15: 4. 15: 5. 15: 6. 16, 21, 22, 60, 61, 64, 66; c.i. pigment green 7, 36, 37, 42, 58; c.i. pigment brown 23, 25, 28; and c.i. pigment black, 7. The organic pigments mentioned above may be used singly or in combination of plural kinds.
The average particle diameter of the primary particles of the pigment (A) is preferably from 10nm to 200nm, more preferably from 20nm to 150nm, most preferably from 30nm to 130 nm.
the pigment (a) is used in an amount of 30 to 300 parts by weight, preferably 40 to 250 parts by weight, more preferably 50 to 200 parts by weight, based on 100 parts by weight of the total alkali-soluble resin (C).
If desired, the pigment (A) can also be used optionally with dispersants such as: cationic, anionic, nonionic, amphoteric, polysiloxane, fluorine-based, and the like surfactants.
The aforementioned surfactants may include, but are not limited to, polyethylene oxide alkyl ethers such as polyethylene oxide dodecyl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, and the like; polyoxyethylene alkyl phenyl ether surfactants such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyethylene glycol diester surfactants such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid ester surfactants; fatty acid modified polyester-based surfactants; tertiary amine modified polyurethane surfactants; manufactured by shin-Etsu chemical industry, a product of type KP, manufactured by Toray Dow Corning Silicon, a product of type SF-8427, manufactured by oil and fat chemical industry of Cogrong, a product of type Polyflow, manufactured by Decham corporation (Tochem Products Co., Ltd.), a product of type F-Top, manufactured by Dainippon ink chemical industry, a product of type Megafac, manufactured by Sumitomo 3M, a product of type Fluorad, manufactured by glass, and a product of type Asahi Guard and Surflon. The surfactant may be used singly or in combination.
dye (B)
The dye (B) of the present invention comprises a dye (B-1) having a structure represented by the formula (I):
In the formula (I), L1To L4each independently represents hydrogen, -L6An aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L6、-OH、-OL6、-SO3 -、-SO3H、-SO3M、-COOH、-COOL6、-SO3L6、 -SO2NHL8or-SO2NL8L9A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms;
L5represents-SO3 -、-SO3H、-SO3M、-COOH、-COOL6、-SO3L6、-SO2NHL8or-SO2NL8L9；
u represents an integer of 0 to 5; when u represents 2 to 5, a plurality of L5Are the same or different;
XbRepresents a halogen atom;
a represents 0 or 1;
L6Represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms which is substituted with a halogen atom, wherein-CH in the alkyl group having 1 to 10 carbon atoms or the alkyl group having 1 to 10 carbon atoms which is substituted with a halogen atom2Is unsubstituted or substituted by-O-, carbonyl or-NL7-；
L7Represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom;
L8And L9Each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or-Q; wherein a hydrogen atom in a straight-chain alkyl group having a carbon number of 1 to 10, a branched-chain alkyl group having a carbon number of 3 to 10 or a cycloalkyl group having a carbon number of 3 to 30 is unsubstituted or substituted by a substituent selected from the group consisting of a hydroxyl group, a halogen atom, -Q, -CH ═ CH2and-CH ═ CH-L6The group consisting of; -CH in a linear alkyl group having a carbon number of 1 to 10, a branched alkyl group having a carbon number of 3 to 10, or a cycloalkyl group having a carbon number of 3 to 302Is unsubstituted or substituted by-O-, carbonyl or-NL7-; or
L8And L9Combined to form a heterocyclic group with a carbon number of 2 to 10, wherein a hydrogen atom in the heterocyclic group with a carbon number of 2 to 10 is unsubstituted or L6-OH, or-Q;
Q representsAn aromatic hydrocarbon group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 10 carbon atoms, a halogen atom, -L6、-OH、-OL6、-NO2、-CH＝CH2or-CH ═ CH-L6Substituted aromatic hydrocarbon radical having 6 to 10 carbon atoms, or via halogen atoms, -L6、-OH、-OL6、-NO2、-CH＝CH2and-CH ═ CH-L6a substituted heteroaryl group having 5 to 10 carbons; and
M represents potassium or sodium.
preferably, L6including but not limited to methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl (neopentyl), cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptane, octyl, cyclooctyl, 2-ethylhexyl, nonyl, decyl, tricyclo [5.3.0.0 ]3,10]Decyl (tricycle [ 5.3.0.0)3,10]decanoyl), methoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, or epoxypropyl.
Preferably, the aromatic hydrocarbon group having 6 to 10 carbon atoms includes, but is not limited to, phenyl or naphthyl.
Preferably, -SO3L6Including but not limited to methylsulfonyl (methanesulfonyl), ethylsulfonyl (ethaneesulfonyl), hexylsulfonyl (hexanesulfonyl), or decylsulfonyl (decanoylsulfonyl).
Preferably, -COOL6including but not limited to methoxycarbonyl (methyxycarbonyl), ethoxycarbonyl (ethylxycarbonyl), propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, cyclooctyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, tricyclo [5.3.0.03,10]Decyl carbonyl, methoxy propoxy carbonyl, hexyloxy propoxy carbonyl, 2-ethylhexyloxy propoxy carbonyl, or methoxy hexyloxy carbonyl.
Preferably, -SO2NHL8Including but not limited toSulfamoyl (sulfamoyl), methylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, isopropylsulfamoyl, butylsulfamoyl, isobutylsulfamoyl, pentylsulfamoyl, isopentylsulfamoyl, neopentylsulfamoyl, cyclopentylsulfamoyl, hexylsulfamoyl, cyclohexylsulfamoyl, heptylsulfamoyl, cycloheptylsulfamoyl, octylsulfamoyl, cyclooctylsulfamoyl, 2-ethylhexylsulfamoyl, nonylsulfamoyl, decylsulfamoyl, tricyclo [5.3.0.0 ] sulfamoyl3 , 10]Decyl sulfamoyl, methoxypropyl sulfamoyl, hexyloxypropyl sulfamoyl, 2-ethylhexylsulfamoyl, methoxyhexyl sulfamoyl, epoxypropyl sulfamoyl, 1, 5-dimethylhexylsulfamoyl, propoxypropylsulfamoyl, isopropoxypropyl sulfamoyl, 3-phenyl-1-methylpropyl sulfamoyl, amino acid, amino, (RaRepresents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom or an alkoxy group having 1 to 3 carbon atoms substituted with a halogen atom)
(RbRepresents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom or an alkoxy group having 1 to 3 carbon atoms substituted with a halogen atom),
Preferably, -SO2NL8L9Including but not limited to (RbRepresents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom or an alkoxy group having 1 to 3 carbon atoms substituted with a halogen atom)
Preferably, the dye (B-1) includes a dye having a structure represented by the formula (I-1):
In the formula (I-1):
L11To L14Each independently represents hydrogen, -L6An aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L6、-OH、-OL6、-SO3 -、-SO3H、-SO3Na、-COOH、-COOL6、-SO3L6、-SO2NHL8or-SO2NL8L9A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms;
L15Represents hydrogen, -SO3 -、-SO3H、-SO2NHL8or-SO2NL8L9；
L16represents-SO3 -、-SO3H、-SO2NHL8or-SO2NL8L9；
X1bRepresents a halogen atom;
a1Represents 0 or 1.
Preferably, the dye (B-1) includes a dye having a structure represented by the formula (I-2):
In the formula (I-2):
L21To L24Each independently represents hydrogen, -L26An aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L26、-OH、-OL26、-SO3 -、-SO3H、-SO3Na、-COOH、-COOL26、-SO3L26or-SO2NHL28A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms;
L25represents-SO3 -、-SO3Na、-COOH、-COOL26、-SO3H. or-SO2NHL28；
u1Represents an integer of 0 to 5; when u is1When representing 2 to 5, a plurality of L25Are the same or different;
X2bRepresents a halogen atom;
a2Represents 0 or 1;
L26Represents an alkyl group having 1 to 10 carbon atoms, or a halogen atom or-OL27A substituted alkyl group having 1 to 10 carbon atoms;
L27Represents an alkyl group having 1 to 10 carbon atoms; and
L28Represents hydrogen, -L26、-COOL26An aromatic hydrocarbon group having 6 to 10 carbon atoms, or a mono-or di-L group26or-OL26a substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.
Preferably, the dye (B-1) includes a dye having a structure as in formula (I-3)
In the formula (I-3):
L31And L32Each independently represents phenyl, or-L via a halogen atom26、-OL26、-COOL26、-SO3L26or-SO2NHL28Substituted phenyl;
L33represents-SO3 -or-SO2NHL28；
L34Represents hydrogen, -SO3 -or-SO2NHL28；
X3bRepresents a halogen atom;
a3represents 0 or 1;
L26Represents an alkyl group having 1 to 10 carbon atoms, or a halogen atom or-OL27A substituted alkyl group having 1 to 10 carbon atoms;
L27represents an alkyl group having 1 to 10 carbon atoms; and
L28Represents hydrogen, -L26、-COOL26An aromatic hydrocarbon group having 6 to 10 carbon atoms, or a mono-or di-L group26or-OL26A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.
preferably, the dye (B-1) includes a dye having a structure according to formula (I-4):
(I-4)
in the formula (I-4):
L41And L42Each independently represents phenyl, or-L26or-SO2NHL28Substituted phenyl;
L43represents-SO3 -or-SO2NHL28；
X4bRepresents a halogen atom;
a4Represents 0 or 1;
L26Represents an alkyl group having 1 to 10 carbon atoms, or a halogen atom or-OL27A substituted alkyl group having 1 to 10 carbon atoms;
L27Represents an alkyl group having 1 to 10 carbon atoms; and
L28Represents hydrogen, -L26、-COOL26An aromatic hydrocarbon group having 6 to 10 carbon atoms, or a mono-or di-L group26or-OL26A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.
In the embodiment of the present invention, the dye (B-1) includes, but is not limited to, compounds represented by the following formulas (1) to (31):
in the formula (1), RcAnd RdEach independently represents hydrogen, -SO3 --COOH or-SO2NHL81；
L81Represents 2-ethylhexyl;
XbRepresents a halogen atom;
a represents 0 or 1.
In the formula (2), ReRepresents hydrogen, -SO3 --COOH or-SO2NHL81；
L81Represents 2-ethylhexyl;
XbRepresents a halogen atom;
a represents 0 or 1.
In formula (3), ReRepresents hydrogen, -SO3 --COOH or-SO2NHL81；
L81Represents 2-ethylhexyl;
XbRepresents a halogen atom;
a represents 0 or 1.
In the formula (4), Rf、RgAnd RhEach independently represents-SO3 -、-SO3Na or-SO2NHL81；
L81represents 2-ethylhexyl.
In formula (5), Rf、RgAnd RhEach independently represents-SO3 -、-SO3Na or-SO2NHL81；
L81Represents 2-ethylhexyl.
In formula (6), Ri、RjAnd Rkeach independently represents hydrogen, -SO3 -、-SO3H or-SO2NHL81；
L81Represents 2-ethylhexyl.
In formula (7), Ri、RjAnd RkEach independently represents hydrogen, -SO3 -、-SO3H or-SO2NHL81；
L81Represents 2-ethylhexyl.
In formula (8), Rl、RmAnd RnEach independently represents-SO3 -、-SO3Na or-SO2NHL81；
L81represents 2-ethylhexyl.
in formula (9), Rl、RmAnd RnEach independently represents-SO3 -、-SO3Na or-SO2NHL81；
L81Represents 2-ethylhexyl.
In formula (10), Rp、RqAnd Rreach independently represents hydrogen, -SO3 -、-SO3H or-SO2NHL81；
L81Represents 2-ethylhexyl.
In formula (11), Rp、Rqand RrEach independently represents hydrogen, -SO3 -、-SO3H or-SO2NHL81；
L81represents 2-ethylhexyl.
A preferred embodiment of the dye (B-1) of the present invention is a dye of the formula (1) (R)cAnd Rdis-SO3 -And a is 0) [ C.I. acid red dye 52]An acid red dye 289 of the formula (22) [ C.I.. acid]A dye of formula (28), a dye of formula (31), or any combination thereof.
In the specific embodiment of the present invention, the dye (B-1) is used in an amount of 3 to 50 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C); preferably 5 to 45 parts by weight; more preferably 10 to 40 parts by weight. When the dye (B-1) is used, the photosensitive resin composition is excellent in contrast.
In a preferred embodiment of the present invention, the dye (B) may further comprise another dye (B-2).
Preferably, the other dye (B-2) includes, but is not limited to, azo-based dyes, anthraquinone-based dyes, phthalocyanine-based dyes, quinoneimine-based dyes, quinoline-based dyes, nitro-based dyes, or triarylmethane-based dyes. Azo dyes include, but are not limited to, c.i. acid yellow 11, acid orange 7, acid red 37, acid red 180, acid blue 29, direct red 28, direct red 83, direct yellow 12, direct orange 26, direct green 28, direct green 59, reactive yellow 2, reactive red 17, reactive red 120, reactive black 5, disperse orange 5, disperse red 58, disperse blue 165, basic blue 41, basic red 18, mordant red 7, mordant yellow 5, mordant black 7, and the like; anthraquinone dyes include, but are not limited to, c.i. bade blue 4(Batblue 4), acid blue 40, acid green 25, reactive blue 19, reactive blue 49, disperse red 60, disperse blue 56, disperse blue 60, and the like; phthalocyanine-based dyes include, but are not limited to, c.i. basic blue 5, and the like; quinone imine based dyes include, but are not limited to, c.i. basic blue 3, basic blue 9, and the like; quinoline dyes c.i. solvent yellow 33, acid yellow 3, disperse yellow 64, and the like; nitro-based dyes include, but are not limited to, c.i. acid yellow 1, acid orange 3, disperse yellow 42, and the like; triarylmethane-based dyes include, but are not limited to, c.i. acid violet 15, 16, 17, 19, 21, 23, 24, 25, 38, 49, 72; c.i. acid blue 1,3, 5, 7, 9, 11, 13, 15, 17, 22, 24, 26, 34, 38, 48, 75, 83, 84, 86, 88, 90: 1. 91, 93: 1. 99, 100, 103, 104, 108, 109, 110, 119, 123, 147, 213, 269; c.i. acid green 3,5, 6,7, 8, 9, 11, 13, 14, 15, 16, 22, 50: 1; c.i. basic blue 7, 81, 83, 88, 89; c.i. basic violet 2; c.i. basic red 9; c.i. direct blue 1,3, 28, 29, 41, 42, 47, 52, 55; c.i. edible violet 3; c.i. vehicle red 29, 42, 52, 62, 76, 78; c.i. intermediate violet 1, 1: 1.3, 6, 8, 10, 11, 15, 16, 17, 18, 19, 21, 23, 27, 28, 33, 36, 39, 49; c.i. medium green 3, 13, 21, 23, 31; or, c.i. mordant brown 26. The above-mentioned other dyes may be generally used singly or in combination of plural kinds.
In the specific embodiment of the present invention, the other dye (B-2) is used in an amount of 0 to 47 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C) used; preferably 0 to 40 parts by weight; more preferably 0 to 30 parts by weight.
The dye (B) is used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C); preferably 10 to 45 parts by weight; more preferably 15 to 40 parts by weight.
Alkali soluble resin (C)
First alkali soluble resin (C-1)
The alkali-soluble resin (C) of the present invention may comprise a first alkali-soluble resin (C-1) obtained by polymerizing a mixture comprising an epoxy compound (C-1-1) having at least two epoxy groups and a compound (C-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. In addition, the mixture may further optionally contain a carboxylic acid anhydride compound (c-1-3) and/or an epoxy group-containing compound (c-1-4).
The epoxy compound (c-1-1) having at least two epoxy groups may have a structure represented by the following formula (II-1) or the following formula (II-2). Here, the description that "the epoxy compound (c-1-1) may have a structure represented by the following formula (II-1) or the following formula (II-2)" also covers the case where a compound having a structure represented by the following formula (II-1) and a compound having a structure represented by the following formula (II-2) are present together as the epoxy compound (c-1-1). Specifically, the epoxy compound (c-1-1) having at least two epoxy groups has, for example, a structure represented by the following formula (II-1):
In the formula (II-1), R1c、R2c、R3cAnd R4ceach of which is the same or different and represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms.
The epoxy compound (c-1-1) having at least two epoxy groups of the aforementioned formula (II-1) may include, but is not limited to, bisphenol fluorene type compounds containing epoxy groups obtained by reacting bisphenol fluorene type compounds (bisphenone) with halogenated propylene oxide (epihalohydride).
Specific examples of the bisphenol fluorene compound include, but are not limited to: 9,9-bis (4-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene ], 9-bis (4-hydroxy-3-methylphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene ], 9-bis (4-hydroxy-3-chlorophenyl) fluorene [9,9-bis (4-hydroxy-3-chlorophenyl) fluorene ], 9-bis (4-hydroxy-3-bromophenyl) fluorene [9,9-bis (4-hydroxy-3-bromophenyl) fluorene ], 9-bis (4-hydroxy-3-fluorophenyl) fluorene [9,9-bis (4-hydroxy-3-fluorophenyl) fluorene ], 9-bis (4-hydroxy-3-hydroxyphenyl) fluorene [9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene ], 9-bis (4-hydroxy-3-methoxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene ],9-3-methoxyphenyl) fluorene, 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene [9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene ], 9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene [9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene ], 9-bis (4-hydroxy-3,5-dibromophenyl) fluorene [9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene ], and the like.
The halogenated propylene oxide (epihalohydhdin) may include, but is not limited to, 3-chloro-1, 2-propylene oxide (epichlorohydhdin) or 3-bromo-1, 2-propylene oxide (epibromohydhdin), and the like.
The above bisphenol fluorene type compound containing an epoxy group obtained by reacting a bisphenol fluorene type compound with a halogenated propylene oxide includes, but is not limited to: (1) commercial product manufactured by Nippon Steel Chemical co., Ltd): such as ESF-300, etc.; (2) a commercial product manufactured by Osaka Gas (Osaka Gas co., Ltd): such as PG-100, EG-210, etc.; (3) a commercial product manufactured by short message Technology (s.m.s Technology co., Ltd): for example, SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, etc.
Next, the above-mentioned epoxy compound (c-1-1) having at least two epoxy groups may also have a structure represented by the following formula (II-2):
In the formula (II-2), R5cTo R18cAre respectively the same or different and may eachIndependently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group having 6 to 15 carbon atoms; and g represents an integer of 0 to 10.
The epoxy compound (c-1-1) having at least two epoxy groups of the formula (II-2) is obtained by reacting a compound having the structure of the following formula (II-2-1) with a halogenated propylene oxide in the presence of an alkali metal hydroxide, for example.
In the formula (II-2-1), R5cTo R18cAnd g is defined as being independently of R in the formula (II-2)5cTo R18cand g are defined the same and are not described herein.
The epoxy compound (c-1-1) having at least two epoxy groups of the formula (II-2) is a compound having a structure of the formula (II-2-1) obtained by condensation reaction of a compound having a structure of the formula (II-2-2) with phenols (phenol) in the presence of an acid catalyst, for example. Then, dehydrohalogenation is carried out by adding an excess of halogenated propylene oxide to obtain an epoxy compound (c-1-1) having at least two epoxy groups as shown in the formula (II-2).
In the above formula (II-2-2), R19cAnd R20cRespectively, the same or different hydrogen atoms, halogen atoms, alkyl groups with 1 to 8 carbon atoms or aryl groups with 6 to 15 carbon atoms; x1and X2Respectively, the same or different halogen atoms, alkyl groups having 1 to 6 carbon atoms or alkoxy groups having 1 to 6 carbon atoms. Preferably, the halogen atom can be, for example, chlorine or bromine, the alkyl group can be, for example, methyl, ethyl or tert-butyl, and the alkoxy group can be, for example, methoxy or ethoxy.
Specific examples of the phenols include, but are not limited to: phenol (cresol), cresol (cresol), ethylphenol (ethylphenol), n-propylphenol (n-propylphenol), isobutylphenol (isobutoylphenol), t-butylphenol (t-butylphenol), octylphenol (octylphenol), nonylphenol (nonylphenol), stubble phenol (xylenol), methylbutylphenol (methylbutylphenol), di-tert-butylphenol (di-t-butylphenol), vinylphenol (vinylphenol), propenylphenol (propenylphenol), ethynylphenol (ethinylphenol), cyclopentylphenol (cyclopropenylphenol), cyclohexylphenol (cyclopentylphenol), or cyclohexylcresol (cyclohexenylphenol), and the like. The above phenols may be used alone or in combination of two or more.
The amount of the phenol to be used is 0.5 to 20 moles, preferably 2 to 15 moles, based on 1 mole of the compound having the structure of the formula (II-2-2) above.
Specific examples of the acid catalyst include: hydrochloric acid, sulfuric acid, p-toluenesulfonic acid (p-toluenesulfonic acid), oxalic acid (oxalic acid), boron trifluoride (boron trifluoride), anhydrous aluminum chloride (anhydrous aluminum chloride), zinc chloride (zinc chloride), and the like, with p-toluenesulfonic acid, sulfuric acid, or hydrochloric acid being preferred. The above acid catalysts may be used singly or in combination of plural kinds.
In addition, although the amount of the above acid catalyst used is not particularly limited, the amount of the acid catalyst used is preferably 0.1 to 30% by weight based on 100% by weight (wt%) of the compound having the structure of the above formula (II-2-2).
The condensation reaction can be carried out in the absence of a solvent or in the presence of an organic solvent. Next, specific examples of the organic solvent include: toluene (tolumen), xylene (xylene), methyl isobutyl ketone (methyl isobutyl ketone), or the like. The above organic solvents may be used singly or in combination of plural kinds.
The organic solvent is used in an amount of 50 to 300 wt%, preferably 100 to 250 wt%, based on 100 wt% of the total amount of the compound having the structure of formula (II-2-2) and the phenol. In addition, the operation temperature of the above condensation reaction is 40 ℃ to 180 ℃, and the operation time of the condensation reaction is 1 hour to 8 hours.
After the completion of the above condensation reaction, neutralization treatment or washing treatment may be carried out. The neutralization treatment is carried out by adjusting the pH of the solution after the reaction to pH 3 to pH 7, preferably pH 5 to pH 7. The above-mentioned washing treatment may be carried out using a neutralizing agent which is an alkaline substance, and specific examples thereof include: alkali metal hydroxides such as sodium hydroxide (sodium hydroxide) and potassium hydroxide (potassium hydroxide); alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; organic amines such as diethylenetriamine (diethylene triamine), triethylenetetramine (triethylene tetramine), aniline (aniline), and phenylenediamine (phenylene diamine); and ammonia (ammonium), sodium dihydrogen phosphate (sodium dihydrogen phosphate), and the like. The washing treatment can be carried out by a known method, for example, by adding an aqueous solution containing a neutralizing agent to the solution after the reaction and repeating the extraction. After neutralization or water washing, decompression heating treatment is carried out, unreacted phenols and solvent are distilled off, and concentration is carried out, thus obtaining the compound with the structure of formula (II-2-1).
Specific examples of the halogenated propylene oxide include: 3-chloro-1,2-epoxypropane (3-chloro-1,2-epoxypropane), 3-bromo-1,2-epoxypropane (3-bromo-1,2-epoxypropane), or any combination thereof. Before the dehydrohalogenation reaction, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or during the reaction. The above dehydrohalogenation reaction is carried out at an operating temperature of 20 ℃ to 120 ℃ for an operating time ranging from 1 hour to 10 hours.
In an embodiment of the present invention, an aqueous solution of the alkali metal hydroxide to be added in the dehydrohalogenation reaction may be used. In this embodiment, the above-mentioned aqueous alkali metal hydroxide solution is continuously added to the hydrogen dehalogenation reaction system, and at the same time, water and halogenated propylene oxide are continuously distilled out under reduced pressure or normal pressure, whereby water is separated and removed, and at the same time, halogenated propylene oxide can be continuously refluxed into the reaction system.
Before the dehydrohalogenation reaction, a quaternary ammonium salt such as tetramethylammonium chloride (tetramethylammonium chloride), tetramethylammonium bromide (tetramethylammonium bromide), or trimethylbenzylammonium chloride (trimethylbenzylammonium chloride) may be added as a catalyst, and the reaction may be carried out at 50 to 150 ℃ for 1 to 5 hours, followed by addition of an alkali metal hydroxide or an aqueous solution thereof and reaction at 20 to 120 ℃ for 1 to 10 hours to carry out the dehydrohalogenation reaction.
The halogenated propylene oxide may be used in an amount of 1 to 20 equivalents, preferably 2 to 10 equivalents, based on 1 equivalent of the total equivalents of hydroxyl groups in the compound having the structure of the above formula (II-2-1). The amount of the alkali metal hydroxide added in the above dehydrohalogenation reaction may be 0.8 to 15 equivalents, preferably 0.9 to 11 equivalents, based on 1 equivalent of the total equivalents of hydroxyl groups in the above compound having a structure of the formula (II-2-1).
In order to facilitate the dehydrohalogenation reaction, the reaction may be carried out by adding thereto an alcohol such as methanol or ethanol, or a non-protic polar solvent such as dimethyl sulfone or dimethyl sulfoxide. In the case of using alcohols, the amount of the alcohols to be used may be 2 to 20% by weight, preferably 4 to 15% by weight, based on 100% by weight of the total amount of the above halogenated propylene oxide. In the case of using the aprotic polar solvent, the amount of the aprotic polar solvent to be used may be 5 to 100% by weight, preferably 10 to 90% by weight, based on 100% by weight of the total amount of the halogenated propylene oxide.
After the dehydrohalogenation reaction is completed, a water washing treatment may be optionally performed. Then, the halogenated propylene oxide, alcohols, aprotic polar solvents, and the like are removed by heating under reduced pressure. The heating and the pressure reduction are carried out, for example, at a temperature of 110 ℃ to 250 ℃ and under a pressure of 1.3kPa (10mmHg) or less.
in order to avoid the addition of hydrolyzable halogen to the epoxy resin formed, the dehydrohalogenation reaction may be carried out again by adding a solvent such as toluene or methyl isobutyl ketone to the solution after the dehydrohalogenation reaction, and adding an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. In the dehydrohalogenation reaction, the alkali metal hydroxide is used in an amount of 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 equivalent of the total equivalents of hydroxyl groups in the above-mentioned compound having the structure of formula (II-2-1). In addition, the above dehydrohalogenation reaction is carried out at an operating temperature ranging from 50 ℃ to 120 ℃ and for an operating time ranging from 0.5 hours to 2 hours.
After the dehydrohalogenation reaction is completed, the salts are removed by filtration and washing with water. In addition, the solvent such as toluene and methyl isobutyl ketone can be distilled off by heating and reducing pressure, and the epoxy compound (c-1-1) having at least two epoxy groups shown in the formula (II-2) can be obtained. The epoxy compound (c-1-1) having at least two epoxy groups of the above formula (II-2) may include, but is not limited to, products manufactured by Nippon Kayaku Co. Ltd., such as Nippon Kayaku Co. Ltd., trade names NC-3000, NC-3000H, NC-3000S and NC-3000P.
The compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is, for example, selected from the group consisting of the following (1) to (3): (1) acrylic acid, methacrylic acid, 2-methacryloyloxyethylsuccinic acid (2-methacryloyloxybutylsuccinic acid), 2-methacryloyloxybutylsuccinic acid, 2-methacryloyloxyethyladipic acid, 2-methacryloyloxybutyladipic acid, 2-methacryloyloxyethylhexahydrophthalic acid, 2-methacryloyloxyethylmaleic acid, 2-methacryloxypropylmaleic acid, 2-methacryloxybutylmaleic acid, 2-methacryloxypropylsuccinic acid, 2-methacryloxypropyladipic acid, 2-methacryloxypropyltetrahydrophthalic acid, 2-methacryloxypropylphthalic acid, 2-methacryloxybutylphthalic acid, or 2-methacryloxybutylhydrogenphthalic acid; (2) compounds obtained by reacting hydroxyl group-containing (meth) acrylates with dicarboxylic acid compounds including, but not limited to, adipic acid, succinic acid, maleic acid, phthalic acid; (3) a half ester compound obtained by reacting a hydroxyl group-containing (meth) acrylate with a carboxylic anhydride compound, wherein the hydroxyl group-containing (meth) acrylate includes, but is not limited to, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, or pentaerythritol trimethacrylate, etc. The carboxylic anhydride compound mentioned here may be the same as the carboxylic anhydride compound (C-1-3) contained in the mixture of the first alkali-soluble resin (C-1) described below, and therefore, the description thereof is omitted.
The mixture of the first alkali-soluble resin (C-1) may further optionally contain a carboxylic acid anhydride compound (C-1-3) and/or an epoxy group-containing compound (C-1-4). The above carboxylic anhydride compound (c-1-3) may be selected from the group consisting of the following (1) to (2): (1) dicarboxylic acid anhydrides such as succinic anhydride (butanedioic anhydride), maleic anhydride (maleic anhydride), Itaconic anhydride (Itaconic anhydride), phthalic anhydride (phthalic anhydride), tetrahydrophthalic anhydride (tetrahydrophthalic anhydride), hexahydrophthalic anhydride (hexahydrophthalic anhydride), methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride (methyl-endomethylenetetrahydrophthalic anhydride), chlorendic anhydride (chlorendic anhydride), glutaric anhydride, and trimellitic anhydride (1, 3-dioxobenzidine-5-carboxylic anhydride); and (2) tetracarboxylic acid anhydride compounds such as Benzophenone Tetracarboxylic Dianhydride (BTDA), biphenyltetracarboxylic acid dianhydride, and biphenyltetracarboxylic acid dianhydride.
the epoxy group-containing compound (c-1-4) is selected from the group consisting of glycidyl methacrylate, 3, 4-epoxycyclohexyl methacrylate, an unsaturated group-containing glycidyl ether compound, an epoxy group-containing unsaturated compound, and any combination thereof. The unsaturated group-containing glycidyl ether compound includes, but is not limited to, compounds such as those sold under the tradenames Denacol EX-111, EX-121Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, and Denacol EX-192 (hereinafter, they are products of Katsumadai chemical industries Co., Ltd.).
The first alkali-soluble resin (C-1) can be prepared by polymerizing an epoxy compound (C-1-1) having at least two epoxy groups of the formula (II-1) with a compound (C-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group to form a reaction product containing a hydroxyl group, and then adding a carboxylic anhydride compound (C-1-3) to the reaction product. The equivalent of the acid anhydride group contained in the carboxylic acid anhydride compound (c-1-3) is preferably 0.4 to 1 equivalent, more preferably 0.75 to 1 equivalent, based on 1 equivalent of the total hydroxyl group equivalent of the above hydroxyl group-containing reaction product. When a plurality of carboxylic anhydride compounds (c-1-3) are used, they may be added sequentially or simultaneously in the reaction. When a dicarboxylic acid anhydride compound and a tetracarboxylic acid anhydride compound are used as the carboxylic acid anhydride compound (c-1-3), the molar ratio of the dicarboxylic acid anhydride compound and the tetracarboxylic acid anhydride compound is preferably 1/99 to 90/10, more preferably 5/95 to 80/20. In addition, the operating temperature range of the above reaction is, for example, in the range of 50 ℃ to 130 ℃.
The first alkali-soluble resin (C-1) can be prepared by reacting an epoxy compound (C-1-1) having at least two epoxy groups of the formula (II-2) with a compound (C-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group to form a reaction product containing a hydroxyl group, and then adding a carboxylic anhydride compound (C-1-3) and/or an epoxy group-containing compound (C-1-4) to the reaction product to perform polymerization. The acid-valent equivalent of the above-mentioned compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is preferably 0.8 to 1.5 equivalents, more preferably 0.9 to 1.1 equivalents, based on 1 equivalent of the total equivalents of epoxy groups on the epoxy compound (c-1-1) having at least two epoxy groups of the formula (II-2). The amount of the carboxylic anhydride compound (c-1-3) used is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, particularly preferably 30 to 100 mol%, based on 100 mol% of the total amount of hydroxyl groups (mol%) of the above hydroxyl group-containing reaction product.
In order to accelerate the reaction in the preparation of the first alkali-soluble resin (C-1), a basic compound is usually added to the reaction solution as a reaction catalyst. The above reaction catalysts may be used alone or in combination, and include, but are not limited to: triphenylphosphine (triphenylphosphonium), triphenylantimony (triphenylstibine), triethylamine (triethylamine), triethanolamine (triethylolamine), tetramethylammonium chloride (tetramethylammonium chloride), benzyltriethylammonium chloride (benzyltriethylammonium chloride), and the like. The amount of the reaction catalyst used is preferably 0.01 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, based on 100 parts by weight of the sum of the amounts of the above-mentioned epoxy compound (c-1-1) having at least two epoxy groups and the compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group.
In addition, in order to control the degree of polymerization, a polymerization inhibitor (polymerization inhibitor) is usually added to the reaction solution. Such polymerization inhibitors may include, but are not limited to: methoxyphenol (methoxyphenol), methylhydroquinone (methylhydroquinone), hydroquinone (hydroquinone), 2, 6-di-tert-butyl-p-cresol (2,6-di-t-butyl-p-cresol), phenothiazine (phenothiazine), and the like. In general, the above polymerization inhibitors may be used singly or in combination of plural kinds. The polymerization inhibitor is preferably used in an amount of 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the sum of the amounts of the above epoxy compound (c-1-1) having at least two epoxy groups and the compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group.
In the preparation of the first alkali-soluble resin (C-1), a polymerization solvent may be used as necessary. Specific examples of the polymerization solvent include: alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, and ethylene glycol; ketone compounds such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbon compounds such as toluene and xylene; celluloid compounds such as celluloid (butyl cellosolve) or butyl celluloid (butyl cellosolve); carbaryl compounds such as Carbaryl (carbitol) and butylCarbaryl (butyl carbitol); propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether (propylene glycol monomethyl ether); poly (propylene glycol) alkyl ethers such as dipropylene glycol monomethyl ether [ di (propylene glycol) methyl ether ], and the like; acetate compounds such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate (ethylene glycol monoethyl ether acetate), propylene glycol monomethyl ether acetate (propylene glycol methyl ether acetate), and the like; alkyl lactate compounds such as ethyl lactate and butyl lactate; or dialkyl glycol ethers; or ethyl 3-ethoxypropionate. The polymerization solvents mentioned above can be used in general singly or in admixture of plural kinds. In addition, the acid value of the first alkali-soluble resin (C-1) is preferably 50mgKOH/g to 200mgKOH/g, more preferably 60mgKOH/g to 150 mgKOH/g.
In addition, the number average molecular weight of the first alkali-soluble resin (C-1) in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is generally 500 to 10,000, preferably 800 to 8,000, more preferably 1,000 to 6,000.
In the specific embodiment of the present invention, the first alkali-soluble resin (C-1) is used in an amount ranging from 10 parts by weight to 100 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resins (C); preferably 15 to 90 parts by weight; more preferably 20 to 80 parts by weight. When the first alkali-soluble resin (C-1) is used, the photosensitive resin composition exhibits better resistance to chemicals.
Second alkali soluble resin (C-2)
The alkali-soluble resin (C) of the present invention may further comprise a second alkali-soluble resin (C-2) obtained by copolymerizing an ethylenically unsaturated monomer (C-2-1) having one or more carboxylic acids or carboxylic acid anhydrides and other copolymerizable ethylenically unsaturated monomers (C-2-2) and then reacting the resultant with an ethylenically unsaturated monomer (C-2-3) having an epoxy group.
In one embodiment, the second alkali-soluble resin (C-2) is prepared by double bond copolymerization of an ethylenically unsaturated monomer (C-2-1) having one or more carboxylic acids or carboxylic acid anhydrides and other copolymerizable ethylenically unsaturated monomers (C-2-2) to form a polymer having a carboxylic acid group in a side chain thereof. Then, the carboxylic acid group in the side chain of the polymer and the ethylenically unsaturated monomer (C-2-3) having an epoxy group are subjected to addition reaction to prepare a second alkali-soluble resin (C-2).
in another embodiment, the second alkali-soluble resin (C-2) is prepared by double bond copolymerization of other copolymerizable ethylenically unsaturated monomer (C-2-2) and ethylenically unsaturated monomer (C-2-3) having epoxy group to form a polymer, wherein the side chain of the polymer has epoxy group. Then, the epoxy group in the side chain of the polymer is subjected to addition reaction with an ethylenically unsaturated monomer (C-2-1) having one or more carboxylic acids or carboxylic acid anhydrides to produce the second alkali-soluble resin (C-2).
In another embodiment, the second alkali-soluble resin (C-2) is prepared by double bond copolymerization of other copolymerizable ethylenically unsaturated monomer (C-2-2) and ethylenically unsaturated monomer (C-2-3) having epoxy group to form a polymer, wherein the polymer has epoxy group in its side chain. Then, the second alkali-soluble resin (C-2) is obtained by addition reaction of an epoxy group in a side chain of the polymer with an ethylenically unsaturated monomer (C-2-1) having one or more carboxylic acids or carboxylic acid anhydrides, and then half-esterification reaction with an acid anhydride compound.
The ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic acid anhydrides can include, but is not limited to, an unsaturated monocarboxylic acid compound, an unsaturated polycarboxylic acid compound, a polycyclic compound having an unsaturated group and one carboxylic acid group, or a polycyclic compound having an unsaturated group and a plurality of carboxylic acid groups.
The aforementioned unsaturated monocarboxylic acid compound may include, but is not limited to, (meth) acrylic acid, crotonic acid, α -chloroacrylic acid, ethacrylic acid, cinnamic acid, 2- (meth) acryloxyethylsuccinate (2- (meth) acryloxyethylsuccinate monomer), 2- (meth) acryloxyhexahydrophthalate, 2- (meth) acryloxyethylphthalate, or omega-carboxylic acid based polycaprolactone monoacrylate, and the like. The omega-carboxylic acid group polycaprolactone polyol monoacrylate can be a commodity which is synthesized and manufactured in east Asia and is ARONIX M-5300.
The aforementioned unsaturated polycarboxylic acid compound may include, but is not limited to, maleic acid, fumaric acid, mesaconic acid, itaconic acid, citraconic acid, or the like.
The polycyclic compound having an unsaturated group and a carboxylic acid group may include, but is not limited to, 5-carboxylic acid group bicyclo [2.2.1] hept-2-ene, 5-carboxylic acid group-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxylic acid group-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxylic acid group-6-methylbicyclo [2.2.1] hept-2-ene, or 5-carboxylic acid group-6-ethylbicyclo [2.2.1] hept-2-ene.
The polycyclic compound having an unsaturated group and a plurality of carboxylic acid groups may be, for example, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene.
Preferably, the ethylenically unsaturated monomer having one or more carboxylic acids is selected from the group consisting of acrylic acid, methacrylic acid, 2-methacryloyl ethoxy succinate, 2-methacryloyl ethoxy hexahydrophthalate, and any combination thereof.
The ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic acid anhydrides, wherein the ethylenically unsaturated monomer having one or more carboxylic acid anhydrides may include, but is not limited to, unsaturated carboxylic acid anhydride compounds or polycyclic compounds having an unsaturated group and carboxylic acid anhydride.
The aforementioned unsaturated carboxylic acid anhydride compound may include, but is not limited to, maleic anhydride, fumaric anhydride, methyl fumaric anhydride, itaconic anhydride, citraconic anhydride, or the like. The polycyclic compound having an unsaturated group and a carboxylic acid anhydride may include, but is not limited to, 5, 6-dicarboxylic anhydride bicyclo [2.2.1] hept-2-ene and the like.
Preferably, the ethylenically unsaturated monomer having one or more carboxylic acid anhydrides is maleic anhydride.
The above-mentioned ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic acid anhydrides may be used singly or in admixture.
In the specific embodiment of the present invention, the total amount of the copolymerizable monomers of the ethylenically unsaturated monomer (C-2-1) having one or more carboxylic acids or carboxylic acid anhydrides and the other copolymerizable ethylenically unsaturated monomer (C-2-2) based on the second alkali-soluble resin (C-2) is 100 parts by weight, and the amount of the ethylenically unsaturated monomer (C-2-1) having one or more carboxylic acids or carboxylic acid anhydrides is in the range of 10 parts by weight to 90 parts by weight; preferably 15 to 85 parts by weight; more preferably 20 to 80 parts by weight.
The aforementioned other copolymerizable ethylenically unsaturated monomer (c-2-2) may include, but is not limited to, alkyl (meth) acrylates, alicyclic (meth) acrylates, aryl (meth) acrylates, unsaturated dicarboxylic acid esters, hydroxyalkyl (meth) acrylates, polyethers having a (meth) acrylate group, styrene compounds, or unsaturated compounds other than the above compounds.
the above-mentioned alkyl (meth) acrylate may include, but is not limited to, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and the like.
The above-mentioned alicyclic (meth) acrylate may include, but is not limited to, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate { or tricyclo [5.2.1.0 ]2,6]Decyl-8-yl (meth) acrylate }, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, or tetrahydrofurfuryl (meth) acrylate, and the like.
The above aryl (meth) acrylate may include, but is not limited to, phenyl (meth) acrylate, benzyl methacrylate, or the like.
The aforementioned unsaturated dicarboxylic acid ester may include, but is not limited to, diethyl maleate, diethyl fumarate, or diethyl itaconate, and the like.
The aforementioned hydroxyalkyl (meth) acrylate may include, but is not limited to, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like.
The aforementioned polyether having a (meth) acrylate group may include, but is not limited to, polyethylene glycol mono (meth) acrylate or polypropylene glycol mono (meth) acrylate, and the like.
The styrene compound may include, but is not limited to, styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene or p-methoxystyrene, etc.
Unsaturated compounds other than the above compounds may include, but are not limited to, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1, 3-butadiene, isoprene, 2, 3-dimethyl-1, 3-butadiene, N-succinimidyl-3-maleimidobenzoate, N-butylimido-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide, N-octylmaleimide (N-octylmaleimide), N-cyclohexylmaleimide (N-cyclohexylmaleimide), N-phenylmaleimide (N-phenylmaleimide), and the like.
The other copolymerizable ethylenically unsaturated monomer (c-2-2) mentioned above may be used singly or in admixture of two or more.
Preferably, the other copolymerizable ethylenically unsaturated monomer (c-2-2) is selected from methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl methacrylate, dicyclopentenyloxyethyl (meth) acrylate, styrene, p-methoxystyrene, or any combination of the above compounds.
In the specific embodiment of the present invention, the total amount of the copolymerizable monomers of the ethylenically unsaturated monomer (C-2-1) having one or more carboxylic acids or carboxylic acid anhydrides and the other copolymerizable ethylenically unsaturated monomer (C-2-2) based on the second alkali-soluble resin (C-2) is 100 parts by weight, and the amount of the other copolymerizable ethylenically unsaturated monomer (C-2-2) is in the range of 10 parts by weight to 90 parts by weight; preferably 15 to 85 parts by weight; more preferably 20 to 80 parts by weight.
The ethylenically unsaturated monomer having an epoxy group (c-2-3) may include, but is not limited to, (meth) acrylate compounds having an epoxy group, α -alkyl acrylate compounds having an epoxy group, glycidyl ether compounds, or the like.
the aforementioned (meth) acrylate compound having an epoxy group may include, but is not limited to, glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, 3, 4-epoxybutyl (meth) acrylate, 6, 7-epoxyheptyl (meth) acrylate, 3, 4-epoxycyclohexyl (meth) acrylate, 3, 4-epoxycyclohexylmethyl (meth) acrylate, and the like.
The α -alkyl acrylate compound having an epoxy group may include, but is not limited to, α -epoxypropyl ethacrylate, α -n-epoxypropyl ethacrylate, or α -6, 7-epoxyheptyl ethacrylate, and the like.
The glycidyl ether compound may include, but is not limited to, o-vinylbenzylglycidyl ether (o-vinylbenzylglycidyl ether), m-vinylbenzylglycidyl ether (m-vinylbenzylglycidyl ether), p-vinylbenzylglycidyl ether (p-vinylbenzylglycidyl ether), and the like.
The ethylenically unsaturated monomer (c-2-3) having an epoxy group may be used singly or in combination.
Preferably, the ethylenically unsaturated monomer having an epoxy group (c-2-3) is selected from glycidyl methacrylate, 2-methyl glycidyl methacrylate, 3, 4-epoxycyclohexylmethyl methacrylate, 6, 7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether or any combination thereof.
In the specific embodiment of the present invention, the total amount of the copolymerizable monomers of the ethylenically unsaturated monomer (C-2-1) having one or more carboxylic acids or carboxylic acid anhydrides and the other copolymerizable ethylenically unsaturated monomer (C-2-2) based on the second alkali-soluble resin (C-2) is 100 parts by weight, and the amount of the ethylenically unsaturated monomer having an epoxy group (C-2-3) is in the range of 1 to 35 parts by weight; preferably 3 to 30 parts by weight; more preferably 5 to 25 parts by weight.
In addition, the number average molecular weight of the second alkali-soluble resin (C-2) in terms of polystyrene measured by Gel Permeation Chromatography (GPC) is generally 1000 to 35,000, preferably 3,000 to 30,000, more preferably 5,000 to 25,000.
In the specific embodiment of the present invention, the second alkali-soluble resin (C-2) is used in an amount of 0 to 90 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resins (C); preferably 10 to 85 parts by weight; more preferably 20 to 80 parts by weight.
Compound (D) containing ethylenically unsaturated group
The compound (D) having an ethylenically unsaturated group of the present invention may contain an unsaturated compound having at least one ethylenically unsaturated group and an unsaturated compound having at least two ethylenically unsaturated groups.
Specific examples of the above unsaturated compound having at least one ethylenically unsaturated group may include, but are not limited to, acrylamide, acryloylmorpholine, methacryloylmorpholine, 7-amino-3, 7-dimethyloctyl acrylate, 7-amino-3, 7-dimethyloctyl methacrylate, isobutoxymethacrylamide, isobutoxymethylmethacrylamide, isobornyloxyethyl acrylate, isobornyloxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethyldiglycol acrylate, ethyldiglycol methacrylate, tert-octylacrylamide, tert-octylmethacrylamide, diacetoneacrylamide, a, Diacetone methacrylamide, dimethylamino acrylate, dimethylamino methacrylate, dodecyl acrylate, dodecyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyloxyethyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, nitrogen-dimethylacrylamide, nitrogen-dimethyl methacrylamide, tetrachlorophenyl acrylate, tetrachlorophenyl methacrylate, 2-tetrachlorophenoxyethyl acrylate, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, tetrabromophenyl acrylate, tetrabromophenyl methacrylate, 2-tetrabromophenyloxyethyl acrylate, 2-tetrabromophenyloxyethyl methacrylate, dimethylamino methacrylate, dodecyl acrylate, dodecyl methacrylate, and dodecyl methacrylate, 2-trichlorophenoxyethyl acrylate, 2-trichlorophenoxyethyl methacrylate, tribromophenyl acrylate, tribromophenyl methacrylate, 2-tribromophenoxyethyl acrylate, 2-tribromophenoxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, vinylcaprolactam, N-vinyl caseidone, phenoxyethyl acrylate, phenoxyethyl methacrylate, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromophenyl acrylate, pentabromophenyl methacrylate, polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate, poly (ethylene glycol monomethacrylate), poly (propylene glycol, Polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, bornyl acrylate, or bornyl methacrylate, and the like. Wherein the unsaturated compound having at least one ethylenically unsaturated group may be used singly or in admixture of a plurality of kinds.
Specific examples of the unsaturated compound having at least two ethylenically unsaturated groups include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate, dicyclopentenyl dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tris (2-hydroxyethyl) isocyanate diacrylate, tris (2-hydroxyethyl) isocyanate dimethacrylate, tris (2-hydroxyethyl) isocyanate triacrylate, tris (2-hydroxyethyl) isocyanate trimethacrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanate triacrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanate trimethacrylate, trimethylolpropane triacrylate, propylene glycol diacrylate, ethylene glycol diacrylate, trimethylolpropane trimethacrylate, ethylene oxide (hereinafter abbreviated as EO) -modified trimethylolpropane triacrylate, EO-modified trimethylolpropane trimethacrylate, propylene oxide (hereinafter abbreviated as PO) -modified trimethylolpropane triacrylate, PO-modified trimethylolpropane trimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1, 4-butanediol diacrylate, 1, 4-butanediol dimethacrylate, 1, 6-hexanediol diacrylate, 1, 6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, polyester diacrylate, poly (ethylene glycol) acrylate, poly, Polyester dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, caprolactone-modified dipentaerythritol hexaacrylate, caprolactone-modified dipentaerythritol hexamethacrylate, caprolactone-modified dipentaerythritol pentaacrylate, caprolactone-modified dipentaerythritol pentamethacrylate, ditrimethylolpropyl tetraacrylate, ditrimethylolpropyl tetramethacrylate, EO-modified bisphenol A diacrylate, EO-modified bisphenol A dimethacrylate, PO-modified bisphenol A diacrylate, DPA, PO-modified bisphenol A dimethacrylate, EO-modified hydrogenated bisphenol A diacrylate, EO-modified hydrogenated bisphenol A dimethacrylate, PO-modified hydrogenated bisphenol A diacrylate, PO-modified hydrogenated bisphenol A dimethacrylate, PO-modified glycerol tripropionate, EO-modified bisphenol F diacrylate, EO-modified bisphenol F dimethacrylate, novolak glycidyl ether acrylate, novolak glycidyl ether methacrylate, a commercial product of TO-1382 available from Toyo Synthesis K.K., a commercial product of KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120 available from Nippon chemical Co., Ltd. Among them, unsaturated compounds having at least two ethylenically unsaturated groups may be used singly or in combination.
Preferably, the compound (D) having an ethylenically unsaturated group is selected from trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropyl tetraacrylate, PO-modified glycerol triacrylate, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120 or any combination of the above compounds.
The above-mentioned compounds (D) having an ethylenically unsaturated group may be used singly or in admixture of two or more.
The compound (D) having an ethylenically unsaturated group is used in an amount of 20 to 200 parts by weight, preferably 30 to 180 parts by weight, and more preferably 50 to 150 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (C) used.
Photoinitiator (E)
Photoinitiator (E-1)
The photoinitiator (E) of the present invention may comprise the photoinitiator (E-1).
The photoinitiator (E-1) has a structure represented by the following formula (III):
In the formula (III), E1、E2、E3、E4、E5、E6、E7And E8Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,COE16、OE17Halogen, NO2Oror
E1And E2、E2and E3、E3and E4、E5And E6、E6And E7Or E7And E8Each independently represents a channelSubstituted alkenyl having 2 to 10 carbon atoms; or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Each independently represent- (CH)2)p-W-(CH2)q-; or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Each independently representsWherein at least one E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7and E8Is composed of
E9、E10、E11And E12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted with at least one group selected from phenyl, halogen, CN, OH, SH, an alkoxy group having 1 to 4 carbon atoms, (CO) OH and (CO) O (R)1) Wherein R is1Represents an alkyl group having 1 to 4 carbon atoms; or
E9、E10、E11And E12Each independently represents an unsubstituted phenyl group or a phenyl group substituted with at least one group represented by the following formula, and at least one group is selected from alkyl having 1 to 6 carbon atoms, halogen, CN, OE17、 SE18Or NE19E20(ii) a Or
E9、E10、E11And E12Independently represent halogen, CN, OE17、SE18、SOE18、SO2E18Or NE19E20Wherein the substituent OE17、SE18Or NE19E20Is optionally via a group E17、E18、 E19And/or E20With one carbon atom of the naphthalene ring of formula (III) to form a five-or six-membered ring; or
E9、E10、E11And E12Each independently representsCOE16Or NO2；
W stands for O, S, NE26or a single bond, p represents an integer of 0 to 3, q represents an integer of 1 to 3, Z1Represents CO or a single bond;
E13Represents an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following formula (I)17、COOE17、 OE17、SE18、CONE19E20、NE19E20、PO(OCkH2k+1)2OrOr
E13Represents an alkyl group having 2 to 20 carbon atoms, wherein one or more of O, S, SO and SO are mixed in the alkyl group having 2 to 20 carbon atoms2、NE26Or CO; or
E13Represents alkenyl with carbon number of 2-12, wherein the alkenyl with carbon number of 2-12 is not interrupted or interrupted with one or more O, CO or NE26，
Wherein the alkyl group interrupted and having a carbon number of 2 to 20 and the alkenyl group not interrupted or interrupted and having a carbon number of 2 to 12 are unsubstituted or substituted by at least one halogen; or
E13Represents cycloalkenyl having 4 to 8 carbon atoms, alkynyl having 2 to 12 carbon atoms, or one or more of O, S, CO or NE without or with intermingling26Cycloalkyl group having 3 to 10 carbon atoms; or
E13Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least one group selected from OE17、SE18、NE19E20、COE16、 CN、NO2Halogen, alkyl of 1 to 20 carbon atoms, haloalkyl of 1 to 4 carbon atoms interrupted by one or more of O, S, CO or NE26And an alkyl group having a carbon number of 2 to 20; or phenyl or naphthyl each interrupted or interrupted by one or more O, S, CO or NE26Interrupted and substituted by cycloalkyl of 3 to 10 carbon atoms;
k represents an integer of 1 to 10;
E14Represents a hydrogen atom, a cycloalkyl group having a carbon number of 3 to 8, an alkenyl group having a carbon number of 2 to 5, an alkoxy group having a carbon number of 1 to 20, or an alkyl group having a carbon number of 1 to 20 which is unsubstituted or substituted with at least one group shown below, and at least one group is selected from a halogen, a phenyl group, an alkylphenyl group having a carbon number of 1 to 20, or CN; or
E14Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least one group represented by the following, and at least one group is selected from alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 4 carbon atoms, halogen, CN, OE17、SE18And/or NE19E20(ii) a Or
E14Represents a heteroaryl group having 3 to 20 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a benzyloxy group or a phenoxy group, the benzyloxy group and the phenoxy group being unsubstituted or substituted by at least one group represented by the following formula, wherein at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms and/or a halogen;
E15Represents aryl group with carbon number of 6-20 or heteroaryl group with carbon number of 3-20, each of which is unsubstituted or substituted by at least one group shown as below, and at least one group is selected from phenyl, halogen, haloalkyl with carbon number of 1-4, CN, NO2、OE17、SE18、NE19E20、PO(OCkH2k+1)2An alkyl group having 1 to 10 carbon atoms bonded to SO, and SO2Alkyl with 1 to 10 carbon atoms, interrupted by one or more O, S or NE26And an alkyl group having a carbon number of 2 to 20; or an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms each substituted with an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group selected from halogen and COOE17、CONE19E20Phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryloxycarbonyl having 3 to 20 carbon atoms, OE17、 SE18Or NE19E20(ii) a Or
E15Represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, one or more O, CO or NE atoms not interrupted or interrupted26And a cycloalkyl group having a carbon number of 3 to 8; or
E15Represents an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following formula, and at least one group is selected from halogen and OE17、SE18Cycloalkyl group having 3 to 8 carbon atoms, heteroaryl group having 3 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms, heteroaryloxycarbonyl group having 3 to 20 carbon atoms, NE19E20、COOE17、CONE19E20、PO(OCkH2k+1)2、 Or phenyl, wherein the alkyl group having 1 to 20 carbon atoms is substituted with phenyl, and phenyl is substituted with halogen, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, OE17、SE18Or NE19E20Substitution; or
E15Represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by one or more of O, SO or SO2The alkyl group which is interrupted and has 2 to 20 carbon atoms is unsubstituted or substituted by at least one group represented byAnd at least one group is selected from halogen, OE17、COOE17、CONE19E20Phenyl or via OE17、SE18or NE19E20Substituted phenyl; or
E15Represents alkanoyl or benzoyl having 2 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented by the following formula, wherein at least one group is selected from alkyl having 1 to 6 carbon atoms, halogen, phenyl, OE17、SE18Or NE19E20(ii) a Or
E15Represents unsubstituted or substituted by at least one OE17Substituted naphthoyl or is heteroarylcarbonyl having 3 to 14 carbon atoms; or
E15Represents alkoxycarbonyl having 2 to 12 carbon atoms, wherein the alkoxycarbonyl having 2 to 12 carbon atoms is not interrupted or interrupted by one or more O, and wherein the alkoxycarbonyl having 2 to 12 carbon atoms is not substituted or substituted by at least one hydroxyl group; or
E15Represents phenoxycarbonyl which is unsubstituted or substituted by at least one group represented by the following formula, and at least one group is selected from alkyl having 1 to 6 carbon atoms, halogen, haloalkyl having 1 to 4 carbon atoms, phenyl, OE17、SE18Or NE19E20(ii) a Or
E15Represents CN, CONE19E20、NO2A C1 to C4 haloalkyl group, S (O)r-R2And S (O)rA bonded phenyl group with S (O)rThe bonded phenyl is unsubstituted or C1-C12 alkyl or SO2-R2Is substituted, and R2Represents an alkyl group having 1 to 6 carbon atoms; or
E15Represents with SO2phenyl bonded to O, with SO2The O-bonded phenyl group is unsubstituted or substituted by an alkyl group having 1 to 12 carbon atoms; or
E15represents diphenylphosphonyl or di (R)3) -phosphono, and R3Represents an alkoxy group having 1 to 4 carbon atoms;
r represents an integer of 1 to 2;
E'14Representative has a meaning for E14One of the definitions;
E'15Representative has a meaning for E15One of the definitions;
Z2represents-O-, -S-, -SO-or-SO2-；
Z3represents-O-, -CO-, -S-or a single bond;
E16Represents aryl group with carbon number of 6-20 or heteroaryl group with carbon number of 3-20, each of which is unsubstituted or substituted by at least one group shown as below, and at least one group is selected from phenyl, halogen, haloalkyl with carbon number of 1-4, CN, NO2、OE17、SE18、NE19E20Interrupted by one or more of O, S or NE26And an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following, wherein at least one group is selected from halogen, COOE17、CONE19E20phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryloxycarbonyl having 3 to 20 carbon atoms, OE17、 SE18Or NE19E20(ii) a Or
E16Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from the group consisting of halogen, phenyl, OH, SH, CN, an alkenyloxy group having 3 to 6 carbon atoms, OCH2CH2CN、OCH2CH2(CO)O(R1)、 O(CO)-(R1) O (CO) -phenyl or (CO) OH or (CO) O (R)1) (ii) a Or
E16Represents an alkyl group having 2 to 12 carbon atoms, wherein the alkyl group having 2 to 12 carbon atoms is interrupted by one or more of O, S or NE26(ii) a Or
E16Is represented by (CH)2CH2O)n+1H、(CH2CH2O)n(CO)-(R4) Alkenyl having 2 to 12 carbon atoms or cycloalkyl having 3 to 8 carbon atoms, wherein R is4represents an alkyl group having 1 to 8 carbon atoms; or
E16Is representative of warp SE18Substituted phenyl radicals in which E18Represents a bond to the COE16A single bond to the phenyl or naphthyl ring of the carbazole moiety attached;
n represents an integer of 1 to 20;
E17Represents a hydrogen atom, phenyl-R5An alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from the group consisting of halogen, OH, SH, CN, an alkenyloxy group having 3 to 6 carbon atoms, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-(R6) Phenyl bonded to O (CO), (CO) OH, (CO) O (R)1) Cycloalkyl group having 3 to 20 carbon atoms, SO2-(R7)、 O(R7) Or cycloalkyl interrupted by one or more O and having a carbon number of 3 to 20, wherein R5Represents an alkyl group having 1 to 3 carbon atoms, R6Represents an alkenyl group having 2 to 4 carbon atoms, and R7represents a haloalkyl group having a carbon number of 1 to 4; or
E17Represents an alkyl group having 2 to 20 carbon atoms, wherein the alkyl group having 2 to 20 carbon atoms is interrupted by one or more of O, S or NE26(ii) a Or
E17Is represented by (CH)2CH2O)n+1H、(CH2CH2O)n(CO)-(R4) Alkanoyl having 1 to 8 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkenoyl having 3 to 6 carbon atoms or cycloalkyl having 3 to 20 carbon atoms, wherein cycloalkyl having 3 to 20 carbon atoms is not interrupted or interrupted with one or more O, S, CO or NE26(ii) a Or
E17Represents a group formed by bonding an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms, and the group is not interrupted or interrupted by one or more O; or
E17Represents benzoyl which is unsubstituted or substituted by at least one group shown below, andAt least one group is selected from alkyl with carbon number of 1 to 6, halogen, OH or alkoxy with carbon number of 1 to 3; or
E17Represents phenyl, naphthyl or heteroaryl with carbon number of 3-20, each of which is unsubstituted or substituted by at least one group shown below, and at least one group is selected from halogen, OH, alkyl with carbon number of 1-12, alkoxy with carbon number of 1-12, CN, NO2phenyl-R8Phenoxy group, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N (R)9)2Diphenyl-amino orWherein R is8Represents an alkoxy group having 1 to 3 carbon atoms, and R9Represents an alkyl group having 1 to 12 carbon atoms; or
E17And is provided withOne of the carbon atoms of the phenyl or naphthyl ring of (a) forms a single bond;
E18Represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl-R5Wherein alkenyl group having 2 to 12 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms and phenyl-R5Is not interrupted or interrupted by one or more O, S, CO, NE26or COOE17(ii) a Or
E18Represents an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following formula, and at least one group is selected from OH, SH, CN, an alkenyloxy group having 3 to 6 carbon atoms, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R6)、O(CO)-(R1) O (CO) -phenyl or- (CO) OE17(ii) a Or
E18Represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by one or more of O, S, CO, NE26Or COOE17(ii) a Or
E18Is represented by (CH)2CH2O)nH、(CH2CH2O)n(CO)-(R4) Alkanoyl having 2 to 8 carbon atoms or alkenoyl having 3 to 6 carbon atoms; or
E18Represents benzoyl which is unsubstituted or substituted by at least one group represented by the following formula, and at least one group is selected from alkyl having 1 to 6 carbon atoms, halogen, OH, alkoxy having 1 to 4 carbon atoms or alkylthio having 1 to 4 carbon atoms; or
E18Represents phenyl, naphthyl or heteroaryl with carbon number of 3-20, each of which is unsubstituted or substituted by at least one group shown as follows, and at least one group is selected from halogen, alkyl with carbon number of 1-12, haloalkyl with carbon number of 1-4, alkoxy with carbon number of 1-12, CN, NO2phenyl-R8Phenoxy group, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N (R)9)2Diphenylamino, (CO) O (R)4)、CO-R4、 (CO)N(R4)2Or
E19And E20Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl-R group5Alkanoyl group having 1 to 8 carbon atoms, alkanoyl oxy group having 1 to 8 carbon atoms, alkenoyl group having 3 to 12 carbon atoms, SO2-R7or a benzoyl group; or
E19And E20Represents phenyl, naphthyl or heteroaryl having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group selected from halogen, haloalkyl having a carbon number of 1 to 4, alkoxy having a carbon number of 1 to 20, alkyl having a carbon number of 1 to 12, benzoyl or alkoxy having a carbon number of 1 to 12; or
E19And E20Is taken together with the nitrogen atom to which it is bound to form non-interrupted or interrupted O, S or NE17A five-or six-membered saturated or unsaturated ring of (A), and a five-or six-membered saturated or unsaturated ringThe saturated or unsaturated ring is unsubstituted or substituted with at least one group selected from the group consisting of an alkyl group having a carbon number of 1 to 20, an alkoxy group having a carbon number of 1 to 20, ═ O, OE17、SE18、NE21E22、(CO)E23、NO2Halogen, C1-4 haloalkyl, CN, phenyl,Or with one or more O, S, CO or NE's without or with intermingling17and a cycloalkyl group having a carbon number of 3 to 20; or
E19And E20is taken together with the attached nitrogen atom to form a heteroaromatic ring system which is unsubstituted or substituted by at least one group selected from the group consisting of alkyl having a carbon number of 1 to 20, haloalkyl having a carbon number of 1 to 4, alkoxy having a carbon number of 1 to 20, ═ O, OE17、 SE18、NE21E22、(CO)E23、Halogen, NO2CN, phenyl, or with one or more O, S, CO or NE groups not interrupted or interrupted17And a cycloalkyl group having a carbon number of 3 to 20;
E21And E22Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group;
E21And E22Together with the nitrogen atom to which they are bonded form non-interrupted or interrupted O, S or NE26wherein the five-or six-membered saturated or unsaturated ring is unfused or fused with a benzene ring;
E23Represents hydrogen atom, OH, alkyl with 1-20 carbon atoms, halogenated alkyl with 1-4 carbon atoms, and at least one O, CO or NE26And alkyl having 2 to 20 carbon atoms, not interrupted or interrupted O, S, CO or NE26And a cycloalkyl group having a carbon number of 3 to 20; or
E23Represents phenyl, naphthyl, phenyl-R1、OE17、SE18Or NE21E22；
E24Represents (CO) OE17、CONE19E20、(CO)E17Or with respect to E19And E20One of the definitions;
E25Represents COOE17、CONE19E20、(CO)E17(ii) a Or E25With respect to E17one of the definitions;
E26Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group interrupted by one or more O or CO and having 2 to 20 carbon atoms; or E26Represents phenyl-R1Cycloalkyl which is not interrupted or interrupted by one or more O or CO and has a carbon number of 3 to 8; or E26Represents (CO) E19(ii) a Or E26Represents phenyl, which is unsubstituted or substituted by at least one group selected from alkyl having 1 to 20 carbon atoms, halogen, haloalkyl having 1 to 4 carbon atoms, OE17、 SE18、NE19E20Or
Provided that the photoinitiator (E-1) having the structure represented by the formula (III) has at least one
The photoinitiator (E-1) having a structure represented by the formula (III) is characterized in that it contains at least one annulated unsaturated ring on the carbazole moiety. In other words, at least one pair E1and E2、E2And E3、E3And E4、 E5And E6、E6And E7Or E7And E8Is that
The aforementioned alkyl group having 1 to 20 carbon atoms is straight or branched and is, for example, an alkyl group having 1 to 18 carbon atoms, 1 to 4 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms or 1 to 4 carbon atoms, or an alkyl group having 4 to 12 carbon atoms or 4 to 8 carbon atoms. Specific examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4, 4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and eicosyl. The alkyl group having a carbon number of 1 to 6 has the same definition as the above-mentioned alkyl group having a carbon number of 1 to 20, and has the highest corresponding carbon number.
An unsubstituted or substituted alkyl group having 1 to 20 carbon atoms and containing at least one carbon-carbon multiple bond is an alkenyl group described later.
the haloalkyl group having a carbon number of 1 to 4 is an alkyl group which is substituted with halogen as defined later and has a carbon number of 1 to 4 as defined previously. The alkyl group may, for example, be mono-or polyhalogenated until all hydrogen atoms are replaced by halogen, and may, for example, be CjHwXyWherein w + y is 2j +1 and X is a halogen atom, preferably a fluorine atom. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl.
The hydroxyalkyl group having a carbon number of 2 to 4 means an alkyl group having a carbon number of 2 to 4 substituted with one or two oxygen atoms. The alkyl group may be straight or branched. Specific examples are 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 4-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 2, 3-dihydroxypropyl or 2, 4-dihydroxybutyl.
the alkoxyalkyl group having 2 to 10 carbon atoms is an alkyl group having 2 to 10 carbon atoms via mono-O-intermission. The alkyl group having a carbon number of 2 to 10 has the same definition as the aforementioned alkyl group having a carbon number of 1 to 20, and has the highest number of corresponding carbon atoms. Specific examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, propoxypropyl.
Interrupted by one or more O, S, NE26Or the C2-20 alkyl group of CO is, for example, O, S, NE26Or CO is interrupted 1 to 9 times, 1 to 5 times, 1 to 3 times, 1 time or 2 times. If more than one group is present, they are of the same kind or different. The two oxygen atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., ethylene groups). The alkyl groups are straight or branched. For example, the following structural units will be present: -CH2-CH2-O-CH2CH3、-[CH2CH2O]y-CH3(wherein y is 1 to 9), - (CH)2-CH2O)7-CH2CH3、-CH2-CH(CH3)-O-CH2-CH2CH3、 -CH2-CH(CH3)-O-CH2-CH3、-CH2-CH2-S-CH2CH3、 -CH2-CH(CH3)-NE26-CH2-CH3、-CH2-CH2-COO-CH2CH3or-CH2-CH(CH3)-OCO-CH2-CH2CH3。
In the present invention, cycloalkyl having 3 to 10 carbon atoms and cycloalkyl having 3 to 8 carbon atoms are understood to be alkyl groups containing at least one ring. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl. In the present invention, cycloalkyl having 3 to 10 carbon atoms also encompasses the bicyclic case, i.e., bridged ring, and the specific examples may be, for example And other corresponding rings. Other embodiments may be, for example, as(e.g. in) OrStructures, and bridged or fused ring systems, for example, as defined hereinetc. wherein R is10Represents a alkylidene group, R11Represents an alkyl group.
Warp O, S, NE26Or C3-20 cycloalkyl interrupted by CO has the same definition as before, wherein the alkyl group has at least one-CH2-the radical is replaced by O, S, NE26Or CO. Specific examples are as(e.g. in)、 And the like.
The group formed by bonding an alkyl group having a carbon number of 1 to 8 and a cycloalkyl group having a carbon number of 3 to 10 means a cycloalkyl group having a carbon number of 3 to 10 as defined above substituted with at least one alkyl group having at most 8 carbon atoms. The concrete example isAnd the like.
The group formed by bonding an alkyl group having 1 to 8 carbon atoms interrupted by one or more O and a cycloalkyl group having 3 to 10 carbon atoms means a cycloalkyl group having 3 to 10 carbon atoms interrupted by one or more O as defined above substituted by at least one alkyl group having up to 8 carbon atoms. Specific examples are asAnd the like.
The alkoxy group having 1 to 12 carbon atoms is an alkyl group having 1 to 12 carbon atoms substituted with one oxygen atom. The alkyl group having a carbon number of 1 to 12 has the same definition as the aforementioned alkyl group having a carbon number of 1 to 20, and has the highest corresponding carbon number. The alkoxy group having a carbon number of 1 to 4 is a straight chain or a branched chain, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy. The alkoxy group having a carbon number of 1 to 8 and the alkoxy group having a carbon number of 1 to 4 are the same as defined above and have the highest corresponding carbon number.
The alkylthio group having a carbon number of 1 to 12 is an alkyl group having a carbon number of 1 to 12 substituted with one sulfur atom. The alkyl group having a carbon number of 1 to 12 has the same definition as the aforementioned alkyl group having a carbon number of 1 to 20, and has the highest corresponding carbon number. The alkylthio group having a carbon number of 1 to 4 is a straight chain or branched chain, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio.
phenyl-R5Can be, for example, benzyl, phenylethyl, α -methylbenzyl or α, α -dimethyl-benzyl, in particular benzyl.
phenyl-R8There may be mentioned, for example, benzyloxy, phenylethoxy, alpha-methylbenzyloxy or alpha, alpha-dimethylbenzyloxy, especially benzyloxy.
The alkenyl group having a carbon number of 2 to 12 is mono-or polyunsaturated and is, for example, an alkenyl group having a carbon number of 2 to 10, an alkenyl group having a carbon number of 2 to 8, an alkenyl group having a carbon number of 2 to 5. Specific examples are vinyl, allyl, methallyl, 1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1, 3-pentadienyl, 5-hexenyl, 7-octenyl or dodecenyl, especially allyl. The alkenyl group having a carbon number of 2 to 5 has the same definition as the aforementioned alkenyl group having a carbon number of 2 to 12, and has the highest corresponding carbon number.
Interrupted by one or more O, S, NE26Or alkenyl of CO having 2 to 12 carbon atoms, e.g. via O, S, NE26Or CO is interrupted 1 to 9 times, 1 to 5 times, 1 to 3 times, 1 time or 2 times. If more than one group is present, they are of the same kind or different. The two oxygen atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., ethylene groups). Alkenyl is straight or branched chain and is as defined above. For example, the following structural units may be formed: -CH ═ CH-O-CH2CH3、-CH＝CH-O-CH＝CH2And the like.
The cycloalkenyl group having a carbon number of 4 to 8 has at least one double bond, and may be, for example, a cycloalkenyl group having a carbon number of 4 to 6 or a cycloalkenyl group having a carbon number of 6 to 8. Specific examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.
Alkenyloxy having a carbon number of 3 to 6 is mono-or polyunsaturated and has one of the definitions as for the aforementioned alkenyl, and the attached oxy group has the highest corresponding number of carbon atoms. Specific examples thereof include allyloxy, methallyloxy, butenyloxy, pentenyloxy, 1, 3-pentadienyloxy and 5-hexenyloxy.
The alkynyl group having a carbon number of 2 to 12 is a mono-or polyunsaturated linear or branched chain, and may be, for example, an alkynyl group having a carbon number of 2 to 8, an alkynyl group having a carbon number of 2 to 6, or an alkynyl group having a carbon number of 2 to 4. Specific examples thereof include ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2-butynyl, pentynyl, hexynyl, 2-hexynyl, 5-hexynyl, octynyl and the like.
The alkanoyl group having a carbon number of 2 to 20 is a straight chain or a branched chain, and may be, for example, an alkanoyl group having a carbon number of 2 to 18, a carbon number of 2 to 14, a carbon number of 2 to 12, a carbon number of 2 to 8, a carbon number of 2 to 6 or a carbon number of 2 to 4 or an alkanoyl group having a carbon number of 4 to 12 or a carbon number of 4 to 8. Specific examples thereof include acetyl, propionyl, butyryl, isobutyryl, valeryl, hexanoyl, heptanoyl, octanoyl, nonanoyl, decanoyl, dodecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, octadecanoyl, eicosanoyl, preferably acetyl. Alkanoyl groups having a carbon number of 1 to 8 have the same definition as the aforementioned alkanoyl groups having a carbon number of 2 to 20, and have the highest corresponding carbon number.
The alkoxycarbonyl group having a carbon number of 2 to 12 is a straight-chain or branched-chain, and is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 1-dimethylpropoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, particularly methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl or isobutyloxycarbonyl, preferably methoxycarbonyl.
The alkoxycarbonyl group having 2 to 12 carbon atoms interrupted by one or more O may be a straight chain or a branched chain. The two oxygen atoms are separated by at least two methylene groups (i.e., ethylene groups). The interrupted alkoxycarbonyl group is unsubstituted or substituted by one or more hydroxy groups. The aryloxycarbonyl group having a carbon number of 6 to 20 may be, for example, a phenyloxycarbonyl group (═ phenyl-O- (CO) O-), a naphthyloxycarbonyl group, an anthracenyloxycarbonyl group, or the like. The heteroarylcarbonyl group having a carbon number of 5 to 20 may be a heteroaryl group having a carbon number of 5 to 20 bonded to-O-CO-.
The cycloalkylcarbonyl group having a carbon number of 3 to 10 may be a cycloalkyl group having a carbon number of 3 to 10 bonded to CO, wherein the cycloalkyl group has the same definition as the foregoing, and has the highest corresponding carbon number. Interrupted by one or more O, S, NE26or cycloalkylcarbonyl of carbon number 3 to 10 of CO means an interrupted cycloalkyl group bonded to CO, wherein the interrupted cycloalkyl group has the same definition as the aforementioned.
The cycloalkoxycarbonyl group having a carbon number of 3 to 10 may be a cycloalkyl group having a carbon number of 3 to 10 bonded with-O- (CO) -wherein the cycloalkyl group has the same definition as the aforementioned and has the highest corresponding carbon number. Interrupted by one or more O, S, NE26Or cycloalkoxycarbonyl with carbon number of CO of 3 to 10, refers to an interrupted cycloalkyl group bonded with-O- (CO) -wherein the interrupted cycloalkyl group has the same definition as the aforementioned.
Alkylphenyl having a carbon number of 1 to 20 refers to phenyl substituted with at least one alkyl group, wherein the total of carbon atoms is at most 20.
The aryl group having a carbon number of 6 to 20 may be, for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a 1, 2-triphenylene group, a tetracenyl group, a terphenylene group, etc., particularly a phenyl group or a naphthyl group, preferably a phenyl group. Naphthyl is 1-naphthyl or 2-naphthyl.
In the context of the photoinitiator (E-1) of the present invention, the heteroaryl group having a carbon number of 3 to 20 comprises a monocyclic or polycyclic system, for example, a fused ring system. Specific examples may be thienyl, benzo [ b ]]Thienyl, naphtho [2,3-b ]]Thienyl, thianthryl, furyl, dibenzofuryl,Alkylene, xanthene, thioxanthyl, phenoxathiyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, quinoxalinyl, quinolyl, and the like,a porphyrin group, a pteridinyl group, a carbazolyl group, a beta-carbolinyl group, a phenanthridinyl group, an acridinyl group, a perimidine group, a phenanthrolinyl group, a phenothiazinyl group, an isothiazolyl group, a phenothiazinyl group, an isoxazolyl group, a furazanyl group, a phenoxanyl group, a 7-phenanthrenyl group, an anthraquinone-2-yl group (═ 9, 10-diphenoxy-9, 10-dihydroanthracen-2-yl group), and a 3-benzo [ b ] group]Thienyl, 5-benzo [ b ]]Thienyl, 2-benzo [ b ]]Thienyl, 4-dibenzofuryl, 4, 7-dibenzofuryl, 4-methyl-7-dibenzofuryl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxathiyl, 2, 7-phenoxathiyl, 2-pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl, 2-pyrazinyl, 5, 6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindolyl, 1-methyl-2-indolyl, 1-methyl-3-indolyl, 1, 5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2, 7-dimethyl-8-purinyl, 2-methoxy-7-methyl-8-purinyl, 2-quinolizinyl, 3-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl, 3-methoxy-6-isoquinolinyl, 2-quinolyl, 6-quinolyl, 2-indolyl, 1-methyl-3-indolyl, 1, 5-dimethyl-2-indolyl, 1-methyl-3-indazolyl, 2, 7-isoquinolyl, 2,7-quinolyl group, 2-methoxy-3-quinolyl group, 2-methoxy-6-quinolyl group, 6-phthalazinyl group, 7-phthalazinyl group, 1-methoxy-6-phthalazinyl group, 1, 4-dimethoxy-6-phthalazinyl group, 1, 8-naphthyridin-2-yl group, 2-quinoxalinyl group, 6-quinoxalinyl group, 2, 3-dimethyl-6-quinoxalinyl group, 2, 3-dimethoxy-6-quinoxalinyl group, 2-quinoxalinyl group, 7-quinoxalinyl group, 2-dimethylamino-6-quinoxalinyl group, 3-Quinoline radical, 6-Quinoline base, 7-Quinoline group, 3-methoxy-7-a corrin group, a 2-pteridinyl group, a 6-pteridinyl group, a 7-pteridinyl group, a 6, 7-dimethoxy-2-pteridinyl group, a 2-carbazolyl group, a 3-carbazolyl group, a 9-methyl-2-carbazolyl group, a 9-methyl-3-carbazolyl group, a beta-carbolin-3-yl group, a 1-methyl-beta-carbolin-6-yl group, a 3-phenanthridinyl group, a 2-acridinyl group, a 3-acridinyl group, a 2-perimidine group, a 1-methyl-5-perimidine group, a 5-phenanthrolinyl group, a 6-phenanthrolinyl group, a 1-phenazinyl group, a 2-phenazinyl group, a 3-isothiazolyl group, 4-isothiazolyl, 5-isothiazolyl, 2-phenothiazinyl, 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 4-methyl-3-furazanyl, 2-phenoxanyl, 10-methyl-2-phenoxanyl, etc.
Preferably, the heteroaryl group having a carbon number of 3 to 20 may be a thienyl group, a benzo [ b ] thienyl group, a thianthryl group, a thioxanthenyl group, a 1-methyl-2-indolyl group or a 1-methyl-3-indolyl group. More preferably, the heteroaryl group having a carbon number of 3 to 20 may be a thienyl group.
Heteroarylcarbonyl having a carbon number of 4 to 20 is a heteroaryl having a carbon number of 3 to 20 as defined above linked to the rest of the molecule via a CO group.
Substituted aryl (phenyl, naphthyl, aryl having a carbon number of 6 to 20, or heteroaryl having a carbon number of 5 to 20) is substituted 1 to 7 times, 1 to 6 times, or 1 to 4 times, respectively, preferably 1 time, 2 times, or 3 times. An aryl group as defined cannot have more substituents than there are free positions on the aryl ring.
The substituents on the phenyl ring are preferably in position 4 or in the 3,4-, 3,4,5-, 2,6-, 2, 4-or 2,4, 6-configuration on the phenyl ring.
A group which is interrupted at least once is interrupted, for example 1 to 19 times, 1 to 15 times, 1 to 12 times, 1 to 9 times, 1 to 7 times, 1 to 5 times, 1 to 4 times, 1 to 3 times or 1 or 2 times (the number of intervening heteroatoms depends on the number of carbon atoms to be interrupted). The at least once substituted radicals have, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3 or 1 or 2 identical or different substituents.
A group substituted with at least one substituent as defined above means having at least one substituent which may be the same or different. Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, more preferably fluorine and chlorine.
For example, if E1And E2、E2And E3、E3And E4or E5And R6、E6and E7、E7And E8Are each independentlyStructures such as those shown in formulas (IIIa) to (IIIi) below are formed:
Among them, the structure of formula (IIIa) is preferable.
The compounds of formula (III) are characterized in that at least one phenyl ring is fused with a carbazole moiety to form a "naphthyl" ring. That is, one of the structures of the above formulas (IIIa) to (IIIi) is illustrated according to formula (III).
If E1And E2、E2And E3、E3And E4Or E5And R6、E6And E7、E7And E8Are each independently- (CH)2)p-W-(CH2)q-, then form, for exampleOrAnd the like.
Substituent OE on the phenyl or naphthyl ring17、SE18、SOE18、SO2E18Or NE19E20Via the radical E17、E18、E19and/or E20And one carbon atom of the naphthyl ring to form a five-or six-membered ring, a structure comprising 3 or more rings (including the naphthyl ring) is obtained. A specific example may be, for example
If E17And is provided withA carbon atom of the phenyl or naphthyl ring of the group(s) forming a single bond, then form, for example And the like.
If E16Is via SE18substituted phenyl radicals in which E18represents a bond to a compound having a COE16The single bond of the phenyl or naphthyl ring of the carbazole moiety of (A) can be, for example, a structure That is, if E16Is via SE18Substituted phenyl radicals in which the radical E18Represents a bond to a compound having a COE16A single bond of the phenyl or naphthyl ring of the carbazole moiety of (a) to form a phenyl or naphthyl ring having both a thioxanthyl moiety and a carbazole moiety.
If E19And E20Is taken together with the nitrogen atom to which it is bound to form non-interrupted or interrupted O, S or NE17With a five-or six-membered saturated or unsaturated ring, the saturated or unsaturated ring formed may be, for example, aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1, 3-diazine, 1, 2-diazine, piperidine or morpholine. Preferably, if E19And E20is taken together with the nitrogen atom to which it is bound to form non-interrupted or interrupted O, S or NE17With a five-or six-membered saturated or unsaturated ring, to form a ring which is not interrupted or interrupted by O or NE17And especially five or six membered saturated rings of O.
If E21And E22Is taken together with the nitrogen atom to which it is bound to form non-interrupted or interrupted O, S or NE26And the benzene ring is optionally condensed with the saturated or unsaturated ring, the saturated or unsaturated ring formed may be, for example, aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1, 3-diazine, 1, 2-diazine, piperidine or morpholine or the corresponding ring (for example)。
If E19And E20Is taken together with the nitrogen atom to which it is bound to form a heteroaromatic ring system, which is meant to include more than one ring (e.g., 2 rings)or 3 rings) and one or more heteroatoms from the same species or different species. Suitable heteroatoms may for example be N, S, O or P, especially N, S or O. Specific examples thereof include carbazole, indole, isoindole, indazole, purine, isoquinoline, quinoline, carboline, phenothiazine and the like.
The expression "and/or" and/or "in the context of the present invention means that not only one of the defined substituents can be present, but also a total of several of the defined substituents, i.e. a mixture of different substituents.
The term "at least" is used to define one or more than one, such as one or two or three, preferably one or two.
throughout this specification and the claims which follow, unless the context requires otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated integer or step or group of integers or steps but not the exclusion of any other integer or step or group of integers or steps. The expression "(meth) acrylate" is intended in the context of the present invention to mean both acrylates and the corresponding methacrylates.
The preferred meanings indicated in the text for the compounds according to the invention in the context of the present invention are intended to be all claim categories, i.e. also the claims for compositions, uses, methods, color filters, etc.
the oxime esters of the formula (III) are prepared by conventional methods, for example by reacting the corresponding oximes with acid halides, in particular chlorides or anhydrides, under the following conditions: in an inert solvent (e.g., tert-butyl methyl ether, Tetrahydrofuran (THF), or dimethylformamide), in the presence of a base (e.g., triethylamine or pyridine), or in a basic solvent (e.g., pyridine). In one embodiment of the invention, the compound of formula (IIIa) is prepared by a process of formula (i) wherein E is7Is an oxime ester groupAnd Z is1Is a single bond. Such asThe compounds of the formulae (IIIb) to (IIIh) are prepared in the same way, but using the appropriate oximes.
In formula (i), E1、E2、E5、E6、E8、E13、E14And E15Is as defined above, X means a halogen atom, in particular a chlorine atom.
Preferably, E14Is methyl.
The above reaction of formula (i) is well known to those skilled in the art and is generally carried out at a temperature of from-15 ℃ to +50 ℃, preferably from 0 ℃ to 25 ℃.
when Z is1In the case of CO, the corresponding oxime is synthesized by nitrosating a methylene group with an alkyl nitrite (e.g., methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite, or isoamyl nitrite). Then, the esterification is carried out under the same conditions as described above, and the detailed preparation is as shown in formula (ii).
Thus, the corresponding oxime compounds can be prepared by reacting the corresponding oxime compounds with, for example, a base or a mixture of basesOr of acyl halides such asTo obtain a compound of formula (III) as defined above, in which X is a halogen atom, and in particular a chlorine atom, and E is14The definition of (1) is as described above.
Oximes required as starting materials can be obtained by various methods described in standard chemical texts (e.g. j. march, Advanced Organic Chemistry, 4 th edition, Wiley inter science, 1992) or in monographs (e.g. s.r. sandler & w. karo, Organic functional group precursors, volume 3, Academic Press).
One of the most convenient methods is, for example, reacting an aldehyde or ketone with hydroxylamine or a salt thereof in a polar solvent such as Dimethylacetamide (DMA), aqueous DMA, ethanol or aqueous ethanol. In this case, a base such as sodium acetate or pyridine is added to control the pH of the reaction mixture. It is well known that the reaction rate is pH dependent and that the base can be added at the beginning or continuously during the reaction. Basic solvents such as pyridine may also be used as a base and/or as a solvent or co-solvent. The reaction temperature is usually from room temperature to the reflux temperature of the mixture, and is generally about 20 ℃ to 120 ℃.
The corresponding ketone intermediates are prepared, for example, by methods described in the literature (e.g., standard chemical texts, such as j. March, Advanced Organic Chemistry, 4 th edition, Wiley Interscience, 1992). In addition, a continuous Friedel-Crafts reaction (Friedel-Crafts reaction) can be effectively used to synthesize intermediates. Such reactions are well known to those skilled in the art.
Another convenient synthesis of oximes is nitrosation of the "active" methylene group with nitrous acid or an alkyl nitrite. Both basic conditions (as described, for example, in Organic Syntheses coll. volume VI (j. wiley & Sons, New York,1988), pages 199 and 840) and acidic conditions (as described, for example, in Organic Syntheses coll. volume V, pages 32 and 373, coll. volume III, pages 191 and 513, coll. volume II, pages 202, 204 and 363) are suitable for preparing the oximes used as starting materials in the present invention. Nitrous acid is typically generated from sodium nitrite. The alkyl nitrite can be, for example, methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite or isoamyl nitrite.
In another embodiment, the photoinitiator (E-1) is a free oxime compound and has the structure shown in formula (IIIA):
In formula (IIIA), E1、E2、E3、E4、E5、E6、E7And E8Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,COE16、OE17Halogen atom, NO2or
Or E1And E2、E2And E3、E3And E4、E5and E6、E6And E7Or E7And E8Each independently represents a channelA substituted alkenyl group having a carbon number of 2 to 10,
or E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Each independently represent- (CH)2)p-W-(CH2)q-；
Or E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Each independently represent the sameWherein at least one E1And E2、E2and E3、E3And E4、E5And E6、 E6And E7Or E7And E8is composed of
E9、E10、E11and E12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted with at least one group selected from phenyl, a halogen atom, CN, OH, SH, an alkoxy group having 1 to 4 carbon atoms, (CO) OH and (CO) O (R)1) Wherein R is1Represents an alkyl group having 1 to 4 carbon atoms; or
E9、E10、E11And E12Each independently represents an unsubstituted phenyl group or a phenyl group substituted with at least one group represented by the following, the at least one group being selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, CN, OE17、SE18Or NE19E20(ii) a Or
E9、E10、E11And E12Each independently represents a halogen atom, CN, OE17、SE18、SOE18、 SO2E18Or NE19E20Wherein the substituent OE17、SE18Or NE19E20Is optionally via a group E17、 E18、E19And/or E20And one carbon atom of the naphthalene ring in the formula (IIIA) to form a five-membered ring or a six-membered ring; or
E9、E10、E11And E12Each independently representsCOE16Or NO2；
W stands for O, S, NE26Or a single bond, p represents an integer of 0 to 3, q represents an integer of 1 to 3, Z1Represents CO or a single bond;
E13Represents an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted with at least one group represented by the following, wherein the at least one group is selected from a halogen atom, E17、 COOE17、OE17、SE18、CONE19E20、NE19E20、PO(OCkH2k+1)2OrOr
E13represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by one or more of O, S, SO2、NE26Or CO; or
E13Represents alkenyl with carbon number of 2-12, wherein the alkenyl with carbon number of 2-12 is not interrupted or interrupted with one or more O, CO or NE26，
Wherein the alkyl group interrupted and having a carbon number of 2 to 20 and the alkenyl group not interrupted or interrupted and having a carbon number of 2 to 12 are unsubstituted or substituted by at least one halogen atom; or
E13Represents cycloalkenyl having 4 to 8 carbon atoms, alkynyl having 2 to 12 carbon atoms, or one or more of O, S, CO or NE without or with intermingling26Cycloalkyl group having 3 to 10 carbon atoms; or
E13Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least one group selected from OE17、SE18、NE19E20、COE16、CN、 NO2Halogen atom, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, interrupted by one or more O, S, CO or NE26and an alkyl group having a carbon number of 2 to 20; or each of which is not interrupted or interrupted by one or more O, S, CO or NE26And cycloalkyl having 3 to 10 carbon atoms;
k represents an integer of 1 to 10;
E15Represents an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from phenyl, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, CN, NO2、OE17、SE18、NE19E20、PO(OCkH2k+1)2an alkyl group having 1 to 10 carbon atoms bonded to SO, and SO2Alkyl with 1 to 10 carbon atoms, interrupted by one or more O, S or NE26And an alkyl group having a carbon number of 2 to 20; or each of which is substituted with an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from a halogen atom, COOE17、CONE19E20Phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryloxycarbonyl having 3 to 20 carbon atoms, OE17、SE18Or NE19E20(ii) a Or
E15Represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, one or more O, CO or NE atoms not interrupted or interrupted26and a cycloalkyl group having a carbon number of 3 to 8; or
E15Represents an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following formula, and at least one group is selected from a halogen atom, OE17、SE18Cycloalkyl group having 3 to 8 carbon atoms, heteroaryl group having 3 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms, heteroaryloxycarbonyl group having 3 to 20 carbon atoms, NE19E20、COOE17、CONE19E20、PO(OCkH2k+1)2、 Or a phenyl group, wherein the alkyl group having 1 to 20 carbon atoms is substituted with a phenyl group, and the phenyl group is substituted with a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, OE17、 SE18Or NE19E20Substitution; or
E15Represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by one or more of O, SO or SO2The alkyl group which is interrupted and has a carbon number of 2 to 20 is unsubstituted or substituted by at least one group shown below, and at least one group is selected from halogenElement atom, OE17、COOE17、CONE19E20Phenyl or via OE17、SE18Or NE19E20Substituted phenyl; or
E15Represents an alkanoyl group or a benzoyl group having 2 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, an OE group17、SE18Or NE19E20(ii) a Or
E15Represents unsubstituted or substituted by at least one OE17substituted naphthoyl or is heteroarylcarbonyl having 3 to 14 carbon atoms; or
E15Represents alkoxycarbonyl having 2 to 12 carbon atoms, wherein the alkoxycarbonyl having 2 to 12 carbon atoms is not interrupted or interrupted by one or more O, and wherein the alkoxycarbonyl having 2 to 12 carbon atoms is not substituted or substituted by at least one hydroxyl group; or
E15Represents phenoxycarbonyl, which is unsubstituted or substituted by at least one group represented by the following formula, wherein at least one group is selected from alkyl having 1 to 6 carbon atoms, halogen atom, haloalkyl having 1 to 4 carbon atoms, phenyl, OE17、SE18Or NE19E20(ii) a Or
E15Represents CN, CONE19E20、NO2A C1 to C4 haloalkyl group, S (O)r-R2And S (O)rA bonded phenyl group with S (O)rThe bonded phenyl is unsubstituted or C1-C12 alkyl or SO2-R2Is substituted, and R2Represents an alkyl group having 1 to 6 carbon atoms; or
E15Represents with SO2O-bonded phenyl, diphenylphosphonyl or di (R)3) -phosphono with SO2The O-bonded phenyl group is unsubstituted or substituted by an alkyl group having 1 to 12 carbon atoms, and R3Represents an alkoxy group having 1 to 4 carbon atoms;
r represents an integer of 1 to 2;
E'15Representative has a meaning for E15one of the definitions;
Z2Represents O, S, SO or SO2；
Z3Represents O, CO, S or a single bond;
E16Represents aryl having 6 to 20 carbon atoms or heteroaryl having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from phenyl, halogen atom, haloalkyl having 1 to 4 carbon atoms, CN, NO2、OE17、SE18、NE19E20interrupted by one or more of O, S or NE26And an alkyl group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following, wherein at least one group is selected from a halogen atom, COOE17、CONE19E20Phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryloxycarbonyl having 3 to 20 carbon atoms, OE17、SE18Or NE19E20(ii) a Or
E16Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from a halogen atom, a phenyl group, OH, SH, CN, an alkenyloxy group having 3 to 6 carbon atoms, OCH2CH2CN、OCH2CH2(CO)O(R1)、 O(CO)-(R1) O (CO) phenyl or (CO) OH or (CO) O (R)1) (ii) a Or
E16Represents an alkyl group having 2 to 12 carbon atoms, wherein the alkyl group having 2 to 12 carbon atoms is interrupted by one or more of O, S or NE26(ii) a Or
E16Is represented by (CH)2CH2O)n+1H、(CH2CH2O)n(CO)-(R4) Alkenyl having 2 to 12 carbon atoms or cycloalkyl having 3 to 8 carbon atoms, wherein R is4Represents an alkyl group having 1 to 8 carbon atoms; or
E16Is representative of warp SE18Substituted phenyl radicals in which E18Represents a bond to the COE16A single bond to the phenyl or naphthyl ring of the carbazole moiety attached;
n represents an integer of 1 to 20;
E17Represents a hydrogen atom, phenyl-R5An alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from a halogen atom, OH, SH, CN, an alkenyloxy group having 3 to 6 carbon atoms, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1)、 O(CO)-(R6) Phenyl bonded to O (CO), (CO) OH, (CO) O (R)1) Cycloalkyl group having 3 to 20 carbon atoms, SO2-(R7)、O(R7) Or cycloalkyl interrupted by one or more O and having a carbon number of 3 to 20, wherein R5Represents an alkyl group having 1 to 3 carbon atoms, R6Represents an alkenyl group having 2 to 4 carbon atoms, and R7Represents a haloalkyl group having a carbon number of 1 to 4; or
E17Represents an alkyl group having 2 to 20 carbon atoms, wherein the alkyl group having 2 to 20 carbon atoms is interrupted by one or more of O, S or NE26(ii) a Or
E17Is represented by (CH)2CH2O)n+1H、(CH2CH2O)n(CO)-(R4) Alkanoyl having 1 to 8 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkenoyl having 3 to 6 carbon atoms or cycloalkyl having 3 to 20 carbon atoms which is not interrupted or interrupted with one or more O, S, CO or NE26(ii) a Or
E17Represents a group formed by bonding an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms, and the group is not interrupted or interrupted by one or more O; or
E17Represents benzoyl which is unsubstituted or substituted by at least one group represented by the following formula, and the at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OH, or an alkoxy group having 1 to 3 carbon atoms; or
E17Represents phenyl, naphthyl or heteroaryl with 3 to 20 carbon atoms,Each of which is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from a halogen atom, OH, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, CN, NO2phenyl-R8Phenoxy group, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N (R)9)2Diphenyl-amino orWherein R is8Represents alkoxy having a carbon number of 1 to 3, and R9Represents an alkyl group having 1 to 12 carbon atoms; or
E17And is provided withOne of the carbon atoms of the phenyl or naphthyl ring of (a) forms a single bond;
E18Represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl-R5Wherein alkenyl group having 2 to 12 carbon atoms, cycloalkyl group having 3 to 20 carbon atoms and phenyl-R5Is not interrupted or interrupted by one or more O, S, CO, NE26Or COOE17(ii) a Or
E18Represents an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the formula (I) below, and at least one group is selected from OH, SH, CN, an alkenyloxy group having 3 to 6 carbon atoms, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R6)、O(CO)-(R1) O (CO) -phenyl or (CO) OE17(ii) a Or
E18Represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by one or more of O, S, CO, NE26Or COOE17(ii) a Or
E18Is represented by (CH)2CH2O)nH、(CH2CH2O)n(CO)-(R4) Alkanoyl having 2 to 8 carbon atoms or alkenoyl having 3 to 6 carbon atoms; or
E18Represents benzoyl, benzylThe acyl group is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OH, an alkoxy group having 1 to 4 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms; or
E18Represents phenyl, naphthyl or heteroaryl with carbon number of 3-20, each of which is unsubstituted or substituted by at least one group shown as follows, and at least one group is selected from halogen atom, alkyl with carbon number of 1-12, haloalkyl with carbon number of 1-4, alkoxy with carbon number of 1-12, CN, NO2phenyl-R8Phenoxy group, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N (R)9)2Diphenylamino, (CO) O (R)4)、 CO-R4、(CO)N(R4)2Or
E19And E20Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl-R group5Alkanoyl group having 1 to 8 carbon atoms, alkanoyl oxy group having 1 to 8 carbon atoms, alkenoyl group having 3 to 12 carbon atoms, SO2-R7Or a benzoyl group; or
E19And E20Represents phenyl, naphthyl or heteroaryl having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group selected from a halogen atom, a haloalkyl group having a carbon number of 1 to 4, an alkoxy group having a carbon number of 1 to 20, an alkyl group having a carbon number of 1 to 12, benzoyl or an alkoxy group having a carbon number of 1 to 12; or
E19and E20Is taken together with the nitrogen atom to which it is bound to form non-interrupted or interrupted O, S or NE17And the five-or six-membered saturated or unsaturated ring is unsubstituted or substituted with at least one group represented by the following formula, wherein at least one group is selected from an alkyl group having a carbon number of 1 to 20, an alkoxy group having a carbon number of 1 to 20, and O, OE17、SE18、NE21E22、(CO)E23、NO2Halogen atom, C1-4 haloalkyl group, CN, phenyl group,Or not interrupted or via at least one O, S, CO or NE17A cycloalkyl group interrupted and having a carbon number of 3 to 20; or
E19And E20Is taken together with the attached nitrogen atom to form a heteroaromatic ring system which is unsubstituted or substituted by at least one group selected from the group consisting of alkyl having a carbon number of from 1 to 20, haloalkyl having a carbon number of from 1 to 4, alkoxy having a carbon number of from 1 to 20, ═ O, OE17、 SE18、NE21E22、(CO)E23、Halogen atom, NO2CN, phenyl, or with one or more O, S, CO or NE not interrupted or interrupted17And a cycloalkyl group having a carbon number of 3 to 20;
E21And E22Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group;
E21And E22Together with the nitrogen atom to which they are bonded form non-interrupted or interrupted O, S or NE26wherein the five-or six-membered saturated or unsaturated ring is unfused or fused with a benzene ring;
E23Represents hydrogen atom, OH, alkyl with 1-20 carbon atoms, halogenated alkyl with 1-4 carbon atoms, and at least one O, CO or NE26And alkyl having 2 to 20 carbon atoms, not interrupted or interrupted O, S, CO or NE26And a cycloalkyl group having a carbon number of 3 to 20; or
E23Represents phenyl, naphthyl, phenyl-R1、OE17、SE18Or NE21E22；
E24Represents (CO) OE17、CONE19E20、(CO)E17Or with respect to E19And E20One of the definitions;
E25Represents COOE17、CONE19E20、(CO)E17(ii) a Or with respect to E17One of the definitions;
E26Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by at least one O or CO; or E26Represents phenyl-R1Cycloalkyl which is not interrupted or interrupted by one or more O or CO and has a carbon number of 3 to 8; or E26Represents (CO) E19(ii) a Or E26Represents phenyl, E26Is unsubstituted or substituted with at least one group represented by the following formula, and the at least one group is selected from alkyl having 1 to 20 carbon atoms, halogen atom, haloalkyl having 1 to 4 carbon atoms, OE17、 SE18、NE19E20Or
Provided that the photoinitiator (E-1) having the structure represented by the formula (IIIA) has at least oneOr
The groups defined for the compounds of the formula (IIIA) preferably correspond to those defined below for the compounds of the formula (III) except for the oxime ester groups defined (for example) Are all replaced by the corresponding free oxime group
Each oxime ester group may exist in two configurations (Z) or (E). The isomers can be separated by conventional methods, but isomer mixtures can also be used, for example, as photoinitiator substances. Thus, the photoinitiator (E-1) of the present invention, a compound represented by the formula (III), comprises a mixture of configurational isomers.
In a preferred embodiment, the photoinitiator (C) comprises a photoinitiator (E-1) having a structure represented by formula (III), wherein E1、E2、E3、E4、E5、E6、E7And E8each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,COE16Or NO2(ii) a Or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Each independently representWherein at least one E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Is composed of
Z1Represents CO or a single bond;
E13Represents an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following formula, and at least one group is selected from a halogen atom, OE17、SE18、COOE17、 CONE19E20Or PO (OC)kH2k+1)2(ii) a Or
E13Represents an alkyl group having 2 to 20 carbon atoms interrupted by one or more O, S carbon atoms、NE26Or CO; or
E13Represents phenyl or naphthyl, both unsubstituted or substituted by at least oneOr COE16Substitution;
E14Represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or an alkoxy group having 1 to 8 carbon atoms;
E15Represents phenyl, naphthyl, heteroaryl with 3 to 20 carbon atoms, each of which is unsubstituted or substituted by at least one group shown below, and the at least one group is selected from phenyl, halogen atom, C1-4 haloalkyl, OE17、SE18An alkyl group interrupted by at least one O or S and having 2 to 20 carbon atoms, or each of which is substituted by one or more alkyl groups having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted by at least one group represented by the following, and at least one group being selected from a halogen atom, COOE17、CONE19E20Phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryloxycarbonyl having 4 to 20 carbon atoms, OE17、SE18、NE19E20Or PO (OC)kH2k+1)2(ii) a Or
E15Represents an alkyl group having 1 to 20 carbon atoms which is unsubstituted or substituted with at least one group represented by OE17、SE18Cycloalkyl group having 3 to 8 carbon atoms, heteroaryl group having 3 to 20 carbon atoms, NE19E20、COOE17、CONE19E20Or PO (OC)kH2k+1)2；
E'14Representative has a meaning for E14One of the definitions;
E'15Representative has a meaning for E15One of the definitions;
E16Represents phenyl which is unsubstituted or substituted by at least one group shown below, and at least one groupThe groups are selected from OE17、SE18、NE19E20At least one of O, S or NE26And an alkyl group having a carbon number of 2 to 20; or
E16Represents phenyl substituted by at least one alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted by at least one group represented by the following formula, and at least one group is selected from a halogen atom, COOE17、CONE19E20Phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryloxycarbonyl having 4 to 20 carbon atoms, OE17、SE18Or NE19E20(ii) a Or
E16Represents an alkyl group having 1 to 20 carbon atoms, E16Is unsubstituted or substituted by at least one group shown below, and at least one group is selected from halogen atom, phenyl, OH, SH, CN, C3-6 alkenyloxy, OCH2CH2(CO)O(R1)、O(CO)-(R1) Or (CO) O (R)1)；
E17Represents an alkyl group having a carbon number of 1 to 20, which is unsubstituted or substituted with at least one group selected from a halogen atom, OCH2CH2(CO)O(R1)、O(R1)、(CO)O(R1) Cycloalkyl having a carbon number of 3 to 20, wherein cycloalkyl having a carbon number of 3 to 20 is not interrupted or interrupted by at least one O; or
E17Represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by at least one O;
E18Represents Via (CO) OE17a substituted methyl group;
E19And E20Each independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms or an alkanoyloxy group having 1 to 8 carbon atoms; or
E19And E20Are taken together with the bonded nitrogen atom to form a heteroaromatic ring system which is unsubstituted or substitutedThe substitution is carried out by the following steps,
With the proviso that the photoinitiator (E-1) of the structure represented by the formula (III) has at least one
Attention must be paid to the compounds of the formula (III) as defined above, in which E1、E2、E3、E4、E5、E6、 E7And E8Each independently represents a hydrogen atom,COE16Or NO2；
E3And E4Together are
E9、E10、E11and E12is a hydrogen atom;
Z1Is a single bond;
E13Is an alkyl group having 1 to 20 carbon atoms;
E14is an alkyl group having 1 to 20 carbon atoms;
E15Is alkyl with carbon number of 1-20 or phenyl substituted by at least one group (OE)17Or an alkyl group having a carbon number of 1 to 20;
E16Is phenyl, which is substituted by at least one group which may be OE17Or an alkyl group having a carbon number of 1 to 20;
E17Is an alkyl group having 1 or 20 carbon atoms which is unsubstituted or substituted with at least one halogen atom or an alkyl group having 1 to 20 carbon atoms interrupted with at least one oxygen atom.
Provided that at least one compound of the formula (III)
in a more preferred embodiment, the photoinitiator (C) comprises a photoinitiator (E-1) having a structure according to formula (III), wherein E1、E2、E3、E4、E5、E6、E7And E8Each independently represents a hydrogen atom; or
E1And E2、E3And E4Or E5And E6Each independently representAnd at least one E1And E2、E3And E4Or E5And E6is composed of
Or E2RepresentsCOE16、NO2OrOr
E7RepresentsOr COE16；
E9、E11And E12represents a hydrogen atom;
E10Represents a hydrogen atom, OE17Or COE16；
Z1Represents CO or a single bond;
E13Represents an alkyl group having a carbon number of 1 to 20, which is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from a halogen atom, E17、OE17、SE18or PO (OC)kH2k+1)2(ii) a Or
E13represents an alkyl group having 2 to 20 carbon atoms, which is interrupted by at least one O; or
E13represents phenyl;
k represents an integer of 2;
E14Represents an alkyl group having a carbon number of 1 to 20 or a thienyl group;
E15Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least one OE17Or alkyl having 1 to 20 carbon atoms; or
E15Represents a thienyl group, a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following formula, and at least one group is selected from OE17、 SE18Cycloalkyl group having 3 to 8 carbon atoms, NE19E20Or COOE17(ii) a Or
E15Represents an alkyl group having 2 to 20 carbon atoms, and SO is interrupted between the alkyl groups having 2 to 20 carbon atoms2；
E16Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least one group selected from OE17、SE18、NE19E20Or an alkyl group having a carbon number of 1 to 20; or
E16Represents thienyl;
E17Represents a hydrogen atom, an alkanoyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted with at least one group selected from the group consisting of a halogen atom, O (CO) - (R)1)、O(CO)-(R6) Or cycloalkyl interrupted by at least one O and having a carbon number of from 3 to 20; or
E17Represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is interrupted by at least one O;
E18Represents cycloalkyl having a carbon number of 3 to 20, alkyl having a carbon number of 1 to 20, which is unsubstituted or substituted by at least one OH, O (CO) - (R)6) Or (CO) OE17Substitution; or
E18Represents phenyl, which is unsubstituted or substituted by at least one halogen atom;
E19And E20each independently represents an alkanoyl group having 1 to 8 carbon atoms or an alkanoyl oxy group having 1 to 8 carbon atoms; or
E19and E20Are taken together with the bonded nitrogen atom to form a five-or six-membered saturated ring interrupted by O,
provided that the photoinitiator (E-1) having the structure represented by the formula (III) has at least one
Specific examples of the photoinitiator (E-1) of the present invention are compounds of formulae (IIIa) to (IIIg) as defined above, of which compounds of formula (IIIa), formula (IIIb), formula (IIIc), in particular formula (IIIa) or formula (IIIc), or formula (IIIa), formula (IIIc) or formula (IIId), in particular formula (IIIa) are of interest.
In one example, E1、E2、E3、E4、E5、E6、E7And E8Each independently represents a hydrogen atom,Or COE16Or E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Each independently represent
in one example, E1And E2Or E3and E4Together areOr E3And E4、E5And E6Together areE3And E4Especially together are
In one example, E1、E5、E6And E8Represents a hydrogen atom. Preferably, E7Represents a hydrogen atom,Or COE16Or E7RepresentsOr COE16Then with E7RepresentsMore preferably. Preferably, E2RepresentsCOE16OrOr E2And E1Together areThen with E2Represents COE16more preferably. Z1preferably a single bond.
In one example, E9、E10、E11And E12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or a phenyl group substituted with at least one group represented by the following, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE17Or SE18(ii) a Or
E9、E10、E11And E12Each independently represents a halogen atom, OE17、SE18Or NE19E20In which the substituent O isE17、SE18Or NE19E20is optionally via a group E17、E18、E19and/or E20forms a five-membered ring or a six-membered ring with one carbon atom of the naphthalene ring in the formula (III); or
E9、E10、E11And E12Each independently representsOr COE16。
In a specific example, E9、E10、E11And E12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or a phenyl group substituted with at least one group represented by the following, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE17Or SE18(ii) a Or
E9、E10、E11And E12Each independently represents a halogen atom, OE17、SE18Or NE19E20(ii) a Or
E9、E10、E11And E12Each independently representsOr COE16。
In one example, E9、E10、E11And E12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or a phenyl group substituted with one or more alkyl groups having 1 to 6 carbon atoms; or E9、 E10、E11And E12Each independently representsOr COE16。
In another example, E9、E10、E11And E12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, orSubstituted phenyl or phenyl substituted with at least one group represented by the following, and at least one group is selected from alkyl having 1 to 6 carbon atoms, halogen atom, OE17Or SE18(ii) a Or
E9、E10、E11And E12Each independently represents a halogen atom, OE17、SE18Or NE19E20In which the radical OE is substituted17、SE18Or NE19E20is optionally via a group E17、E18、E19And/or E20And one carbon atom of the naphthalene ring in the formula (III) to form a five-membered ring or a six-membered ring.
Further, in one example, E9、E10、E11And E12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or a phenyl group substituted with at least one group represented by the following formula (I), at least one group being selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE17Or SE18(ii) a Or E9、E10、E11And E12each independently represents a halogen atom, OE17、SE18、NE19E20Or COE16。
Or, in one example, E9、E10、E11and E12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or a phenyl group substituted with at least one group represented by the following formula (I), at least one group being selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE17Or SE18(ii) a Or E9、E10、E11And E12Each independently represents a halogen atom, OE17、COE16Or NE19E20。
Preferably, E9、E11And E12Is a hydrogen atom, and E10Is a hydrogen atom, OE17Or COE16。
E13Is, for example, an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented byWherein at least one group is selected from halogen atom and COOE17Or CONE19E20(ii) a Or
E13Represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by one or more of O, S, SO2、NE26Or CO;
E13Represents an alkenyl group having 2 to 12 carbon atoms, wherein the alkenyl group having 2 to 12 carbon atoms is not interrupted or interrupted with one or more O, CO or NE26(ii) a Or
E13represents a cycloalkyl group having 3 to 10 carbon atoms, the cycloalkyl group being interrupted or interrupted by one or more of O, S, CO or NE26(ii) a Or
E13Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least one group selected from OE17、SE18、NE19E20、COE16、NO2A halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group which is interrupted by at least one O and has 2 to 20 carbon atoms; or represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented by the following formula, wherein the at least one group is selected from a halogen atom, E17、COOE17、 OE17、SE18、CONE19E20Or PO (OC)kH2k+1)2(ii) a Or represents an alkyl group having 2 to 20 carbon atoms, interrupted by one or more O.
Furthermore, E13Represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented by the following formula, wherein the at least one group is selected from a halogen atom, E17、COOE17、OE17、SE18、 CONE19E20Or PO (OC)kH2k+1)2(ii) a Or represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by one O; or an alkenyl group having 2 to 12 carbon atoms, having 3 to 10 carbon atomsCycloalkyl groups of (a); or E13Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least one group selected from OE17、SE18、NE19E20、COE16、NO2A halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by one or more O.
In another embodiment, E13Represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented by the following, wherein the at least one group is selected from a halogen atom, E17、OE17、 SE18Or PO (OC)kH2k+1)2(ii) a Or represents an alkyl group interrupted by one or more O and having 2 to 20 carbon atoms; or an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group or a naphthyl group.
Or, E13For example, it may represent an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented by the following, wherein the at least one group is selected from a halogen atom, E17、OE17、SE18Or PO (OC)kH2k+1)2(ii) a Or represents at least one alkyl group having 2 to 20 carbon atoms, wherein O is an hetero atom; or represents phenyl, alkenyl having 2 to 12 carbon atoms, or cycloalkyl having 3 to 10 carbon atoms.
Or, E13May represent an alkyl group having 1 to 20 carbon atoms, a phenyl group, an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Or E13is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 10 carbon atoms. Preferably, E13May represent an alkyl group having a carbon number of 1 to 20, especially an alkyl group having a carbon number of 1 to 8, such as 2-ethylhexyl.
E14May for example represent a hydrogen atom, a cycloalkyl group having a carbon number of 3 to 8, an alkenyl group having a carbon number of 2 to 5, an alkoxy group having a carbon number of 1 to 20 or an alkyl group having a carbon number of 1 to 20, which is unsubstituted orSubstituted by at least one halogen atom or phenyl group; or
E14Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least one group represented by the following, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a halogen atom, OE17、SE18And/or NE19E20(ii) a Or
E14Represents a heteroaryl group having a carbon number of 3 to 5, such as a thienyl group, or represents an alkoxy group having a carbon number of 1 to 8, a benzyloxy group or a phenoxy group.
Or, E14May represent, for example, an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms being substituted with at least one halogen atom or a phenyl group; or
E14Represents a heteroaryl group having a carbon number of 3 to 5 (e.g., thienyl group) or represents a phenyl group which is unsubstituted or substituted with at least one group represented by the following, and at least one group is selected from an alkyl group having a carbon number of 1 to 6, a haloalkyl group having a carbon number of 1 to 4, a halogen atom, OE17、SE18And/or NE19E20(ii) a Or
E14Represents an alkoxy group having a carbon number of 1 to 8, a benzyloxy group or a phenoxy group.
in another embodiment, E14Represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with a phenyl group;
or E14Is phenyl, and the phenyl is unsubstituted or substituted by at least one alkyl group having 1 to 6 carbon atoms.
Preferably, E14Is an alkyl group having 1 to 20 carbon atoms, a heteroaryl group having 3 to 5 carbon atoms (e.g., thienyl group), or a phenyl group, particularly an alkyl group having 1 to 20 carbon atoms or a thienyl group, more preferably an alkyl group having 1 to 8 carbon atoms.
E15Can be, for example, an aryl group having a carbon number of 6 to 20 or a heteroaryl group having a carbon number of 5 to 20, each of which is unsubstituted or substituted with at least one group selected from phenyl, a halogen atom, a haloalkyl group having a carbon number of 1 to 4, CN, NO2、OE17、SE18、NE19E20an alkyl group having 1 to 20 carbon atoms;
Or E15Is a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, wherein the cycloalkyl group having 3 to 8 carbon atoms is not interrupted or interrupted with one or more O, CO or NE26；
Or E15Is an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group selected from a halogen atom, OE17cycloalkyl group having 3 to 8 carbon atoms, heteroaryl group having 5 to 20 carbon atoms, phenoxycarbonyl group having 8 to 20 carbon atoms, heteroaryloxy-carbonyl group having 5 to 20 carbon atoms, NE19E20、COOE17、CONE19E20、PO(OCkH2k+1)2、phenyl or phenyl substituted by a group selected from halogen atoms, C1-20 alkyl, C1-4 haloalkyl, OE17Or NE19E20；
Or E15Is an alkyl group having 2 to 20 carbon atoms, wherein at least one of O, S or SO is doped between the alkyl groups having 2 to 20 carbon atoms2，
Or E15Is alkanoyl group having 2 to 20 carbon atoms, benzoyl group, alkoxycarbonyl group having 2 to 12 carbon atoms, phenoxycarbonyl group, CONE19E20、NO2Or a haloalkyl group having a carbon number of 1 to 4.
Furthermore, E15Can be, for example, a hydrogen atom, an aryl group having a carbon number of from 6 to 20, in particular a phenyl or naphthyl group, which are each unsubstituted or substituted by alkyl groups having a carbon number of from 1 to 12; or a heteroaryl group having a carbon number of 3 to 5, such as thienyl; or a cycloalkyl group having a carbon number of 3 to 8, an alkyl group having a carbon number of 1 to 20, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OE17、SE17Cycloalkyl having 3 to 8 carbon atoms, NE19E20Or COOE17；
Or E15Is an alkyl group having 2 to 20 carbon atoms, wherein at least one O or SO is interrupted between the alkyl groups having 2 to 20 carbon atoms2。
In the compounds of the formula (III), E15Can be, for example, a hydrogen atom, a phenyl group, a naphthyl group, each of which is unsubstituted or substituted by an alkyl group having 1 to 8 carbon atoms; or
E15Is thienyl, alkyl having 1 to 20 carbon atoms, unsubstituted or substituted with at least one group selected from OE17、SE17Cycloalkyl group having 3 to 8 carbon atoms, NE19E20Or COOE17(ii) a Or
E15Is an alkyl group having 2 to 20 carbon atoms, wherein at least one O or SO is interrupted between the alkyl groups having 2 to 20 carbon atoms2。
E15Especially, for example, a cycloalkyl group having a carbon number of 3 to 8 or an alkyl group having a carbon number of 1 to 20, preferably an alkyl group having a carbon number of 1 to 20, more preferably an alkyl group having a carbon number of 1 to 12.
E'14And E'15Respectively have the same meanings as above for E14And E15One of the definitions.
Z2Is for example O, S or SO, for example O or S, especially O.
E16Can be, for example, an aryl group having a carbon number of from 6 to 20 (in particular phenyl or naphthyl, in particular phenyl) or a heteroaryl group having a carbon number of from 5 to 20 (in particular thienyl), each unsubstituted or substituted by at least one group selected from phenyl, a halogen atom, a haloalkyl group having a carbon number of from 1 to 4, CN, NO2、 OE17、SE18、NE19E20or an alkyl group interrupted by at least one O having a carbon number of 1 to 20; or each of which is substituted with at least one alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted with at least one group selected from a halogen atom, COOE17、CONE19E20Phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 5 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryloxycarbonyl having 5 to 20 carbon atoms, OE17、SE18Or NE19E20(ii) a Or
E16Is hydrogen atom, alkyl group with 1-20 carbon atoms, wherein the alkyl group with 1-20 carbon atoms is unsubstituted or substituted by at least one group shown as follows, and at least one group is selected from halogen atom, phenyl, OH, SH, 3-6 carbon atoms alkenyloxy, OCH2CH2(CO)O(R1)、O(CO)-(R1) O (CO) -phenyl, (CO) OH or (CO) O (R)1) (ii) a Or
E16Is an alkyl group having 2 to 12 carbon atoms, wherein at least one O is interrupted between the alkyl groups having 2 to 12 carbon atoms; or
E16Is (CH)2CH2O)n+1H、(CH2CH2O)n(CO)-(R4) Alkenyl having a carbon number of 2 to 12 or cycloalkyl having a carbon number of 3 to 8, and n is 1 to 20, for example 1 to 12 or 1 to 8, especially 1 or 2.
Furthermore, E16Can be, for example, phenyl or naphthyl, in particular phenyl, thienyl or carbazole, each unsubstituted or substituted by at least one group selected from phenyl, halogen atoms, haloalkyl having 1 to 4 carbon atoms, OE17、SE18、NE19E20Or an alkyl group having a carbon number of 1 to 20; or
E16Is alkyl with carbon number of 1-20, the alkyl with carbon number of 1-20 is unsubstituted or substituted by at least one group shown as follows, and at least one group is selected from halogen atom, phenyl, OH, SH, alkenyloxy with carbon number of 3-6, OCH2CH2(CO)O(R1)、O(CO)-(R1) O (CO) -phenyl, (CO) OH or (CO) O (R)1) (ii) a Or
E16Is an alkyl group having 2 to 12 carbon atoms, and the alkyl group having 2 to 12 carbon atoms is interrupted by at least one O; or
E16Is (CH)2CH2O)n+1H、(CH2CH2O)n(CO)-(R4) Alkenyl having a carbon number of from 2 to 12 or cycloalkyl having a carbon number of from 3 to 8, and n is from 1 to 20, for example from 1 to 12 or from 1 to 8, in particular 1 or 2。
Furthermore, E16It may be, for example, phenyl or naphthyl, in particular phenyl, each of which is unsubstituted or substituted by at least one group, selected from phenyl, halogen atoms, haloalkyl having 1 to 4 carbon atoms, OE17、SE18、NE19E20or an alkyl group having a carbon number of 1 to 20; or
E16Is heteroaryl having a carbon number of from 3 to 5, especially thienyl.
E16Especially, for example, phenyl, unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OE17、SE18、NE19E20Or an alkyl group having 1 to 20 carbon atoms, or E16Is thienyl.
Preferably, E16Is, for example, phenyl or naphthyl, each of which is unsubstituted or substituted by at least one alkyl group having 1 to 20 carbon atoms.
E16In particular phenyl, and the phenyl group is substituted by at least one alkyl group having 1 to 20 carbon atoms.
E17Can be, for example, a hydrogen atom, phenyl-R5Alkyl with 1 to 20 carbon atoms, which is unsubstituted or substituted by at least one group shown below, and at least one group is selected from halogen atom, OH, OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-(R6) O (CO) -phenyl, (CO) OH, (CO) O (R)1) Cycloalkyl having 3 to 20 carbon atoms or cycloalkyl having 3 to 20 carbon atoms interrupted by at least one O; or
E17Is an alkyl group having 2 to 20 carbon atoms, wherein at least one O is interrupted between the alkyl groups having 2 to 20 carbon atoms; or
E17is (CH)2CH2O)n+1H、(CH2CH2O)n(CO)-(R4) Alkanoyl having 1 to 8 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkenoyl having 3 to 6 carbon atoms or cycloalkyl having 3 to 20 carbon atoms, which is not interrupted or interrupted with at least one O; or
E17Is benzoyl, and benzeneformyl is unsubstituted or substituted with at least one group shown below, and at least one group is selected from alkyl having 1 to 6 carbon atoms, halogen atom, OH or alkoxy having 1 to 3 carbon atoms; or
E17Is phenyl, naphthyl or heteroaryl with carbon number of 5-20, each of which is unsubstituted or substituted with at least one group selected from halogen atom, OH, alkyl with carbon number of 1-12, alkoxy with carbon number of 1-12, CN, NO2phenyl-R8Phenoxy group, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N (R)9)2Diphenyl-amino or
In another embodiment, E17Is, for example, a hydrogen atom, phenyl-R5An alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group selected from the group consisting of halogen atom, O (CO) - (R)1)、O(CO)-(R6) Or an alkyl group having 2 to 20 carbon atoms interrupted by at least one O; or
E17Is an alkanoyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 6 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted with at least one O, a cycloalkyl group having 3 to 20 carbon atoms not interrupted or interrupted with at least one O; or
E17Is benzoyl which is unsubstituted or substituted by at least one group represented by the following formula, and at least one group is selected from alkyl having 1 to 6 carbon atoms, halogen atom, OH or alkoxy having 1 to 3 carbon atoms; or
E17Is phenyl or naphthyl, each of which is unsubstituted or substituted with at least one group shown below, and at least one group is selected from a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
E17Also being, for example, a hydrogen atom, phenyl-R5alkanoyl group having 1 to 8 carbon atoms, alkyl group having 1 to 20 carbon atoms which is unsubstituted or at least one member selected from the group consisting ofOne group is substituted, and at least one group is selected from halogen atom, C3-20 cycloalkyl, O (CO) - (R)1)、O(CO)-(R6) Or C2-20 alkyl interrupted by at least one O, or E17Is an alkyl group having 2 to 20 carbon atoms, interrupted by at least one O.
E17Especially hydrogen atom, alkanoyl group having 1 to 8 carbon atoms, alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group selected from O (CO) - (R)1)、 O(CO)-(R6) Or C2-20 alkyl interrupted by at least one O, or E17Is an alkyl group having 2 to 20 carbon atoms, interrupted by at least one O.
E18Is, for example, cycloalkyl having a carbon number of 3 to 20, which is not interrupted or interrupted by at least one O; or
E18Is an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group selected from OH, O (CO) - (R)6)、O(CO)-(R1) Or (CO) OE17(ii) a Or
E18Is an alkyl group having 2 to 20 carbon atoms, interrupted by at least one of O, S, CO, NE26Or COOE17(ii) a Or
E18Is alkanoyl with 2-8 carbon atoms or alkenoyl with 3-6 carbon atoms, benzoyl; or
E18Is phenyl, naphthyl or heteroaryl having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or NO2。
In another embodiment, E18Is, for example, cycloalkyl having a carbon number of 3 to 20, alkyl having a carbon number of 1 to 20, unsubstituted or substituted with at least one group selected from OH, O (CO) - (R)6)、O(CO)-(R1) Or (CO) OE17(ii) a Or
E18Is phenyl or naphthyl, each of which is unsubstituted orSubstituted by at least one halogen atom or alkyl group having 1 to 12 carbon atoms, especially a halogen atom.
E18Is, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a phenyl-R5Alkanoyl having 2 to 8 carbon atoms, benzoyl, phenyl or naphthyl.
For example, E18is an alkyl group having 1 to 20 carbon atoms, which is substituted with at least one group selected from OH, O (CO) - (R)6)、O(CO)-(R1) Or (CO) OE17Or E18Is phenyl, which is substituted by at least one halogen atom.
Preferably, E18Is an alkyl group having a carbon number of 1 to 8, which is substituted as defined above.
For example, E19And E20Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl-R5Phenyl or naphthyl, alkanoyl with 1 to 8 carbon atoms, alkanoyloxy with 1 to 8 carbon atoms, alkenoyl with 3 to 12 carbon atoms or benzoyl; or
E19And E20Is taken together with the nitrogen atom to which it is bound to form non-interrupted or interrupted O, S or NE17A five-or six-membered saturated or unsaturated ring of (a); or
E19And E20Is taken together with the bound nitrogen atom to form a heteroaromatic ring system which is unsubstituted or substituted by at least one group selected from alkyl having 1 to 20 carbon atoms, haloalkyl having 1 to 4 carbon atoms, or
Also, for example, E19And E20Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl-R5Alkanoyl group having 1 to 8 carbon atoms, alkanoyloxy group having 1 to 8 carbon atoms, alkanoyl group having 3 to 8 carbon atoms12 enoyl or benzoyl; or
E19And E20is taken together with the nitrogen atom to which it is bound to form a non-interrupted or interrupted O or NE17a five-or six-membered saturated ring; or
E19And E20Are taken together with the nitrogen atom to which they are bonded to form a carbazole ring.
For example, E19And E20Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl-R5Alkanoyl having 1 to 8 carbon atoms, alkanoyloxy having 1 to 8 carbon atoms, alkenoyl having 3 to 12 carbon atoms or benzoyl; or
E19And E20Is taken together with the nitrogen atom to which it is bound to form a non-interrupted or interrupted O or NE17A five-or six-membered saturated ring.
Preferably, E19And E20Each independently represents an alkanoyl group having 1 to 8 carbon atoms or an alkanoyloxy group having 1 to 8 carbon atoms; or
E19And E20Is formed with a morpholine ring together with the nitrogen atom to which it is bonded.
For example, E21And E22Each independently is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group; or
E21And E22Is formed with a morpholine ring together with the nitrogen atom to which it is bonded. E21And E22In particular each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.
E23is, for example, a hydrogen atom, OH, phenyl or an alkyl group having 1 to 20 carbon atoms. E23Especially hydrogen atoms, OH or alkyl groups having 1 to 4 carbon atoms.
E24Are preferably as for E19And E20One of the definitions. E25Are preferably as for E17One of the definitions.
E26Is, for example, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon numberis a halogenated alkyl group of 1 to 4, an alkyl group of 2 to 20 carbon atoms, interrupted by at least one O or CO; or
E26Is phenyl-R1Cycloalkyl having a carbon number of 3 to 8, and cycloalkyl having a carbon number of 3 to 8 is not interrupted or interrupted by one or more O or CO; or
E26is (CO) E19Or phenyl, wherein the phenyl is unsubstituted or substituted by at least one group selected from alkyl having 1 to 20 carbon atoms, halogen atom, haloalkyl having 1 to 4 carbon atoms, OE17、 SE18、NE19E20。
Or E26Represents, for example, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms; is phenyl-R1Cycloalkyl group having 3 to 8 carbon atoms, (CO) E19Or phenyl, and the phenyl is unsubstituted or substituted with at least one alkyl group having 1 to 20 carbon atoms. Furthermore, E26For example, hydrogen or alkyl having 1 to 20 carbon atoms, in particular 1 to 4 carbon atoms.
Specific examples of the aforementioned photoinitiator (E-1) having a structure represented by formula (III) may include photoinitiators having structures represented by the following formulas (III-1) to (III-86).
The photoinitiator (E-1) is used in an amount of 0.1 to 15 parts by weight, preferably 1 to 12 parts by weight, and more preferably 3 to 10 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C). If the photosensitive resin composition contains the photoinitiator (E-1), it can have better resistance to chemicals.
Other free radical type photoinitiators (E-2)
The photoinitiator (E) of the present invention may further comprise other radical type photoinitiators (E-2).
The other radical photoinitiator (E-2) may be selected from acetophenone-based compounds (acetophenones), diimidazole-based compounds (diimidazoles), acyloxime-based compounds (acyloximes), or a combination thereof.
The acetophenone compound is selected from p-dimethylaminoacetophenone (p-dimethylamino-acetophenone), α '-dimethoxyazoxyacetophenone (α, α' -dimethoxyazoxy-acetophenone), 2 '-dimethyl-2-phenylacetophenone (2, 2' -dimethyl-2-phenyl-acetophenone), p-methoxyacetophenone (p-methoxy-acetophenone), 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone [2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone ], 2-benzyl-2-nitrogen, nitrogen-dimethylamino-1- (4-morpholinophenyl) -1-butanone [ 2-benzyl-2-phenyl-2-N, n-di-methyl lamino-1- (4-morpholinophenyl) -1-butanone ].
the above-mentioned diimidazole compound is selected from 2,2 '-bis (o-chlorophenyl) -4, 4', 5,5 '-tetraphenyldiimidazole [2, 2' -bis (o-chlorophenyl) -4,4 ', 5, 5' -tetraphenyldiimidazole ], 2 '-bis (o-fluorophenyl) -4,4,5, 5' -tetraphenyldiimidazole [2,2 '-bis (o-fluorophenylyl) -4, 4', 5,5 '-tetraphenyldiimidazole ], 2' -bis (o-methylphenyl) -4,4 ', 5, 5' -tetraphenyldiimidazole [2,2 '-bis (o-methyl phenyl) -4, 4', 5,5 '-tetraphenyldiimidazole ], 2' -bis (o-methoxyphenyl) -4,4 ', 5, 5' -tetraphenyldiimidazole [2,2 '-bis (o-methoxyphenyl) -4, 4', 5,5 '-tetraphenyldiimidazole ], 2' -bis (o-ethylphenyl) -4,4 ', 5, 5' -tetraphenyldiimidazole [2,2 '-bis (o-ethylphenyl) -4, 4', 5,5 '-tetraphenyldiimidazole ], 2' -bis (p-methoxyphenyl) -4,4 ', 5, 5' -tetraphenyldiimidazole [2,2 '-bis (p-methoxyphenyl) -4, 4', 5,5 '-tetraphenyldiimidazole ], 2' -bis (2,2 ', 4, 4' -tetramethoxyphenyl) -4,4 ', 5, 5' -tetraphenyldiimidazole [2 ], 2 ' -bis (2,2 ', 4,4 ' -tetramethyloxyphenyl) -4,4 ', 5,5 ' -tetramethylphenyl-biipidazole ], 2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole [2,2 ' -bis (2-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole ], 2 ' -bis (2,4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole [2,2 ' -bis (2,4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole ].
The acyloxime compound is selected from the group consisting of an alkanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9-hydro-carbazol-3-substituent ] -,1- (oxy-acetyloxime) [ Ethanone,1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime), such as CGI-242 available from Ciba Specialty Chemicals, and having a structure represented by the following formula (E-2-1), 1- [4- (phenylthio) phenyl ] -octane-1, 2-dione-2- (O-benzoyloxime) [1- [4- (phenylthio) phenyl ] -octane-1, 2-dione-2- (O-benzoxyimine), such as the product sold under the name CGI-124 by Ciba Specialty Chemicals, the structure of the compound is shown in the following formula (E-2-2), and the compound is 1- [9-ethyl-6- (2-chloro-4-benzyl-thio-benzoyl) -9-H-carbazole-3-substituent ] -,1- (O-acetyl oxime) [ Ethanone,1- [9-ethyl-6- (2-chloro-4-benzyl-thio-benzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyl oxime) such as that manufactured by Asahi electro chemical company, and the structure is shown in the following formula (E-2-3) ]:
Preferably, the further radical photoinitiator (E-2) is 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2-benzyl-2-nitrogen, nitrogen-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2 ' -bis (o-chlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole, ethanone,1- [9-ethyl-6- (2-methylbenzoyl) -9-hydro-carbazol-3-substituent ] -,1- (oxy-acetyloxime) or a combination thereof.
Other radical type photoinitiator (E-2) of the present invention may further comprise the following compounds: benzophenone compounds such as thioxanthone (thioxanthone), 2, 4-diethylthioxanthone (2, 4-diethyl-thioxanthone), thioxanthone-4-sulfone (thioxanthone-4-sulfone), benzophenone (benzophenone), 4 '-bis (dimethylamino) benzophenone [4, 4' -bis (dimethylamino) benzophenone ], 4 '-bis (diethylamino) benzophenone [4, 4' -bis (diethylamino) benzophenone ], and the like; α -diketone (α -diketone) compounds such as benzil (benzil) and acetyl (acetyl); ketone alcohol (acylin) compounds such as benzoin and the like; ketone alcohol ether (acylin ether) compounds such as benzoin methyl ether (benzoin methyl ether), benzoin ethyl ether (benzoin ethyl ether), benzoin isopropyl ether (benzoin isopropyl ether); acylphosphine oxide (acylphosphine oxide) compounds such as 2,4, 6-trimethylbenzoyldiphenylphosphine oxide (2,4, 6-trimethyl-phenyl-phosphinoxide) and bis- (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylphenylphosphine oxide [ bis- (2,6-dimethoxy-benzoyl) -2,4, 4-trimethyl-benzoyl-phosphinoxide ]; quinone compounds such as anthraquinone (quinone) compounds and 1,4-naphthoquinone (1, 4-naphthoquinone); halides such as phenacyl chloride (phenacyl chloride), tribromomethyl phenylsulfone (tribromomethyl-phenylsulfone), tris (trichloromethyl) -s-triazine [ tris (trichloromethyl) -s-triazine ]; and peroxides such as di-t-butyl peroxide (di-tert-butyl peroxide). Among them, benzophenone compounds are preferable, and 4, 4' -bis (diethylamino) benzophenone is more preferable.
The other radical type photoinitiators (E-2) mentioned above may be used singly or in combination of two or more.
In the specific embodiment of the present invention, the other radical type photoinitiator (E-2) is used in an amount ranging from 9.9 parts by weight to 85 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C); preferably from 14 to 78 parts by weight; more preferably 17 to 70 parts by weight.
The photoinitiator (E) is used in an amount of 10 to 100 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C); preferably 15 to 90 parts by weight; more preferably 20 to 80 parts by weight.
Benzophenone compound (F) having unsaturated group
the photosensitive resin composition of the present invention may comprise an unsaturated group-containing benzophenone compound (F), wherein the unsaturated group contained in the benzophenone compound (F) has a structure represented by the formula (IV-1):
in the formula (IV-1), b represents an integer of 0 or 1.
In one embodiment, the unsaturated group-containing benzophenone compound (F) of the present invention may have a structure represented by the following formula (IV):
In the formula (IV), R1fMay represent a hydrogen atom or an unsaturated group represented by the above formula (IV-1), and R2fCan represent an unsaturated group represented by the formula (IV-1), a benzyl group or an alkyl group having 1 to 8 carbon atoms, wherein R is1fAnd R2fAt least one of them is an unsaturated group represented by the formula (IV-1).
Specific examples of the unsaturated group-containing benzophenone compound (F) may be, for example, 2-hydroxy-4-allyloxybenzophenone (2-hydroxy-4-allyloxybenzophenone), 2-hydroxy-4-vinyloxybenzophenone (2-hydroxy-4-vinyloxybenzophenone), 2-hydroxy-3-allyl-4-ethoxybenzophenone, 2-hydroxy-3-allyl-4-propoxybenzophenone, 2-hydroxy-3-allyl-4-hexyloxybenzophenone, 2-hydroxy-3-allyl-4-octyloxybenzophenone (2-hydroxy-3-allyl-4-octyloxybenzophenone), 2-hydroxy-3-allyl-4-benzyloxybenzophenone (2- hydroxy-3-allyl-4-phenyloxy benzophenone) or a combination thereof.
The amount of the unsaturated group-containing benzophenone compound (F) used is 0.1 to 30 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C) used; preferably 0.6 to 27 parts by weight; more preferably 1 to 24 parts by weight.
If the unsaturated group-containing benzophenone compound (F) is not used, the photosensitive resin composition has a problem of poor chemical resistance.
Solvent (G)
The photosensitive resin composition of the present invention is usually prepared by dissolving the components other than the pigment (A) in the solvent (G) to prepare a liquid composition, and then adding the pigment (A) to the liquid composition and uniformly mixing the mixture. The solvent (G) is selected from the group consisting of a soluble dye (B), an alkali-soluble resin (C), an ethylenically unsaturated group-containing compound (D), a photoinitiator (E) and an unsaturated group-containing benzophenone compound (F), and is not required to react with these components and to have a suitable volatility.
The amount of the solvent (G) used ranges from 500 parts by weight to 5000 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resins (C); preferably 800 to 4500 parts by weight; more preferably 1000 to 4000 parts by weight.
In addition, the solvent (G) may be the same as the solvent used for preparing the alkali-soluble resin (C), and will not be described herein. Preferably, the solvent (G) is selected from propylene glycol methyl ether acetate, cyclohexanone or ethyl 3-ethoxypropionate.
Additive (H)
in a preferred embodiment of the present invention, the photosensitive resin composition further comprises an additive (H) such as: fillers, high molecular weight compounds other than the alkali-soluble resin (C), adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like.
The additive (H) may be used alone or in combination, and includes, but is not limited to, fillers such as glass, aluminum, etc.; high-molecular compounds other than the alkali-soluble resin (C) such as polyvinyl alcohol, polyethylene glycol monoalkyl ether, and polyalkylfluoroacrylate; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, adhesion promoters such as 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methylpropenyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; antioxidants such as 2, 2-thiobis (4-methyl-6-tert-butylphenol) and 2, 6-di-tert-butylphenol; ultraviolet absorbers such as 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorophenyl azide and alkoxyphenone; and anti-agglomeration agents such as sodium polyacrylate.
The additive (H) is used in an amount ranging from 0.1 to 10 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C); preferably 0.3 to 7 parts by weight; more preferably 0.5 to 4 parts by weight.
preparation of color Filter
The invention also provides a method for manufacturing the color filter, which uses the photosensitive resin composition for the color filter to form a pixel layer on a substrate.
The invention also provides a color filter which is manufactured by the method.
The method for manufacturing a color filter of the present invention is mainly to coat the photosensitive composition for a color filter mixed in a solution state on a substrate by coating methods such as spin coating, cast coating, ink-jet coating (ink-jet), roll coating, and the like. After coating, most of the solvent is removed by drying under reduced pressure, and then the solvent is removed by pre-baking to form a pre-baked coating. The conditions of reduced pressure drying and prebaking vary depending on the kinds of the respective components and the mixing ratio, and generally, reduced pressure drying is carried out at a pressure of 0 to 200mmHg for 1 to 60 seconds, and prebaking is carried out at a temperature of 70 to 110 ℃ for 1 to 15 minutes. After prebaking, the prebaked coating film is exposed to a prescribed mask (mask), and developed by immersing it in a developing solution at a temperature of 23 ± 2 ℃ for 15 seconds to 5 minutes, and unnecessary portions are removed to form a pattern. The light used for exposure is preferably ultraviolet rays such as g-rays, h-rays, i-rays, etc., and the ultraviolet ray device may be an (ultra) high pressure mercury lamp or a metal halide lamp.
Specific examples of the substrate include: alkali-free glass, soda lime glass, hard glass (pyrex glass), quartz glass, soda glass, and transparent conductive films attached to these glasses, which are used for liquid crystal display devices; or a photoelectric conversion device substrate (e.g., a silicon substrate) used for a solid-state imaging device or the like. These substrates are typically formed by first forming a black matrix (black matrix) that separates the colored layers of each pixel.
Specific examples of the developer include: an aqueous alkaline solution of an alkaline compound such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methylsilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1, 8-diazabicyclo- (5,4,0) -7-undecene, is usually used in a concentration of 0.001 to 10% by weight, preferably 0.005 to 5% by weight, more preferably 0.01 to 1% by weight.
when the developer composed of the above-mentioned alkaline aqueous solution is used, it is generally washed with water after development, and the pattern is air-dried by compressed air or compressed nitrogen gas.
The air-dried substrate having the photo-setting coating layer is heated at a temperature of 100 to 280 ℃ for 1 to 15 minutes by a heating device such as a hot plate or an oven to remove volatile components in the coating film and to cause a thermo-setting reaction of unreacted ethylenically unsaturated double bonds in the coating film. The same procedure was repeated three times using photosensitive resin compositions of respective colors (mainly including three colors of red, green, and blue) on a predetermined pixel to obtain pixel coloring layers of three colors of red, green, and blue.
Then, an ITO (indium tin oxide) vapor deposited film is formed on the pixel coloring layer at a temperature of 220 to 250 ℃ under vacuum, and after etching and wiring of the ITO vapor deposited film are performed as necessary, polyimide for a liquid crystal alignment film is further coated and then fired, thereby obtaining a color filter for a liquid crystal display.
The liquid crystal alignment film used in the above is not particularly limited as it is used to limit the alignment of liquid crystal molecules, and any of inorganic substances and organic substances may be used. The technology for forming the liquid crystal alignment film is well known to anyone skilled in the art and is not the key point of the present invention, and thus is not described herein.
Preparation of liquid Crystal display element
The present invention also provides a liquid crystal display device, which includes the color filter.
The liquid crystal display element of the present invention is mainly composed of a color filter substrate formed by the above-mentioned color filter forming method and a driving substrate provided with a Thin Film Transistor (TFT), wherein a gap (cell gap) is interposed between 2 substrates and arranged oppositely, the peripheral parts of the 2 substrates are bonded by a sealant, and a liquid crystal is filled in the gap defined by the substrate surface and the sealant to seal the filling hole to form a liquid crystal cell (cell). Then, a polarizing plate is attached to the outer surface of the liquid crystal cell, that is, the other side surface of each substrate constituting the liquid crystal cell to obtain a liquid crystal display device.
As for the liquid crystal used in the foregoing, that is, the liquid crystal compound or the liquid crystal composition, there is no particular limitation, but any of the liquid crystal compound and the liquid crystal composition may be used.
The photosensitive resin composition, the color filter, the manufacturing method thereof and the application thereof can ensure that the manufactured color filter and the liquid crystal display device comprising the color filter have good chemical resistance and contrast.
Drawings
In order to make the aforementioned and other objects, features, and advantages of the invention, as well as others which will become apparent, reference should be made to the following detailed description of the preferred embodiments, taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic view showing a comparative measurement state (I) of a photosensitive resin layer; and
FIG. 2 is a schematic view showing a comparative measurement state (II) of the photosensitive resin layer;
Wherein, the notation:
1: photosensitive resin layers 2 and 3: polarizing plate
4: light source 5: a luminance meter.
Detailed Description
The invention is described in detail in the following examples, but it is not intended that the invention be limited to the examples disclosed.
Preparation of the first alkali-soluble resin (C-1)
Synthesis example C-1
100 parts by weight of a fluorene epoxy compound (model ESF-300, manufactured by Nippon iron chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 part by weight of benzyltriethylammonium chloride, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were continuously added to a 500mL four-necked flask, the feeding rate was controlled at 25 parts by weight/min, the temperature was maintained in the range of 100 ℃ to 110 ℃, and after 15 hours of reaction, a pale yellow transparent mixed solution having a solid content of 50 wt% was obtained.
Then, 100 parts by weight of the above mixed solution was dissolved in 25 parts by weight of ethylene glycol monoethyl ether acetate, and 6 parts by weight of tetrahydrophthalic anhydride and 13 parts by weight of benzophenone tetracarboxylic dianhydride were simultaneously added, and the mixture was heated to 110 ℃ to 115 ℃ to react for 2 hours, thereby obtaining a first alkali-soluble resin (C-1-1) having an acid value of 98.0mgKOH/g and a number average molecular weight of 1,623.
Synthesis example C-1-2
100 parts by weight of a fluorene epoxy compound (model ESF-300, manufactured by Nippon iron chemical Co., Ltd.; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 part by weight of benzyltriethylammonium chloride, 0.1 part by weight of 2,6-di-t-butyl-p-cresol and 130 parts by weight of propylene glycol monomethyl ether acetate were continuously added to a 500mL four-necked flask, the feeding rate was controlled at 25 parts by weight/min, the temperature was maintained in the range of 100 ℃ to 110 ℃, and after 15 hours of reaction, a pale yellow transparent mixed solution having a solid content of 50 wt% was obtained.
Then, 100 parts by weight of the above mixed solution was dissolved in 25 parts by weight of ethylene glycol monoethyl ether acetate, and 13 parts by weight of benzophenone tetracarboxylic dianhydride was added at the same time to react at 90 ℃ to 95 ℃ for 2 hours, and then 6 parts by weight of tetrahydrophthalic anhydride was added to react at 90 ℃ to 95 ℃ for 4 hours, to obtain a first alkali-soluble resin (C-1-2) having an acid value of 99.0mgKOH/g and a number average molecular weight of 2,162.
Synthesis example C-1-3
400 parts by weight of an epoxy compound (model NC-3000, manufactured by Nippon chemical Co., Ltd.; epoxy equivalent 288), 102 parts by weight of acrylic acid, 0.3 part by weight of methoxyphenol, 5 parts by weight of triphenylphosphine, and 264 parts by weight of propylene glycol monomethyl ether acetate were placed in a reaction flask, and the temperature was maintained at 95 ℃ and after 9 hours of reaction, an intermediate having an acid value of 2.2mgKOH/g was obtained. Subsequently, 151 parts by weight of tetrahydrophthalic anhydride (tetrahydrophthalic anhydride) was added thereto and reacted at 95 ℃ for 4 hours to obtain a first alkali-soluble resin (C-1-3) having an acid value of 102mgKOH/g and a number average molecular weight of 2,589.
Synthesis example C-1-4
An intermediate product having an acid value of 2.5mgKOH/g was obtained by placing 200 parts by weight of an epoxy compound (model NC-3000, manufactured by Nippon Kagaku K.K.; epoxy equivalent 288), 60 parts by weight of acrylic acid, 0.15 parts by weight of methoxyphenol (methoxyphenol), 2.5 parts by weight of triphenylphosphine, and 200 parts by weight of propylene glycol monomethyl ether acetate in a reaction flask, and reacting at 95 ℃ for 9 hours. Then, 85 parts by weight of tetrahydrophthalic anhydride (tetrahydrophthalic anhydride) was added thereto and reacted at 95 ℃ for 4 hours to obtain a first alkali-soluble resin (C-1-4) having an acid value of 105mgKOH/g and a number average molecular weight of 3,410.
Preparation of the second alkali-soluble resin (C-2)
synthesis example C-2-1
A four-necked flask was equipped with a stirrer, a thermometer, a condenser tube and a nitrogen inlet, and nitrogen was introduced. Then, 100 parts by weight of propylene glycol methyl ether acetate (abbreviated as PGMEA) was added, and the temperature was raised to 100 ℃. Next, 25 parts by weight of 2-methacryloylethoxy succinate (abbreviated as HOMS), 70 parts by weight of 2-hydroxyethyl methacrylate (abbreviated as HEMA), 15 parts by weight of 3, 4-epoxycyclohexylmethyl methacrylate (ECMMA), 10 parts by weight of o-vinylbenzylglycidyl ether (abbreviated as VBGE), and 4.5 parts by weight of 2, 2' -azobis-2-methylbutyronitrile (abbreviated as AMBN) were dissolved in 100 parts by weight of propylene glycol methyl ether acetate, and the mixed solution was dropwise added to the above four-necked flask over 2 hours. After 6.5 hours of reaction at 100 ℃,5 parts by weight of acrylic acid (abbreviated as AA) was charged into a four-necked flask filled with nitrogen, and the temperature was raised to 110 ℃. After 6 hours of reaction, the second alkali-soluble resin of Synthesis example C-2-1 was obtained.
Synthesis examples C-2-2 to C-2-6 production methods
Synthesis examples C-2-2 to C-2-6A second alkali-soluble resin (C-2) was prepared in the same procedure as in Synthesis example C-2-1, except that: the kinds and amounts of the ingredients were varied and are detailed in Table 1.
Preparation of photosensitive resin
example 1
100 parts by weight of the second alkali-soluble resin (C-2-1) obtained in the above synthesis example, 50 parts by weight of C.I. pigment Red 254 (hereinafter referred to as A-1), 15 parts by weight of C.I. acid Red 37 (hereinafter referred to as B-2-1), 30 parts by weight of dipentaerythritol hexaacrylate (hereinafter referred to as D-2), 50 parts by weight of 1- [4- (phenylthio) phenyl ] -octane-1,2-dione 2- (O-benzoyl oxime) (hereinafter referred to as E-2-1), 5 parts by weight of 2,2 ' -bis (2,4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole (hereinafter referred to as E-2-2), 3 parts by weight of 2-hydroxy-3-allyl-4-benzyl benzophenone (F-1), 1500 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as G-1) was added thereto, and the mixture was dissolved and mixed with a shaking stirrer to prepare a photosensitive resin composition, which was evaluated in the following measurement and evaluation methods, and the results are shown in Table 2.
Examples 2 to 12 and comparative examples 1 to 7
The photosensitive resin compositions of examples 2 to 12 and comparative examples 1 to 7 were prepared using the same method as in example 1. Except that the kind of the composition used in examples 2 to 12 and comparative examples 1 to 7 or the amount thereof used was changed, and the detailed conditions and evaluation results are shown in Table 2 and will not be described herein.
Evaluation method
1. resistance to chemical attack
The photosensitive resin composition is spin-coated on the surface of a soda glass substrate, wherein the soda glass substrate is provided with a silicon dioxide film for preventing sodium precipitation. Next, a prebaking treatment was performed on a hot plate at 90 ℃ for 2 minutes to form a coating film having a film thickness of 2.5 μm.
Then, the pre-baked substrate was cooled to room temperature, and a mask was placed between the substrate and a high-pressure mercury lamp at wavelengths of 365nm, 405nm and 436nm, respectively, and with an exposure of 400J/m2Exposing the substrate to radiation. Thereafter, the exposed substrate was subjected to shower development using an aqueous solution of potassium hydroxide having a concentration of 0.04 wt% at 23 ℃ with a nozzle diameter of 1mm and a development pressure of 1kgf/cm2。
Then, after the substrate was cleaned with ultrapure water and blown with air , post-baking treatment was performed at 230 ℃ for 30 minutes to form pattern dots on the substrate. Next, the patterned substrate was immersed in Propylene Glycol Methyl Ether Acetate (PGMEA) at 80 ℃ for 40 minutes.
The substrate before immersion had color saturation coordinate values of (x, Y) and saturation Y, and the color difference Δ E ab of the substrate before and after immersion was measured as an evaluation criterion. The evaluation method is as follows:
◎：△E*ab≦1
○：1＜△E*ab≦2
△：2＜△E*ab≦3
╳：3＜△E*ab
2. contrast ratio
The photosensitive resin composition was applied onto a 100mm × 100mm glass substrate by spin coating, dried under reduced pressure for 30 seconds at a pressure of 100mmHg, and then prebaked at a temperature of 80 ℃ for 2 minutes to form a prebaked coating film having a thickness of 2.5 μm. Then using ultraviolet light (Canon PLA-501F)100mJ/cm2After the prebaked coating film was irradiated with the light of (2), the prebaked coating film was immersed in a developing solution at 23 ℃ for 1 minute and washed with pure water.
Then, after baking at 235 ℃ for 30 minutes, a photosensitive resin layer with a thickness of 2.0 μm was formed on the glass substrate.
The obtained photosensitive resin layer was subjected to the measurement method shown in fig. 1 and 2, and the measured luminance was used for calculation and comparison; wherein the obtained photosensitive resin layer 1 is placed between two polarizing plates 2,3, light irradiated from a light source 4 sequentially passes through the polarizing plate 2, the photosensitive resin layer 1, the polarizing plate 3, and finally passes through the luminance (cd/cm) of the polarizing plate 32) The measurement was carried out by a luminance meter 5 (model BM-5A, manufactured by Topcon, Japan).
As shown in fig. 1, when the polarization direction of the polarizing plate 3 and the polarization direction of the polarizing plate 2 are parallel to each other (measurement state (one)), the measured luminance is a (cd/cm 2); further, as shown in fig. 2, when the polarization direction of the polarizing plate 3 and the polarization direction of the polarizing plate 2 are perpendicular to each other (measurement state (two)), the measured luminance is B (cd/cm)2) (ii) a The contrast can be obtained by the ratio of the luminance A to the luminance B (luminance A/luminance B), which is evaluatedthe valence standards are as follows.
Very good: (luminance A/luminance B) ≧ 3500
O: 3300 ≦ (luminance A/luminance B) < 3500
And (delta): 3000 ≦ (luminance A/luminance B) < 3300
Gamma rays: (luminance A/luminance B) < 3000
As can be seen from the evaluation results in Table 2 below, when the photosensitive resin composition of the present invention includes the dye (B-1), the contrast thereof is better exhibited. When the photosensitive resin composition comprises the first alkali-soluble resin (C-1) and/or the photoinitiator (E-1), the resistance is better. In addition, when the photosensitive resin composition does not contain the unsaturated group benzophenone compound (F), the resistance is not good.
Therefore, the photosensitive resin composition, the color filter and the manufacturing method and application thereof of the invention can effectively overcome the defects of poor chemical resistance and contrast of the color filter manufactured by the conventional photosensitive resin composition.
Although the present invention has been described with reference to the above embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention.
TABLE 2
Table 2 (continuation)
A-1 C.I. pigment Red 254
A-2 C.I. pigment Green 36
Pigment blue 15: 6 of A-3 G.I. pigment
Pigment blue 66 of A-4 C.I. pigment
Pigment Red 177A-5 C.I
B-1-1 Compound (R) represented by the formula (1)cAnd Rdis-SO3 -A is 0)
B-1-2 Compound represented by formula (22)
B-1-3 Compound represented by the formula (28)
Acid red 37 of B-2-1 C.I
B-2-2 c.i. disperse red 60
B-2-3 C.I. disperse blue 60
D-1 EO-modified trimethylolpropane triacrylate
D-2 dipentaerythritol hexaacrylate
D-3 caprolactone modified dipentaerythritol hexaacrylate
E-1-1 Compound represented by the formula (III-1)
E-1-2 Compound represented by the formula (III-8)
E-1-3 Compound represented by the formula (III-27)
E-2-11- [4- (Phenylthio) phenyl ] -octane-1,2-dione 2- (O-benzoyl oxime)
E-2-22, 2 ' -bis (2,4-dichlorophenyl) -4,4 ', 5,5 ' -tetraphenyldiimidazole
E-2-34, 4' -bis (diethylamine) benzophenone
E-2-42-benzyl-2-aza, aza-dimethylamino-1- (4-morpholinophenyl) -1-butanone
F-12-hydroxy-3-allyl-4-benzylbenzophenone
F-22-hydroxy-4-vinyloxy benzophenone
F-32-hydroxy-4-allyloxybenzophenone
G-13-Ethoxypropionic acid ethyl ester
G-2 propylene glycol methyl ether acetate
G-3 Cyclohexanone
H-13-mercaptopropyltrimethoxysilane
H-22, 2-thiobis (4-methyl-6-tert-butylphenol)
H-32-hydroxy-4-methoxybenzophenone

Claims (14)

1. A photosensitive resin composition characterized by comprising:
A pigment (A);
a dye (B);
An alkali-soluble resin (C);
A compound (D) containing an ethylenically unsaturated group;
A photoinitiator (E);
A benzophenone compound (F) containing an unsaturated group having a structure represented by the following formula (IV), wherein the unsaturated group contained in the benzophenone compound (F) has a structure represented by the following formula (IV-1); and
A solvent (G) which is a mixture of,
In the formula (IV), R1fRepresents a hydrogen atom or an unsaturated group represented by the formula (IV-1), R2fRepresents an unsaturated group represented by the formula (IV-1), a benzyl group or an alkyl group having 1 to 8 carbon atoms, and R1fAnd R2fAt least one of them is an unsaturated group represented by the formula (IV-1);
In the formula (IV-1), b represents an integer of 0 or 1.
2. the photosensitive resin composition according to claim 1, wherein the dye (B) comprises a dye (B-1) having a structure represented by formula (I):
in the formula (I), L1To L4Each independently represents hydrogen, -L6An aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L6、-OH、-OL6、-SO3 -、-SO3H、-SO3M、-COOH、-COOL6、-SO3L6、-SO2NHL8or-SO2NL8L9A substituted aromatic hydrocarbon group having 6 to 10 carbon atoms;
L5represents-SO3 -、-SO3H、-SO3M、-COOH、-COOL6、-SO3L6、-SO2NHL8or-SO2NL8L9；
u represents an integer of 0 to 5; when u represents 2 to 5, a plurality of L5Are the same or different;
XbRepresents a halogen atom;
a represents 0 or 1;
L6Represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom, wherein-CH in the alkyl group having 1 to 10 carbon atoms or the alkyl group having 1 to 10 carbon atoms substituted with a halogen atom2Is unsubstituted or substituted by-O-, carbonyl or-NL7-；
L7Represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom;
L8And L9Each independently represents a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or-Q; wherein a hydrogen atom in a straight-chain alkyl group having a carbon number of 1 to 10, a branched-chain alkyl group having a carbon number of 3 to 10, or a cycloalkyl group having a carbon number of 3 to 30 is unsubstituted or substituted by a substituent selected from the group consisting of a hydroxyl group, a halogen atom, -Q, -CH ═ CH2and-CH ═ CH-L6The group consisting of; a linear alkyl group having a carbon number of 1 to 10, -CH in a branched alkyl group having a carbon number of 3 to 10 or a cycloalkyl group having a carbon number of 3 to 302Is unsubstituted or substituted by-O-, carbonyl or-NL7-; or
L8And L9Combined to form a heterocyclic group with a carbon number of 2 to 10, wherein a hydrogen atom in the heterocyclic group with a carbon number of 2 to 10 is unsubstituted or L6-OH, or-Q;
Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 10 carbon atoms, a halogen atom, -L6、-OH、-OL6、-NO2、-CH＝CH2or-CH ═ CH-L6Substituted aromatic hydrocarbon groups having 6 to 10 carbon atoms, or via halogen atoms, -L6、-OH、-OL6、-NO2、-CH＝CH2and-CH ═ CH-L6A substituted heteroaromatic group having 5 to 10 carbon atoms; and
m represents potassium or sodium.
3. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (C) comprises a first alkali-soluble resin (C-1), and the first alkali-soluble resin (C-1) is obtained by polymerizing a mixture comprising an epoxy compound (C-1-1) having at least two epoxy groups and a compound (C-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group.
4. The photosensitive resin composition according to claim 3, wherein the epoxy compound (c-1-1) having at least two epoxy groups has a structure represented by the formula (II-1) or the formula (II-2);
In the formula (II-1), R1c、R2c、R3cand R4cAre the same or different and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 6 to 12 carbon atoms;
In the formula (II)In-2), R5cTo R18cEach independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group having 6 to 15 carbon atoms; and g represents an integer of 0 to 10.
5. The photosensitive resin composition according to claim 1, wherein the photoinitiator (E) comprises a photoinitiator (E-1) having a structure represented by formula (III):
In the formula (III), E1、E2、E3、E4、E5、E6、E7And E8Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,COE16、OE17Halogen atom, NO2OrOr
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Each independently represents a channelSubstituted alkenyl having 2 to 10 carbon atoms; or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7or E7And E8Each independently represent- (CH)2)p-W-(CH2)q-; or
E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7And E8Each independently representWherein at least one E1And E2、E2and E3、E3And E4、E5and E6、E6And E7Or E7And E8Is composed of
E9、E10、E11And E12Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, the alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted with at least one group selected from phenyl, a halogen atom, CN, OH, SH, an alkoxy group having 1 to 4 carbon atoms, (CO) OH and (CO) O (R)1) Wherein R is1Represents an alkyl group having 1 to 4 carbon atoms; or
E9、E10、E11And E12Each independently represents an unsubstituted phenyl group or a phenyl group substituted with at least one group represented by the following, the at least one group being selected from an alkyl group having a carbon number of 1 to 6, a halogen atom, CN, OE17、SE18Or NE19E20(ii) a Or
E9、E10、E11And E12Each independently represents a halogen atom, CN, OE17、SE18、SOE18、SO2E18or NE19E20Wherein said substituent OE17、SE18Or NE19E20Is absent or via said group E17、E18、E19And/or E20With one carbon atom of the naphthalene ring in formula (III)A five-membered ring or a six-membered ring; or
E9、E10、E11And E12Each independently representsCOE16Or NO2；
W stands for O, S, NE26Or a single bond, p represents an integer of 0 to 3, q represents an integer of 1 to 3, Z1Represents CO or a single bond;
E13Represents an alkyl group having a carbon number of 1 to 20, the alkyl group having a carbon number of 1 to 20 being unsubstituted or substituted with at least one group represented by the following, wherein the at least one group is selected from a halogen atom, E17、COOE17、OE17、SE18、CONE19E20、NE19E20、PO(OCkH2k+1)2OrOr
E13Represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by one or more of O, S, SO2、NE26Or CO; or
E13Represents an alkenyl group having 2 to 12 carbon atoms, which is not interrupted or interrupted with one or more O, CO or NE26，
Wherein the alkyl group that is interrupted and has a carbon number of 2 to 20 and the alkenyl group that is not interrupted or interrupted and has a carbon number of 2 to 12 are unsubstituted or substituted with at least one halogen atom; or
E13Represents cycloalkenyl having 4 to 8 carbon atoms, alkynyl having 2 to 12 carbon atoms, or one or more of O, S, CO or NE without or with intermingling26Cycloalkyl group having 3 to 10 carbon atoms; or
E13Represents phenyl or naphthyl, and said phenyl or said naphthyl are each unsubstituted or substituted by at least one group as shown below, wherein said at least one group is selected from OE17、SE18、NE19E20、COE16、CN、NO2halogen atom, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, interrupted by one or more of O, S, CO or NE26And an alkyl group having a carbon number of 2 to 20; or said phenyl or said naphthyl each being substituted by cycloalkyl having 3 to 10 carbon atoms or each being interrupted by one or more O, S, CO or NE26And cycloalkyl having a carbon number of 3 to 10;
k represents an integer of 1 to 10;
E14Represents a hydrogen atom, a cycloalkyl group having a carbon number of 3 to 8, an alkenyl group having a carbon number of 2 to 5, an alkoxy group having a carbon number of 1 to 20, or an alkyl group having a carbon number of 1 to 20 which is unsubstituted or substituted with at least one group shown below, and the at least one group is selected from a halogen atom, a phenyl group, an alkylphenyl group having a carbon number of 1 to 20, or CN; or
E14Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least one group represented by the following, and the at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a halogen atom, CN, OE17、SE18And/or NE19E20(ii) a Or
E14Represents a heteroaryl group having a carbon number of 3 to 20, an alkoxy group having a carbon number of 1 to 8, a benzyloxy group or a phenoxy group, said benzyloxy group and said phenoxy group being unsubstituted or substituted with at least one group represented by the following, and said at least one group is selected from an alkyl group having a carbon number of 1 to 6, a haloalkyl group having a carbon number of 1 to 4 and/or a halogen atom;
E15represents an aryl group having a carbon number of 6 to 20 or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group selected from a phenyl group, a halogen atom, a haloalkyl group having a carbon number of 1 to 4, CN, NO2、OE17、SE18、NE19E20、PO(OCkH2k+1)2An alkyl group having 1 to 10 carbon atoms bonded to SO, and SO2Alkyl with 1 to 10 carbon atoms, interrupted by one or more O, S or NE26And an alkyl group having a carbon number of 2 to 20; or each of which is substituted with an alkyl group having a carbon number of 1 to 20, wherein the alkyl group having a carbon number of 1 to 20 is unsubstituted or substituted with at least one group shown below and the at least one group is selected from a halogen atom, COOE17、CONE19E20Phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryloxycarbonyl having 3 to 20 carbon atoms, OE17、SE18Or NE19E20(ii) a Or
E15Represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, one or more O, CO or NE atoms not interrupted or interrupted26And a cycloalkyl group having a carbon number of 3 to 8; or
E15Represents an alkyl group having a carbon number of 1 to 20, the alkyl group having a carbon number of 1 to 20 being unsubstituted or substituted with at least one group represented by the following, and the at least one group is selected from a halogen atom, OE17、SE18Cycloalkyl group having 3 to 8 carbon atoms, heteroaryl group having 3 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms, heteroaryloxycarbonyl group having 3 to 20 carbon atoms, NE19E20、COOE17、CONE19E20、PO(OCkH2k+1)2、Phenyl, wherein the alkyl group having 1 to 20 carbon atoms is substituted with phenyl, and the phenyl is substituted with a halogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, OE17、SE18Or NE19E20substitution; or
E15Represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by one or more of O, SO or SO2Said alkyl group interrupted and having a carbon number of 2 to 20 being unsubstituted or substituted by at least one group selected from halogen atoms, OE17、COOE17、CONE19E20phenyl or via OE17、SE18Or NE19E20Substituted phenyl; or
E15Represents an alkanoyl group or a benzoyl group having 2 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented by the following, and the at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, an OE group17、SE18Or NE19E20(ii) a Or
E15Represents unsubstituted or substituted by at least one OE17Substituted naphthoyl or is heteroarylcarbonyl having 3 to 14 carbon atoms; or
E15Represents an alkoxycarbonyl group having a carbon number of 2 to 12, which is not interrupted or interrupted by at least one O, wherein the alkoxycarbonyl group having a carbon number of 2 to 12 is unsubstituted or substituted by at least one hydroxyl group; or
E15Represents a phenoxycarbonyl group which is unsubstituted or substituted by at least one group represented by the following formula, and the at least one group is selected from an alkyl group having a carbon number of 1 to 6, a halogen atom, a haloalkyl group having a carbon number of 1 to 4, a phenyl group, an OE group17、SE18or NE19E20(ii) a Or
E15Represents CN, CONE19E20、NO2A C1 to C4 haloalkyl group, S (O)r-R2And S (O)rA bonded phenyl group, wherein said is with S (O)rThe bonded phenyl is unsubstituted or C1-C12 alkyl or SO2-R2Is substituted, and R2Represents an alkyl group having 1 to 6 carbon atoms; or
E15Represents with SO2O-bonded phenyl, diphenylphosphonyl or di (R)3) -phosphono, wherein said with SO2The O-bonded phenyl group is unsubstituted or substituted by an alkyl group having 1 to 12 carbon atoms, and R3Represents an alkoxy group having 1 to 4 carbon atoms;
r represents an integer of 1 to 2;
E'14Representative has a meaning for E14In definitionOne of them;
E'15Representative has a meaning for E15One of the definitions;
Z2Represents O, S, SO or SO2；
Z3Represents O, CO, S or a single bond;
E16Represents an aryl group having a carbon number of 6 to 20 or a heteroaryl group having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group selected from a phenyl group, a halogen atom, a haloalkyl group having a carbon number of 1 to 4, CN, NO2、OE17、SE18、NE19E20Interrupted by one or more of O, S or NE26And an alkyl group having a carbon number of 1 to 20 or an alkyl group having a carbon number of 1 to 20, wherein the alkyl group having a carbon number of 1 to 20 is unsubstituted or substituted with at least one group represented by the following, wherein the at least one group is selected from a halogen atom, COOE17、CONE19E20Phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryloxycarbonyl having 3 to 20 carbon atoms, OE17、SE18Or NE19E20(ii) a Or
E16Represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group represented by the following, and the at least one group is selected from a halogen atom, a phenyl group, OH, SH, CN, an alkenyloxy group having 3 to 6 carbon atoms, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1) O (CO) -phenyl or (CO) OH or (CO) O (R)1) (ii) a Or
E16Represents an alkyl group having 2 to 12 carbon atoms, the alkyl group of 2 to 12 being interrupted by one or more of O, S or NE26(ii) a Or
E16Is represented by (CH)2CH2O)n+1H、(CH2CH2O)n(CO)-(R4) Alkenyl having 2 to 12 carbon atoms or cycloalkyl having 3 to 8 carbon atoms, wherein R is4Represents an alkyl group having 1 to 8 carbon atoms; or
E16Is representative of warp SE18Substituted phenyl radicals in which E18Represents a bond to the COE16A single bond to the phenyl or naphthyl ring of the carbazole moiety attached;
n represents an integer of 1 to 20;
E17Represents a hydrogen atom, phenyl-R5An alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented by the following, and the at least one group is selected from a halogen atom, OH, SH, CN, an alkenyloxy group having 3 to 6 carbon atoms, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R1)、O(CO)-(R6) Phenyl bonded to O (CO), (CO) OH, (CO) O (R)1) Cycloalkyl group having 3 to 20 carbon atoms, SO2-(R7)、O(R7) Or cycloalkyl interrupted by at least one O and having a carbon number of 3 to 20, wherein R5Represents an alkyl group having 1 to 3 carbon atoms, R6Represents an alkenyl group having 2 to 4 carbon atoms, and R7Represents a haloalkyl group having a carbon number of 1 to 4; or
E17Represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is interrupted by one or more O, S or NE26(ii) a Or
E17Is represented by (CH)2CH2O)n+1H、(CH2CH2O)n(CO)-(R4) Alkanoyl having 1 to 8 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkenoyl having 3 to 6 carbon atoms or cycloalkyl having 3 to 20 carbon atoms which is not interrupted or interrupted with one or more O, S, CO or NE26(ii) a Or
E17Represents a group formed by bonding an alkyl group with a carbon number of 1 to 8 and a cycloalkyl group with a carbon number of 3 to 10, wherein the group is not interrupted or interrupted by at least one O; or
E17Represents a benzoyl group which is unsubstituted or substituted by at least one group represented by the following, and the at least one group is selected from an alkyl group having a carbon number of 1 to 6, a halogen atom, OH, or an alkoxy group having a carbon number of 1 to 3; or
E17Represents phenyl, naphthyl orHeteroaryl having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group represented by the following, and the at least one group is selected from a halogen atom, OH, an alkyl group having a carbon number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, CN, NO2phenyl-R8Phenoxy group, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N (R)9)2Diphenyl-amino orWherein R is8Represents an alkoxy group having 1 to 3 carbon atoms, and R9Represents an alkyl group having 1 to 12 carbon atoms; or
E17and is provided withOne of the carbon atoms of the phenyl or naphthyl ring of (a) forms a single bond;
E18Represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or a phenyl-R5Wherein the alkenyl group having a carbon number of 2 to 12, the cycloalkyl group having a carbon number of 3 to 20, and the phenyl-R5Is not interrupted or interrupted by one or more O, S, CO, NE26Or COOE17(ii) a Or
E18Represents an alkyl group having a carbon number of 1 to 20, the alkyl group having a carbon number of 1 to 20 being unsubstituted or substituted with at least one group represented by the formula (I) below, and the at least one group is selected from OH, SH, CN, an alkenyloxy group having a carbon number of 3 to 6, OCH2CH2CN、OCH2CH2(CO)O(R1)、O(CO)-(R6)、O(CO)-(R1) O (CO) -phenyl or (CO) OE17(ii) a Or
E18Represents an alkyl group having 2 to 20 carbon atoms, wherein the alkyl group having 2 to 20 carbon atoms is interrupted by one or more of O, S, CO and NE26Or COOE17(ii) a Or
E18Is represented by (CH)2CH2O)nH、(CH2CH2O)n(CO)-(R4) Alkanoyl having 2 to 8 carbon atoms or alkenoyl having 3 to 6 carbon atoms; or
E18Represents a benzoyl group which is unsubstituted or substituted with at least one group represented by the following, and the at least one group is selected from an alkyl group having a carbon number of 1 to 6, a halogen atom, OH, an alkoxy group having a carbon number of 1 to 4, or an alkylthio group having a carbon number of 1 to 4; or
E18Represents phenyl, naphthyl or heteroaryl having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, CN, NO2phenyl-R8Phenoxy, alkylthio having 1 to 12 carbon atoms, phenylthio, -N (R)9)2Diphenylamino, (CO) O (R)4)、-(CO)-R4、-(CO)N(R4)2Or
E19And E20Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, or a phenyl-R group5Alkanoyl group having 1 to 8 carbon atoms, alkanoyloxy group having 1 to 8 carbon atoms, alkenoyl group having 3 to 12 carbon atoms, SO2-R7Or a benzoyl group; or
E19And E20Represents phenyl, naphthyl or heteroaryl having a carbon number of 3 to 20, each of which is unsubstituted or substituted with at least one group represented by the following, and the at least one group is selected from a halogen atom, a haloalkyl having a carbon number of 1 to 4, an alkoxy having a carbon number of 1 to 20, an alkyl having a carbon number of 1 to 12, a benzoyl group or an alkoxy having a carbon number of 1 to 12; or
E19And E20Is taken together with the nitrogen atom to which it is bound to form non-interrupted or interrupted O, S or NE17And the five-or six-membered saturated or unsaturated ring is unsubstituted or substituted by at least one group shown belowwherein the at least one group is selected from the group consisting of an alkyl group having a carbon number of 1 to 20, an alkoxy group having a carbon number of 1 to 20, ═ O, OE17、SE18、NE21E22、(CO)E23、NO2Halogen atom, C1-4 haloalkyl group, CN, phenyl group,Or with one or more O, S, CO or NE's without or with intermingling17And a cycloalkyl group having a carbon number of 3 to 20; or
The E19And E is20Is taken together with the attached nitrogen atom to form a heteroaromatic ring system which is unsubstituted or substituted by at least one group selected from the group consisting of an alkyl group having a carbon number of 1 to 20, a haloalkyl group having a carbon number of 1 to 4, an alkoxy group having a carbon number of 1 to 20, ═ O, OE17、SE18、NE21E22、(CO)E23、Halogen atom, NO2CN, phenyl, or with one or more O, S, CO or NE groups not interrupted or interrupted17And a cycloalkyl group having a carbon number of 3 to 20;
E21and E22Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or a phenyl group;
E21And E22Together with the nitrogen atom to which they are bonded form non-interrupted or interrupted O, S or NE26Wherein the five-or six-membered saturated or unsaturated ring is unfused or fused with a benzene ring;
E23Represents hydrogen atom, OH, alkyl with 1-20 carbon atoms, halogenated alkyl with 1-4 carbon atoms, and at least one O, CO or NE26And alkyl having 2 to 20 carbon atoms, not interrupted or interrupted O, S, CO or NE26And a cycloalkyl group having a carbon number of 3 to 20; or
E23represents phenyl, naphthyl, phenyl-R1、OE17、SE18Or NE21E22；
E24Represents (CO) OE17、CONE19E20、(CO)E17Or with respect to E19And E20One of the definitions;
E25Represents COOE17、CONE19E20、(CO)E17(ii) a Or the E25With respect to E17One of the definitions;
E26Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by at least one O or CO; or E26Represents phenyl-R1Cycloalkyl which is not interrupted or interrupted by at least one O or CO and has a carbon number of from 3 to 8; or E26Represents (CO) E19(ii) a Or E26Represents phenyl, E26Is unsubstituted or substituted with at least one group represented by the following formula, and the at least one group is selected from an alkyl group having a carbon number of 1 to 20, a halogen atom, a haloalkyl group having a carbon number of 1 to 4, and OE17、SE18、NE19E20Or
Provided that the photoinitiator (E-1) having the structure represented by the formula (III) has at least one
6. The photosensitive resin composition according to claim 5, wherein said photoinitiator (E-1) has E of formula (III)1、E2、E3、E4、E5、E6、E7And E8Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,COE16Or NO2(ii) a Or
E1And E2、E2And E3、E3And E4、E5And E6、E6and E7Or E7And E8Each independently representWherein at least one E1And E2、E2And E3、E3And E4、E5And E6、E6And E7Or E7and E8Is composed ofZ1Represents CO or a single bond;
E13Represents an alkyl group having a carbon number of 1 to 20, the alkyl group having a carbon number of 1 to 20 being unsubstituted or substituted with at least one group represented by the following, and the at least one group is selected from a halogen atom, OE17、SE18、COOE17、CONE19E20Or PO (OC)kH2k+1)2(ii) a Or
E13Represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by one or more O, S, NE26Or CO; or
E13Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least oneOr COE16Substitution;
E14Represents an alkyl group having 1 to 20 carbon atoms, a phenyl group or an alkoxy group having 1 to 8 carbon atoms;
E15Represents phenyl, naphthyl, heteroaryl with 3 to 20 carbon atoms, each of which is unsubstituted or substituted by at least one group shown below, and the at least one group is selected from phenyl, halogen atom, haloalkyl with 1 to 4 carbon atoms, OE17、SE18An alkyl group having at least one O or S and a carbon number of 2 to 20, or each of which is substituted with one or more alkyl groups having a carbon number of 1 to 20, the alkyl group having a carbon number of 1 to 20 being unsubstituted or substituted with at least one group represented by the following, and the at least one group is selected from a halogen atom, COOE17、CONE19E20Phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryloxycarbonyl having 4 to 20 carbon atoms, OE17、SE18、NE19E20Or PO (OC)kH2k+1)2(ii) a Or
E15Represents an alkyl group having a carbon number of 1 to 20, the alkyl group having a carbon number of 1 to 20 being unsubstituted or substituted with at least one group represented by OE17、SE18Cycloalkyl group having 3 to 8 carbon atoms, heteroaryl group having 3 to 20 carbon atoms, NE19E20、COOE17、CONE19E20Or PO (OC)kH2k+1)2；
E'14Representative has a meaning for E14One of the definitions;
E'15Representative has a meaning for E15One of the definitions;
E16Represents phenyl, E16Is unsubstituted or substituted by at least one group selected from OE17、SE18、NE19E20At least one of O, S or NE26And an alkyl group having a carbon number of 2 to 20; or
E16Represents a phenyl group, and the phenyl group is substituted with at least one alkyl group having a carbon number of 1 to 20, wherein the alkyl group having a carbon number of 1 to 20 is unsubstituted or substituted with at least one group selected from a halogen atom, COOE17、CONE19E20Phenyl, cycloalkyl having 3 to 8 carbon atoms, heteroaryl having 3 to 20 carbon atoms, aryloxycarbonyl having 6 to 20 carbon atoms, heteroaryloxycarbonyl having 4 to 20 carbon atoms, OE17、SE18Or NE19E20(ii) a Or
E16Represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group represented by the following formula (I), wherein the at least one group is selected from a halogen atom, a phenyl group, OH, SH, CN, an alkenyloxy group having 3 to 6 carbon atoms, OCH2CH2(CO)O(R1)、O(CO)-(R1) Or (CO) O (R)1)；
E17Represents an alkyl group having a carbon number of 1 to 20, the alkyl group having a carbon number of 1 to 20 being unsubstituted or substituted with at least one group represented by the following, and the at least one group is selected from a halogen atom, -OCH2CH2(CO)O(R1)、O(R1)、(CO)O(R1) Cycloalkyl having a carbon number of 3 to 20, wherein the cycloalkyl having a carbon number of 3 to 20 is not interrupted or interrupted by at least one O; or
E17Represents an alkyl group having a carbon number of 2 to 20, the alkyl group having a carbon number of 2 to 20 being interrupted by at least one O;
E18Represents Via (CO) OE17A substituted methyl group;
E19And E20Each independently represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkanoyl group having 1 to 8 carbon atoms or an alkanoyloxy group having 1 to 8 carbon atoms; or
E19And E20Are taken together with the bonded nitrogen atom to form a heteroaromatic ring system which is unsubstituted or substitutedThe substitution is carried out by the following steps,
Provided that the photoinitiator (E-1) having the structure represented by the formula (III) has at least one
7. The photosensitive resin composition according to claim 5, wherein said photoinitiator (E-1) has E of formula (III)1、E2、E3、E4、E5、E6、E7And E8Each independently represents a hydrogen atom; or
E1And E2、E3And E4Or E5And E6each independently representAnd at least one E1And E2、E3And E4Or E5And E6Is composed ofor
E2RepresentsCOE16、NO2OrOr
E7RepresentsOr COE16；
E9、E11And E12Represents a hydrogen atom;
E10Represents a hydrogen atom, OE17Or COE16；
Z1Represents CO or a single bond;
E13Represents an alkyl group having a carbon number of 1 to 20, the alkyl group having a carbon number of 1 to 20 being unsubstituted or substituted with at least one group represented by the following, and the at least one group is selected from a halogen atom, E17、OE17、SE18Or PO (OC)kH2k+1)2(ii) a Or
E13Represents an alkyl group having 2 to 20 carbon atoms, the alkyl group having 2 to 20 carbon atoms being interrupted by at least one O; or
E13Represents phenyl;
k represents an integer of 2;
E14Represents an alkyl group having a carbon number of 1 to 20 or a thienyl group;
E15Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least one OE17Or alkyl having 1 to 20 carbon atoms; or
E15Represents a thienyl group, a hydrogen atom or an alkyl group having a carbon number of 1 to 20, wherein the alkyl group having a carbon number of 1 to 20 is unsubstituted or substituted with at least one group shown below and the at least one group is selected from OE17、SE18Cycloalkyl group having 3 to 8 carbon atoms, NE19E20Or COOE17(ii) a Or
E15Represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is interrupted with SO2；
E16Represents phenyl or naphthyl, each of which is unsubstituted or substituted by at least one group selected from OE17、SE18、NE19E20Or an alkyl group having a carbon number of 1 to 20; or
E16represents thienyl;
E17Represents a hydrogen atom, an alkanoyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 20 carbon atoms, said alkyl group having 1 to 20 carbon atoms being unsubstituted or substituted with at least one group selected from the group consisting of a halogen atom, O (CO) - (R)1)、O(CO)-(R6) Or cycloalkyl interrupted by at least one O and having a carbon number of from 3 to 20; or
E17Represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is interrupted by at least one O;
E18Represents cycloalkyl having a carbon number of 3 to 20, alkyl having a carbon number of 1 to 20, and the alkyl having a carbon number of 1 to 20 is unsubstituted or substituted with at least one OH, O (CO) - (R)6) Or (CO) OE17Substitution; or
E18Represents a phenyl group, said phenyl group being unsubstituted or substituted by at least one halogen atom;
E19And E is20Each independently represents an alkanoyl group having 1 to 8 carbon atoms or an alkanoyloxy group having 1 to 8 carbon atoms; or
E19And E20Are taken together with the bonded nitrogen atom to form a five-or six-membered saturated ring interrupted by O,
Provided that the photoinitiator (E-1) having the structure represented by the formula (III) has at least one
8. The photosensitive resin composition according to claim 1, wherein the pigment (a) is used in an amount of 30 to 300 parts by weight, the dye (B) is used in an amount of 5 to 50 parts by weight, the ethylenically unsaturated group-containing compound (D) is used in an amount of 20 to 200 parts by weight, the photoinitiator (E) is used in an amount of 10 to 100 parts by weight, the unsaturated group-containing benzophenone compound (F) is used in an amount of 0.1 to 30 parts by weight, and the solvent (G) is used in an amount of 500 to 5000 parts by weight, based on 100 parts by weight of the alkali-soluble resin (C).
9. The photosensitive resin composition according to claim 2, wherein the dye (B-1) is used in an amount of 3 to 50 parts by weight based on 100 parts by weight of the alkali-soluble resin (C).
10. The photosensitive resin composition according to claim 3, wherein the first alkali-soluble resin (C-1) is used in an amount of 10 to 100 parts by weight based on 100 parts by weight of the alkali-soluble resin (C).
11. The photosensitive resin composition according to claim 5, wherein the photoinitiator (E-1) is used in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the alkali-soluble resin (C).
12. A method for manufacturing a color filter, comprising forming a pixel layer on a substrate by using the photosensitive resin composition according to any one of claims 1 to 11.
13. A color filter obtained by the method according to claim 12.
14. A liquid crystal display device comprising the color filter according to claim 13.
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