CN105867068A

CN105867068A - Blue photosensitive resin composition for color filter and application thereof

Info

Publication number: CN105867068A
Application number: CN201610069696.2A
Authority: CN
Inventors: 何维凯; 许荣宾
Original assignee: Chi Mei Corp
Current assignee: Chi Mei Corp
Priority date: 2015-02-06
Filing date: 2016-02-01
Publication date: 2016-08-17

Abstract

The invention relates to a blue photosensitive resin composition for a color filter and application thereof, wherein the composition comprises an organic pigment (A); a dye (B); an alkali-soluble resin (C); an ethylenically unsaturated group compound (D); a photoinitiator (E); and an organic solvent (F); it has the advantages of good sputtering adaptability of indium tin oxide and good pigment dispersibility. The invention also provides a manufacturing method of the color filter, the color filter and a liquid crystal display device.

Description

Blue photosensitive resin composition for color filter and application thereof

Technical Field

The invention relates to a blue photosensitive resin composition for a color filter of a liquid crystal display and the color filter formed by the blue photosensitive resin composition. In particular to a blue photosensitive resin composition for a color filter, which has good sputtering suitability and pigment dispersibility for indium tin oxide (hereinafter referred to as ITO).

Background

In recent years, flat panel displays including liquid crystal displays and organic electroluminescence displays have been widely used, in which color filters are applied to the displays, and in order to comply with the current trend of energy saving, it is necessary to improve the brightness and contrast of the liquid crystal displays. Pigments currently used in color filters in photosensitive resin compositions are used for improving brightness and high contrast, and for example, qianzhiqing (color material association, 12 months 1967, page 608) discloses a method of dispersing pigment particle diameters having a color generation wavelength of less than 1/2; however, blue pigments have a shorter wavelength than other red and green pigments, and in this case, additional fine dispersion is required, resulting in problems of increased cost and poor stability after dispersion.

On the other hand, dyes as colorants are also under development, for example, Japanese patent laid-open publication No. 2008-304766 discloses a triarylmethane derivative dye, which has a disadvantage of insufficient brightness and heat resistance, and in order to improve the disadvantage, Japanese patent laid-open publications Nos. 2011-132492 and 2011-133844 disclose molecular modification of a specific structure with respect to an anion of a triarylmethane salt; in addition, in order to improve the heat resistance of the dye, Japanese patent laid-open Nos. 2009-122650 and 2010-134278 disclose a photosensitive resin composition having an antioxidant.

Although the brightness and contrast of the photosensitive resin composition have been improved in the prior art, the ITO sputtering suitability and pigment dispersibility of the photosensitive resin compositions of the prior art have not been accepted yet. In view of the above, how to simultaneously improve ITO sputtering suitability and pigment dispersibility to meet the requirements of the present industry is an object of the present invention.

Disclosure of Invention

The invention provides a blue photosensitive resin composition for a color filter, which has good ITO sputtering adaptability and pigment dispersibility by using components of special alkali-soluble resin and special dye.

Accordingly, the present invention provides a blue photosensitive resin composition for a color filter, comprising:

an organic pigment (A);

a dye (B);

an alkali-soluble resin (C);

an ethylenically unsaturated group compound (D);

a photoinitiator (E); and

an organic solvent (F);

wherein:

the dye (B) comprises a red dye (B-1) having a structure represented by formula (I):

in the formula,

B¹to B⁴Each independently represents hydrogen, -B⁶、C₆To C₁₀With an aromatic hydrocarbon radical of, or via a halogen atom, -B⁶、-OH、-OB⁶、-SO₃ ^-、-SO₃H、-SO₃M、-COOH、-COOB⁶、-SO₃B⁶、-SO₂NHB⁸or-SO₂NB⁸B⁹Substituted C₆To C₁₀An aromatic hydrocarbon group of (1);

B⁵represents-SO₃ ^-、-SO₃H、-SO³M、-COOH、-COOB⁶、-SO₃B⁶、-SO₂NHB⁸or-SO₂NB⁸B⁹；

s represents an integer of 0 to 5; when s represents 2 to 5, a plurality of B⁵Are the same or different;

t represents a halogen atom;

a represents 0 or 1;

B⁶is represented by C₁To C₁₀Alkyl or C substituted by halogen atoms₁To C₁₀Alkyl of (2), wherein C₁To C₁₀Alkyl or via halogenAtom-substituted C₁To C₁₀Of alkyl groups of (A) to (B) (-CH)₂Unsubstituted or substituted by-O-, carbonyl or-NB⁷-；

B⁷Is represented by C₁To C₁₀Alkyl or C substituted by halogen atoms₁To C₁₀Alkyl groups of (a);

B⁸and B⁹Each independently represents C₁To C₁₀Straight chain alkyl group of (1), C₁To C₁₀Branched alkyl of C₃To C₃₀Cycloalkyl of (a), or-Q; wherein, C₁To C₁₀Straight chain alkyl group of (1), C₁To C₁₀Branched alkyl or C₃To C₃₀The hydrogen atom in the cycloalkyl group of (a) is unsubstituted or substituted by a substituent selected from the group consisting of a hydroxyl group, a halogen atom, -Q, -CH ═ CH₂and-CH ═ CH-B⁶The group consisting of; c₁To C₁₀Straight chain alkyl group of (1), C₁To C₁₀Branched alkyl or C₃To C₃₀Of cycloalkyl group of (2) — CH₂Unsubstituted or substituted by-O-, carbonyl or-NB⁷-; or

B⁸And B⁹Form C by bonding₁To C₁₀In which C is₁To C₁₀The hydrogen atom in the heterocyclic group of (a) is unsubstituted or substituted by B⁶-OH, or-Q;

q represents C₆To C₁₀Aromatic hydrocarbon group of (2), C₅To C₁₀A heteroaromatic radical of (a), via a halogen atom, -B⁶、-OH、-OB⁶、-NO₂、-CH＝CH₂or-CH ═ CH-B⁶Substituted C₆To C₁₀With an aromatic hydrocarbon radical of, or via a halogen atom, -B⁶、-OH、-OB⁶、-NO₂、-CH＝CH₂and-CH ═ CH-B⁶Substituted C₅To C₁₀The heteroaromatic group of (a); and

m represents potassium or sodium; and

the alkali-soluble resin (C) comprises a first alkali-soluble resin (C-1), the first alkali-soluble resin (C-1) having a structure represented by the formula (II):

wherein,

l represents a hydrogen atom or C₁To C₃₀An organic group of (2).

The invention also provides a method for manufacturing the color filter, which uses the blue photosensitive resin composition for the color filter to form a pixel layer.

The invention also provides a color filter which is manufactured by the method.

The invention further provides a liquid crystal display device comprising the color filter.

Drawings

FIG. 1 is a schematic view showing a comparative measurement state (I) of a photosensitive resin layer.

FIG. 2 is a schematic view showing a comparative measurement state (II) of the photosensitive resin layer.

The numbers in the figures represent the following:

1: photosensitive resin layer, 2: polarizing plate, 3: polarizing plate, 4: light source, 5: a luminance meter.

Detailed Description

The present invention provides a blue photosensitive resin composition for a color filter, which comprises the following components:

an organic pigment (A);

a dye (B);

an alkali-soluble resin (C);

an ethylenically unsaturated group compound (D);

a photoinitiator (E); and

an organic solvent (F);

wherein:

in the formula,

B⁵represents-SO₃ ^-、-SO₃H、-SO³M、-COOH、-COOB⁶、-SO₃B⁶、-SO₂NHB⁸or-SO₂NB⁸B⁹(ii) a s represents an integer of 0 to 5; when s represents 2 to 5, a plurality of B⁵Are the same or different;

t represents a halogen atom;

a represents 0 or 1;

B⁶is represented by C₁To C₁₀Alkyl or C substituted by halogen atoms₁To C₁₀Alkyl of (2), wherein C₁To C₁₀Alkyl or C substituted by halogen atoms₁To C₁₀Of alkyl groups of (A) to (B) (-CH)₂Unsubstituted or substituted by-O-, carbonyl or-NB⁷-；

m represents potassium or sodium; and

wherein,

l represents a hydrogen atom or C₁To C₃₀An organic group of (2).

According to a particular embodiment of the invention, the organic pigments (A) of the invention are blue pigments.

In one embodiment of the present invention, the organic pigment (a) is used in an amount of 50 to 450 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C); preferably 60 to 400 parts by weight; more preferably 70 to 350 parts by weight.

Preferably, the organic pigment (A) comprises a blue organic pigment (A-1) having a copper phthalocyanine structure as a main component. The blue pigment (a-1) mainly having a copper phthalocyanine structure may be used alone or in combination, and the blue pigment (a-1) mainly having a copper phthalocyanine structure includes, but is not limited to, c.i. pigment blue 15:1(c.i. pb15:1), c.i. pigment blue 15:2(c.i. pb15:2), c.i. pigment blue 15:3(c.i. pb15:3), c.i. pigment blue 15:4(c.i. pb15:4), c.i. pigment blue 15:5(c.i. pb15:5), or c.i. pigment blue 15:6(c.i. pb15: 6).

In one embodiment of the present invention, the blue organic pigment (A-1) mainly having a copper phthalocyanine structure is used in an amount of 30 to 300 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resins (C); preferably 40 to 270 parts by weight; more preferably 50 to 250 parts by weight.

Preferably, the organic pigment (A) further comprises a violet organic pigment (A-2). The violet pigment (a-2) may be used alone or in combination, and the violet pigment (a-2) includes, but is not limited to, c.i. pigment violet 14(c.i. pv14), c.i. pigment violet 19(c.i. pv19), c.i. pigment violet 23(c.i. pv23), c.i. pigment violet 29(c.i. pv29), c.i. pigment violet 32(c.i. pv32), c.i. pigment violet 33(c.i. pv33), c.i. pigment violet 36(c.i. pv36), c.i. pigment violet 37(c.i. pv37), c.i. pigment violet 38(c.i. pv38), c.i. pigment violet 40(c.i. pv40), or c.i. pigment violet 50(c.i. pv50).

In one embodiment of the present invention, the violet organic pigment (A-2) is used in an amount of 0 to 150 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C) used; preferably 5 to 120 parts by weight; more preferably 10 to 100 parts by weight.

The organic pigment (A) may contain a blue pigment (A-3) other than (A-1).

The blue pigment (a-3) other than (a-1) includes, but is not limited to, c.i. pigment blue 1, c.i. pigment blue 21, c.i. pigment blue 22, c.i. pigment blue 60, c.i. pigment blue 61, c.i. pigment blue 64, or a combination thereof. The blue pigments (A-3) other than (A-1) may be used alone or in combination.

In another embodiment of the present invention, the organic pigment (A) may contain a green pigment mainly having a halogenated phthalocyanine structure for adjusting the chroma.

Preferably, the green pigment based on a halogenated phthalocyanine structure includes, but is not limited to, c.i. pigment green 07, c.i. pigment green 36, c.i. pigment green 37, c.i. pigment green 42, or c.i. pigment green 58. More preferably, the green pigment component having a halogenated phthalocyanine structure as a main component is c.i. pigment green 07, c.i. pigment green 36, c.i. pigment green 37, c.i. pigment green 42, c.i. pigment green 58, or a combination thereof. The green pigments based on halogenated phthalocyanine structures can be used alone or in mixtures.

The dye (B) according to the present invention is useful for improving the luminance of the blue photosensitive resin composition for a color filter and for assisting in adjusting the chromaticity of the blue photosensitive resin composition for a color filter.

Preferably, the dye (B) comprises a red dye (B-1) having a structure represented by formula (I):

in the formula (I), the compound represented by the formula (I),

t represents a halogen atom;

a represents 0 or 1;

q represents C₆To C₁₀Aromatic hydrocarbon group of (2), C₅To C₁₀A heteroaromatic radical of (a), via a halogen atom, -B⁶、-OH、-OB⁶、-NO₂、-CH＝CH₂or-CH ═ CH-B⁶Substituted C₆To C₁₀With an aromatic hydrocarbon radical of, or via a halogen atom, -B⁶、-OH、-OB⁶、-NO₂、-CH＝CH₂and-CH ═ CH-B⁶Substituted C₅To C₁₀The heteroaromatic group of (a); and M represents potassium or sodium.

Preferably, B⁶Including 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 [ tricycles (5.3.0.0)^3,10)decanyl]Methoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, or epoxypropyl.

Preferably, C₆To C₁₀The aromatic hydrocarbon group of (1) includes, but is not limited to, phenyl or naphthyl and the like.

Preferably, -SO₃B⁶Including but not limited to methylsulfonyl(methanesulfonyl), ethylsulfonyl (ethaneesulfonyl), hexylsulfonyl (hexanesulfonyl), or decylsulfonyl (decanoylsulfonyl).

Preferably, -COOB⁶Including 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 [5.3.0.0^3,10]Decylcarbonyl, methoxypropoxycarbonyl, hexyloxypropoxycarbonyl, 2-ethylhexyloxypropoxycarbonyl, or methoxyhexyloxycarbonyl.

Preferably, -SO₂NHB⁸Including but not limited to aminosulfonyl, methylaminosulfonyl, ethylaminosulfonyl, propylaminosulfonyl, isopropylaminosulfonyl, butylaminosulfonyl, isobutylaminosulfonyl, pentylaminosulfonyl, isopentylaminosulfonyl, neopentylamine sulfonyl, cyclopentylamine sulfonyl, hexylamine sulfonyl, cyclohexylamine sulfonyl, heptylaminosulfonyl, cycloheptylamine sulfonyl, octylamine sulfonyl, cyclooctylamine sulfonyl, 2-ethylhexylamine sulfonyl, nonylaminosulfonyl, decylamine sulfonyl, tricyclo [5.3.0.0 ]^3,10]Decylamine sulfonyl, methoxypropylamine sulfonyl, hexyloxypropylamine sulfonyl, 2-ethylhexylamine sulfonyl, methoxyhexylamine sulfonyl, epoxypropylamine sulfonyl, 1, 5-dimethylhexylamine sulfonyl, propoxypropylamine sulfonyl, isopropoxypropylamine sulfonyl, 3-phenyl-1-methylpropylamine sulfonyl, dodecylamine sulfonyl, ethylhexylamine sulfonyl,

(R^ais represented by C₁To C₃Alkyl of (C)₁To C₃Alkoxy group of (2), C substituted by halogen atom₁To C₃Alkyl or C substituted by halogen atoms₁To C₃Alkoxy of (a),

(R^bIs represented by C₁To C₃Alkyl of (C)₁To C₃Alkoxy group of (2), C substituted by halogen atom₁To C₃Alkyl or C substituted by halogen atoms₁To C₃Alkoxy of (a),

Preferably, -SO₂NB⁸B⁹Including but not limited to

Preferably, the dye (B) includes a red dye having a structure represented by the formula (I-1):

in the formula (I-1),

B¹¹to B¹⁴Each independently represents hydrogen, -B⁶、C₆To C₁₀With an aromatic hydrocarbon radical of, or via a halogen atom, -B⁶、-OH、-OB⁶、-SO₃ ^-、-SO₃H、-SO₃Na、-COOH、-COOB⁶、-SO₃B⁶、-SO₂NHB⁸or-SO₂NB⁸B⁹Substituted C₆To C₁₀An aromatic hydrocarbon group of (1);

B¹⁵represents hydrogen,-SO₃ ^-、-SO₃H、-SO₂NHB⁸or-SO₂NB⁸B⁹；

B¹⁶represents-SO₃ ^-、-SO₃H、-SO₂NHB⁸or-SO₂NB⁸B⁹；

T¹Represents a halogen atom;

a¹represents 0 or 1.

Preferably, the dye (B) includes a red dye having a structure represented by the formula (I-2):

in the formula (I-2),

B²¹to B²⁴Each independently represents hydrogen, -B²⁶、C₆To C₁₀With an aromatic hydrocarbon radical of, or via a halogen atom, -B²⁶、-OH、-OB²⁶、-SO₃ ^-、-SO₃H、-SO₃Na、-COOH、-COOB²⁶、-SO₃B²⁶or-SO₂NHB²⁸Substituted C₆To C₁₀An aromatic hydrocarbon group of (1);

B²⁵represents-SO₃ ^-、-SO₃Na、-COOH、-COOB²⁶、-SO₃H. or-SO₂NHB²⁸；

s¹Represents an integer of 0 to 5; when s is¹When representing 2 to 5, a plurality of B²⁵Are the same or different;

T²represents a halogen atom;

a²represents 0 or 1;

B²⁶is represented by C₁To C₁₀Alkyl of (2), or via halogenAn elemental atom or-OB²⁷Substituted C₁To C₁₀Alkyl groups of (a);

B²⁷is represented by C₁To C₁₀Alkyl groups of (a); and

B²⁸represents hydrogen, -B²⁶、-COOB²⁶、C₆To C₁₀Or with an aromatic hydrocarbon radical of formula (I), or via a²⁶or-OB²⁶Substituted C₆To C₁₀The aromatic hydrocarbon group of (1).

Preferably, dye (B) comprises a red dye having the structure of formula (I-3):

in the formula (I-3),

B³¹and B³²Each independently represents phenyl, or-B via a halogen atom²⁶、-OB²⁶、-COOB²⁶、-SO₃B²⁶or-SO₂NHB²⁸Substituted phenyl;

B³³represents-SO₃ ^-or-SO₂NHB²⁸；

B³⁴Represents hydrogen, -SO₃ ^-or-SO₂NHB²⁸；

T³Represents a halogen atom;

a³represents 0 or 1;

B²⁶is represented by C₁To C₁₀Or via a halogen atom or-OB²⁷Substituted C₁To C₁₀Alkyl groups of (a);

B²⁷is represented by C₁To C₁₀Alkyl groups of (a); and

Preferably, dye (B) comprises a red dye having the structure of formula (I-4):

in the formula (I-4),

B⁴¹and B⁴²Each independently represents phenyl, or via-B²⁶or-SO₂NHB²⁸Substituted phenyl;

B⁴³represents-SO₃ ^-or-SO₂NHB²⁸；

T⁴Represents a halogen atom;

a⁴represents 0 or 1;

B²⁷is represented by C₁To C₁₀Alkyl groups of (a); and

In one embodiment of the present invention, the dye (B) includes, but is not limited to, the following formulas (1) to (31):

R^cand R^dEach independently represents hydrogen, -SO₃ ^--COOH or-SO₂NHB⁸¹；

B⁸¹Represents 2-ethylhexyl;

t represents a halogen atom;

a represents 0 or 1.

R^eRepresents hydrogen, -SO₃ ^--COOH or-SO₂NHB⁸¹；

B⁸¹Represents 2-ethylhexyl;

t represents a halogen atom;

a represents 0 or 1.

R^eRepresents hydrogen, -SO₃ ^--COOH or-SO₂NHB⁸¹；

B⁸¹Represents 2-ethylhexyl;

t represents a halogen atom;

a represents 0 or 1.

R^f、R^gAnd R^hEach independently represents-SO₃ ^-、-SO₃Na or-SO₂NHB⁸¹；

B⁸¹Represents 2-ethylhexyl。

B⁸¹Represents 2-ethylhexyl.

Rⁱ、R^jAnd R^kEach independently represents hydrogen, -SO₃ ^-、-SO₃H or-SO₂NHB⁸¹；

B⁸¹Represents 2-ethylhexyl.

R^l、R^mAnd RⁿEach independently represents-SO₃ ^-、-SO₃Na or-SO₂NHB⁸¹；

B⁸¹Represents 2-ethylhexyl.

R^p、R^qAnd R^rEach independently represents hydrogen, -SO₃ ^-、-SO₃H or-SO₂NHB⁸¹；

B⁸¹Represents 2-ethylhexyl.

A preferred embodiment of the dyes (B) according to the invention is of the formula (1) (R)^cAnd R^dis-SO₃ ^-A is 0) [ C.I. acid red dye 52]An acid red dye 289 of the formula (22) [ C.I.. acid]Formula (28), formula (31), or a combination thereof.

In the specific embodiment of the present invention, the dye (B-1) is used in an amount of 10 to 90 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C); preferably 13 to 80 parts by weight; more preferably 15 to 70 parts by weight. When the dye (B-1) is not used, the pigment dispersibility and contrast of the pixel layer obtained from the blue photosensitive resin composition are poor.

In a preferred embodiment of the present invention, the dye (B) may further comprise another dye (B-2).

Preferably, the other dye (B-2) comprises azo-based dye or anthraquinone-based dye, wherein the azo-based dye includes, but is not limited to, acid red 37, acid red 180, direct red 28, direct red 83, reactive red 17, reactive red 120, disperse red 58, basic red 18, mordant red 7(mordant red 7), and the like; anthraquinone dyes include, but are not limited to, disperse Red 60 and the like. 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 dye (B) is used in an amount of 10 to 90 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C); preferably 13 to 80 parts by weight; more preferably 15 to 70 parts by weight.

According to a specific embodiment of the present invention, the alkali-soluble resin (C) of the present invention comprises a first alkali-soluble resin (C-1), the first alkali-soluble resin (C-1) having a structure represented by formula (II):

wherein L represents a hydrogen atom or C₁To C₃₀An organic group of (2).

In the above formula (II), specific examples of L include, but are not limited to, a hydrogen atom; chain saturated hydrocarbon groups include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, t-pentyl, n-hexyl, s-hexyl, n-heptyl, n-octyl, s-octyl, t-octyl, 2-ethylhexyl, octanoic acid, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, seryl, or triacontyl (melissyl); substituting the chain saturated hydrocarbon group with an alkoxy group that substitutes a portion of the hydrogen atoms of the chain saturated hydrocarbon group with an alkoxy group, wherein the alkoxy group includes, but is not limited to, methoxyethyl, methoxyethoxyethyl, 3-methoxy-butyl, ethoxyethyl, ethoxyethoxyethyl, phenoxyethyl, or phenoxyethoxyethyl; a chain saturated hydrocarbon group is substituted by a hydrocarbon group in which a part of hydrogen atoms of the chain saturated hydrocarbon group is substituted by the hydrocarbon group, wherein the hydrocarbon group includes but is not limited to hydroxyethyl, hydroxypropyl or hydroxybutyl; a halogen substituted chain saturated hydrocarbon group in which a part of hydrogen atoms of the chain saturated hydrocarbon group is substituted with a halogen, the halogen substituted chain saturated hydrocarbon group including, but not limited to, fluoroethyl, difluoroethyl, chloroethyl, dichloroethyl, bromoethyl or dibromoethyl; the chain unsaturated hydrocarbon group includes, but is not limited to, a vinyl group, an allyl group, a methallyl group, a butenyl group or a propynyl group, and a chain unsaturated hydrocarbon group in which a part of hydrogen atoms thereof is substituted with an alkoxy group, a hydrocarbon group or a halogen; alicyclic hydrocarbon groups include, but are not limited to, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, tricyclodecyl, isobornyl, adamantyl, or dicyclopentadienyl, and alicyclic hydrocarbon groups having a part of hydrogen atoms thereof substituted with alkoxy groups, hydrocarbon groups, or halogens; and aromatic hydrocarbons including, but not limited to, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, 4-tert-butylphenyl, benzyl, diphenylmethyl, diphenylethyl, triphenylmethyl, cinnamyl, naphthyl or anthryl, and aromatic hydrocarbons in which a part of hydrogen atoms thereof is substituted with alkoxy, hydrocarbon group or halogen. Wherein the organic group may further bond a substituent. In formula (II), L may be the same or two or more different.

The content of the unit of the first alkali-soluble resin (C-1) having a structure represented by the formula (II) of the present invention can be suitably adjusted according to the purpose, use or molecular weight of the first alkali-soluble resin of the present invention, and generally, the content of the repeating structural unit is 5 to 80 mol%, preferably 10 to 70 mol%, more preferably 15 to 60 mol%.

Although not wishing to be bound by theory, it is believed that the first alkali-soluble resin (C-1) has a tetrahydrofuran ring in the main chain and methylene groups on both sides, and thus is presumed to have excellent dispersion stability of the colored material, because the tetrahydrofuran ring reacts with a Lewis base (donor of lone electron pair) and the colored material and the dispersant do not interfere with each other by the action of a strong base; further, since the tetrahydrofuran ring has a lewis base group, it is easy to interact with a functional group on the surface of another substrate, and good adhesion is exhibited. Further, since the tetrahydrofuran ring has oxygen-capturing properties, inhibition of radical curing by oxygen in radical curing using heat or active energy rays can be reduced, and there is an advantage that surface curing properties and film curing properties can be improved.

Furthermore, since tetrahydrofuran has an extremely broad capability of dissolving substances and is therefore commonly used as a solvent for industrial analysis or research, the alkali-soluble resin of the present invention has advantages of excellent compatibility and dry resolubility.

The first alkali-soluble resin (C-1) of the present invention is obtained by polymerizing a monomer (C-1) containing a monomer represented by the formula (III), and when polymerized, the structure represented by the formula (II) is formed at a high ratio, and therefore, it is less likely to cause an abnormal increase in molecular weight or gelation.

Wherein L represents a hydrogen atom or C₁To C₃₀An organic group of (2).

In the above formula (III), L is defined as the same as L in the formula (II), and is not described herein.

Specific examples of the monomer (c-1) represented by the above formula (III) include: alpha-allyloxymethylacrylic acid, alpha-allyloxymethylmethacrylate ethyl ester, alpha-allyloxymethylacrylate-n-propyl ester, alpha-allyloxymethylacrylate-i-propyl ester, alpha-allyloxymethylacrylate-n-butyl ester, alpha-allyloxymethylacrylate-s-butyl ester, alpha-allyloxymethylacrylate-t-butyl ester, alpha-allyloxymethylacrylate-n-pentyl ester, alpha-allyloxymethylacrylate-s-pentyl ester, alpha-allyloxymethylacrylate-t-pentyl ester, alpha-allyloxymethylacrylate-n-hexyl ester, alpha-allyloxymethylacrylate-s-hexyl ester, alpha-allyloxymethylacrylate-n-hexyl ester, alpha-allyloxymethylacrylate-s-hexyl ester, alpha-allyl, N-heptyl alpha-allyloxymethylacrylate, n-octyl alpha-allyloxymethylacrylate, s-octyl alpha-allyloxymethylacrylate, t-octyl alpha-allyloxymethylacrylate, 2-ethylhexyl alpha-allyloxymethylacrylate, octanoic alpha-allyloxymethylacrylate, nonyl alpha-allyloxymethylacrylate, decyl alpha-allyloxymethylacrylate, undecyl alpha-allyloxymethylacrylate, dodecyl alpha-allyloxymethylacrylate, tridecyl alpha-allyloxymethylacrylate, tetradecyl alpha-allyloxymethylacrylate, pentadecyl alpha-allyloxymethylacrylate, hexadecyl alpha-allyloxymethylacrylate, octyl alpha-allyloxymethylacrylate, nonyl alpha-allyloxymethylacrylate, decyl alpha-allyloxymethylacrylate, dodecyl alpha-allyloxymethylacrylate, octyl alpha-, Heptadecyl alpha-allyloxymethylacrylate, octadecyl alpha-allyloxymethylmethacrylate, nonadecyl alpha-allyloxymethylacrylate, eicosyl alpha-allyloxymethylmethacrylate, serine alpha-allyloxymethylacrylate (alpha-allyloxymethyl acrylate) and triacontyl alpha-allyloxymethylmethacrylate, methoxyethyl alpha-allyloxymethylacrylate, methoxyethoxyethyl alpha-allyloxymethylacrylate, methoxyethoxyethoxyethyl alpha-allyloxymethylacrylate, 3-methoxybutyl alpha-allyloxymethylacrylate, ethoxyethyl alpha-allyloxymethylacrylate, ethoxyethoxyethoxyethyl alpha-allyloxymethylacrylate, phenoxyethyl alpha-allyloxymethylacrylate, nonadecyl alpha-allyloxymethylacrylate, eicosyl-allyloxymethyl, Phenoxyethoxyethyl alpha-allyloxymethylacrylate, hydroxyethyl alpha-allyloxymethylacrylate, hydroxypropyl alpha-allyloxymethylacrylate, hydroxybutyl alpha-allyloxymethylacrylate, fluoroethyl alpha-allyloxymethylacrylate, difluoroethyl alpha-allyloxymethylacrylate, chloroethyl alpha-allyloxymethylacrylate, dichloroethyl alpha-allyloxymethylacrylate, bromoethyl alpha-allyloxymethylacrylate, dibromoethyl alpha-allyloxymethylacrylate, vinyl alpha-allyloxymethylacrylate, allyl alpha-allyloxymethylmethacrylate, methallyl alpha-allyloxymethylacrylate, butenyl alpha-allyloxymethylacrylate, propargyl alpha-allyloxymethylacrylate, hydroxyethyl alpha-, Cyclopentyl α -allyloxymethylacrylate, cyclohexyl α -allyloxymethylmethacrylate, 4-methylcyclohexyl α -allyloxymethylmethacrylate, 4-t-butylcyclohexyl α -allyloxymethylmethacrylate, tricyclodecanyl α -allyloxymethylacrylate, isobornyl α -allyloxymethylacrylate, adamantyl α -allyloxymethylacrylate, dicyclopentadienyl α -allyloxymethylacrylate, phenyl α -allyloxymethylacrylate, methylphenyl α -allyloxymethylacrylate, dimethylphenyl α -allyloxymethylacrylate, trimethylphenyl α -allyloxymethylacrylate, 4-t-butylphenyl α -allyloxymethylacrylate, tert-butylphenyl-acrylate, tert-butylphenyl-allyloxymethylacrylate, Benzyl α -allyloxymethylacrylate, diphenylmethyl α -allyloxymethylacrylate, diphenylethyl α -allyloxymethylacrylate, triphenylmethyl α -allyloxymethylacrylate, cinnamyl α -allyloxymethylacrylate, naphthyl α -allyloxymethylacrylate, anthracenyl α -allyloxymethylacrylate. The monomer (c-1) represented by the above formula (III) may be used alone or in combination of two or more.

The content of the monomer (c-1) represented by the formula (III) may be suitably adjusted depending on the purpose, use or molecular weight of the alkali-soluble resin of the present invention, and in general, the content of the monomer is from 5 to 80 mol%, preferably from 10 to 70 mol%, more preferably from 15 to 60 mol%.

When the first alkali-soluble resin of the present invention has a high molecular weight, the performance (excellent pigment dispersibility) tends to be exhibited even if the content of the structural unit represented by formula (II) is small, and when the molecular weight is low, the performance tends to be easily exhibited by increasing the content. The reason for this is related to the number of structural units represented by the formula (II) contained in 1 main chain (hereinafter, expressed as the average number of functional groups), and the average number of functional groups is preferably 0.5 or more, more preferably 1.0 or more, and particularly preferably 2.0 or more. Wherein the average number of functional groups is represented as follows:

average number of functional groups A/P

A: the number of moles (mol/g) of the structural unit represented by the formula (II) contained per unit mass;

p: the number of moles (mol/g) of the first alkali-soluble resin (C-1) contained per unit mass;

if there are two or more kinds of the structural units represented by the formula (II), A can be calculated by the following equation;

A＝∑A_X(X＝l,2,3,…)；

A_Xunit mass × (C)_X/100)/F_X；

A_X: the number of moles (mol/g) of the constitutional unit represented by formula (II) of the X (X ═ l,2,3, …) contained in the unit mass;

C_X: the mass ratio (% by mass) of the constitutional unit represented by the formula (II) of the X (X ═ l,2,3, …) contained in the unit mass;

F_X: the molecular weight (g/mol) of the X (X ═ l,2,3, …) structural unit represented by formula (II);

p represents the number average molecular weight (Mn) of the first alkali-soluble resin (C-1) and is represented by the following formula:

p is unit mass/Mn; and

mn: the number average molecular weight of the first alkali-soluble resin (C-1).

Thus, the average number of functional groups is expressed as follows:

average number of functional groups Mn ×∑ { (C)_X/100)×(l/F_X)}(X＝l,2,3,…)

Further, when the cyclization ratio of the monomer represented by the formula (III) (the ratio of the monomer represented by the formula (III) to the structural unit represented by the formula (II)) is high, C is_XAnd F_XAs follows:

C_X: the mass ratio (% by mass) of the monomer represented by the formula (III) to all monomers reacted, X ═ l,2,3, …, of the reaction;

F_X: molecular weight (g/mol) of the monomer represented by formula (III) X (X ═ l,2,3, …).

When the reaction rate (conversion rate) of each monomer used in the polymerization is high (for example, the reaction rate is 90 mol% or more), C_XAs follows:

C_X: the mass ratio (% by mass) of the monomer represented by the formula (III) in the X-th (X ═ l,2,3, …) in the monomer component.

The monomer (c-1) represented by the formula (III) is used in an amount of 5 to 80 parts by weight based on 100 parts by weight of the sum of the amounts of the monomers (c-1), (c-2) and (c-3); preferably 10 to 70 parts by weight; more preferably 15 to 60 parts by weight.

In an embodiment of the present invention, the first alkali-soluble resin (C-1) is obtained by polymerizing a monomer (C-1) represented by formula (III), an ethylenically unsaturated monomer (C-2) having one or more carboxylic acid groups, and another copolymerizable ethylenically unsaturated monomer (C-3).

The ethylenically unsaturated monomer (c-2) having one or more carboxylic acid groups may include, but is not limited to, an unsaturated monocarboxylic acid monomer, an unsaturated polycarboxylic acid monomer, a polycyclic monomer having an unsaturated group and one carboxylic acid group, or a polycyclic monomer having an unsaturated group and a plurality of carboxylic acid groups.

The unsaturated monocarboxylic acid monomer may include, but is not limited to, (meth) acrylic acid, crotonic acid, alpha-chloroacrylic acid, ethacrylic acid, cinnamic acid, 2- (meth) acryloxyethoxy succinate (2-methacryloxyethoxy succinatemoenoester), 2- (meth) acryloxyethoxy hexahydrophthalate, 2- (meth) acryloxyethoxy phthalate, omega-carboxy polycaprolactone polyol monoacrylate, or the like. The omega-carboxy polycaprolactone polyol monoacrylate may be a commercial product made synthetically in east Asia, model number ARONIX M-5300.

The unsaturated polycarboxylic acid monomer may include, but is not limited to, maleic acid, fumaric acid, mesaconic acid, itaconic acid, or citraconic acid, etc.

Polycyclic monomers having an unsaturated group and one carboxylic acid group may include, but are not limited to, 5-carboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, or 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, and the like.

Polycyclic monomers having an unsaturated group and a plurality of carboxyl groups include, for example, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene.

The unsaturated carboxylic acid monomers mentioned above may be used singly or in combination of plural kinds.

Preferably, the unsaturated carboxylic acid monomer is selected from acrylic acid, methacrylic acid, 2-methacryloyl ethoxy succinate, 2-methacryloyl ethoxy hexahydrophthalate, or any combination of the above monomers.

The unsaturated carboxylic acid anhydride monomer may include, but is not limited to, an unsaturated carboxylic acid anhydride monomer or a polycyclic monomer having an unsaturated group and a carboxylic acid anhydride.

The unsaturated carboxylic acid anhydride monomer may include, but is not limited to, maleic anhydride, fumaric anhydride, methyl fumaric anhydride, itaconic anhydride, or citraconic anhydride, and the like. The polycyclic monomer 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.

The unsaturated carboxylic acid anhydride monomers may be used singly or in combination.

Preferably, the unsaturated carboxylic acid anhydride monomer is maleic anhydride.

The ethylenically unsaturated monomer (c-2) having one or more carboxylic acid groups is used in an amount of 5 to 50 parts by weight, based on 100 parts by weight of the sum of the amounts of the monomers (c-1), (c-2) and (c-3); preferably 7 to 45 parts by weight; more preferably 10 to 40 parts by weight.

Other copolymerizable ethylenically unsaturated monomer (c-3) may include, but is not limited to, alkyl (meth) acrylate, alicyclic (meth) acrylate, aryl (meth) acrylate, unsaturated dicarboxylic acid ester, hydroxyalkyl (meth) acrylate, polyether having a (meth) acrylate group, styrene monomer, or unsaturated monomer other than the above monomers.

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 alicyclic (meth) acrylate may include, but is not limited to, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate { or tricyclo [5.2.1.02,6] dec-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 unsaturated dicarboxylic acid ester may include, but is not limited to, diethyl maleate, diethyl fumarate, or diethyl itaconate, and the like.

The hydroxyalkyl (meth) acrylate may include, but is not limited to, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and the like.

The 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 styrenic monomer may include, but is not limited to, styrene, alpha-methylstyrene, meta-methylstyrene, para-methylstyrene or para-methoxystyrene, and the like.

Unsaturated monomers other than the above monomers 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-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, N- (9-acridinyl) maleimide and the like.

The other copolymerizable ethylenically unsaturated monomer (c-3) may be used singly or in admixture of two or more.

Preferably, the other copolymerizable ethylenically unsaturated monomer (c-3) 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, dicyclopentanyloxyethyl (meth) acrylate, styrene, p-methoxystyrene or any combination of the above monomers.

The other copolymerizable ethylenically unsaturated monomer (c-3) is used in an amount of 10 to 90 parts by weight, based on 100 parts by weight of the sum of the amounts of the monomers (c-1), (c-2) and (c-3); preferably 15 to 80 parts by weight; more preferably 20 to 70 parts by weight.

The above polymerization method may be appropriately selected depending on the purpose or use, for example: conventional polymerization methods such as bulk polymerization, solution polymerization, and emulsion polymerization are preferred to be solution polymerization, and the molecular weight and other structures can be easily adjusted, which is advantageous for industrial use; further, the polymerization mechanism includes a conventional polymerization method using a radical polymerization initiator, an anionic polymerization initiator, a cationic polymerization initiator, a coordination polymerization initiator, etc., wherein the higher the cyclization ratio (the ratio of the monomer represented by the formula (III) to the structural unit represented by the formula (II)) is, the more industrially advantageous when the radical polymerization initiator is used.

As the method for initiating the polymerization of the monomer component, a conventional method may be employed, for example, a method in which energy necessary for the polymerization is supplied to the monomer component by an energy source such as self-heating, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.) or electron beams, and it is preferable to use a polymerization initiator in combination, whereby the energy necessary for the initiation of the polymerization can be reduced and the reaction can be controlled easily.

The molecular weight can be controlled by conventional methods such as controlling the polymerization initiator, polymerization temperature, and chain transfer agent.

When the monomer is a solution polymerization method, the solvent used in the polymerization is not particularly limited as long as it is appropriately set according to the polymerization conditions such as the kind and amount of the monomer used, the polymerization temperature, and the polymerization concentration.

Specific examples of solvents may include, but are not limited to, monoalcohols such as: methanol, ethanol, isopropanol, n-butanol, s-butanol, etc.; alcohols, for example: ethylene glycol, propylene glycol, and the like; cyclic ethers, such as: tetrahydrofuran, dioxane, and the like; ethylene glycol monoethyl ethers, for example: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol, etc.; glycol ethers, for example: ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and the like; ethylene glycol monomethyl ether esters, for example: ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyrate, and the like; alkyl esters, for example: methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl3-ethoxypropionate, methyl acetoacetate, ethyl acetoacetate, and the like; ketones, for example: acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like; aromatic hydrocarbons, for example: benzene, toluene, xylene, ethylbenzene, etc.; aliphatic hydrocarbons, for example: n-hexane, cyclohexane, octane, etc.; amides, such as: dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. The above solvents may be used singly or in combination of two or more.

The amount of the solvent used is 40 to 1000 parts by weight based on 100 parts by weight of the sum of the amounts of the monomers (c-1), (c-2) and (c-3); preferably 100 to 400 parts by weight.

The radical polymerization initiator is not particularly limited as long as it can generate radicals by supplying thermal energy, and among them, a polymerization initiator that generates radicals by heat is industrially advantageous.

Specific examples of the radical polymerization initiator may include, but are not limited to, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethyl hexanoate, azobisisobutyronitrile, 1' -azobis (cyclohexanecarbonitrile), 2' -azobis (2, 4-dimethyl), 2' -azobis (2-methylpropionate), hydrogen peroxide, persulfate, and the like. The above-mentioned radical polymerization initiator may be used singly or in combination of plural kinds. Meanwhile, the radical polymerization initiator may be used in combination with a transition metal salt or amine.

The amount of the radical polymerization initiator to be used is not particularly limited as long as it is appropriately set according to the kind or amount of the monomer to be used, the polymerization temperature, the polymerization concentration and other polymerization conditions. However, in order to obtain a polymer having a weight average molecular weight of several thousands to several tens of thousands, the radical polymerization initiator is preferably used in an amount of 0.05 parts by weight to 20 parts by weight, based on the total amount of the monomers (c-1), (c-2) and (c-3) used as 100 parts by weight; more preferably 0.1 to 15 parts by weight.

When necessary during the polymerization, a chain transfer agent may be used in combination, wherein when a chain transfer agent is used, there is a tendency that the molecular weight distribution of the polymer in the reaction is suppressed to avoid gelation thereof. Specific examples of the chain transfer agent include, but are not limited to, mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; mercaptocarboxylic acid esters such as methyl thioglycolate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, n-octyl 3-mercaptopropionate, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and dipentaerythritol hexa (3-mercaptopropionate); alkyl mercaptans such as ethanethiol, t-butylmercaptan, n-dodecylmercaptan, and 1, 2-dimercaptoethane; mercaptoalcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; aromatic thiols such as benzenethiol, m-toluenethiol, p-toluenethiol, and 2-naphthalenethiol; mercaptoisocyanurates such as tris [ (3-mercaptopropionyloxy) -ethyl ] isocyanurate.

As the chain transfer agent, a chain transfer agent other than the compound having a sulfur group may be used, for example: disulfides such as 2-hydroxyethyl disulfide and tetraethylthiuram disulfide; dithiocarbamates such as diethyldibenzyl; monomer dimers such as α -methylstyrene dimer; halogenated alkanes such as carbon tetrabromide. The chain transfer agent is preferably a compound having a mercapto group such as a mercaptocarboxylic acid, a mercaptocarboxylic acid ester, an alkylthiol, a mercaptoalcohol, an aromatic thiol, and a mercaptoisocyanurate, in terms of the availability, the anti-crosslinking ability, and the degree of reduction in the polymerization rate. The above chain transfer agents may be used singly or in combination.

The amount of the chain transfer agent to be used is not particularly limited as long as it is appropriately set according to the kind or amount of the monomer to be used, the polymerization temperature, the polymerization concentration and other polymerization conditions. However, in order to obtain a polymer having a weight average molecular weight of several thousands to several tens of thousands, the amount of the chain transfer agent to be used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the sum of the amounts of the monomers (c-1), (c-2) and (c-3); more preferably 0.5 to 15 parts by weight.

The temperature at which the above polymerization reaction is carried out may be appropriately set depending on the kind or amount of the monomer used, the polymerization conditions such as the polymerization initiator, etc., and is preferably 50 to 200 ℃ and more preferably 70 to 150 ℃.

In another embodiment of the present invention, the first alkali-soluble resin (C-1) can be obtained by polymerizing a copolymer obtained by copolymerizing the monomers (C-1), (C-2) and (C-3) with an ethylenically unsaturated monomer (C-4) having an epoxy group.

The ethylenically unsaturated monomer (c-4) having an epoxy group may include, but is not limited to, (meth) acrylate monomers having an epoxy group, α -alkyl acrylate compounds having an epoxy group, or glycidyl ether monomers, and the like.

The (meth) acrylate monomer 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, or 3, 4-epoxycyclohexylmethyl (meth) acrylate, and the like.

The alpha-alkyl acrylate monomer having an epoxy group may include, but is not limited to, glycidyl alpha-ethacrylate, glycidyl alpha-n-propylacrylate, glycidyl alpha-n-butylacrylate, or 6, 7-epoxyheptyl alpha-ethacrylate, and the like.

The glycidyl ether monomer 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-4) having an epoxy group may be used singly or in combination.

Preferably, the ethylenically unsaturated monomer (c-4) having an epoxy group is selected from glycidyl methacrylate, 3, 4-epoxycyclohexylmethyl methacrylate, 6, 7-epoxyheptyl methacrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether or any combination of the above monomers.

The ethylenically unsaturated monomer (c-4) having an epoxy group is used in an amount of 3 to 40 parts by weight based on 100 parts by weight of the sum of the amounts of the monomers (c-1), (c-2) and (c-3); preferably 5 to 35 parts by weight; more preferably 10 to 30 parts by weight.

When the first alkali-soluble resin (C-1) is a copolymer obtained by polymerizing the monomer (C-1) represented by the above formula (III), the ethylenically unsaturated monomer (C-2) having one or more carboxylic acid groups, and the other copolymerizable ethylenically unsaturated monomer (C-3), and the ethylenically unsaturated monomer (C-4) having an epoxy group, it reacts to form a resin having an ethylenically unsaturated group, for example, a structure represented by the formula (IV):

wherein L is¹Represents a hydrogen atom or a methyl group. The average molecular weight of the first alkali-soluble resin (C-1) of the present invention may be appropriately determined according to the purpose and use, and the average molecular weight is 2,000 to 250,000, preferably 3,000 to 200,000, and more preferably 400 to 150,000, in order to obtain good ITO sputtering suitability and pigment dispersibility.

In the specific embodiment of the present invention, the first alkali-soluble resin (C-1) is used in an amount of 5 to 100 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resins (C); preferably 7 to 80 parts by weight; more preferably 10 to 60 parts by weight. When the monomer (C-1) represented by the formula (III) is not used in the synthesis of the first alkali-soluble resin (C-1), the ITO sputtering suitability and pigment dispersibility of the pixel layer prepared from the blue photosensitive resin composition are poor; when the first alkali-soluble resin (C-1) has an ethylenically unsaturated group, the sputtering suitability of ITO can be further improved.

According to an embodiment of the present invention, the alkali-soluble resin (C) of the present invention may further comprise a second alkali-soluble resin (C-2), wherein the second alkali-soluble resin (C-2) is obtained by polymerizing a mixture comprising an epoxy resin (C1) having at least two epoxy groups and a compound (C2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. In addition, the above mixture may further optionally contain a carboxylic acid anhydride compound (c3) and/or an epoxy group-containing compound (c 4).

According to an embodiment of the present invention, the epoxy resin (c1) having at least two epoxy groups of the present invention may have a structure as shown in the following formula (V) or the following formula (VI). Here, the description that "the epoxy resin (c1) may have a structure represented by the following formula (V) or the following formula (VI)" also covers the case where a compound having a structure represented by the following formula (V) and a compound having a structure represented by the following formula (VI) are present together as the epoxy resin (c 1). Specifically, the epoxy resin (c1) having at least two epoxy groups has, for example, a structure represented by the following formula (V):

wherein:

R⁶¹、R⁶²、R⁶³and R⁶⁴Independently selected from hydrogen, halogen and C₁To C₅Alkyl groups of (a);

the epoxy resin (c1) having at least two epoxy groups of the formula (V) 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 type compound include: 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-chlorophenyl) fluorene [9,9-bis (4-hydroxy-3-fluorophenyl) 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-methoxyphenyl) fluorene [9,9-bis (4-hydroxy-3-hydroxyphenyl) fluorene ], 9-bis (4-hydroxy-3-methoxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene ],9-3-bis (4-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): such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, and the like.

Next, the epoxy resin (c1) having at least two epoxy groups may have a structure represented by the following formula (VI):

wherein,

R⁶⁵to R⁷⁸Independently selected from hydrogen, halogen, C₁To C₈Alkyl and C₆To C₁₅The aromatic group of (a); and v represents an integer of 0 to 10.

The epoxy resin (c1) having at least two epoxy groups of the formula (VI) is obtained, for example, by reacting a compound having the structure of the following formula (VI-1) with a halogenated propylene oxide in the presence of an alkali metal hydroxide:

in the above formula (VI-1), R⁶⁵To R⁷⁸And v is as defined for R in formula (VI)⁶⁵To R⁷⁸And v are defined identically and are not repeated herein.

The epoxy resin (c1) having at least two epoxy groups of the formula (VI) is a compound having a structure of the formula (VI-1) obtained by condensation reaction of a compound having a structure of the formula (VI-2) with phenols (phenols) in the presence of an acid catalyst, for example. Subsequently, dehydrohalogenation is carried out by adding an excess of halogenated propylene oxide to obtain an epoxy resin (c1) having at least two epoxy groups as shown in formula (VI):

in the above formula (VI-2), R⁷⁹And R⁸⁰Respectively being the same or different hydrogen atom, halogen atom, C₁To C₈Alkyl or C₆To C₁₅An aromatic group of (a); l is²And L³Respectively being the same or different halogen atoms, C₁To C₆Alkyl or C₁To C₆Alkoxy group of (2). Preferably, the halogen atom may be, for example, chlorine or bromine, the alkyl group may be, for example, methyl, ethyl or tert-butyl, and the alkoxy group may be, for example, methoxy or ethoxy.

Specific examples of the phenols include: 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), cyclohexylcresol (cyclohexylphenol), cyclohexylcresol (cyclohexylcresol), 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 (VI-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), 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 above compound having the structure of formula (VI-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 (VI-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 (calcium hydroxide) and magnesium hydroxide (magnesium hydroxide); organic amines such as diethylenetriamine (diethylenetriamine), triethylenetetramine (triethylenetetramine), aniline (aniline), and phenylenediamine (phenylenediamine); and ammonia (ammonium), sodium dihydrogen phosphate (sodium dihydrogen phosphate), and the like. The washing treatment can be carried out by a conventional method, for example, by adding an aqueous solution containing a neutralizing agent to the solution after the reaction and repeating the extraction. Neutralizing or washing with water, heating under reduced pressure, distilling off unreacted phenols and solvent, and concentrating to obtain compound with formula (VI-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 dehydrohalogenation 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 the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above 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 above 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 above compound having the structure of formula (VI-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 the structure of formula (VI-1).

In order to facilitate the dehydrohalogenation reaction, an aprotic polar solvent such as dimethyl sulfone (dimethyl sulfone) or dimethyl sulfoxide (dimethyl sulfoxide) may be added in addition to an alcohol such as methanol or ethanol to carry out the reaction. 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 of hydroxyl groups in the above-mentioned compound having the structure of formula (VI-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, washing with water, and the like. Alternatively, the solvent such as toluene or methyl isobutyl ketone may be distilled off by heating under reduced pressure to obtain the epoxy resin (c1) having at least two epoxy groups as shown in formula (VI). The epoxy resin (c1) having at least two epoxy groups of the formula (VI) may include, but is not limited to, those commercially available from Nippon Kayaku Co. Ltd., such as those sold under the trade names NC-3000, NC-3000H, NC-3000S and NC-3000P.

The compound (c2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is selected from the group consisting of the following (1) to (3), for example: (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 (c3), wherein the hydroxyl group-containing (meth) acrylate includes, but is not limited to, 2-hydroxyethyl acrylate [ (2-hydroxyethoxy) acrylate ], 2-hydroxyethyl methacrylate [ (2-hydroxyethoxy) methacrylate ], 2-hydroxypropyl acrylate [ (2-hydroxypropyl) methacrylate ], 4-hydroxybutyl acrylate [ (4-hydroxybutyl) acrylate ], 4-hydroxybutyl methacrylate [ (4-hydroxybutyl) methacrylate ], pentaerythritol trimethacrylate, and the like. The carboxylic anhydride compound mentioned here may be the same as the carboxylic anhydride compound (C3) contained in the mixture of the second alkali-soluble resin (C-2) described below, and therefore, the description thereof is omitted.

The mixture of the second alkali-soluble resin (C-2) may further optionally contain a carboxylic acid anhydride compound (C3) and/or an epoxy group-containing compound (C4). The above carboxylic anhydride compound (c3) may be selected from the group consisting of the following (1) to (2): (1) dicarboxylic acid anhydride compounds 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, methylnadic (methyltetrahydrophthalic 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), bisphenyltetracarboxylic acid dianhydride, and bisphenylene ether tetracarboxylic acid dianhydride.

The epoxy group-containing compound (c4) 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 having tradenames Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, and Denacol EX-192 (hereinafter referred to as trademarks of Kazakhstan Kaisha).

The second alkali-soluble resin (C-2) can be prepared by polymerizing an epoxy resin (C1) having at least two epoxy groups of formula (V) with a compound (C2) 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 (C3) to the reaction product. The equivalent of the acid anhydride group contained in the carboxylic anhydride compound (c3) 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 (c3) are used, they may be added sequentially or simultaneously in the reaction. When a dicarboxylic anhydride compound and a tetracarboxylic anhydride compound are used as the carboxylic anhydride compound (c3), the molar ratio of the dicarboxylic anhydride compound and the tetracarboxylic 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 second alkali-soluble resin (C-2) can be prepared by reacting an epoxy resin (C1) having at least two epoxy groups of formula (VI) with a compound (C2) having at least one carboxylic acid group and at least one ethylenically unsaturated group to form a hydroxyl group-containing reaction product, and then adding a carboxylic anhydride compound (C3) and/or an epoxy group-containing compound (C4) to the reaction product to polymerize the reaction product. The acid-valent equivalent of the above-mentioned compound (c2) 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 resin (c1) having at least two epoxy groups of the formula (VI). The amount of the carboxylic anhydride compound (c3) 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 second alkali-soluble resin (C-2), 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 (tetramethyllammonium 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 epoxy resin having at least two epoxy groups (c1) and the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (c 2).

In addition, in order to control the degree of polymerization, a polymerization inhibitor (polymerizioninhibitor) 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-t-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 resin having at least two epoxy groups (c1) and the compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (c 2).

In preparing the second alkali-soluble resin (C-2), 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) methyl ether (methyl ether); 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. The polymerization solvents mentioned above can be used in general singly or in admixture of plural kinds. In addition, the acid value of the above-mentioned first alkali-soluble resin (C-1) is preferably from 50mgKOH/g to 200mgKOH/g, more preferably from 60mgKOH/g to 150 mgKOH/g.

Further, the number average molecular weight of the second alkali-soluble resin (C-2) in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is preferably 800 to 8,000, more preferably 1,000 to 6,000.

In the specific embodiment of the present invention, the second alkali-soluble resin (C-2) is used in an amount of 0 to 95 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resins (C); preferably 20 to 93 parts by weight; more preferably 40 to 90 parts by weight. When the second alkali-soluble resin (C-2) is used, the pigment dispersibility of the pixel layer obtained from the blue photosensitive resin composition is good.

Preferably, the alkali-soluble resin (C) of the present invention may further comprise a third alkali-soluble resin (C-3), wherein the third alkali-soluble resin (C-3) is obtained by copolymerizing an ethylenically unsaturated monomer having one or more carboxylic acid groups with another copolymerizable ethylenically unsaturated monomer. The second alkali-soluble resin (C-3) is preferably obtained by copolymerizing 50 to 95 parts by weight of an ethylenically unsaturated monomer having one or more carboxylic acid groups and 5 to 50 parts by weight of another copolymerizable ethylenically unsaturated monomer, based on 100 parts by weight of the copolymerizable monomer.

The ethylenically unsaturated monomer containing one or more carboxylic acid groups may be used alone or in combination, and the ethylenically unsaturated monomer containing a carboxylic acid group includes, but is not limited to, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid (MAA), crotonic acid, α -chloroacrylic acid, ethacrylic acid, cinnamic acid, 2-acryloyloxyethoxy succinate, or 2-methacryloyloxyethoxysuccinate (HOMS); unsaturated dicarboxylic acids (anhydrides) such as maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, citraconic acid, and citraconic anhydride; unsaturated polycarboxylic acids (anhydrides) having three or more carboxylic acid groups. Preferably, the ethylenically unsaturated monomer containing a carboxylic acid group is selected from acrylic acid, methacrylic acid, 2-acryloylethoxysuccinate, or 2-methacryloyloxyethoxysuccinate. More preferably, the carboxylic acid group-containing ethylenically unsaturated monomer is selected from 2-acryloxyethoxy succinate or 2-methacryloxyethoxy succinate, which can improve pigment dispersibility and improve development speed and reduce residue generation.

Other copolymerizable ethylenically unsaturated monomers may be used alone or in combination, and include, but are not limited to, aromatic vinyl compounds such as Styrene (SM), α -methylstyrene, vinyltoluene, p-chlorostyrene, methoxystyrene, etc.; maleimides such as N-Phenylmaleimides (PMI), N-o-hydroxyphenylmaleimides, N-m-hydroxyphenylmaleimides, N-p-hydroxyphenylmaleimides, N-o-methylphenylmaleimides, N-m-methylphenylmaleimides, N-p-methylphenylmaleimides, N-o-methoxyphenylmaleimides, N-m-methoxyphenylmaleimides, N-p-methoxyphenylmaleimide, and N-cyclohexylmaleimide; methyl Acrylate (MA), methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, n-butyl acrylate, isobutyl methacrylate, n-butyl methacrylate, Unsaturated carboxylic acid esters such as 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate (BzMA), phenyl acrylate, phenyl methacrylate, triethylene glycol methoxy acrylate, triethylene glycol methoxy methacrylate, dodecyl methacrylate, tetradecyl methacrylate, hexadecyl methacrylate, octadecyl methacrylate, eicosyl methacrylate, docosyl methacrylate, dicyclopentenyloxyethyl acrylate (DCPOA); acrylic acid-nitrogen, nitrogen-dimethylaminoethyl ester, methacrylic acid-nitrogen, nitrogen-dimethylaminoethyl ester, acrylic acid-nitrogen, nitrogen-diethylaminopropyl ester, methacrylic acid-nitrogen, nitrogen-dimethylaminopropyl ester, acrylic acid nitrogen, nitrogen-dibutylaminopropyl ester, nitrogen-methacrylic acid iso-butylaminoethyl ester; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, and vinyl butyrate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether and methallyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, and vinylidene cyanide; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, nitrogen-hydroxyethyl acrylamide, and nitrogen-hydroxyethyl methacrylamide; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chlorinated butadiene.

Preferably, the other copolymerizable ethylenically unsaturated monomer is selected from styrene, N-phenyl maleimide, methyl acrylate, methyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate, dicyclopentenyloxyethyl acrylate, or combinations thereof.

In the preparation of the third alkali-soluble resin (C-3), a solvent may be used, which may be used alone or in combination, and includes, but is not limited to, (poly) alkylene glycol monoalkyl ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol n-propyl ether, diethylene glycol n-butyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol n-butyl ether, tripropylene glycol methyl ether, tripropylene glycol ethyl ether, etc.; (poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate (PGMEA for short), propylene glycol ethyl ether acetate, etc.; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl3-ethoxypropionate (EEP), ethyl ethoxyacetate, ethyl glycolate, methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl propionate, ethyl butyrate, n-propyl butyrate, ethyl butyrate, n-butyl butyrate, other esters such as n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-methoxybutyrate; aromatic hydrocarbons such as toluene and xylene; amides such as nitrogen-methylpyrrolidone, nitrogen-dimethylformamide, or nitrogen, nitrogen-dimethylacetamide. Preferably, the solvent is selected from propylene glycol methyl ether acetate, ethyl3-ethoxypropionate, or combinations thereof. (poly) alkylene glycol monoalkyl ethers refer to alkylene glycol monoalkyl ethers or polyalkylene glycol monoalkyl ethers. (poly) alkylene glycol monoalkyl ether acetates refer to alkylene glycol monoalkyl ether acetates or polyalkylene glycol monoalkyl ether acetates.

The initiator used in the preparation of the third alkali-soluble resin (C-3) is generally a radical type polymerization initiator, and specifically, for example: azo (azo) compounds such as 2,2' -azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), 2' -azobis (4-methoxy-2, 4-dimethylvaleronitrile), 2' -azobis-2-methylbutyronitrile (2,2' -azobis-2-methyl butyronitrile, abbreviated as AMBN); and a peroxy compound such as dibenzoyl peroxide.

In addition, the number average molecular weight of the third alkali-soluble resin (C-3) in terms of polystyrene as measured by Gel Permeation Chromatography (GPC) is preferably 3,000 to 30,000, more preferably 5,000 to 25,000.

The ethylenically unsaturated compound (D) of the present invention is selected from the group consisting of a first ethylenically unsaturated compound (D-1), a second ethylenically unsaturated compound (D-2) and a combination thereof.

The first ethylenically unsaturated group compound (D-1) is a (meth) acrylate compound obtained by reacting a caprolactone-modified polyol with (meth) acrylic acid.

The caprolactone-modified polyol is prepared by reacting caprolactone with polyol having more than 4 functional groups, wherein the caprolactone can be gamma-caprolactone, or-caprolactone, and preferably-caprolactone. The polyhydric alcohol having 4 or more functional groups may be pentaerythritol, ditrimethylolpropane, dipentaerythritol. Preferably, the caprolactone is contained in an amount ranging from 1 to 12 moles based on 1 mole of the polyol having 4 or more functional groups.

The first ethylenically unsaturated group-containing compound (D-1) is selected from pentaerythritol caprolactone-modified tetra (meth) acrylate compounds, ditrimethylolpropane caprolactone-modified tetra (meth) acrylate compounds, dipentaerythritol caprolactone-modified poly (meth) acrylate compounds, etc., the dipentaerythritol caprolactone modified poly (meth) acrylate compound may be dipentaerythritol caprolactone modified di (meth) acrylate compound, dipentaerythritol caprolactone modified tri (meth) acrylate compound, dipentaerythritol caprolactone modified tetra (meth) acrylate compound, dipentaerythritol caprolactone modified penta (meth) acrylate compound, dipentaerythritol caprolactone modified hexa (meth) acrylate compound.

The first ethylenically unsaturated group-containing compound (D-1) has a structure represented by the formula (VII):

wherein:

Z¹and Z²Each independently represents hydrogen or methyl;

t represents an integer of 1 to 2; and

b represents an integer of 1 to 6; c represents an integer of 0 to 5, wherein the sum of b and c is an integer of 2 to 6.

The first ethylenically unsaturated group-containing compound (D-1) is used in an amount of 10 to 50 parts by weight, preferably 13 to 45 parts by weight, more preferably 15 to 40 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (C). When the first ethylenically unsaturated group-containing compound (D-1) is used, the pixel layer obtained from the blue photosensitive resin composition has a good ITO sputtering suitability.

The second ethylenically unsaturated group-containing compound (D-2) has a functional group represented by the formula (IX):

in the formula (IX), Z³Represents hydrogen or methyl.

The second ethylenically unsaturated group-containing compound (D-2) is selected from the group consisting of acrylamide, (meth) acryloylmorpholine, 7-amino-3, 7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobornyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyldiglycol (meth) acrylate, tert-octyl (meth) acrylamide, diacetone (meth) acrylamide, dimethylamino (meth) acrylate, dodecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, nitrogen-dimethyl (meth) acrylamide, tetrachlorophenyl (meth) acrylate, 2-tetrachlorophenoxyethyl (meth) acrylate, and mixtures thereof, Tetrahydrofurfuryl (meth) acrylate, tetrabromophenyl (meth) acrylate, 2-tetrabromophenoxyethyl (meth) acrylate, 2-trichlorophenoxyethyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-tribromophenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, vinylcaprolactam, N-vinyl caseidone, phenoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, bornyl (meth) acrylate, ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, and mixtures thereof, Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tris (2-hydroxyethyl) isocyanate tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide (hereinafter abbreviated as EO) -modified trimethylolpropane tri (meth) acrylate, propylene oxide (hereinafter abbreviated as PO) -modified trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, 1, 4-butanediol di (meth) acrylate, 1, 6-hexanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and mixtures thereof, Polyester di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate (a product of Toyo Synthesis Co., Ltd., Japan, trade name TO-1382), dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, EO-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ditrimethylolpropyl tetra (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, EO-modified hydrogenated bisphenol A di (meth) acrylate, PO-modified glyceryl tripropionate, EO-modified bisphenol F di (meth) acrylate, Novolac polyglycidyl ether (meth) acrylate, trimethylolpropane triacrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropyl tetraacrylate.

Preferably, the second ethylenically unsaturated compound (D-2) 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, a commercial product available under the trade name TO-1382 from Toyo Synthesis Japan, or a combination thereof.

The second ethylenically unsaturated group-containing compound (D-2) is used in an amount of 40 to 400 parts by weight, preferably 45 to 350 parts by weight, more preferably 50 to 300 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (C).

The ethylenically unsaturated group-containing compound (D) is used in an amount of 50 to 450 parts by weight, preferably 55 to 400 parts by weight, more preferably 60 to 350 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resin (C).

The photoinitiator (E) according to the present invention comprises a photoinitiator (E-1) having a structure represented by formula (VIII):

wherein R is₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Independently of one another are hydrogen, C₁-C₂₀Alkyl, aryl, heteroaryl, and heteroaryl,COR₁₆、OR₁₇Halogen, NO₂OrOr R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Independently of one another areSubstituted C₂-C₁₀Alkenyl or R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Independently of one another are together- (CH)₂)_p-Y-(CH₂)_q-；

Or R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Independently of one another together are

With the proviso that R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈At least one pair of them is

R₉、R₁₀、R₁₁And R₁₂Independently of one another are hydrogen, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogenElement, phenyl, CN, OH, SH, C₁-C₄Alkoxy, (CO) OH or (CO) O (C)₁-C₄Alkyl groups);

or R₉、R₁₀、R₁₁And R₁₂Independently of one another, unsubstituted phenyl or phenyl substituted by one or more of the following groups: c₁-C₆Alkyl, halogen, CN, OR₁₇、SR₁₈Or NR₁₉R₂₀；

Or R₉、R₁₀、R₁₁And R₁₂Independently of one another, halogen, CN, OR₁₇、SR₁₈、SOR₁₈、SO₂R₁₈Or NR₁₉R₂₀Wherein the substituent OR₁₇、SR₁₈Or NR₁₉R₂₀Optionally via a group R₁₇、R₁₈、R₁₉And/or R₂₀Form a 5-or 6-membered ring with one carbon atom in the naphthyl ring;

or R₉、R₁₀、R₁₁And R₁₂Independently of one another areCOR₁₆Or NO₂；

Y is O, S, NR₂₆Or a direct bond;

p is an integer 0, 1,2 or 3;

q is an integer 1,2 or 3;

x is CO or a direct bond;

R₁₃is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, R₁₇、COOR₁₇、OR₁₇、SR₁₈、CONR₁₉R₂₀、NR₁₉R₂₀、PO(OC_kH_2k+1)₂Or

Or R₁₃Is C₂-C₂₀Alkyl interrupted by one or more O, S, SO₂、NR₂₆Or a combination of CO and at least one of CO,

or is C₂-C₁₂Alkenyl which is not interrupted or interrupted by one or more O, CO or NR₂₆Wherein is interrupted by C₂-C₂₀Alkyl and C which is not interrupted or interrupted₂-C₁₂Alkenyl is unsubstituted or substituted with one or more halogen;

or R₁₃Is C₄-C₈Cycloalkenyl radical, C₂-C₁₂Alkynyl or not interrupted or interrupted by one or more O, S, CO or NR₂₆C of (A)₃-C₁₀A cycloalkyl group;

or R₁₃Is phenyl OR naphthyl, each of which is unsubstituted OR substituted by one OR more groups OR₁₇、SR₁₈、NR₁₉R₂₀、COR₁₆、CN、NO₂Halogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, interrupted by one or more O, S, CO or NR₂₆C of (A)₂-C₂₀An alkyl group; or each channel thereof C₃-C₁₀Cycloalkyl or interrupted by one or more O, S, CO or NR₂₆C of (A)₃-C₁₀Cycloalkyl substitution;

k is an integer from 1 to 10;

R₁₄is hydrogen, C₃-C₈Cycloalkyl radical, C₂-C₅Alkenyl radical, C₁-C₂₀Alkoxy or C₁-C₂₀Alkyl, unsubstituted or substituted by one or more halogens, phenyl, C₁-C₂₀Alkylphenyl or CN;

or R₁₄Is phenyl or naphthaleneEach of which is unsubstituted or substituted with one or more of the following groups: c₁-C₆Alkyl radical, C₁-C₄Haloalkyl, halogen, CN, OR₁₇、SR₁₈And/or NR₁₉R₂₀；

Or R₁₄Is C₃-C₂₀Heteroaryl group, C₁-C₈Alkoxy, benzyloxy or phenoxy which are unsubstituted or substituted by one or more C₁-C₆Alkyl radical, C₁-C₄Haloalkyl and/or halogen substitution;

R₁₅is C₆-C₂₀Aryl or C₃-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C1-C4 haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀、PO(OC_kH_2k+1)₂、SO-C₁-C₁₀Alkyl, SO₂-C₁-C₁₀Alkyl, interrupted by one or more O, S or NR₂₆C of (A)₂-C₂₀An alkyl group; or each channel thereof C₁-C₂₀Alkyl substitution of the C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR₁₇、CONR₁₉R₂₀Phenyl, C₃-C₈Cycloalkyl radical, C₃-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₃-C₂₀Heteroaryloxycarbonyl radical, OR₁₇、SR₁₈Or NR₁₉R₂₀；

Or R₁₅Is hydrogen, C₂-C₁₂Alkenyl, not interrupted or interrupted by one or more O, CO or NR₂₆C of (A)₃-C₈A cycloalkyl group;

or R₁₅Is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OR₁₇、SR₁₈、C₃-C₈A cycloalkyl group, a,C₃-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₃-C₂₀Heteroaryloxycarbonyl radical, NR₁₉R₂₀、COOR17、CONR₁₉R₂₀、PO(OC_kH_2k+1)₂、A phenyl group; or the C₁-C₂₀Alkyl substituted by phenyl, which phenyl is substituted by halogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, OR₁₇、SR₁₈Or NR₁₉R₂₀Substitution;

or R₁₅Is C₂-C₂₀Alkyl interrupted by one or more O, SO or SO₂And the m is hetero C₂-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, OR₁₇、COOR₁₇、CONR₁₉R₂₀Phenyl OR via OR₁₇、SR₁₈Or NR₁₉R₂₀Substituted phenyl;

or R₁₅Is C2-C20 alkanoyl or benzoyl, unsubstituted or substituted with one or more of the following groups: c₁-C₆Alkyl, halogen, phenyl, OR₁₇、SR₁₈Or NR₁₉R₂₀；

Or R₁₅Unsubstituted OR via one OR more OR₁₇Substituted naphthoyl or is C3-C14 heteroarylcarbonyl;

or R₁₅Is C₂-C₁₂Alkoxycarbonyl which is not interrupted or interrupted by one or more O and which is interrupted or interrupted by C₂-C₁₂Alkoxycarbonyl unsubstituted or substituted by one or more hydroxy groups;

or R₁₅Is a phenoxycarbonyl group, unsubstituted or substituted with one or more of the following groups: C1-C6 alkyl, halogen, C₁-C₄Haloalkyl, phenyl, OR₁₇、SR₁₈Or NR₁₉R₂₀；

Or R₁₅Is CN, CONR₁₉R₂₀、NO₂、C₁-C₄Haloalkyl, S (O)_m-C₁-C₆Alkyl, unsubstituted or substituted by C₁-C₁₂Alkyl or SO₂-C₁-C₆Alkyl substituted S (O)_m-a phenyl group;

or R₁₅Is SO₂O-phenyl unsubstituted or substituted by C1-C₁₂Alkyl substitution; or is diphenylphosphonyl or di (C)₁-C₄Alkoxy) -phosphono;

m is 1 or 2;

R'₁₄having a function of R₁₄One of the meanings given;

R'₁₅having a function of R₁₅One of the meanings given;

X₁is O, S, SO or SO₂；

X₂Is O, CO, S or a direct bond;

R₁₆is C₆-C₂₀Aryl or C₃-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C₁-C₄Haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀Or interrupted by one or more O, S or NR₂₆C of (A)₁-C₂₀An alkyl group; or each of which is passed through one or more C₁-C₂₀Alkyl substitution of the C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR₁₇、CONR₁₉R₂₀Phenyl, C₃-C₈Cycloalkyl radical, C₃-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₃-C₂₀Heteroaryloxycarbonyl radical, OR₁₇、SR₁₈Or NR₁₉R₂₀；

Or R₁₆Is hydrogen, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, CN, C₃-C₆Alkenyloxy, OCH₂CH₂CN、OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (CO) - (C)₁-C₄Alkyl), O (CO) -phenyl, (CO) OH or (CO) O (C)₁-C₄Alkyl groups);

or R₁₆Is C₂-C₁₂Alkyl interrupted by one or more O, S or NR₂₆；

Or R₁₆Is (CH)₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C₁-C₈Alkyl group), C₂-C₁₂Alkenyl or C₃-C₈A cycloalkyl group;

or R₁₆Is through SR₁₈Substituted phenyl, wherein the radical R18 represents a bond to the radical in which COR is attached₁₆A direct bond to the phenyl or naphthyl ring of the carbazole moiety of (a);

n is 1 to 20;

R₁₇is hydrogen, phenyl-C₁-C₃Alkyl radical, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C₃-C₆Alkenyloxy, OCH₂CH₂CN、OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (CO) - (C)₁-C₄Alkyl), OCO) - (C₂-C₄) Alkenyl, O (CO) -phenyl, (CO) OH, (CO) O (C)₁-C₄Alkyl group), C₃-C₂₀Cycloalkyl, SO₂-(C₁-C₄Haloalkyl), O (C)₁-C₄Haloalkyl) or C interrupted by one or more O₃-C₂₀A cycloalkyl group;

or R₁₇Is C₂-C₂₀Alkyl interrupted by one or more O, S or NR₂₆；

Or R₁₇Is (CH)₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C₁-C₈Alkyl group), C₁-C₈Alkanoyl radical, C₂-C₁₂Alkenyl radical, C₃-C₆Alkenoyl with or without intermingling or intermingling one or more of O, S, CO or NR₂₆C of (A)₃-C₂₀A cycloalkyl group;

or R₁₇Is C1-C8 alkyl-C3-C10 cycloalkyl which is not interrupted or interrupted by one or more O;

or R₁₇Is benzoyl, which is unsubstituted or substituted by one or more C1-C6 alkyl, halogen, OH or C1-C3 alkoxy;

or R₁₇Is phenyl, naphthyl or C₃-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OH, C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, CN, NO₂phenyl-C₁-C₃Alkoxy, phenoxy, C₁-C₁₂Alkylthio, phenylthio, N (C)₁-C₁₂Alkyl radical)₂Diphenyl-amino or

Or R₁₇Form bonds to have groups thereonA direct bond to a carbon atom of the phenyl or naphthyl ring of (a);

R₁₈is hydrogen, C₂-C₁₂Alkenyl radical, C₃-C₂₀Cycloalkyl or phenyl-C₁-C₃Alkyl radical, wherein C₂-C₁₂Alkenyl radical, C₃-C₂₀Cycloalkyl or phenyl-C₁-C₃The alkyl group being not interrupted or interrupted by one or more O, S, CO, NR₂₆Or COOR₁₇；

Or R₁₈Is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C₃-C₆Alkenyloxy, OCH₂CH₂CN、OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (CO) - (C)₂-C₄) Alkenyl, O (CO) - (C)₁-C₄Alkyl), O (CO) -phenyl OR (CO) OR₁₇；

Or R₁₈Is C₂-C₂₀Alkyl interrupted by one or more O, S, CO, NR₂₆Or COOR₁₇；

Or R₁₈Is (CH)₂CH₂O)_nH、(CH₂CH₂O)_n(CO)-(C₁-C₈Alkyl group), C₂-C₈Alkanoyl or C₃-C₆An alkenoyl group;

or R₁₈Is benzoyl, which is unsubstituted or substituted with one or more of the following groups: c₁-C₆Alkyl, halogen, OH, C₁-C₄Alkoxy or C₁-C₄An alkylthio group;

or R₁₈Is phenyl, naphthyl or C₃-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C₁-C₁₂Alkyl radical, C₁-C₄Haloalkyl, C₁-C₁₂Alkoxy, CN, NO₂phenyl-C₁-C₃Alkoxy, phenoxy, C₁-C₁₂Alkylthio, phenylthio, N (C)₁-C₁₂Alkyl radical)₂Diphenylamino, (CO) O (C)₁-C₈Alkyl group), (CO) -C₁-C₈Alkyl, (CO) N (C)₁-C₈Alkyl radical)₂Or

R₁₉And R₂₀Independently of one another are hydrogen, C₁-C₂₀Alkyl radical, C₂-C₄Hydroxyalkyl radical, C₂-C₁₀Alkoxyalkyl group, C₂-C₅Alkenyl radical, C₃-C₂₀Cycloalkyl, phenyl-C₁-C₃Alkyl radical, C₁-C₈Alkanoyl radical, C₁-C₈Alkanoyloxy, C₃-C₁₂Alkenoyl, SO₂-(C₁-C₄Haloalkyl) or benzoyl;

or R₁₉And R₂₀Is phenyl, naphthyl or C₃-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C₁-C₄Haloalkyl, C₁-C₂₀Alkoxy radical, C₁-C₁₂Alkyl, benzoyl or C₁-C₁₂An alkoxy group;

or R₁₉And R₂₀Together with the N atom to which they are attached form not interrupted or interrupted O, S or NR₁₇And the 5-or 6-membered saturated or unsaturated ring of (a), and the 5-or 6-membered saturated or unsaturated ring is unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy group, ═ O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO)R₂₃、NO₂Halogen, C₁-C₄-haloalkyl, CN, phenyl,Or C₃-C₂₀Cycloalkyl radical, C₃-C₂₀The cycloalkyl being not interrupted or interrupted by one or more O, S, CO or NR₁₇；

Or R₁₉And R₂₀To the N atom-to which it is attachedTo form a heteroaromatic ring system, which is unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C₁-C₂₀Alkoxy group, ═ O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO)R₂₃、Halogen, NO₂CN, phenyl or C₃-C₂₀Cycloalkyl radical, C₃-C₂₀The cycloalkyl being not interrupted or interrupted by one or more O, S, CO or NR₁₇；

R₂₁And R₂₂Independently of one another are hydrogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C₃-C₁₀Cycloalkyl or phenyl;

or R₂₁And R₂₂Together with the N atom to which they are attached form not interrupted or interrupted O, S or NR₂₆A 5-or 6-membered saturated or unsaturated ring, and the 5-or 6-membered saturated or unsaturated ring is not fused or the 5-or 6-membered saturated or unsaturated ring is fused with a benzene ring;

R₂₃is hydrogen, OH, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, interrupted by one or more O, CO or NR₂₆C of (A)₂-C₂₀Alkyl, not interrupted or interrupted O, S, CO or NR₂₆C of (A)₃-C₂₀Cycloalkyl, or R₂₃Is phenyl, naphthyl, phenyl-C₁-C₄Alkyl, OR₁₇、SR₁₈Or NR₂₁R₂₂；R₂₄Is (CO) OR₁₇、CONR₁₉R₂₀、(CO)R₁₇(ii) a Or R₂₄Having a function of R₁₉And R₂₀One of the meanings given;

R₂₅is COOR₁₇、CONR₁₉R₂₀、(CO)R₁₇(ii) a Or R₂₅Having a function of R₁₇Is given byOne of the meanings; r₂₆Is hydrogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C interrupted by one or more O or CO₂-C₂₀An alkyl group; or is phenyl-C₁-C₄Alkyl, C not interrupted or interrupted by one or more O or CO₃-C₈A cycloalkyl group; or is (CO) R₁₉(ii) a Or is phenyl, which is unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl, halogen, C₁-C₄Haloalkyl, OR₁₇、SR₁₈、NR₁₉R₂₀Or

With the proviso that at least one group is present in the molecule

The photoinitiator (E-1) having a structure represented by formula (VIII) is characterized in that it contains one or more annulated unsaturated rings on the carbazole moiety. In other words, R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈At least one pair of them is

In one embodiment, the photoinitiator (E-1), C has a structure represented by formula (VIII)₁-C₂₀Alkyl is straight-chain or branched and is, for example, C₁-C₁₈-、C₁-C₄-、C₁-C₁₂-、C₁-C₈-、C₁-C₈-or C₁-C₄Alkyl or C₄-C₁₂-or C₄-C₈An alkyl group. Examples are methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexylHeptyl, 2,4, 4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and eicosyl. C₁-C₆Alkyl has the same meanings as above for C₁-C₂₀Alkyl groups are given the same meaning and have the highest number of corresponding C atoms.

Unsubstituted or substituted C containing one or more C-C multiple bonds₁-C₂₀Alkyl refers to alkenyl as explained below.

C₁-C₄Haloalkyl is C1-C4 alkyl as defined above substituted with halogen as defined below. Alkyl groups are, for example, mono-or polyhalogenated until all H-atoms are replaced with halogen. It is, for example, C_nH_xHal_yWherein x + y is 2n +1 and Hal is halogen, preferably F. Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl. C₂-C₄Hydroxyalkyl means C substituted by one or two O atoms₂-C₄An alkyl group. The alkyl group is linear or branched. 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. C₂-C₁₀Alkoxyalkyl being C interrupted by one O atom₂-C₁₀An alkyl group. C₂-C₁₀Alkyl has the same meanings as above for C₁-C₂₀Alkyl groups are given the same meaning and have the highest number of corresponding C atoms. Examples are methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, propoxypropyl.

Interrupted by one or more O, S, NR₂₆Or C of CO₂-C₂₀Alkyl radical O, S, NR₂₆Or CO is interrupted, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times, or 1 or 2 times. If more than one group is present, they are of the same kind or different. Two O atoms are formed byOne methylene group, preferably at least two methylene groups (i.e., ethylene groups) are separated. The alkyl group is a straight chain or a branched chain. 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)-NR₂₆-CH₂-CH₃、-CH₂-CH₂-COO-CH₂CH₃or-CH₂-CH(CH₃)-OCO-CH₂-CH₂CH₃。

C₃-C₁₀Cycloalkyl radical, C₃-C₁₀Cycloalkyl and C₃-C₈Cycloalkyl is understood in the context of the present application to be an alkyl group comprising at least one ring. These are, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl. C₃-C₁₀Cycloalkyl in the context of the present invention is also intended to encompass bicyclic, that is to say, bridged, rings, e.g.And corresponding rings. Other examples are such as (e.g. in) OrIsostructures, and bridged or fused ring systems, for exampleIs intended to coverAnd the like.

Interrupted by O, S, CO, NR₂₆C of (A)₃-C₂₀Cycloalkyl has the meaning given above, wherein at least one CH in the alkyl group₂Replacement of the radical by O, S, CO or NR₂₆. Examples are (e.g. in)、 And the like.

C₁-C₈alkyl-C₃-C₁₀C as defined above with cycloalkyl substituted by one or more alkyl groups having up to 8 carbon atoms₃-C₁₀A cycloalkyl group. Examples areAnd the like.

C interrupted by one or more O₁-C₈alkyl-C₃-C₁₀O-m-hetero C as defined above, the cycloalkyl group being substituted by one or more alkyl groups having up to 8 carbon atoms₃-C₁₀A cycloalkyl group. Examples areAnd the like.

C₁-C₁₂C with alkoxy radicals substituted by one O atom₁-C₁₂An alkyl group. C₁-C₁₂Alkyl has the same meanings as above for C₁-C₂₀Alkyl groups are given the same meaning and have the highest number of corresponding C atoms. The C is₁-C₄Alkoxy is straight-chain or branched, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy or tert-butoxy. C₁-C₈Alkoxy and C₁-C₄-alkoxy has the same meaning as described above and has the highest number of corresponding C atoms.

C₁-C₁₂C with alkylthio radicals substituted by one S atom₁-C₁₂An alkyl group. C₁-C₁₂Alkyl has the same meanings as above for C₁-C₁₂Alkyl groups are given the same meaning and have the highest number of corresponding C atoms. The C is₁-C₄Alkylthio is straight-chain or branched, for example methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, isobutylthio, tert-butylthio.

phenyl-C₁-C₃Alkyl is, for example, benzyl, phenylethyl, α -methylbenzyl or α -dimethyl-benzyl, especially benzyl.

phenyl-C₁-C₃Alkoxy is, for example, benzyloxy, phenylethoxy, α -methylbenzyloxy or α -dimethylbenzyloxy, especially benzyloxy.

C₂-C₁₂Alkenyl is mono-or polyunsaturated and is, for example, C₂-C₁₀-、C₂-C₈-、C₂-C₅Alkenyl, such as vinyl, allyl, methallyl, 1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1, 3-pentadienyl, 5-hexenyl, 7-octenyl or dodecenyl, especially allyl. C₂-C₅Alkenyl radicals having the meaning given above for C₂-C₁₂Alkenyl groups are given the same meaning and have the highest number of corresponding C atoms.

Interrupted by one or more O, CO or NR₂₆C of (A)₂-C₁₂Alkenyl radical O, S, NR₂₆Or CO is interrupted, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times, or 1 or 2 times. If more than one group is present, they are of the same kind or different. The two O 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.

C₄-C₈Cycloalkenyl having one or more double bonds and being, for example, C₄-C₆-Cycloalkenyl or C₆-C₈-cycloalkenyl groups. Examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, preferably cyclohexenyl.

The C is₃-C₆The alkenyloxy radical is mono-or polyunsaturated and has one of the meanings given above for the alkenyl radical, and the connecting oxy radical has the highest number of corresponding C atoms. Examples are allyloxy, methallyloxy, butenyloxy, pentenyloxy, 1, 3-pentadienyloxy, 5-hexenyloxy.

C₂-C₁₂Alkynyl is mono-or polyunsaturated, straight-chain or branched and is, for example, C₂-C₈-、C₂-C₆-or C₂-C₄Alkynyl. Examples are ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2-butynyl, pentynyl hexynyl, 2-hexynyl, 5-hexynyl, octynyl and the like.

C₂-C₂₀Alkanoyl is straight-chain or branched and is, for example, C₂-C₁₈-、C₂-C₁₄-、C₂-C₁₂-、C₂-C₈-、C₂-C₆-or C₂-C₄Alkanoyl or C₄-C₁₂-or C₄-C₈An alkanoyl group. Examples are acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanylAcyl, octanoyl, nonanoyl, decanoyl, dodecanoyl, tetradecanoyl, pentadecanoyl, hexadecanoyl, octadecanoyl, eicosanoyl, preferably acetyl. C₁-C₈Alkanoyl having the same as above for C₂-C₂₀Alkanoyl groups have the same meaning given and have the highest number of corresponding C atoms.

C₂-C₁₂Alkoxycarbonyl is straight-chain or branched and is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 1-dimethylpropoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl, especially methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl or isobutoxycarbonyl, preferably methoxycarbonyl.

C interrupted by one or more O₂-C₁₂Alkoxycarbonyl is straight or branched chain. The two O 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. C₆-C₂₀Aryloxycarbonyl is, for example, phenyloxycarbonyl [ ═ phenyl-O- (CO) -]Naphthoxycarbonyl, anthracenoxycarbonyl, and the like. C₅-C₂₀Heteroaryloxycarbonyl radical as C₅-C₂₀heteroaryl-O-CO-.

C₃-C₁₀Cycloalkyl carbonyl being C₃-C₁₀cycloalkyl-CO-wherein the cycloalkyl group has one of the meanings indicated above and has the highest number of corresponding C atoms. The interimpurities having one or more of O, S, CO, NR₂₆C of (A)₃-C₁₀Cycloalkylcarbonyl means a m-heterocycloalkyl-CO-group in which the m-heterocycloalkyl group is as defined above.

C₃-C₁₀Cycloalkoxycarbonyl radical being C₃-C₁₀cycloalkyl-O- (CO) -, wherein cycloalkyl has one of the meanings indicated above and has the highest number of corresponding C atoms. Interrupted by one or more O, S, CO, NR₂₆C of (A)₃-C₁₀Cycloalkoxycarbonyl means a meta-heterocycloalkyl-O- (CO) -, wherein meta-heterocycloalkyl is as defined above.

C₁-C₂₀Alkylphenyl refers to phenyl substituted with one or more alkyl groups, wherein the sum of the C atoms is at most 20.

C₆-C₂₀Aryl is, for example, phenyl, naphthyl, anthracyl, phenanthryl, pyrenyl, mesityl, tetracenyl, triphenylenyl, etc., especially phenyl or naphthyl, preferably phenyl. Naphthyl is 1-naphthyl or 2-naphthyl.

In the context of the present invention, this C₃-C₂₀Heteroaryl is intended to encompass monocyclic or polycyclic ring systems, such as fused ring systems. Examples are thienyl, benzo [ b ]]Thienyl, naphtho [2,3-b ]]Thienyl, thianthryl, furyl, dibenzofuryl,Alkene, xanthene, thioxanthyl, phenoxathiyl, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, indolyl, indazolyl, purinyl, quinolizinyl, isoquinolyl, quinolyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, linyl, pteridinyl, carbazolyl, β -carbolinyl, phenanthridinyl, acridinyl, perimidine, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, xanthyl, phenoxathiyl, 7-phenanthrenyl, anthraquinone-2-yl (═ 9, 10-diphenoxy-9, 10-dihydroanthracene-2-yl), 3-benzo [ b ] b]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, and the like, 2-pyrazinyl, 5, 6-dimethyl-2-pyrazinyl, 2-intermediate nitrogenIndenyl, 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-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 3-methoxy-6-isoquinolyl, 2-quinolyl, 6-quinolyl, 7-quinolyl, 2-methoxy-3-quinolyl, 2-methoxy-6-quinolyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy-6-phthalazinyl, 1, 4-dimethoxy-6-phthalazinyl, 1, 8-naphthyridine-2-yl, 2-quinolyl, 6-quinolyl, 2, 3-dimethyl-6-quinolyl, 2, 3-dimethoxy-6-phthalazinyl, 2, 3-naphthyridine-2-yl, 5-phenanthroline-2-3-5-3-phenanthryl, 5-methyl-3-5-phenanthroline-2-3-5-methyl-5-phenanthroline-2-3-5-3-5-methyl-3-thienyl, 5-3-5-phenanthroline, 5-3-methyl-3-5-2-3-5-3-thienyl, 5-3-thienyl, 5-3-2-thienyl, 3-2-thienyl, 3-2-quinolyl, 3-quinolyl, 3-5-phenanthroline, 3-2-quinolyl, 3-2-quinolyl, 3-quinolyl.

C₃-C₂₀Heteroaryl is especially thienyl, benzo [ b ]]Thienyl, thianthryl, thioxanthyl, 1-methyl-2-indolyl or 1-methyl-3-indolyl; especially thienyl.

C₄-C₂₀C as defined above with the heteroarylcarbonyl group attached to the rest of the molecule through a CO group₃-C₂₀A heteroaryl group.

Substituted aryl radicals (phenyl, naphthyl, C)₆-C₂₀Aryl or C₅-C₂₀Heteroaryl) is substituted 1 to 7 times, 1 to 6 times or 1 to 4 times, in particular 1,2 or 3 times, respectively. Obviously, is defined asAn aryl group cannot have more substituents than the number of free positions at 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.

The m-interrupted group m-interrupted 1 or more times is (for example) m-interrupted 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 (obviously, the number of m-interrupted atoms depends on the number of C-atoms to be m-interrupted). Substituted radicals substituted 1 or more times 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 one or more defined substituents is intended to have one substituent or a plurality of substituents with the same or different definitions as given. Halogen is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine. If R is₁Substituents of different definitions. Halogen is fluorine, chlorine, bromine and iodine, especially fluorine, chlorine and bromine, preferably fluorine and chlorine. If R is₁And R₂、R₂And R₃、R₃And R₄Or R₅And R₆、R₆And R₇、R₇And R₈Independently of one another together areThe following structures (Ia) -i (i), for example, are formed:

or, for example, structures such as (Id) - (Ih):

preferably structure (Ia).

The photoinitiator (E-1) having a structure represented by formula (VIII) is characterized in that at least one phenyl ring is fused with a carbazole moiety to form a "naphthyl" ring. That is, one of the above structures is given by the structure shown in formula (VIII).

If R is₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Independently of one another are together- (CH)₂)_p-Y-(CH₂)_q-, then form, for example, aAnd the like.

If substituents OR on phenyl OR naphthyl rings₁₇、SR₁₈、SOR₁₈、SO₂R₁₈Or NR₁₉R₂₀By the radical R₁₇、R₁₈、R₁₉And/or R₂₀And form a 5-or 6-membered ring with one carbon atom of the naphthyl ring, a structure comprising 3 or more rings (including the naphthyl ring) is obtained.

Examples are

And the like.

If R is₁₇Form bonds to have groups thereonA direct bond to a carbon atom of the phenyl or naphthyl ring of (A), thenAnd the like.

If R is₁₆By SR₁₈Substituted phenyl, in which the radical R₁₉Represents a bond to which COR is attached₁₆Direct bonds to the phenyl or naphthyl ring of the carbazole part of the group, forming, for example, a group such as

And the like. That is, if R₁₆By SR₁₈Substituted phenyl, in which the radical R₁₈Represents a bond to which COR is attached₁₆A direct bond to the phenyl or naphthyl ring of the carbazole moiety of the group, the thioxanthene moiety is then formed together with one of the phenyl or naphthyl rings of the carbazole moiety.

If R is₁₉And R₂₀Together with the N atom to which they are attached form an optional hetero ring of O, S or NR₁₇A 5-or 6-membered saturated or unsaturated ring of (a) then forms a saturated or unsaturated ring, for example aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1, 3-diazine, 1, 2-diazine, piperidine or morpholine. Preferably, if R₁₉And R₂₀Together with the N atom to which they are attached form an optional hetero ring of O, S or NR₁₇A 5-or 6-membered saturated or unsaturated ring of (A) forms an uninterrupted or interrupted O or NR₁₇Especially a 5-or 6-membered saturated ring of O.

If R is₂₁And R₂₂Together with the N atom to which they are attached form an optional hetero ring of O, S or NR₂₆And the phenyl ring is optionally fused to the saturated or unsaturated ring, form a saturated or unsaturated ring, for example aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1, 3-diazine, 1, 2-diazine, piperidine or morpholine or a corresponding ring (for example) And the like.

If R is₁₉And R₂₀Together with the N atom to which they are attached form a heteroaromatic ring system, which ring system is intended to comprise more than one ring (e.g. 2 or 3 rings) and one or more heteroatoms from the same or different classes. Suitable heteroatoms are, for example, N, S, O or P, especially N, S or O. Examples are carbazole, indole, isoindole, indazole, purine, isoquinoline, quinoline, carboline, phenothiazine and the like.

The term "and/or" or/and "in the context of the present invention is intended to express that not only one of the defined alternatives (substituents) may be present, but also that a total of several of the defined alternatives (substituents) may be present, i.e. a mixture of different alternatives (substituents).

The term "at least" is intended to define one or more than one, such as one or two or three, preferably one or two.

The term "optionally substituted" means that the group to which it refers is unsubstituted or substituted.

The term "optionally interrupted" means that the group to which it refers is not interrupted or interrupted.

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 term "(meth) acrylate" is intended in the context of the present application to mean acrylate as well as the corresponding methacrylate.

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 application range classes, i.e. also the application ranges for the compositions, the uses, the methods, the color filters, etc.

The photoinitiator (E-1) having the structure represented by formula (VIII) is prepared by a method described in the literature, for example, by reacting the corresponding oxime with an acid halide under the following conditionsEspecially chloride or anhydride reaction: in an inert solvent such as tert-butyl methyl ether, Tetrahydrofuran (THF) or dimethylformamide, in the presence of a base such as triethylamine or pyridine, or in a basic solvent such as pyridine. The preparation of compounds of the formula Ia, in which R is₇Is an oxime ester group and X is a direct bond [ starting from the appropriate oxime the reaction of the compounds (Ib) to (Ih)]：

R₁、R₂、R₅、R₆、R₈、R₁₃、R₁₄And R₁₅Hal means a halogen atom, in particular Cl, as defined above.

R₁₄Preferably methyl.

These reactions are well known to those skilled in the art and are generally carried out at temperatures of from-15 ℃ to +50 ℃, preferably from 0 to 25 ℃.

When X is 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). The esterification was then carried out under the same conditions as described above:

accordingly, the object of the present invention is also a process for preparing a photoinitiator (E-1) having the structure shown in formula (VIII) as defined above by reacting the corresponding oxime compound with an acid halide of formula (a) or an acid anhydride of formula (b) in the presence of a base or a mixture of bases.

Wherein Hal is halogen, especially Cl, and R₁₄As defined above.

Oximes required as starting materials can be obtained by standard chemical textbooks (e.g. j. march, Advanced organic chemistry, 4 th edition, Wiley Interscience, 1992) or by a variety of methods described 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. These 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 alkyl nitrites. 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.

Another embodiment of the present invention is a photoinitiator (E-1) having a structure represented by free formula (IA):

wherein R is₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Independently of one another are hydrogen, C₁-C₂₀Alkyl, aryl, heteroaryl, and heteroaryl,COR₁₆、OR₁₇Halogen, NO₂Or

Or R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Independently of one another areSubstituted C₂-C₁₀An alkenyl group;

or R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Independently of one another are together- (CH)₂)_p-Y-(CH₂)_q-；

With the proviso that R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈At least one pair of them isR₉、R₁₀、R₁₁And R₁₂Independently of one another are hydrogen, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, CN, OH, SH, C₁-C₄Alkoxy, (CO) OH or (CO) O (C)₁-C₄Alkyl groups);

Y is O, S, NR₂₆Or a direct bond;

p is an integer 0, 1,2 or 3;

q is an integer 1,2 or 3;

x is CO or a direct bond;

Or R₁₃Is C₂-C₂₀Alkyl interrupted by one or more O, S, SO₂、NR₂₆Or CO, or is C₂-C₁₂Alkenyl which is not interrupted or interrupted by one or more O, CO or NR₂₆Wherein is interrupted by C₂-C₂₀Alkyl and C which is not interrupted or interrupted₂-C₁₂Alkenyl is unsubstituted or substituted with one or more halogen;

or R₁₃Is C₄-C₈Cycloalkenyl radical, C₂-C₁₂Alkynyl or C₃-C₁₀Cycloalkyl, uninterrupted or interrupted by one or more O, S, CO or NR₂₆；

Or R₁₃Is phenyl OR naphthyl, each of which is unsubstituted OR substituted by one OR more groups OR₁₇、SR₁₈、NR₁₉R₂₀、COR₁₆、CN、NO₂Halogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C₂-C₂₀Alkyl interrupted by one or more O, S, CO or NR₂₆(ii) a Or each channel thereof C₃-C₁₀Cycloalkyl or interrupted by one or more O, S, CO or NR₂₆C of (A)₃-C₁₀Cycloalkyl substitution;

k is an integer from 1 to 10;

R₁₅is C₆-C₂₀Aryl or C₃-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C₁-C₄Haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀、PO(OC_kH_2k+1)₂、SO-C₁-C₁₀Alkyl, SO₂-C₁-C₁₀Alkyl, interrupted by one or more O, S or NR₂₆C of (A)₂-C₂₀An alkyl group; or each channel thereof C₁-C₂₀Alkyl substitution, C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR₁₇、CONR₁₉R₂₀Phenyl, C₃-C₈Cycloalkyl radical, C₃-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₃-C₂₀Heteroaryloxycarbonyl radical, OR₁₇、SR₁₈Or NR₁₉R₂₀；

Or R₁₅Is hydrogen, C₂-C₁₂Alkenyl radical, C₃-C₈Cycloalkyl, uninterrupted or interrupted by one or more O, CO or NR₂₆；

Or R₁₅Is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OR₁₇、SR₁₈、C₃-C₈Cycloalkyl radical, C₃-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₃-C₂₀Heteroaryloxycarbonyl radical, NR₁₉R₂₀、COOR₁₇、CONR₁₉R₂₀、PO(OC_kH_2k+1)₂、A phenyl group; or the C₁-C₂₀Alkyl substituted by phenyl, which phenyl is substituted by halogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, OR₁₇、SR₁₈Or NR₁₉R₂₀Substitution; or R₁₅Is C₂-C₂₀Alkyl interrupted by one or more O, SO or SO₂And the m is hetero C₂-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, OR₁₇、COOR₁₇、CONR₁₉R₂₀Phenyl OR via OR₁₇、SR₁₈Or NR₁₉R₂₀Substituted phenyl;

or R₁₅Is C₂-C₂₀Alkanoyl or benzoyl, unsubstituted or substituted with one or more of the following groups: c₁-C₆Alkyl, halogen, phenyl, OR₁₇、SR₁₈Or NR₁₉R₂₀；

Or R₁₅Is unsubstituted OR via one OR more OR₁₇Substituted naphthoyl or is C₃-C₁₄A heteroaryl carbonyl group;

or R₁₅Is a phenoxycarbonyl group, unsubstituted or substituted with one or more of the following groups: c₁-C₆Alkyl, halogen, C₁-C₄Haloalkyl, phenyl, OR₁₇、SR₁₈Or NR₁₉R₂₀(ii) a Or R₁₅Is CN, CONR₁₉R₂₀、NO₂、C₁-C₄Haloalkyl, S (O)_m-C₁-C₆Alkyl, unsubstituted or substituted by C₁-C₁₂Alkyl orSO₂-C₁-C₆Alkyl substituted S (O)_m-a phenyl group;

or R₁₅Is SO₂O-phenyl unsubstituted or substituted by C₁-C₁₂Alkyl substitution; or is diphenylphosphonyl or di (C)₁-C₄Alkoxy) -phosphono;

m is 1 or 2;

R'₁₅having a function of R₁₅One of the meanings given;

X₁is O, S, SO or SO₂；

X₂Is O, CO, S or a direct bond;

R₁₆is C₆-C₂₀Aryl or C₃-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C₁-C₄Haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀Or interrupted by one or more O, S or NR₂₆C of (A)₁-C₂₀An alkyl group; or each through one or more C₁-C₂₀Alkyl substitution, C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR₁₇、CONR₁₉R₂₀Phenyl, C₃-C₈Cycloalkyl radical, C₃-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₃-C₂₀Heteroaryloxycarbonyl radical, OR₁₇、SR₁₈Or NR₁₉R₂₀(ii) a Or R₁₆Is hydrogen, unsubstituted or substituted by one or more of the following groups C₁-C₂₀Alkyl groups: halogen, phenyl, OH, SH, CN, C₃-C₆Alkenyloxy, OCH₂CH₂CN、OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (CO) - (C)₁-C₄Alkyl), O (CO) -phenyl, (CO) OH or (CO) O (C)₁-C₄Alkyl groups); or R₁₆Interrupted by one or more O, S or NR₂₆C of (A)₂-C₁₂An alkyl group; or R₁₆Is (CH)₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C₁-C₈Alkyl group), C₂-C₁₂Alkenyl or C₃-C₈A cycloalkyl group;

or R₁₆By SR₁₈Substituted phenyl, in which the radical R₁₈Represents a bond to which COR is attached₁₆A direct bond to the phenyl or naphthyl ring of the carbazole moiety of the group;

n is 1 to 20;

R₁₇is hydrogen, phenyl-C₁-C₃Alkyl radical, C_1-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C₃-C₆Alkenyloxy, OCH₂CH₂CN、OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (CO) - (C)₁-C₄Alkyl), O (CO) - (C)₂-C₄) Alkenyl, O (CO) -phenyl, (CO) OH, (CO) O (C)₁-C₄Alkyl), SO₂-(C₁-C₄Haloalkyl), O (C)₁-C₄Haloalkyl), C₃-C₂₀Cycloalkyl or C interrupted by one or more O₃-C₂₀A cycloalkyl group; or R₁₇Is C₂-C₂₀Alkyl interrupted by one or more O, S or NR₂₆(ii) a Or R₁₇Is (CH)₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C₁-C₈Alkyl group), C₁-C₈Alkanoyl radical, C₂-C₁₂Alkenyl radical, C₃-C₆Alkenoyl or C₃-C₂₀Cycloalkyl, uninterrupted or interrupted by one or more O, S, CO or NR₂₆；

Or R₁₇Is C₁-C₈alkyl-C₃-C₁₀Cycloalkyl radicals, which are not interrupted or interruptedOne or more O;

or R₁₇Is benzoyl, unsubstituted or substituted by one or more C₁-C₆Alkyl, halogen, OH or C₁-C₃Alkoxy substitution;

Or R₁₈Is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: OH, SH, CN, C₃-C₆Alkenyloxy, OCH₂CH₂CN、OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (CO) - (C)_2-C₄) Alkenyl, O (CO) - (C)₁-C₄Alkyl), O (CO) -phenyl OR (CO) OR₁₇；

Or R₁₈Is C₂-C₂₀Alkyl interrupted by one or more O, S, CO, NR₂₆Or COOR₁₇(ii) a Or R₁₈Is (CH)₂CH₂O)_nH、(CH₂CH₂O)_n(CO)-(C₁-C₈Alkyl group), C₂-C₈Alkanoyl or C₃-C₆An alkenoyl group; or R₁₈Is benzoyl, which is unsubstituted or substituted with one or more of the following groups: c₁-C₆Alkyl, halogen, OH, C₁-C₄Alkoxy or C₁-C₄An alkylthio group;

R₁₉And R₂₀Independently of one another are hydrogen, C₁-C₂₀Alkyl radical, C₂-C₄Hydroxyalkyl radical, C₂-C₁₀Alkoxyalkyl group, C₂-C₅Alkenyl radical, C₃-C₂₀Cycloalkyl, phenyl-C₁-C₃Alkyl, SO₂-(C₁-C₄Haloalkyl), C₁-C₈Alkanoyl radical, C₁-C₈Alkanoyloxy, C₃-C₁₂Alkenoyl or benzoyl; or R₁₉And R₂₀Is phenyl, naphthyl or C₃-C₂₀Heteroaromatic compoundsEach of which is unsubstituted or substituted with one or more of the following groups: halogen, C₁-C₄Haloalkyl, C₁-C₂₀Alkoxy radical, C₁-C₁₂Alkyl, benzoyl or C₁-C₁₂An alkoxy group;

or R₁₉And R₂₀Together with the N atom to which they are attached form not interrupted or interrupted O, S or NR₁₇And the 5-or 6-membered saturated or unsaturated ring of (a), and the 5-or 6-membered saturated or unsaturated ring is unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy group, ═ O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO)R₂₃、NO₂Halogen, C₁-C₄-haloalkyl, CN, phenyl,Or C₃-C₂₀Cycloalkyl radical, C₃-C₂₀The cycloalkyl being not interrupted or interrupted by one or more O, S, CO or NR₁₇(ii) a Or R₁₉And R₂₀Together with the N atom to which they are attached form a heteroaromatic ring system, which ring system is unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C₁-C₂₀Alkoxy group, ═ O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO)R₂₃、Halogen, NO₂CN, phenyl or C₃-C₂₀Cycloalkyl radical, C₃-C₂₀The cycloalkyl being not interrupted or interrupted by one or more O, S, CO or NR₁₇；

or R₂₁And R₂₂Together with the N atom to which they are attached form not interrupted or interrupted O, S or NR₂₆And the 5-or 6-membered saturated or unsaturated ring, and the 5-or 6-membered saturated or unsaturated ring is not fused or the 5-or 6-membered saturated or unsaturated ring is fused with a benzene ring;

R₂₅is COOR₁₇、CONR₁₉R₂₀、(CO)R₁₇(ii) a Or R₂₅Having a function of R₁₇One of the meanings given; r₂₆Is hydrogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C₂-C₂₀Alkyl interrupted by one or more O or CO; or is phenyl-C₁-C₄Alkyl radical, C₃-C₈Cycloalkyl, uninterrupted or interrupted by one or more O or CO; or is (CO) R₁₉(ii) a Or is phenyl, which is unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl, halogen, C₁-C₄Haloalkyl, OR₁₇、SR₁₈、NR₁₉R₂₀Or

With the proviso that at least one group is present in the molecule

Preferred ones of the groups defined for the photoinitiator (E-1) of the structure of formula (IA) correspond to those given for the photoinitiator (E-1) of the structure of formula (VIII) as given below, except that each oxime ester group defined (e.g.) Are all replaced by the corresponding free oxime groups

Each oxime ester group may exist in two configurations (Z) or (E). The isomers may be separated by conventional methods, but mixtures of isomers may also be used, for example, as photo-starting materials. The invention therefore also relates to mixtures of configurational isomers of the photoinitiator (E-1) of the structure of the formula (VIII).

Preferred is a photoinitiator (E-1) having a structure represented by the formula (VIII) as defined above, wherein R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Independently of one another are hydrogen, C₁-C₂₀Alkyl, aryl, heteroaryl, and heteroaryl,COR₁₆Or NO₂Or R is₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Independently of one another together are

X is CO or a direct bond;

R₁₃is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OR₁₇、SR₁₈、COOR₁₇、CONR₁₉R₂₀Or PO (OC)_kH_2k+1)₂；

Or R₁₃Is C₂-C₂₀Alkyl interrupted by one or more O, S, NR₂₆Or CO;

or R₁₃Is phenyl or naphthyl, both unsubstituted or substituted by one or moreOr COR₁₆Substitution;

R₁₄is C₁-C₂₀Alkyl, phenyl or C₁-C₈An alkoxy group;

R₁₅is phenyl, naphthyl, C₃-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C₁-C₄Haloalkyl, OR₁₇、SR₁₈Or C₂-C₂₀Alkyl interrupted by one or more O or S; or each of which is passed through one or more C₁-C₂₀Alkyl substitution of the C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR₁₇、CONR₁₉R₂₀Phenyl, C₃-C₈Cycloalkyl radical, C₃-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₄-C₂₀Heteroaryloxycarbonyl radical, OR₁₇、SR₁₈、NR₁₉R₂₀Or PO (OC)_kH_2k+1)₂；

Or R₁₅Is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: OR (OR)₁₇、SR₁₈、C₃-C₈Cycloalkyl radical, C₃-C₂₀Heteroaryl, NR₁₉R₂₀、COOR₁₇、CONR₁₉R₂₀Or PO (OC)_kH_2k+1)₂；

R'₁₄Having a function of R₁₄One of the meanings given;

R'₁₅having a function of R₁₅One of the meanings given;

R₁₆is phenyl, unsubstituted or substituted with one or more of the following groups: OR (OR)₁₇、SR₁₈、NR₁₉R₂₀Or interrupted by one or more O, S or NR₂₆C of (A)₂-C₂₀Alkyl, or R₁₆Is phenyl, which is substituted by one or more C₁-C₂₀Alkyl substitution of the C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR₁₇、CONR₁₉R₂₀Phenyl, C₃-C₈Cycloalkyl radical, C₃-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₄-C₂₀Heteroaryloxycarbonyl radical, OR₁₇、SR₁₈Or NR₁₉R₂₀；

Or R₁₆Is C₁-C₂₀Alkyl, unsubstituted or substituted with: halogen, phenyl, OH, SH, CN, C₃-C₆Alkenyloxy, OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (CO) - (C)₁-C₄Alkyl) or (CO) O (C)₁-C₄Alkyl groups);

R₁₇is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (C)₁-C₄Alkyl group), (CO) O (C)₁-C₄Alkyl group), C₃-C₂₀Cycloalkyl or C interrupted by one or more O₃-C₂₀A cycloalkyl group; or

R₁₇Is C₂-C₂₀Alkyl interrupted by one or more O;

R₁₈via (CO) OR₁₇A substituted methyl group;

R₁₉and R₂₀Independently of one another hydrogen, phenyl, C₁-C₂₀Alkyl radical, C₁-C₈Alkanoyl or C₁-C₈An alkanoyloxy group;

or R₁₉And R₂₀Together with the N atom to which they are attached form a heteroaromatic ring system which is unsubstituted or substitutedSubstitution;

with the proviso that at least one group is present in the moleculeOr

It is important to note that the photoinitiator (E-1) of the structure represented by the formula (VIII) as defined above, wherein R is₁、R₂、R₅、R₆、R₇And R₈Independently of one another are hydrogen,COR₁₆Or NO₂，R₃And R₄Together are

R₉、R₁₀、R₁₁And R₁₂Is hydrogen;

x is a direct bond;

R₁₃is C₁-C₂₀An alkyl group;

R₁₄is C₁-C₂₀An alkyl group;

R₁₅is C₁-C₂₀Alkyl OR phenyl groups, via one OR more OR₁₇Or C₁-C₂₀Alkyl substitution;

R₁₆is phenyl, which is substituted by one or more C₁-C₂₀Alkyl OR OR₁₇Substitution; and is

R₁₇C unsubstituted or substituted by one or more halogen₁-C₂₀Alkyl or C interrupted by one or more O₂-C₂₀An alkyl group;

with the proviso that at least one group is present in the molecule

The object of the present invention is further a photoinitiator (E-1) of the structure represented by formula (VIII) as defined above, wherein R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Independently of one another, hydrogen, or R₁And R₂、R₃And R₄Or R₅And R₆Independently of one another together are

With the proviso that R₁And R₂、R₃And R₄Or R₅And R₆At least one pair of them is

Or R₂Is composed ofCOR₁₆、NO₂Or

Or R₇Is composed ofOr COR₁₆；

R₉、R₁₁And R₁₂Is hydrogen;

R₁₀is hydrogen, OR₁₇Or COR₁₆；

X is CO or a direct bond;

R₁₃is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, R₁₇、OR₁₇、SR₁₈Or PO (OC)_kH_2k+1)₂；

Or R₁₃Is C₂-C₂₀Alkyl interrupted by one or more O;

or R₁₃Is phenyl;

k is an integer of 2;

R₁₄is C₁-C₂₀Alkyl or thienyl;

R₁₅is phenyl OR naphthyl, each of which is unsubstituted OR substituted by one OR more OR₁₇Or C₁-C₂₀Alkyl substitution; or R₁₅Is thienyl, hydrogen, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: OR (OR)₁₇、SR₁₈、C₃-C₈Cycloalkyl, NR₁₉R₂₀Or COOR₁₇；

Or R₁₅Is C₂-C₂₀Alkyl radicals interrupted by SO₂；

R₁₆Is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR (OR)₁₇、SR₁₈、NR₁₉R₂₀Or C₁-C₂₀An alkyl group;

or R₁₆Is thienyl;

R₁₇is hydrogen, C₁-C₈Alkanoyl radical, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, O (CO) - (C)₁-C₄Alkyl), O (CO) - (C)₂-C₄) C with alkenyl or interrupted by one or more O₃-C₂₀A cycloalkyl group;

or R₁₇Is C₂-C₂₀Alkyl interrupted by one or more O;

R₁₈is C₃-C₂₀Cycloalkyl radical, C₁-C₂₀Alkyl, unsubstituted or substituted by one or more OH, O (CO) - (C)₂-C₄) Alkenyl OR (CO) OR₁₇Substitution;

or R₁₈Is phenyl, unsubstituted or substituted with one or more halogens;

R₁₉and R₂₀Independently of one another are C₁-C₈Alkanoyl or C₁-C₈An alkanoyloxy group;

or R₁₉And R₂₀Together with the N atom to which they are attached form a 5-or 6-membered saturated ring interrupted by O;

with the proviso that at least one group is present in the molecule

Examples of compounds of the invention are compounds of formulae (Ia) - (Ig) as defined above. Of interest are compounds of formula (Ia), (Ib), (Ic), in particular of formula (Ia) or (Ic), or of formula (Ia), (Ic) or (Id), in particular of formula (Ia).

For example, R₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Independently of one another are hydrogen,Or COR₁₆Or R is₁And R₂、R₂And R₃、R₃And R₄Or R₅And R₆、R₆And R₇、R₇And R₈Independently of one another together are

For example, R₃And R₄Or R₁And R₂Together areOr R₃And R₄And R₅And R₆Together areR₃And R₄Especially together are

For example, R₁、R₅、R₆And R₈Is hydrogen.

R₇In particular hydrogen,Or COR₁₆. Or R₇Is composed ofOr COR₁₆Especially of

R₂In particular toCOR₁₆OrOr R₂And R₁Together areR₂Especially COR₁₆。

X is preferably a direct bond.

For example, R₉、R₁₀、R₁₁And R₁₂Independently of one another are hydrogen, C₁-C₂₀Alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: c₁-C₆Alkyl, halogen, OR₁₇Or SR₁₈(ii) a Or R₉、R₁₀、R₁₁And R₁₂Independently of one another, halogen, OR₁₇、SR₁₈Or NR₁₉R₂₀Wherein the substituent OR₁₇、SR₁₈Or NR₁₉R₂₀Optionally via a group R₁₇、R₁₈、R₁₉And/or R₂₀Form a 5-or 6-membered ring with one carbon atom of the naphthyl ring; or R₉、R₁₀、R₁₁And R₁₂Independently of one another areOr COR₁₆。

Specifically, for example, R₉、R₁₀、R₁₁And R₁₂Independently of one another are hydrogen, C₁-C₂₀Alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: c₁-C₆Alkyl, halogen, OR₁₇Or SR₁₈(ii) a Or R₉、R₁₀、R₁₁And R₁₂Independently of one another, halogen, OR₁₇、SR₁₈Or NR₁₉R₂₀(ii) a Or R₉、R₁₀、R₁₁And R₁₂Independently of one another areOr COR₁₆。

For example, R₉、R₁₀、R₁₁And R₁₂Independently of one another are hydrogen, C₁-C₂₀Alkyl, unsubstituted phenyl or through one or more C₁-C₆Alkyl-substituted phenyl; or R₉、R₁₀、R₁₁And R₁₂Independently of one another areOr COR₁₆。

In another embodiment, for example, R₉、R₁₀、R₁₁And R₁₂Independently of one another are hydrogen, C₁-C₂₀Alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: c₁-C₆Alkyl, halogen, OR₁₇Or SR₁₈(ii) a Or R₉、R₁₀、R₁₁And R₁₂Independently of one another, halogen, OR₁₇、SR₁₈Or NR₁₉R₂₀Wherein the substituent OR₁₇、SR₁₈Or NR₁₉R₂₀Optionally via a group R₁₇、R₁₈、R₁₉And/or R₂₀And one carbon atom of the naphthyl ring to form a 5-or 6-membered ring.

Also, for example, R₉、R₁₀、R₁₁And R₁₂Are connected with each otherIndependently of one another is hydrogen, C₁-C₂₀Alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: c₁-C₆Alkyl, halogen, OR₁₇Or SR₁₈Or R is₉、R₁₀、R₁₁And R₁₂Independently of one another, halogen, OR₁₇、SR₁₈、NR₁₉R₂₀Or COR₁₆。

Or for example, R₉、R₁₀、R₁₁And R₁₂Independently of one another are hydrogen, C₁-C₂₀Alkyl, unsubstituted phenyl or phenyl substituted with one or more of the following groups: c₁-C₆Alkyl, halogen, OR₁₇Or SR₁₈Or R is₉、R₁₀、R₁₁And R₁₂Independently of one another, halogen, OR₁₇、COR₁₆Or NR₁₉R₂₀。

Preferably, R₉、R₁₁And R₁₂Is hydrogen and R₁₀Is hydrogen, OR₁₇Or COR₁₆。

R₁₃Is, for example, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, COOR₁₇Or CONR₁₉R₂₀(ii) a Or R₁₃Is C₂-C₂₀Alkyl interrupted by one or more O, S, SO₂、NR₂₆Or CO, or is C₂-C₁₂Alkenyl optionally interrupted by one or more O, CO or NR₂₆Or R is₁₃Is C₃-C₁₀Cycloalkyl optionally interrupted by one or more O, S, CO, NR₂₆Or R is₁₃Is phenyl or naphthyl, both unsubstituted or substituted with one or more of the following groups: OR (OR)₁₇、SR₁₈、NR₁₉R₂₀、COR₁₆、NO₂Halogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C₂-C₂₀Alkyl interrupted by one or more O; or is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, R₁₇、COOR₁₇、OR₁₇、SR₁₈、CONR₁₉R₂₀Or PO (OC)_kH_2k+1)₂(ii) a Or is C₂-C₂₀Alkyl interrupted by one or more O.

Furthermore, R₁₃Is, for example, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, R₁₇、COOR₁₇、OR₁₇、SR₁₈、CONR₁₉R₂₀Or PO (OC)_kH_2k+1)₂(ii) a Or is C₂-C₂₀Alkyl interrupted by one or more O; or is C₂-C₁₂Alkenyl radical, C₃-C₁₀A cycloalkyl group; or R₁₃Is phenyl or naphthyl, both unsubstituted or substituted with one or more of the following groups: OR (OR)₁₇、SR₁₈、NR₁₉R₂₀、COR₁₆、NO₂Halogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C₂-C₂₀Alkyl interrupted by one or more O.

In another embodiment, R₁₃Is, for example, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, R₁₇、OR₁₇、SR₁₈Or PO (OC)_kH_2k+1)₂(ii) a Or is C₂-C₂₀Alkyl interrupted by one or more O; or is C₂-C₁₂Alkenyl radical, C₃-C₁₀Cycloalkyl, phenyl or naphthyl.

Or R₁₃Is, for example, C₁-C₂₀Alkyl radical ofSubstituted or substituted with one or more of the following groups: halogen, R₁₇、OR₁₇、SR₁₈Or PO (OC)_kH_2k+1)₂(ii) a Or is C₂-C₂₀Alkyl interrupted by one or more O; or is phenyl, C₂-C₁₂Alkenyl or C₃-C₁₀A cycloalkyl group.

Or R₁₃Is, for example, C₁-C₂₀Alkyl, phenyl, C₂-C₁₂Alkenyl or C₃-C₁₀A cycloalkyl group.

Or R₁₃Is, for example, C₁-C₂₀Alkyl radical, C₂-C₁₂Alkenyl or C₃-C₁₀A cycloalkyl group.

Preferably, R₁₃Is C₁-C₂₀Alkyl, especially C₁-C₈Alkyl radicals, for example the 2-ethylhexyl radical.

R₁₄Is, for example, hydrogen, C₃-C₈Cycloalkyl radical, C₂-C₅Alkenyl radical, C₁-C₂₀Alkoxy or C₁-C₂₀Alkyl, unsubstituted or substituted with one or more halogen or phenyl; or R₁₄Is phenyl or naphthyl, both unsubstituted or substituted with one or more of the following groups: c₁-C₆Alkyl radical, C₁-C₄Haloalkyl, halogen, OR₁₇、SR₁₈And/or NR₁₉R₂₀(ii) a Or R₁₄Is C₃-C₅Heteroaryl, e.g. thienyl, or is C₁-C₈Alkoxy, benzyloxy, or phenoxy.

Or R₁₄Is, for example, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more halogen or phenyl;

or R₁₄Is C₃-C₅Heteroaryl (e.g., thienyl) or phenyl which is unsubstituted or substituted with one or more of the following: c₁-C₆Alkyl radical, C₁-C₄Haloalkyl, halogen, OR₁₇、SR₁₈And/or NR₁₉R₂₀(ii) a Or R₁₄Is C₁-C₈Alkoxy, benzyloxy, or phenoxy.

In another embodiment, R₁₄Is represented by C₁-C₂₀Alkyl, unsubstituted or substituted with phenyl; or R₁₄Is phenyl, unsubstituted or substituted by one or more C₁-C₆Alkyl substitution.

Preferably, R₁₄Is C₁-C₂₀Alkyl radical, C₃-C₅Heteroaryl (e.g. thienyl), or phenyl, especially C₁-C₂₀Alkyl or thienyl, especially C₁-C₈An alkyl group.

R₁₅Is, for example, C₆-C₂₀Aryl or C₅-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C₁-C₄Haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀、C₁-C₂₀An alkyl group; or R₁₅Is hydrogen, C₃-C₈Cycloalkyl radical, C₃-C₈Cycloalkyl optionally interrupted by one or more O, CO or NR₂₆(ii) a Or R₁₅Is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OR₁₇、C₃-C₈Cycloalkyl radical, C₅-C₂₀Heteroaryl group, C₈-C₂₀Phenoxycarbonyl group, C₅-C₂₀Heteroaryloxy-carbonyl, NR₁₉R₂₀、COOR₁₇、CONR₁₉R₂₀、PO(OC_kH_2k+1)₂、Phenyl or phenyl substituted with: halogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, OR₁₇Or NR₁₉R₂₀(ii) a Or R₁₅Is C₂-C₂₀Alkyl interrupted by one or more O, S or SO₂Or R is₁₅Is C₂-C₂₀Alkanoyl, benzoyl, C₂-C₁₂Alkoxycarbonyl, phenoxycarbonyl, CONR₁₉R₂₀、NO₂Or C₁-C₄A haloalkyl group.

Furthermore, R₁₅Is, for example, hydrogen, C₆-C₂₀Aryl, especially phenyl or naphthyl, each unsubstituted or substituted by C₁-C₁₂Alkyl substitution; or is C₃-C₅Heteroaryl, such as thienyl; or is C₃-C₈Cycloalkyl radical, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: OR (OR)₁₇、SR₁₇、C₃-C₈-cycloalkyl, NR₁₉R₂₀Or COOR₁₇(ii) a Or R₁₅Is C₂-C₂₀Alkyl interrupted by one or more O or SO₂。

Of interest is the photoinitiator (E-1) having a structure represented by the formula (VIII), wherein R₁₅Is, for example, hydrogen, phenyl, naphthyl, each of which is unsubstituted or C₁-C₈Alkyl substitution; or R₁₅Is thienyl, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: OR (OR)₁₇、SR₁₇、C₃-C₈-cycloalkyl, NR₁₉R₂₀Or COOR₁₇(ii) a Or R₁₅Is C₂-C₂₀Alkyl interrupted by one or more O or SO₂。

R₁₅Especially, for example, C₃-C₈Cycloalkyl or C₁-C₂₀Alkyl, especially C₁-C₂₀Alkyl, especially C₁-C₁₂An alkyl group.

R'₁₄And R'₁₅Are preferably as described above for R, respectively₁₄And R₁₅Is given byIn (1).

X₁For example O, S or SO, for example O or S, especially O.

R₁₆Is, for example, C₆-C₂₀Aryl (especially phenyl or naphthyl, especially phenyl) or C₅-C₂₀Heteroaryl (especially thienyl), each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C₁-C₄Haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀Or C interrupted by one or more O₁-C₂₀An alkyl group; or each of which is passed through one or more C₁-C₂₀Alkyl substitution of the C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR₁₇、CONR₁₉R₂₀Phenyl, C₃-C₈Cycloalkyl radical, C₅-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₅-C₂₀Heteroaryloxycarbonyl radical, OR₁₇、SR₁₈Or NR₁₉R₂₀(ii) a Or R₁₆Is hydrogen, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, C₃-C₆Alkenyloxy, OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (CO) - (C)₁-C₄Alkyl), O (CO) -phenyl, (CO) OH or (CO) O (C)₁-C₄Alkyl groups); or R₁₆Is C₂-C₁₂Alkyl interrupted by one or more O; or is (CH)₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C₁-C₈Alkyl group), C₂-C₁₂Alkenyl or C₃-C₈Cycloalkyl, and n is 1 to 20, such as 1 to 12 or 1 to 8, especially 1 or 2.

Furthermore, R₁₆Is, for example, phenyl or naphthyl, especially phenyl, thienyl or carbazole, each of which is unsubstituted or substituted with one or more of the following groups: phenyl radicalHalogen, C₁-C₄Haloalkyl, OR₁₇、SR₁₈、NR₁₉R₂₀Or C₁-C₂₀An alkyl group; or R₁₆Is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, phenyl, OH, SH, C₃-C₆Alkenyloxy, OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (CO) - (C)₁-C₄Alkyl), O (CO) -phenyl, (CO) OH or (CO) O (C)₁-C₄Alkyl groups); or R₁₆Is C₂-C₁₂Alkyl interrupted by one or more O; or is (CH)₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C₁-C₈Alkyl group), C₂-C₁₂Alkenyl or C₃-C₈Cycloalkyl, and n is 1 to 20, such as 1 to 12 or 1 to 8, especially 1 or 2.

Furthermore, R₁₆Is, for example, phenyl or naphthyl, especially phenyl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C₁-C₄Haloalkyl, OR₁₇、SR₁₈、NR₁₉R₂₀Or C₁-C₂₀An alkyl group; or R₁₆Is C₃-C₅Heteroaryl, especially thienyl.

R₁₆In particular, for example, phenyl, which is unsubstituted or substituted by one or more of the following groups: OR (OR)₁₇、SR₁₈、NR₁₉R₂₀Or C₁-C₂₀Alkyl, or R₁₆Is thienyl.

Preferably, R₁₆Are, for example, phenyl or naphthyl, each of which is unsubstituted or substituted by one or more C1-C20 alkyl groups.

R₁₆Especially phenyl, which is substituted by one or more C₁-C₂₀Alkyl substitution.

R₁₇Is, for example, hydrogen, phenyl-C₁-C₃Alkyl radical, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OH, OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (CO) - (C)₁-C₄Alkyl), O (CO) - (C)₂-C₄) Alkenyl, O (CO) -phenyl, (CO) OH, (CO) O (C)₁-C₄Alkyl group), C₃-C₂₀Cycloalkyl or C interrupted by one or more O₃-C₂₀A cycloalkyl group; or R₁₇Is C₂-C₂₀Alkyl interrupted by one or more O; is (CH)₂CH₂O)_n+1H、(CH₂CH₂O)_n(CO)-(C₁-C₈Alkyl group), C₁-C₈Alkanoyl radical, C₂-C₁₂Alkenyl radical, C₃-C₆Alkenoyl or C₃-C₂₀Cycloalkyl optionally interrupted by one or more O; or R₁₇Is benzoyl, unsubstituted or substituted by one or more C₁-C₆Alkyl, halogen, OH or C₁-C₃Alkoxy substitution; or R₁₇Is phenyl, naphthyl or C₅-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, OH, C₁-C₁₂Alkyl radical, C₁-C₁₂Alkoxy, CN, NO₂phenyl-C₁-C₃Alkoxy, phenoxy, C₁-C₁₂Alkylthio, phenylthio, N (C)₁-C₁₂Alkyl radical)₂Diphenyl-amino or

In another embodiment, R₁₇Is, for example, hydrogen, phenyl-C₁-C₃Alkyl radical, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, O (CO) - (C)₁-C₄Alkyl), O (CO) - (C)₂-C₄Alkenyl) or C interrupted by one or more O₂-C₂₀An alkyl group; or is C₁-C₈Alkanoyl radical, C₂-C₁₂Alkenyl radical, C₃-C₆Alkenoyl, C interrupted by one or more O' s₂-C₂₀Alkyl, C optionally interrupted by one or more O₃-C₂₀A cycloalkyl group; or is benzoyl, which is unsubstituted or substituted by one or more of the following groups: c₁-C₆Alkyl, halogen, OH or C₁-C₃An alkoxy group; or is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C₁-C₁₂Alkyl or C₁-C₁₂An alkoxy group.

R₁₇Also being, for example, hydrogen, phenyl-C₁-C₃Alkyl radical, C₁-C₈Alkanoyl radical, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, C₃-C₂₀Cycloalkyl, O (CO) - (C)₁-C₄Alkyl), O (CO) - (C)₂-C₄Alkenyl) or C interrupted by one or more O₂-C₂₀Alkyl, or R₁₇Is C₂-C₂₀Alkyl interrupted by one or more O.

R₁₇Especially hydrogen, C₁-C₈Alkanoyl radical, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: o (CO) - (C)₁-C₄Alkyl), O (CO) - (C)₂-C₄Alkenyl) or C interrupted by one or more O₂-C₂₀Alkyl, or R₁₇Is C₂-C₂₀Alkyl interrupted by one or more O.

R₁₈Is, for example, C₃-C₂₀Cycloalkyl which is not interrupted or interrupted by one or more O; or R₁₈Is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: OH, O (CO) - (C)₂-C₄) Alkenyl, O (CO) - (C)₁-C₄Alkyl) OR (CO) OR₁₇(ii) a Or R₁₈Is C₂-C₂₀Alkyl interrupted by one or more O, S, CO, NR₂₆Or COOR₁₇(ii) a Or R₁₈Is C₂-C₈Alkanoyl or C₃-C₆Alkenoyl, benzoyl; or R₁₈Is phenyl, naphthyl or C₃-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: halogen, C₁-C₁₂Alkyl radical, C₁-C₄Haloalkyl, C₁-C₁₂Alkoxy or NO₂。

In another embodiment, R₁₈Is, for example, C₃-C₂₀Cycloalkyl radical, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: OH, O (CO) - (C)₂-C₄) Alkenyl, O (CO) - (C)₁-C₄Alkyl) OR (CO) OR₁₇(ii) a Or R₁₈Is phenyl or naphthyl, each of which is unsubstituted or substituted by one or more halogen or C₁-C₁₂Alkyl, especially halogen.

R₁₈Is, for example, C₁-C₂₀Alkyl radical, C₂-C₁₂Alkenyl radical, C₃-C₂₀Cycloalkyl, phenyl-C₁-C₃Alkyl radical, C₂-C₈Alkanoyl, benzoyl, phenyl or naphthyl.

For example, R₁₈Is C₁-C₂₀Alkyl substituted with one or more of the following groups: OH, O (CO) - (C)₂-C₄) Alkenyl, O (CO) - (C)₁-C₄Alkyl) OR (CO) OR₁₇Or R is₁₈Is phenyl, which is substituted with one or more halogens.

Preferably, R₁₈Is C₁-C₈Alkyl, which is substituted as defined above.

For example, R₁₉And R₂₀Independently of one another are hydrogen, C₁-C₂₀Alkyl radical, C₂-C₄Hydroxyalkyl radical, C₃-C₂₀Cycloalkyl, phenyl-C₁-C₃Alkyl, phenyl or naphthyl, C₁-C₈Alkanoyl radical, C₁-C₈Alkanoyloxy, C₃-C₁₂Alkenoyl or benzoyl; or R₁₉And R₂₀Together with the N atom to which they are attached form an optional hetero ring of O, S or NR₁₇A 5-or 6-membered saturated or unsaturated ring of (a); or R₁₉And R₂₀Together with the N atom to which they are attached form a heteroaromatic ring system, which ring system is unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, or

Also, for example, R₁₉And R₂₀Independently of one another are hydrogen, C₁-C₂₀Alkyl radical, C₂-C₄Hydroxyalkyl radical, C₃-C₂₀Cycloalkyl, phenyl-C₁-C₃Alkyl radical, C₁-C₈Alkanoyl radical, C₁-C₈Alkanoyloxy, C₃-C₁₂Alkenoyl or benzoyl; or R₁₉And R₂₀Together with the N atom to which they are attached form an optionally interrupted O or NR₁₇A 5-or 6-membered saturated ring of (a); or R₁₉And R₂₀Together with the N atom to which they are attached form a carbazole ring.

For example, R₁₉And R₂₀Independently of one another are hydrogen, C₁-C₂₀Alkyl radical, C₂-C₄Hydroxyalkyl radical, C₃-C₂₀Cycloalkyl, phenyl-C₁-C₃Alkyl radical, C₁-C₈Alkanoyl radical, C₁-C₈Alkanoyloxy, C₃-C₁₂Alkenoyl or benzoyl; or R₁₉And R₂₀Together with the N atom to which they are attached form an optionally interrupted O or NR₁₇A 5-or 6-membered saturated ring.

Preferably, R₁₉And R₂₀Independently of one another are C₁-C₈Alkanoyl radical、C₁-C₈An alkanoyloxy group; or R₁₉And R₂₀Together with the N atom to which they are attached form a morpholine ring.

For example, R₂₁And R₂₂Independently of one another are hydrogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C₃-C₁₀Cycloalkyl or phenyl; or R₂₁And R₂₂Together with the N atom to which they are attached form a morpholine ring. R₂₁And R₂₂In particular independently of one another hydrogen or C₁-C₂₀An alkyl group.

R₂₃Is, for example, hydrogen, OH, phenyl or C₁-C₂₀An alkyl group. R₂₃Especially hydrogen, OH or C₁-C₄An alkyl group.

R₂₄As for R₁₉And R₂₀Given below. R₂₅As for R₁₇Given below.

R₂₆Is, for example, hydrogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C₂-C₂₀Alkyl interrupted by one or more O or CO; or is phenyl-C₁-C₄Alkyl radical, C₃-C₈Cycloalkyl optionally interrupted by one or more O or CO; or is (CO) R₁₉Or phenyl, unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl, halogen, C₁-C₄Haloalkyl, OR₁₇、SR₁₈、NR₁₉R₂₀。

Or R₂₆Denotes, for example, hydrogen, C₁-C₂₀Alkyl radical, C₁-C₄A haloalkyl group; is phenyl-C₁-C₄Alkyl radical, C₃-C₈Cycloalkyl, (CO) R₁₉Or phenyl, unsubstituted or substituted by one or more C₁-C₂₀Alkyl substitution. Furthermore, R₂₆Is, for example, hydrogen or C₁-C₂₀Alkyl, especially C₁-C₄An alkyl group.

Examples of the photoinitiator (E-1) having the structure represented by formula (VIII) of the present invention are shown below:

use of the photoinitiator (E-1) having a structure represented by formula (VIII) for photopolymerizing a composition comprising at least one ethylenically unsaturated photopolymerizable compound.

In the specific embodiment of the present invention, the photoinitiator (E-1) having a structure represented by formula (VIII) is used in an amount of 2 to 20 parts by weight, preferably 2 to 15 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resins (C). When the photoinitiator (E-1) having the structure represented by formula (VIII) is used, ITO sputtering suitability of the pixel layer obtained from the blue photosensitive resin composition is excellent.

The photoinitiator (E) may further comprise other radical type photoinitiators (E-2).

The other radical type photoinitiator (E-2) may be selected from acetophenone compounds (acetophenones), bisimidazoles (diimidazoles), acyloximes (acyloximes) or combinations thereof.

The acetophenone compound is selected from p-dimethylaminoacetophenone, α '-dimethoxyazoxyacetophenone, 2' -dimethyl-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone [2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone ], 2-benzyl-2-nitrogen, N-dimethylamine-1- (4-morpholinophenyl) -1-butanone [2-benzyl-2-N, n-dimethyllamino-1- (4-morpholinophenyl) -1-butanone ].

The above-mentioned diimidazole compounds are selected from the group consisting of 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-methylphenyl) -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 oxime compound is selected from the group consisting of Ethanone,1- [9-ethyl-6- (2-methylbenzoyl) -9-hydro-carbazol-3-substituent ] -,1- (O-acetyl oxime) [ Ethanone,1- [9-ethyl-6- (2-methylbenzoxy) -9H-carbazol-3-yl ] -,1- (O-acetyl oxime), such as the product sold under the name CGI-242 by Ciba Specialty Chemicals, having the structure shown in formula (32) below, 1- [4- (phenylthio) phenyl ] -octane-1, 2-dione2- (O-benzoyl oxime) [1- [4- (benzoxy) phenyl ] -heptane-1,2-dione2- (O-benzoyl oxime), for example, a product having a trade name CGI-124 manufactured by Ciba specialty Chemicals, and having a structure represented by the following formula (33) ], Ethanone,1- [9-ethyl-6- (2-chloro-4-benzyl-thio-benzoyl) -9-hydro-carbazol-3-substituent ] -,1- (oxy-acetoxy oxime) [ Ethanone,1- [9-ethyl-6- (2-chloro-4-benzyl-thio-benzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyl oxide, manufactured by Asahi electro chemical Co., Ltd., having a structure represented by the following formula (34) ]:

preferably, the other radical type photoinitiator (E-2) is 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-propanone, 2-benzyl-2-aza, aza-dimethylamine-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 (dimethylamine) benzophenone [4, 4' -bis (dimethylamino) benzophenone ], 4 '-bis (diethylamine) benzophenone [4, 4' -bis (dimethylamino) 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 ethers (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-trimethyi-phenyl-diphenyl-phosphinoxide) and bis- (2, 6-dimethoxybenzoyl) -2,4, 4-trimethylphenylphosphine oxide [ bis- (2, 6-dimethy-phenyl) -2,4, 4-trimethyi-phenyl-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), and tris (trichloromethyl) -s-triazine [ tris (trichloromethyl) -s-triazine ]; and peroxides such as di-tert-butyl peroxide (di-tert-butyl peroxide). Among them, benzophenone compounds are preferable, and 4, 4' -bis (diethylamine) benzophenone is more preferable.

When the photoinitiator (E-1) having the structure represented by formula (VIII) and the other radical type photoinitiator (E-2) are used together, the ITO sputtering suitability of the pixel layer obtained from the blue photosensitive resin composition is better.

The blue photosensitive resin composition for a color filter of the present invention is usually prepared by dissolving the components other than the organic pigment (a) in the organic solvent (F) to prepare a liquid composition, and then adding the organic pigment (a) to the liquid composition and uniformly mixing the mixture. The organic solvent (F) is selected from the group consisting of a soluble dye (B), an alkali-soluble resin (C), an ethylenically unsaturated compound (D) and a photoinitiator (E), and is not reactive with these components and has a suitable volatility.

In the specific embodiment of the present invention, the organic solvent (F) is used in an amount ranging from 500 parts by weight to 5,000 parts by weight, based on 100 parts by weight of the total amount of the alkali-soluble resins (C); preferably 550 to 4500 parts by weight; more preferably 600 to 4000 parts by weight.

In addition, the organic solvent (F) may be the same as the solvent used for preparing the alkali-soluble resin (C), and will not be described herein. Preferably, the organic solvent (F) is selected from propylene glycol methyl ether acetate or ethyl 3-ethoxypropionate.

Preferably, the blue photosensitive resin composition for a color filter of the present invention further comprises a functional additive (G) according to an embodiment of the present invention.

The functional additives (G) may be used alone or in combination, and include, but are not limited to, fillers such as glass and aluminum; alkali-soluble resins (polymeric compounds other than C) such as polyvinyl alcohol, polyethylene glycol monoalkyl ether, and polyalkylfluoroacrylate; adhesion promoters such as vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane 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-chlorophenylazide and alkoxyphenone; and anti-agglomeration agents such as sodium polyacrylate; and thermal acid generators such as Irgacure 250 and Irgacure 261 (manufactured by Ciba specialty Chemicals Co., Ltd.).

The invention also provides a method for manufacturing a color filter, which uses the blue photosensitive resin composition for the color filter to form a pixel layer.

The invention also provides a color filter which is manufactured by the method.

Preferably, the color filter includes a pixel layer, and the pixel layer is formed using the photosensitive resin composition for a color filter.

The method for forming a color filter of the present invention is a method for forming a color filter, which comprises applying the photosensitive composition for a color filter mixed in a solution state onto a substrate by an application method such as spin coating, cast coating, ink-jet coating (ink-jet), or roll coating. After coating, most of the solvent is removed by drying under reduced pressure, and then the solvent is removed by prebaking (pre-bake) to form a prebaked coating film. 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 performed at a pressure of 0 to 200mmHg for 1 to 60 seconds, and prebaking is performed 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 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 used for liquid crystal display devices and the like, and substrates to which transparent conductive films are attached to these glasses; or a substrate (e.g., silicon substrate) for a photoelectric conversion device such as a solid-state imaging device. These substrates are generally formed by first forming a black matrix (black matrix) that separates the colored layers of each pixel.

Further, specific examples of the developing solution may 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 then the pattern is air-dried with compressed air or compressed nitrogen.

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 light-cured 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 applied and then fired, thereby obtaining a color filter for a liquid crystal display.

The invention also provides a liquid crystal display device comprising the color filter.

The liquid crystal display module 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 with a sealing agent, a liquid crystal is filled in the gap defined by the substrate surface and the sealing agent, and the filling hole is sealed to constitute 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 surfaces of the respective substrates constituting the liquid crystal cell to obtain a liquid crystal display module.

The present invention will now be described in detail by way of the following examples, which are not intended to limit the invention to the forms disclosed herein.

Preparation examples 1 to 5: synthesis of monomer represented by the formula (III)

According to Japanese patent laid-open No. 10-226669, a monomer represented by the formula (III) was synthesized from allyl alcohol and the corresponding respective α -hydroxymethylacrylate (HMA-R) as shown in Table 1 using 1, 4-diazabicyclo [2.2.2] octane as a catalyst.

Table 1:

synthesis example 1: method for producing first alkali-soluble resin (C-1-1)

A stirrer, a thermometer, a condenser tube and a nitrogen inlet were provided in the four-necked flask, and nitrogen was introduced. Then, 100 parts by weight of propylene glycol monomethyl ether acetate was added, and the temperature was raised to 100 ℃. Next, 5 parts by weight of α -allyloxymethylmethacrylate (AMA-M) obtained in preparation example 1, 40 parts by weight of methacrylic acid (abbreviated as MAA), 10 parts by weight of 2-hydroxyethyl methacrylate (abbreviated as HEMA), 40 parts by weight of benzyl methacrylate (abbreviated as BzMA), 5 parts by weight of isobornyl methacrylate (abbreviated as ibama) and 4 parts by weight of azobisisovaleronitrile were dissolved in 100 parts by weight of propylene glycol monomethyl ether acetate, and the mixed solution was dropwise added to a four-necked flask over 2 hours. After 6.5 hours at 100 ℃, 15 parts by weight of glycidyl methacrylate (abbreviated as GMA) and 10 parts by weight of 6, 7-epoxyheptyl methacrylate (abbreviated as EP-MA) were charged into a four-necked conical flask filled with nitrogen, and the temperature was raised to 110 ℃. After 6 hours of reaction, the first alkali-soluble resin (C-1-1) of Synthesis example 1 was obtained.

Synthesis examples 2 to 6: method for producing first alkali-soluble resins (C-1-2) to (C-1-6)

Synthesis examples C-1-2 to C-1-6A first alkali-soluble resin (C-1) was prepared in the same procedure as in Synthesis example C-1-1, except that: the kinds of the components, the amounts used and the reaction conditions were changed and are described in detail in Table 2.

Table 2: synthesis example of first alkali-soluble resin (C-1)

Table 2 (continuation)

In table 2:

synthesis example 7: method for producing second alkali-soluble resin (C-2-1)

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-neck flask, and the feeding rate was controlled at 25 parts by weight/min, and the temperature was maintained in the range of 100 ℃ to 110 ℃ to react for 15 hours, thereby obtaining a pale yellow transparent mixed solution having a solid content of 50 wt%.

Then, 100 parts by weight of the above-mentioned 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 added at the same time, and heated to 110 ℃ to 115 ℃ to react for 2 hours, so that a second alkali-soluble resin (C-2-1) having an acid value of 98.0mgKOH/g and a number average molecular weight of 1,623 was obtained.

Synthesis example 8: method for producing second alkali-soluble resin (C-2-2)

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 second alkali-soluble resin (C-2-2) having an acid value of 99.0mgKOH/g and a number average molecular weight of 2,162.

Synthesis example 9: method for producing second alkali-soluble resin (C-2-3)

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 ℃ for 9 hours, whereby 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 second alkali-soluble resin (C-2-3) having an acid value of 102mgKOH/g and a number average molecular weight of 2,589.

Synthesis example 10: method for producing third alkali-soluble resin (C-3-1)

1 part by weight of 2,2' -azobisisobutyronitrile, 240 parts by weight of propylene glycol methyl ether acetate, 30 parts by weight of 2-methacryloylethoxy succinate (abbreviated as HOMS), 10 parts by weight of 2-hydroxyethyl methacrylate (abbreviated as HEMA), 30 parts by weight of isobornyl methacrylate (abbreviated as IBOMA), 10 parts by weight of butadiene and 20 parts by weight of styrene were placed in a round-bottomed flask equipped with a stirrer and a condenser, and the inside of the flask was filled with nitrogen gas. Then, the mixture was slowly stirred and heated to 80 ℃ to uniformly mix the reactants and carry out a polymerization reaction for 4 hours. Subsequently, the temperature was further raised to 100 ℃ and 0.5 part by weight of 2,2' -azobisisobutyronitrile was added. After polymerization for 1 hour, the third alkali-soluble resin (C-3-1) was obtained.

Synthesis example 11: method for producing third alkali-soluble resin (C-3-2)

A stirrer, a thermometer, a condenser tube and a nitrogen inlet were provided in the four-necked flask, and nitrogen was introduced. Then, 135 parts by weight of propylene glycol monomethyl ether acetate was added, and the temperature was raised to 100 ℃. Next, 15 parts by weight of methacrylic acid (abbreviated as MAA), 15 parts by weight of 2-methacryloyloxyethylsuccinate (abbreviated as HOMS), 30 parts by weight of benzyl methacrylate (abbreviated as BzMA), 20 parts by weight of isobornyl methacrylate (abbreviated as IBOMA), 20 parts by weight of styrene and 2.6 parts by weight of azobisisobutyronitrile were dissolved in 100 parts by weight of propylene glycol monomethyl ether acetate, and the mixed solution was dropwise added to a four-necked flask over 2 hours. After 5 hours of reaction at 100 ℃,10 parts by weight of glycidyl methacrylate (abbreviated as GMA) and 5 parts by weight of 6, 7-epoxyheptyl methacrylate were charged into a four-necked conical flask filled with nitrogen, and the temperature was raised to 110 ℃. After 6 hours of reaction, the third alkali-soluble resin (C-3-2) is obtained.

Example 1:

using 100 parts by weight of the first alkali-soluble resin (C-1-1) obtained in the above synthesis example, 50 parts by weight of the organic pigment (A-1), 10 parts by weight of the dye (B-1), and a compound represented by the formula (VII) (wherein t is 1, B is 3, C is 3, and Z is¹And Z²All are hydrogen) (hereinafter referred to as D-1-1)10 parts by weight, dipentaerythritol hexaacrylate (hereinafter referred to as D-2-1)40 parts by weight, E-1-12 parts by weight, and (1- [4- (phenylthio) phenyl ] acrylate]15 parts by weight of (E) -1, 2-octanedione 2- (O-benzoyloxime)) (hereinafter referred to as E-2-1), 500 parts by weight of ethyl3-ethoxypropionate (hereinafter referred to as F-1) as an organic solvent were added, and the mixture was dissolved and mixed in a shaking mixer to prepare a solutionThe photosensitive resin composition for a color filter was obtained, and the blue photosensitive resin composition for a color filter was evaluated in the following measurement and evaluation methods, and the results are shown in table 3.

Examples 2 to 13 and comparative examples 1 to 7:

examples 2 to 13 and comparative examples 1 to 7 were carried out by the same method as that for producing the blue photosensitive resin composition for a color filter in example 1 except that the kinds and the amounts of the raw materials used in the blue photosensitive resin composition for a color filter were changed in examples 2 to 13 and comparative examples 1 to 7, and the formulations and the following evaluation results were shown in tables 3 and 4.

Table 3: example Z of a blue photosensitive resin composition

Table 4: comparative example of blue photosensitive resin composition

In tables 3 and 4:

evaluation method:

and (3) comparison:

the photosensitive resin composition was applied by spin coating onto a glass substrate 100mm × 100mm, dried under reduced pressure at 100mmHg for 30 seconds, pre-baked at 80 deg.C for 2 minutes to form a pre-baked coating film 2.5 μm in thickness, and irradiated with 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 having a thickness of 2.0 μm was formed on the glass substrate.

From the obtained photosensitive resin layer, the luminance measured by the method shown in FIG. 1 and FIG. 2 was compared; 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 were parallel to each other, the measured luminance was A (cd/cm)²) (ii) a In addition, as shown in FIG. 2, when the polarization direction of the polarizing plate 3 and the polarization direction of the polarizing plate 2 were perpendicular to each other, the measured luminance was 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), and the evaluation criteria 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

Pigment dispersibility:

a photosensitive resin composition containing no photopolymerization initiator was prepared, and the composition was allowed to stand in a thermostatic bath at 40 ℃ for 7 days after completion of the preparation and then measured by a type E viscometer, and the evaluation criteria thereof were as follows.

Very good: the viscosity change rate is less than 15 percent

O: the viscosity change rate is less than 20 percent and is more than 15 percent

And (delta): the viscosity change rate is more than 20 percent and less than 25 percent

Gamma rays: 25% < viscosity change rate

Suitability for ITO sputtering:

ITO was vapor-deposited according to a conventional method (film thickness)The vapor deposition temperature was 200 ℃ C., and then the Ra value was measured by an atomic force microscope (SPA-400AFM, manufactured by Seiko electronics Co., Ltd.), and the evaluation criteria were as follows.

◎：Ra＜3nm

○：3nm＜Ra＜8nm

△：8nm＜Ra＜10nm

╳：10nm＜Ra

The above embodiments are merely illustrative of the principles and effects of the present invention, and do not limit the present invention. Modifications and variations of the above-described embodiments may be made by those skilled in the art without departing from the spirit of the invention.

Claims

1. A blue photosensitive resin composition for a color filter, comprising:

an organic pigment (A);

a dye (B);

an alkali-soluble resin (C);

an ethylenically unsaturated group compound (D);

a photoinitiator (E); and

an organic solvent (F);

wherein:

in the formula,

t represents a halogen atom;

a represents 0 or 1;

B⁸and B⁹Each independently represents C₁To C₁₀Straight chain alkyl group of (1), C₁To C₁₀Branched alkyl of C₃To C₃₀Cycloalkyl of (a), or-Q; wherein, C₁To C₁₀Straight chain alkyl group of (1), C₁To C₁₀Branched alkyl or C₃To C₃₀In the cycloalkyl radical having no hydrogen atomsSubstituted or unsubstituted by a substituent selected from the group consisting of hydroxy, halogen, -Q, -CH ═ CH₂and-CH ═ CH-B⁶The group consisting of; c₁To C₁₀Straight chain alkyl group of (1), C₁To C₁₀Branched alkyl or C₃To C₃₀Of cycloalkyl group of (2) — CH₂Unsubstituted or substituted by-O-, carbonyl or-NB⁷-; or

q represents C₆To C₁₀Aromatic hydrocarbon group of (2), C₅To C₁₀A heteroaromatic radical of (a), via a halogen atom, -B⁶、-OH、-OB⁶、-NO₂、-CH＝CH₂or-CH ═ CH-B⁶Substituted C₆To C₁₀With an aromatic hydrocarbon radical of, or via a halogen atom, -B⁶、-OH、-OB⁶、-NO₂、-CH＝CH₂and-CH ═ CH-R⁶Substituted C₅To C₁₀The heteroaromatic group of (a); and

m represents potassium or sodium; and the alkali-soluble resin (C) comprises a first alkali-soluble resin (C-1), the first alkali-soluble resin (C-1) having a structure represented by formula (II):

wherein L represents a hydrogen atom or C₁To C₃₀An organic group of (2).

2. The blue photosensitive resin composition for a color filter according to claim 1, wherein the first alkali-soluble resin (C-1) is obtained by polymerizing a monomer (C-1) containing a group represented by the formula (III);

wherein L represents a hydrogen atom or C₁To C₃₀An organic group of (2).

3. The blue photosensitive resin composition for a color filter according to claim 2, wherein the first alkali-soluble resin (C-1) contains an ethylenically unsaturated group, and the first alkali-soluble resin (C-1) is obtained by reacting a copolymer obtained by copolymerizing a monomer (C-1) represented by formula (III), an ethylenically unsaturated monomer (C-2) having one or more carboxylic acid groups, and another copolymerizable ethylenically unsaturated monomer (C-3), with an ethylenically unsaturated monomer (C-4) having an epoxy group.

4. The blue photosensitive resin composition for a color filter according to claim 1, wherein the first alkali-soluble resin (C-1) is used in an amount of 5 to 100 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resins (C).

5. The blue photosensitive resin composition for a color filter according to claim 1, wherein the alkali-soluble resin (C) further comprises a second alkali-soluble resin (C-2), and the second alkali-soluble resin (C-2) is obtained by polymerizing an epoxy resin (C1) having at least two epoxy groups and a compound (C2) having at least one carboxylic acid group and at least one ethylenically unsaturated group.

6. The blue photosensitive resin composition for a color filter according to claim 5, wherein the epoxy resin (c1) having at least two epoxy groups has a structure represented by the following formula (V) or formula (VI):

wherein: r⁶¹、R⁶²、R⁶³And R⁶⁴Independently selected from hydrogen, halogen and C₁To C₅Alkyl groups of (a);

wherein,

R⁶⁵to R⁷⁸Independently selected from hydrogen, halogen, C₁To C₈Alkyl and C₆To C₁₅The aromatic group of (a); and

v represents an integer of 0 to 10.

7. The blue photosensitive resin composition for a color filter according to claim 6, wherein the amount of the second alkali-soluble resin (C-2) is 0 to 95 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resins (C).

8. The blue photosensitive resin composition for a color filter according to claim 1, wherein the ethylenically unsaturated group compound (D) comprises a first ethylenically unsaturated group compound (D-1), and the first ethylenically unsaturated group compound (D-1) has a structure represented by formula (VII):

wherein:

Z¹and Z²Each independently represents hydrogen or methyl;

t represents an integer of 1 to 2; and

9. The blue photosensitive resin composition for a color filter according to claim 8, wherein the amount of the first ethylenically unsaturated group-containing compound (D-1) is 10 to 50 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C).

10. The blue photosensitive resin composition for a color filter according to claim 1, wherein the photoinitiator (E) comprises a photoinitiator (E-1) having a structure represented by formula (VIII):

With the proviso that R₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈At least one pair of (A) isR₉、R₁₀、R₁₁And R₁₂Independently of one another are hydrogen, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, phenyl, CN, OH, SH, C₁-C₄Alkoxy, (CO) OH or (CO) O (C)₁-C₄Alkyl groups);

Or R₉、R₁₀、R₁₁And R₁₂Independently of one another, halogen, CN, OR₁₇、SR₁₈、SOR₁₈、SO₂R₁₈Or NR₁₉R₂₀Wherein the substituents OR₁₇、SR₁₈Or NR₁₉R₂₀Optionally via a group R₁₇、R₁₈、R₁₉And/or R₂₀Form a 5-or 6-membered ring with one carbon atom in the naphthyl ring;

Y is O, S, NR₂₆Or a direct bond;

p is an integer 0, 1,2 or 3;

q is an integer 1,2 or 3;

x is CO or a direct bond;

R₁₃is C₁-C₂₀An alkyl group which is unsubstituted or substituted with one or more of the following groups: halogen, R₁₇、COOR₁₇、OR₁₇、SR₁₈、CONR₁₉R₂₀、NR₁₉R₂₀、PO(OC_kH_2k+1)₂Or

or R₁₃Is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: OR (OR)₁₇、SR₁₈、NR₁₉R₂₀、COR₁₆、CN、NO₂Halogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, interrupted by one or more O, S, CO or NR_26-C of (A)₂-C₂₀An alkyl group; or each channel thereof C₃-C₁₀Cycloalkyl or interrupted by one or more O, S, CO or NR₂₆C of (A)₃-C₁₀Cycloalkyl substitution;

k is an integer from 1 to 10;

R₁₄is hydrogen、C₃-C₈Cycloalkyl radical, C₂-C₅Alkenyl radical, C₁-C₂₀Alkoxy or C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, phenyl, C₁-C₂₀Alkylphenyl or CN;

or R₁₄Is phenyl or naphthyl, each of which is unsubstituted or substituted with one or more of the following groups: c₁-C₆Alkyl radical, C₁-C₄Haloalkyl, halogen, CN, OR₁₇、SR₁₈And/or NR₁₉R₂₀；

Or R₁₄Is C₃-C₂₀Heteroaryl group, C₁-C₈Alkoxy, benzyloxy or phenoxy, benzyloxy and phenoxy being unsubstituted or substituted with one or more of the following groups: c₁-C₆Alkyl radical, C₁-C₄Haloalkyl and/or halogen;

R₁₅is C₆-C₂₀Aryl or C₃-C₂₀Heteroaryl groups, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C₁-C₄Haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀、PO(OC_kH_2k+1)₂、SO-C₁-C₁₀Alkyl, SO₂-C₁-C₁₀Alkyl, interrupted by one or more O, S or NR₂₆C of (A)₂-C₂₀An alkyl group; or each channel thereof C₁-C₂₀Alkyl substitution, C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR₁₇、CONR₁₉R₂₀Phenyl, C₃-C₈Cycloalkyl radical, C₃-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₃-C₂₀Heteroaryloxycarbonyl radical, OR₁₇、SR₁₈Or NR₁₉R₂₀；

or R₁₅Is C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OR₁₇、SR₁₈、C₃-C₈Cycloalkyl radical, C₃-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₃-C₂₀Heteroaryloxycarbonyl radical, NR₁₉R₂₀、COOR₁₇、CONR₁₉R₂₀、PO(OC_kH_2k+1)₂、A phenyl group; or the C₁-C₂₀Alkyl substituted by phenyl, which phenyl is substituted by halogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, OR₁₇、SR₁₈Or NR₁₉R₂₀Substitution;

or R₁₅Is C₂-C₁₂Alkoxycarbonyl which is not interrupted or interrupted by one or more O and which is interrupted or interrupted by C₂-C₁₂Alkoxycarbonyl unsubstituted or substituted by one or more hydroxy groupsSubstituted by radicals;

or R₁₅Is a phenoxycarbonyl group, unsubstituted or substituted with one or more of the following groups: c₁-C₆Alkyl, halogen, C₁-C₄Haloalkyl, phenyl, OR₁₇、SR₁₈Or NR₁₉R₂₀；

m is 1 or 2;

R'₁₄having a function of R₁₄One of the meanings given;

R'₁₅has one of the meanings given for R15;

X₁is O, S, SO or SO₂；

X₂Is O, CO, S or a direct bond;

R₁₆is C₆-C₂₀Aryl or C₃-C₂₀Heteroaryl, each of which is unsubstituted or substituted with one or more of the following groups: phenyl, halogen, C₁-C₄Haloalkyl, CN, NO₂、OR₁₇、SR₁₈、NR₁₉R₂₀Or interrupted by one or more O, S or NR₂₆C of (A)₁-C₂₀An alkyl group; or each of which is passed through one or more C₁-C₂₀Alkyl substitution of the C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, COOR₁₇、CONR₁₉R₂₀Phenyl, C₃-C₈Cycloalkyl radical, C₃-C₂₀Heteroaryl group, C₆-C₂₀Aryloxycarbonyl group, C₃-C₂₀Heteroaromatic compoundsOxycarbonyl radical, OR₁₇、SR₁₈Or NR₁₉R₂₀；

or R₁₆Is C₂-C₁₂Alkyl interrupted by one or more O, S or NR₂₆；

or R₁₆By SR₁₈Substituted phenyl, wherein the radical R₁₈Represents a bond to the COR₁₆A direct bond to the phenyl or naphthyl ring of the carbazole moiety to which a group is attached;

n is 1 to 20;

R₁₇is hydrogen, phenyl-C₁-C₃Alkyl radical, C₁-C₂₀Alkyl, unsubstituted or substituted with one or more of the following groups: halogen, OH, SH, CN, C₃-C₆Alkenyloxy, OCH₂CH₂CN、OCH₂CH₂(CO)O(C₁-C₄Alkyl), O (CO) - (C)₁-C₄Alkyl), O (CO) - (C)₂-C₄) Alkenyl, O (CO) -phenyl, (CO) OH, (CO) O (C)₁-C₄Alkyl group), C₃-C₂₀Cycloalkyl, SO₂-(C₁-C₄Haloalkyl), O (C)₁-C₄Haloalkyl) or C interrupted by one or more O₃-C₂₀A cycloalkyl group;

or R₁₇Is C₂-C₂₀Alkyl, interrupted by oneOr more than one O, S or NR₂₆；

or R₁₇Is C₁-C₈alkyl-C₃-C₁₀Cycloalkyl which is not interrupted or interrupted by one or more O;

Or R₁₇Form a bond to the groupA direct bond of one of the carbon atoms of the phenyl or naphthyl ring in which it is located;

R₁₈is hydrogen, C₂-C₁₂Alkenyl radical, C₃-C₂₀Cycloalkyl or phenyl-C₁-C₃Alkyl radical, wherein the C₂-C₁₂Alkenyl radical, C₃-C₂₀Cycloalkyl or phenyl-C₁-C₃The alkyl group being not interrupted or interrupted by one or more O, S,CO、NR₂₆Or COOR₁₇；

or R₁₉And R₂₀Together with the N atom to which they are attached form not interrupted or interrupted O, S or NR₁₇And the 5-or 6-membered saturated or unsaturated ring of (a), and the 5-or 6-membered saturated or unsaturated ring is unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl radical, C₁-C₂₀Alkoxy group, ═ O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO)R₂₃、NO₂Halogen, C₁-C₄-haloalkyl, CN, phenyl,Or not interrupted or interrupted by one or more O, S, CO or NR₁₇C of (A)₃-C₂₀A cycloalkyl group;

or R₁₉And R₂₀Together with the N atom to which they are attached form a heteroaromatic ring system, which ring system is unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C₁-C₂₀Alkoxy group, ═ O, OR₁₇、SR₁₈、NR₂₁R₂₂、(CO)R₂₃、Halogen, NO₂CN, phenyl or not interrupted or interrupted by one or more O, S, CO or NR₁₇C of (A)₃-C₂₀A cycloalkyl group;

R₂₃is hydrogen, OH, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, interrupted by one or more O, CO or NR₂₆C of (A)₂-C₂₀Alkyl, not interrupted or interrupted O, S, CO or NR₂₆C of (A)₃-C₂₀Cycloalkyl, or R₂₃Is phenyl, naphthyl, phenyl-C₁-C₄Alkyl, OR₁₇、SR₁₈Or NR₂₁R₂₂；

R₂₄Is (CO) OR₁₇、CONR₁₉R₂₀、(CO)R₁₇(ii) a Or R₂₄Having a function of R₁₉And R₂₀One of the meanings given;

R₂₅is COOR₁₇、CONR₁₉R₂₀、(CO)R₁₇(ii) a Or R₂₅Having a function of R₁₇One of the meanings given;

R₂₆is hydrogen, C₁-C₂₀Alkyl radical, C₁-C₄Haloalkyl, C₂-C₂₀Alkyl interrupted by one or more O or CO; or is phenyl-C₁-C₄Alkyl radical, C₃-C₈Cycloalkyl, uninterrupted or interrupted by one or more O or CO; or is (CO) R₁₉(ii) a Or is phenyl, which is unsubstituted or substituted with one or more of the following groups: c₁-C₂₀Alkyl, halogen, C₁-C₄Haloalkyl, OR₁₇、SR₁₈、NR₁₉R₂₀Or

With the proviso that at least one group is present in the moleculeOr

11. The blue photosensitive resin composition for a color filter according to claim 10, wherein the photoinitiator (E) comprises a photoinitiator (E-1) having a structure represented by formula (VIII), wherein R is₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Independently of one another are hydrogen, C₁-C₂₀Alkyl, aryl, heteroaryl, and heteroaryl,COR₁₆Or NO₂Or R is₁And R₂、R₂And R₃、R₃And R₄、R₅And R₆、R₆And R₇Or R₇And R₈Independently of one another together are

X is CO or a direct bond;

Or R₁₃Is C₂-C₂₀Alkyl interrupted by one or more O, S, NR₂₆Or CO;

R₁₄is C₁-C₂₀Alkyl, phenyl or C₁-C₈An alkoxy group;

R'₁₄Having a function of R₁₄One of the meanings given;

R'₁₅having a function of R₁₅One of the meanings given;

R₁₇Is C₂-C₂₀Alkyl interrupted by one or more O;

R₁₈via (CO) OR₁₇A substituted methyl group;

with the proviso that at least one group is present in the moleculeOr

12. The blue photosensitive resin composition for a color filter according to claim 10, wherein the photoinitiator (E) comprises a photoinitiator (E-1) having a structure represented by formula (VIII), wherein R is₁、R₂、R₃、R₄、R₅、R₆、R₇And R₈Independently of one another, hydrogen, or R₁And R₂、R₃And R₄Or R₅And R₆Independently of one another together are

Or R₂Is composed ofCOR₁₆、NO₂Or

Or R₇Is composed ofOr COR₁₆；

R₉、R₁₁And R₁₂Is hydrogen;

R₁₀is hydrogen, OR₁₇Or COR₁₆；

X is CO or a direct bond;

Or R₁₃Is C₂-C₂₀Alkyl interrupted by one or more O;

or R₁₃Is phenyl;

k is an integer of 2;

R₁₄is C₁-C₂₀Alkyl or thienyl;

R₁₅is phenyl OR naphthyl, each of which is unsubstituted OR substituted by one OR more OR₁₇Or C₁-C₂₀Alkyl substitution;

or R₁₅Is thienyl, hydrogen, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: OR (OR)₁₇、SR₁₈、C₃-C₈Cycloalkyl, NR₁₉R₂₀Or COOR₁₇；

Or R₁₅Is C₂-C₂₀Alkyl radicals interrupted by SO₂；

or R₁₆Is thienyl;

R₁₇is hydrogen, C₁-C₈Alkanoyl radical, C₁-C₂₀Alkyl radical, C₁-C₂₀Alkyl is unsubstituted or substituted with one or more of the following groups: halogen, O (CO) - (C)₁-C₄Alkyl), O (CO) - (C)₂-C₄) C with alkenyl or interrupted by one or more O₃-C₂₀A cycloalkyl group;

or R₁₇Is C₂-C₂₀Alkyl interrupted by one or more O;

or R₁₈Is phenyl, unsubstituted or substituted with one or more halogens;

with the proviso that at least one group is present in the molecule

13. The blue photosensitive resin composition for a color filter according to claim 10, wherein the photoinitiator (E-1) having a structure represented by formula (VIII) is used in an amount of 2 to 20 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resins (C).

14. The blue photosensitive resin composition for a color filter according to claim 1, wherein the organic pigment (a) is used in an amount of 50 to 450 parts by weight based on 100 parts by weight of the total amount of the alkali-soluble resin (C); the dye (B) is used in an amount of 10 to 90 parts by weight; the amount of the ethylenically unsaturated group-containing compound (D) is 50 to 450 parts by weight; the photoinitiator (E) is used in an amount of 17 to 170 parts by weight; the organic solvent (F) is used in an amount of 500 to 5000 parts by weight.

15. A method for manufacturing a color filter, which forms a pixel layer using the blue photosensitive resin composition for a color filter according to any one of claims 1 to 14.

16. A color filter produced by the method according to claim 15.

17. A liquid crystal display device characterized by comprising the color filter according to claim 16.