TWI638233B - Photosensitive resin composition, color filters, method of producing the same and application thereof - Google Patents

Abstract

The present invention provides a photosensitive resin composition comprising a pigment (A), a dye (B), an alkali-soluble resin (C), an ethylenically unsaturated group-containing compound (D), a photoinitiator (E), An unsaturated group-containing benzophenone compound (F) and a solvent (G). The invention also provides a color filter, a manufacturing method and application thereof. By using the photosensitive resin composition of the present invention, a color filter having good chemical resistance and contrast can be obtained.

Description

Photosensitive resin composition, color filter and its manufacturing Manufacturing method and application

The present invention relates to a photosensitive resin composition, a color filter, and a manufacturing method and application thereof, and in particular to a photosensitive resin composition, a color filter, and the like, which can have good chemical resistance and contrast. Manufacturing methods and applications.

At present, color filters have been widely used in the field of office equipment such as color liquid crystal displays, color fax machines, and color cameras. With the increasing market demand, the manufacturing technology of color filters also tends to be diversified. At present, manufacturing methods such as dyeing, printing, plating, and dispersion methods have been developed. Among them, dispersion method is the mainstream process.

The dispersion process involves first dispersing a colored pigment in a photosensitive resin, then coating the photosensitive resin on a glass substrate, and then exposing, developing, and other steps to obtain a specific pattern. After repeating the operation three times, the pattern of the pixel colored layer of red (R), green (G) and blue (B) can be obtained. It is necessary that a protective film can be applied to the pattern of the pixel colored layer.

The photosensitive resin used in the dispersion process is disclosed in Japanese Unexamined Patent Publication No. 6-95211 and Japanese Unexamined Patent Publication No. 8-183819, for example, a copolymer obtained by polymerizing (meth) acrylic acid as a monomer component. It is an alkali-soluble resin as a photosensitive resin.

However, in the manufacturing process of color filters, multiple heat treatment steps are required, such as red (R), green (G), and blue (B) pixel-colored layer patterns are formed and then post-bake. And transparent conductive film (ITO film) formation steps, these steps generally need to be operated at a high temperature of 200 ℃ or more, but if the conventional photosensitive resin is heated at 180 ℃ for about 1 hour, it is easy to color pixels Pigment agglomerated particles are generated in the layer (the particle size of general pigment agglomerated particles is between 1 μm and 10 μm), and the heat resistance of the pixel coloring layer is not good.

In order to improve the above problems, Japanese Patent Application Laid-Open No. 2001-075273 discloses a photosensitive resin composition comprising a polymer obtained by polymerizing an unsaturated monomer having a carboxylic acid group and a monomer containing an epoxy group, and The above-mentioned polymer is used as the alkali-soluble resin of the photosensitive resin. However, the color filter produced using the photosensitive resin composition of this conventional technique has problems of poor chemical resistance and contrast.

Therefore, how to overcome the problems of chemical resistance and poor contrast at the same time to meet the current industry requirements is the goal of hard research in the technical field to which the present invention belongs.

Therefore, an object of the present invention is to provide a photosensitive resin composition which can provide good chemical resistance and contrast for subsequent applications.

Another object of the present invention is to provide a method for manufacturing a color filter, which uses the aforementioned photosensitive resin composition to form a pixel layer on a substrate.

Another object of the present invention is to provide a color filter, which is obtained by using the aforementioned method for manufacturing a color filter.

Another object of the present invention is to provide a liquid crystal display device including the aforementioned color filter.

Photosensitive resin composition

According to the above object of the present invention, a photosensitive resin composition is first proposed. In one embodiment, the photosensitive resin composition includes a pigment (A), a dye (B), an alkali-soluble resin (C), an ethylenically unsaturated group-containing compound (D), a photoinitiator (E), and An unsaturated benzophenone compound (F) and a solvent (G). Each of them is explained in detail below.

Pigment (A)

The pigment (A) of the present invention may be an inorganic pigment, an organic pigment, or a combination thereof.

The above-mentioned inorganic pigments may be metal compounds such as metal oxides and metal salts, which may be selected from oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, lead, antimony, and A composite oxide of the aforementioned metals.

The above organic pigments are selected from C.1. Pigment Yellow 1, 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 93, 95, 97, 98, 99, 100, 101, 104, 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 126, 127, 128, 129, 138, 139, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175; CI Pigment Orange 1, 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 61, 63, 64 , 71, 73; CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48: 1, 48: 2, 48: 3, 48: 4, 49: 1, 49: 2, 50: 1, 52: 1, 53: 1, 57, 57: 1, 57: 2, 58: 2, 58: 4, 60: 1, 63: 1, 63: 2, 64: 1, 81: 1, 83, 88, 90: 1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 193, 194, 202, 206, 207, 208, 209, 215, 216, 220, 224, 226, 242, 243, 245, 254, 255, 264, 265; CI Pigment Violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38, 39, 40, 50; CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 16, 21, 22, 60 , 61, 64, 66; CI Pigment Green 7, 36, 37, 42, 58; CI Pigment Brown 23, 25, 28; and CI Pigment Black 1, 7. These organic pigments may be used alone or in combination.

The average particle diameter of the primary particles of the pigment (A) is preferably 10 nm to 200 nm, more preferably 20 nm to 150 nm, and most preferably 30 nm to 130 nm.

Based on the total use amount of the alkali-soluble resin (C), 100 parts by weight, and the use amount of the pigment (A) is 30 parts by weight to 300 parts by weight, preferably 40 parts by weight to 250 parts by weight, and more preferably 50 parts by weight to 200 parts by weight.

If necessary, the pigment (A) can also selectively use a dispersant, for example, a cationic, anionic, nonionic, amphoteric, polysiloxane, and fluorine-based surfactant.

The aforementioned surfactant may include but is not limited to polyethylene oxide alkyl ethers such as polyethylene oxide dodecyl ether, polyethylene oxide stearyl ether, polyethylene oxide oleyl ether, etc .; Polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether and other polyethylene oxide alkyl phenyl ether surfactants; polyethylene glycol dilaurate, polyethylene glycol dihard Polyethylene glycol diester surfactants such as fatty acid esters; sorbitan fatty acid ester surfactants; fatty acid modified polyester surfactants; tertiary amine modified polyurethanes Surfactants; manufactured by Shin-Etsu Chemical Co., Ltd., a product of model KP, manufactured by Toray Dow Corning Silicon, a product of model SF-8427, manufactured by Kyoeisha Oil Chemical Industry, a product of model Polyflow, Tochem Products (Tochem Products Co., Ltd.), model F-Top, Dainippon Ink Chemical Industry, model Megafac, Sumitomo 3M, model Fluorad, Asahi Glass, model Asahi Guard and Surflon commodity. The surfactant can be used singly or in combination.

Dye (B)

The dye (B) of the present invention includes a dye (B-1) having the formula (I):

In formula (I), L ₁ to L ₄ each independently represent hydrogen, -L ₆ , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L ₆ , -OH, -OL ₆ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -COOH, -COOL ₆ , -SO ₃ L ₆ , -SO ₂ NHL ₈ or -SO ₂ NL ₈ L ₉ substituted aromatic hydrocarbon groups having 6 to 10 carbon atoms; L ₅ represents ^{_{-SO 3 -, -SO 3 H,}} -SO 3 M, -COOH, -COOL 6, -SO 3 L 6, -SO 2 NHL 8 or -SO ₂ NL ₈ L _9; u represents 0 to 5 An integer; when u represents 2 to 5, a plurality of L ₅ are the same or different; X ^b represents a halogen atom; a represents 0 or 1; L ₆ represents an alkyl group having 1 to 10 carbon atoms or substituted by a halogen atom An alkyl group having 1 to 10 carbon atoms, wherein -CH ₂ -in the alkyl group having 1 to 10 carbon atoms or the alkyl group having 1 to 10 carbon atoms substituted with a halogen atom is unsubstituted or substituted with- O-, carbonyl or -NL _7- ; L ₇ represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom; L ₈ and L ₉ each independently represent a carbon number of 1 A straight-chain alkyl group having 10 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q; wherein the straight-chain alkyl group having 1 to 10 carbon atoms, carbon Number is 3 to 10 Branched alkyl or a hydrogen atom based carbon atoms a cycloalkyl group of 3 to 30 in the unsubstituted or substituted with a substituent group, the substituent is selected from the group consisting of a hydroxyl group, a halogen atom, -Q, -CH = CH ₂ And -CH = CH-L ₆ ; a group of a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms- CH ₂ -is unsubstituted or substituted with -O-, carbonyl, or -NL _7- ; or L ₈ and L ₉ combine to form a heterocyclic group having 2 to 10 carbon atoms, in which the heterocyclic group has 2 to 10 carbon atoms The hydrogen atom in the cyclic group is unsubstituted or substituted with L ₆ , -OH, or -Q; Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms, a heteroaromatic group having 5 to 10 carbon atoms, and a halogen atom , -L ₆ , -OH, -OL ₆ , -NO ₂ , -CH = CH ₂ or -CH = CH-L ₆ substituted aromatic hydrocarbon group having 6 to 10 carbon atoms, or halogen atom, -L ₆ , -OH, -OL ₆ , -NO ₂ , -CH = CH ₂ and -CH = CH-L ₆ substituted heteroaromatic groups having 5 to 10 carbon atoms; and M represents potassium or sodium.

Preferably, L ₆ includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, Cyclohexyl, heptyl, cycloheptane, octyl, cyclooctyl, 2-ethylhexyl, nonyl, decyl, tricyclo [5.3.0.0 ^3,10 ] decyl [tricycle (5.3.0.0 ^3,10 ) decanyl], methoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, or epoxypropyl.

Preferably, the aromatic hydrocarbon group having 6 to 10 carbon atoms includes, but is not limited to, phenyl, naphthyl, and the like.

Preferably, -SO ₃ L ₆ includes, but is not limited to, methanesulfonyl, ethanesulfonyl, hexanesulfonyl, or decanesulfonyl.

Preferably, -COOL ₆ includes but is not limited to methyloxycarbonyl, ethyloxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, pentyl Oxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, ring Octyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonoxycarbonyl, decyloxycarbonyl, tricyclic [5.3.0.0 ^3,10 ] decylcarbonyl, methoxypropoxycarbonyl, hexyloxypropyl Oxycarbonyl, 2-ethylhexyloxypropoxycarbonyl, or methoxyhexyloxycarbonyl.

Preferably, -SO ₂ NHL ₈ includes but is not limited to sulfamoyl, methylamine sulfonyl, ethylamine sulfonyl, propylamine sulfonyl, isopropylamine sulfonyl, Butylaminesulfonyl, isobutylaminesulfonyl, pentylaminesulfonyl, isoamylaminesulfonyl, neopentylaminesulfonyl, cyclopentylaminesulfonyl, hexylaminesulfonyl Base, cyclohexylaminesulfonyl, heptylaminesulfonyl, cycloheptylaminesulfonyl, octylaminesulfonyl, cyclooctylaminesulfonyl, 2-ethylhexylaminesulfonyl, nonyl Sulfamoyl, decylaminosulfonyl, tricyclic [5.3.0.0 ^3,10 ] decylaminesulfonyl, methoxypropylaminesulfonyl, hexyloxypropylaminesulfonyl, 2-ethylhexyloxypropylaminesulfonyl, methoxyhexylaminesulfonyl, epoxypropylaminesulfonyl, 1,5-dimethylhexylaminesulfonyl, propoxypropyl Sulfamoyl, isopropyloxypropylsulfanyl, 3-phenyl-1-methylpropylsulfanyl, , , (R ^a represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom, or 1 to 3 carbon atoms substituted with a halogen atom 3 alkoxy), , , , (R ^b represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom, or 1 to 3 carbon atoms substituted with a halogen atom 3 alkoxy), , ,

Preferably, -SO ₂ NL ₈ L ₉ includes but is not limited to , (R ^b represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group having 1 to 3 carbon atoms substituted with a halogen atom, or 1 to 3 carbon atoms substituted with a halogen atom 3 alkoxy), , ,

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

In the formula (I-1): L ₁₁ to L ₁₄ each independently represent hydrogen, -L ₆ , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L ₆ , -OH, -OL ₆ ,- ^{_{SO 3 -, -SO 3 H,}} -SO 3 Na, -COOH, -COOL 6, -SO 3 L 6, -SO 2 NHL 8 or -SO ₂ NL ₈ L ₉ carbon atoms substituted with an aromatic of 6 to 10 of hydrocarbon group; L ₁₅ represents ^{_{hydrogen, -SO 3 -, -SO 3 H}} , -SO 2 NHL 8 or _{-SO 2 NL 8 L 9; L} 16 represents ^{_{-SO 3 -, -SO 3 H,}} -SO 2 NHL 8 or -SO ₂ NL ₈ L ₉ ; X ^1b represents a halogen atom; a ¹ represents 0 or 1.

Preferably, the dye (B-1) includes a dye having a structure represented by formula (I-2):

In the formula (I-2): L ₂₁ to L ₂₄ each independently represent hydrogen, -L ₂₆ , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L ₂₆ , -OH, -OL ₂₆ ,- ^{_{SO 3 -, -SO 3 H,}} -SO 3 Na, -COOH, -COOL 26, -SO 3 L 26, or -SO ₂ NHL ₂₈ carbon atoms of the substituted aromatic hydrocarbon group of 6 to 10; L ₂₅ represents -SO ^{_{3 -, -SO 3 Na, -COOH}} , -COOL 26, -SO 3 H, or -SO ₂ NHL _28; u ¹ represents an integer of 0-5; when u ¹ represents 2 to 5, a plurality of L ₂₅ The same or different; X ^2b represents a halogen atom; a ² represents 0 or 1; L ₂₆ represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom or -OL ₂₇ ; L ₂₇ represents an alkyl group having a carbon number of 1 to 10; and L ₂₈ represents hydrogen, -L ₂₆ , -COOL ₂₆ , an aromatic hydrocarbon group having a carbon number of 6 to 10, or a carbon number substituted with -L ₂₆ or -OL ₂₆ It is an aromatic hydrocarbon group of 6 to 10.

Preferably, the dye (B-1) includes a dye having a structure of formula (I-3);

In formula (I-3): L ₃₁ and L ₃₂ each independently represent a phenyl group, or are substituted with a halogen atom, -L ₂₆ , -OL ₂₆ , -COOL ₂₆ , -SO ₃ L ₂₆ , or -SO ₂ NHL ₂₈ L ₃₃ represents -SO ₃ ^- or -SO ₂ NHL ₂₈ ; L ₃₄ represents hydrogen, -SO ₃ ^- or -SO ₂ NHL ₂₈ ; X ^3b represents a halogen atom; a ³ represents 0 or 1; L ₂₆ represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom or -OL ₂₇ ; L ₂₇ represents an alkyl group having 1 to 10 carbon atoms; and L ₂₈ represents hydrogen , -L ₂₆ , -COOL ₂₆ , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms substituted with -L ₂₆ or -OL ₂₆ .

Preferably, the dye (B-1) includes a dye having a structure of formula (I-4):

In the formula (I-4): L ₄₁ and L ₄₂ each independently represents a phenyl group, or by -L ₂₆ or -SO ₂ NHL ₂₈ of the substituted phenyl group; L ₄₃ represents -SO ₃ ^-, or -SO ₂ NHL ₂₈ X ^4b represents a halogen atom; a ⁴ represents 0 or 1; L ₂₆ represents an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom or -OL ₂₇ ; L ₂₇ represents An alkyl group having 1 to 10 carbon atoms; and L ₂₈ represents hydrogen, -L ₂₆ , -COOL ₂₆ , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or 6 to 10 carbon atoms substituted with -L ₂₆ or -OL ₂₆ Aromatic hydrocarbon group of 10.

In a specific example of the present invention, the dye (B-1) includes, but is not limited to, compounds represented by the following formula (1) to formula (31):

In formula (1), R ^c and R ^d each independently represent hydrogen, -SO ₃ ^-, -COOH, or -SO ₂ NHL _81; L ₈₁ represents a 2-ethylhexyl group; X ^b represents a halogen atom; A represents 0 or 1.

In formula (2), R ^e represents hydrogen, -SO ₃ ^-, -COOH, or -SO ₂ NHL _81; L ₈₁ represents a 2-ethylhexyl group; X ^b represents a halogen atom; A represents 0 or 1.

In formula (3), R ^e represents hydrogen, -SO ₃ ^-, -COOH, or -SO ₂ NHL _81; L ₈₁ represents a 2-ethylhexyl group; X ^b represents a halogen atom; A represents 0 or 1.

In formula (4), R ^f , R ^g, and R ^h each independently represent —SO ₃ ^— , —SO ₃ Na, or —SO ₂ NHL ₈₁ ; L ₈₁ represents 2-ethylhexyl.

In Formula (5), R ^f , R ^g, and R ^h each independently represent —SO ₃ ^— , —SO ₃ Na, or —SO ₂ NHL ₈₁ ; and L ₈₁ represents 2-ethylhexyl.

In the formula ^{(6), R i, R} j and R ^k each independently represent hydrogen, -SO ₃ ^-, -SO ₃ H or -SO ₂ NHL _81; L ₈₁ represents a 2-ethylhexyl group.

In the formula ^{(7), R i, R} j and R ^k each independently represent hydrogen, -SO ₃ ^-, -SO ₃ H or -SO ₂ NHL _81; L ₈₁ represents a 2-ethylhexyl group.

In the formula ^{(8), R l, R} m and R ⁿ each independently represent -SO ₃ ^-, -SO ₃ Na or -SO ₂ NHL _81; L ₈₁ represents a 2-ethylhexyl group.

In the formula ^{(9), R l, R} m and R ⁿ each independently represent -SO ₃ ^-, -SO ₃ Na or -SO ₂ NHL _81; L ₈₁ represents a 2-ethylhexyl group.

In Formula (10), R ^p , R ^q and R ^r each independently represent hydrogen, —SO ₃ ^— , —SO ₃ H, or —SO ₂ NHL ₈₁ ; L ₈₁ represents 2-ethylhexyl.

In formula (11), R ^p , R ^q and R ^r each independently represent hydrogen, —SO ₃ ^— , —SO ₃ H, or —SO ₂ NHL ₈₁ ; L ₈₁ represents 2-ethylhexyl.

Dye (B-1) of the present invention particularly preferred embodiment of formula (1) (R ^c and R ^d is -SO ₃ ^-, a is 0) [CI Acid Red 52 dye], formula (22) [CI Acid Red dye 289], a dye of formula (28), a dye of formula (31), or any combination thereof.

In specific examples of the present invention, the total amount of the alkali-soluble resin (C) used is 100 parts by weight, and the amount of the dye (B-1) used is 3 to 50 parts by weight; preferably 5 to 45 parts by weight Parts by weight; more preferably 10 to 40 parts by weight. When the dye (B-1) is used, the contrast of the photosensitive resin composition is better.

In a preferred embodiment of the present invention, the dye (B) may further include Contains other dyes (B-2).

Preferably, the other dye (B-2) includes, but is not limited to, an azo dye, an anthraquinone dye, a phthalocyanine dye, a quinimine dye, a quinoline dye, or a nitro dye. Azo dyes include but are not limited to CI Acid Yellow 11, Acid Orange 7, Acid Red 37, Acid Red 180, Acid Blue 29, Direct Red 28, Direct Red 83, Direct Yellow 12, Direct Orange 26, Direct Green 28, Direct Green 59, Reactive Yellow 2, Reactive Red 17, Reactive Red 120, Reactive Black 5, Disperse Orange 5, Disperse Red 58, Disperse Blue 165, Basic Blue 41, Basic Red 18, Medium Red 7, Medium Yellow 5, Medium Black 7 and others; anthraquinone-based dyes include but are not limited to CI Batblue 4, Acid Blue 40, Acid Green 25, Reactive Blue 19, Reactive Blue 49, Disperse Red 60, Disperse Blue 56, Disperse Blue 60, etc. ; Phthalocyanine dyes include, but are not limited to, CI Basic Blue 5, etc .; quinone imine dyes include, but are not limited to, CI Basic Blue 3, Basic Blue 9, etc .; quinoline dyes CI Solvent Yellow 33, Acid Yellow 3, Disperse Yellow 64 and the like; nitro-based dyes include but are not limited to CI Acid Yellow 1, Acid Orange 3, Disperse Yellow 42 and the like. The above-mentioned other dyes can be used singly or in combination.

In a specific example of the present invention, the total amount of the alkali-soluble resin (C) used is 100 parts by weight, and the amount of the other dyes (B-2) is 0 to 47 parts by weight; preferably 0 to parts by weight 40 parts by weight; more preferably 0 to 30 parts by weight.

Based on the total amount of the alkali-soluble resin (C) used being 100 parts by weight, the amount of the dye (B) used is 5 parts by weight to 50 parts by weight; preferably 10 parts by weight to 45 parts by weight; more preferably 15 parts by weight to 40 parts by weight.

Alkali soluble resin (C) First alkali-soluble resin (C-1)

The alkali-soluble resin (C) of the present invention may include a first alkali-soluble resin (C-1), which is prepared by polymerizing a mixture containing an epoxy compound having at least two epoxy groups. (c-1-1), and a compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group. In addition, the mixture may further optionally include a carboxylic anhydride compound (c-1-3) and / or an epoxy group-containing compound (c-1-4).

The epoxy compound (c-1-1) having at least two epoxy groups may have a structure represented by the following formula (II-1) or the following formula (II-2). Here, the description of "the epoxy compound (c-1-1) may have a structure represented by the following formula (II-1) or the following formula (II-2)" also covers a formula having the following formula (II-1) In the case where the compound having the structure shown and the compound having the structure represented by the following formula (II-2) coexist as the epoxy compound (c-1-1). Specifically, the aforementioned epoxy compound (c-1-1) having at least two epoxy groups has a structure represented by the following formula (II-1), for example:

In formula (II-1), R ^1c , R ^2c , R ^3c and R ^4c are the same or different, and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, and a carbon number of 1 to 5 An alkoxy group, an aromatic group having 6 to 12 carbons, or an aralkyl group having 6 to 12 carbons.

The epoxy compound (c-1-1) of the aforementioned formula (II-1) having at least two epoxy groups may include a bisphenol fluorene type compound (bisphenol Fluorene) is an epoxy-containing bisphenol fluorene type compound obtained by reacting with halogenated propylene oxide (epihalohydrin), but it is not limited thereto.

Specific examples of the bisphenol fluorene type compound include, but are not limited to, 9,9-bis (4-hydroxyphenyl) fluorene [9,9-bis (4-hydroxyphenyl) fluorene], 9,9-bis (4-hydroxy-3-methylphenyl) fluorene [9,9-bis (4-hydroxy-3-methylphenyl) fluorene], 9,9-bis (4-hydroxy-3-chlorophenyl) fluorene [9 , 9-bis (4-hydroxy-3-chlorophenyl) fluorene], 9,9-bis (4-hydroxy-3-bromophenyl) fluorene [9,9-bis (4-hydroxy-3-bromophenyl) fluorene] , 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene [9,9-bis (4-hydroxy-3-fluorophenyl) fluorene], 9,9-bis (4-hydroxy-3-methoxy) Phenyl) fluorene [9,9-bis (4-hydroxy-3-methoxyphenyl) fluorene], 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene [9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene], 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene [9,9-bis (4-hydroxy-3,5-dichlorophenyl) ) fluorene], 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene [9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene] and other compounds.

The above-mentioned halogenated propylene oxide (epihalohydrin) may include, but is not limited to, 3-chloro-1,2-epoxypropane (epichlorohydrin) or 3-bromo-1,2-epoxypropane (epibromohydrin) and the like.

The epoxy-containing bisphenol fluorene type compound obtained by reacting the bisphenol fluorene type compound with halogenated propylene oxide includes, but is not limited to: (1) products manufactured by Nippon Steel Chemical Co., Ltd. : For example ESF-300, etc .; (2) Made by Osaka Gas Co., Ltd. Commodities: such as PG-100, EG-210, etc .; (3) Commodities manufactured by S.M.S Technology Co., Ltd: such as SMS-F9PhPG, SMS-F9CrG, SMS-F914PG, etc.

Second, the epoxy compound (c-1-1) having at least two epoxy groups may also have a structure represented by the following formula (II-2):

In the formula (II-2), R ^5c to R ^18c are the same or different, and each may independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aromatic group having 6 to 15 carbon atoms. ; And g represents an integer from 0 to 10.

The epoxy compound (c-1-1) having the at least two epoxy groups in the aforementioned formula (II-2) has, for example, the following formula (II-2-1) in the presence of an alkali metal hydroxide The structured compound is obtained by reacting a halogenated propylene oxide.

In formula ^{(II-2-1), R 5c} R 18c is defined to g, respectively, and the lines ^5c and R ^18c is defined to g of the same formula R (II-2) in the, and is not repeated herein.

The epoxy compound (c-1-1) having at least two epoxy groups in the aforementioned formula (II-2) is, for example, a compound having the following formula (II-2-2) in the presence of an acid catalyst. After the condensation reaction of the compounds with phenols, To a compound having the structure of formula (II-2-1). Next, by adding an excess of halogenated propylene oxide to perform a dehydrohalogenation reaction, an epoxy compound (c-1-1) having at least two epoxy groups as shown in formula (II-2) is obtained. .

In the above formula (II-2-2), R ^19c and R ^20c are respectively the same or different hydrogen atom, halogen atom, alkyl group having 1 to 8 carbons, or aromatic group having 6 to 15 carbons; X ¹ and X ² are respectively the same or different halogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. Preferably, the aforementioned halogen atom may be, for example, chlorine or bromine, the aforementioned alkyl group may be, for example, methyl, ethyl, or third butyl, and the aforementioned alkoxy group may be, for example, methoxy or ethoxy.

Specific examples of the above phenols include, but are not limited to, phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t -T-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol , Vinylphenol, propenylphenol, ethinylphenol, cyclopentylphenol, cyclohexylphenol or cyclohexylcresol, etc. These phenols can be used singly or in combination.

Based on the above-mentioned compound having the structure of the formula (II-2-2), the usage amount is 1 mole, and the usage amount of the phenols is 0.5 to 20 moles, with 2 to 15 moles being preferred.

Specific examples of the acid catalyst include hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, oxalic acid, boron trifluoride, and anhydrous aluminum chloride. ), Zinc chloride and the like, among which p-toluenesulfonic acid, sulfuric acid or hydrochloric acid is preferred. These acid catalysts can be used alone or in combination.

In addition, although the usage amount of the acid catalyst is not particularly limited, based on the usage amount of the compound having the formula (II-2-2) is 100 weight percent (wt%), the usage amount of the acid catalyst is better. It is 0.1 wt% to 30 wt%.

The above-mentioned condensation reaction can be performed without a solvent or in the presence of an organic solvent. Next, specific examples of the organic solvent include toluene, xylene, methyl isobutyl ketone, and the like. These organic solvents can be used alone or in combination.

Based on the total amount of the compound and the phenols having the structure of formula (II-2-2) being 100% by weight, the amount of the organic solvent used is 50% to 300% by weight, and 100% to 250% by weight is preferred. In addition, the operation temperature of the condensation reaction is 40 ° C to 180 ° C, and the operation time of the condensation reaction is 1 hour to 8 hours.

After the above condensation reaction is completed, neutralization treatment or water Wash treatment. In the above neutralization treatment, the pH value of the solution after the reaction is adjusted to pH 3 to pH 7, and pH 5 to pH 7 is preferred. The above-mentioned water washing treatment can be performed using a neutralizing agent, and the neutralizing agent is an alkaline substance, and specific examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; hydrogen Alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide; diethylene triamine, triethylene tetramine, aniline, and phenylenediamine (phenylene diamine) and other organic amines; and ammonia (ammonia), sodium dihydrogen phosphate (sodium dihydrogen phosphate), and so on. The above-mentioned water washing treatment can be performed by a conventional method. For example, an aqueous solution containing a neutralizing agent is added to the solution after the reaction, and extraction can be performed repeatedly. After the neutralization treatment or the water washing treatment, the unreacted phenols and the solvent are distilled off under reduced pressure and heat treatment, and then concentrated to obtain a compound having the structure of formula (II-2-1).

Specific examples of the halogenated propylene oxide include 3-chloro-1,2-epoxypropane, 3-bromo-1,2-epoxypropane (3 -bromo-1,2-epoxypropane) or any combination thereof. Before carrying out the dehydrohalogenation reaction, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide may be added in advance or during the reaction. The operation temperature of the above dehalogenation reaction is 20 ° C to 120 ° C, and the operation time range is 1 hour to 10 hours.

In a specific example of the present invention, an aqueous solution of the alkali metal hydroxide added in the dehydrohalogenation reaction may be used. In this specific example, the alkali metal hydroxide aqueous solution is continuously added to the dehydrohalogenation reaction system. At the same time in the system, water and halogenated propylene oxide can be continuously distilled under reduced or normal pressure, thereby separating and removing water, and at the same time, the halogenated propylene oxide can be continuously refluxed into the reaction system.

Before the above dehydrohalogenation reaction proceeds, tetramethyl ammonium chloride, tetramethyl ammonium bromide, trimethyl benzyl ammonium chloride, etc. may be added. Grade ammonium salt as a catalyst, and react at 50 ° C to 150 ° C for 1 hour to 5 hours, and then add an alkali metal hydroxide or an aqueous solution thereof, and react it at a temperature of 20 ° C to 120 ° C for 1 hour to 10 hours for dehydrohalogenation reaction.

Based on the total equivalents of the hydroxyl groups in the compound having the formula (II-2-1) is 1 equivalent, the amount of the halogenated propylene oxide used may be 1 to 20 equivalents, with 2 to 10 equivalents being preferred. Based on the total equivalents of the hydroxyl groups in the compound having the structure of the formula (II-2-1) is 1 equivalent, the amount of the alkali metal hydroxide added in the above dehydrohalogenation reaction may be 0.8 equivalent to 15 equivalents, of which 0.9 Equivalents to 11 equivalents are preferred.

In addition, in order to make the dehydrohalogenation reaction proceed smoothly, in addition to alcohols such as methanol and ethanol, aprotic such as dimethyl sulfone and dimethyl sulfoxide may be added. Polar solvents and the like to carry out the reaction. In the case of using alcohols, based on the total amount of the above-mentioned halogenated propylene oxide being 100% by weight, the amount of alcohols used may be 2% to 20% by weight, preferably 4% to 15% by weight. In the case of using an aprotic polar solvent, based on the total amount of halogenated propylene oxide being 100 wt%, the amount of aprotic polar solvent used can be 5 wt% Up to 100% by weight, with 10% to 90% by weight being preferred.

After the dehydrohalogenation reaction is completed, a water washing treatment may be optionally performed. After that, halogenated propylene oxide, alcohols, aprotic polar solvents, and the like are removed by heating and decompression. The heating and decompression are performed, for example, in an environment having a temperature of 110 ° C to 250 ° C and a pressure of 1.3 kPa (10 mmHg) or less.

In order to avoid the formation of epoxy resins containing hydrolyzable halogens, the solution after the dehydrohalogenation reaction can be added to solvents such as toluene and methyl isobutyl ketone, and alkalis such as sodium hydroxide and potassium hydroxide can be added. The metal hydroxide aqueous solution is dehydrohalogenated again. In the dehydrohalogenation reaction, based on the total equivalents of the hydroxyl groups in the compound having the structure of the formula (II-2-1) above, the equivalent amount of the alkali metal hydroxide is 0.01 mol to 0.3 mol. It is preferably from 0.05 mol to 0.2 mol. In addition, the operation temperature range of the above-mentioned dehydrohalogenation reaction is from 50 ° C to 120 ° C, and the operation time range is from 0.5 hours to 2 hours.

After the dehydrohalogenation reaction is completed, the salts are removed by steps such as filtration and water washing. In addition, solvents such as toluene and methyl isobutyl ketone can be distilled off by heating and decompression to obtain an epoxy compound having at least two epoxy groups as shown in formula (II-2). (c-1-1). The epoxy compound (c-1-1) of the above formula (II-2) having at least two epoxy groups may include but is not limited to, for example, trade names such as NC-3000, NC-3000H, NC-3000S and NC-3000P And other products manufactured by Nippon Kayaku Co. Ltd.

The aforementioned has at least one carboxylic acid group and at least one ethylenic compound The saturated compound (c-1-2) is, for example, selected from the group consisting of (1) to (3): (1) acrylic acid, methacrylic acid, and 2-methacrylic acid ethoxybutyl 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxyethylbutanedioic acid, 2-methacryloyloxybutanedioic acid, 2-methacrylic acid Methacrylic acid oxyethyl hexahydrophthalic acid, 2-methacrylic acid oxyethyl maleic acid, 2-methacrylic acid oxypropyl maleic acid, 2-methacrylic acid oxybutyl maleic acid Maleic acid, 2-methacrylic acid oxypropyl succinic acid, 2-methacrylic acid oxypropyl adipic acid, 2-methacrylic acid oxypropyltetrahydrophthalic acid, 2-methacrylic acid Hydroxypropyl phthalic acid, 2-methacrylic acid oxobutyl phthalic acid, or 2-methacrylic acid oxobutylhydrophthalic acid; (2) by (hydroxy) -containing (methyl) A compound obtained by reacting an acrylate with a dicarboxylic acid compound, wherein the dicarboxylic acid compound includes, but is not limited to, adipic acid, succinic acid, maleic acid, and phthalic acid; (3) Based on the reaction of acrylates with carboxylic anhydride compounds Half-ester compounds, in which the hydroxyl-containing (meth) acrylates include but are not limited to 2-hydroxyethyl acrylate [(2-hydroxyethyl) acrylate], 2-hydroxyethyl methacrylate [(2-hydroxyethyl) methacrylate ], 2-hydroxypropyl acrylate [(2-hydroxypropyl) acrylate], 2-hydroxypropyl methacrylate [(2-hydroxypropyl) methacrylate], 4-hydroxybutyl acrylate [(4-hydroxybutyl) acrylate ], 4- (4-hydroxybutyl) methacrylate, or pentaerythritol trimethacrylate. In addition, the carboxylic acid anhydride compound described herein may be the same as the carboxylic acid anhydride compound (c-1-3) contained in the mixture of the first alkali-soluble resin (C-1) described below, and will not be repeated here.

The mixture of the first alkali-soluble resin (C-1) may further optionally include a carboxylic anhydride compound (c-1-3) and / or an epoxy group-containing compound (c-1-4). The above carboxylic anhydride compound (c-1-3) can be selected from the group consisting of (1) to (2): (1) butanedioic anhydride, maleic anhydride, clothing Itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride , Methyl hexahydrophthalic anhydride, methyl endo-methylene tetrahydro phthalic anhydride, chlorendic anhydride, glutaric anhydride, or trimellitic acid Acid anhydrides (1,3-dioxoisobenzofuran-5-carboxylic anhydride) and other dicarboxylic anhydride compounds; and (2) benzophenone tetracarboxylic dianhydride (BTDA), bistetracarboxylic dianhydride or bisbenzene Tetracarboxylic acid anhydride compounds such as ether tetracarboxylic dianhydride.

The epoxy-group-containing compound (c-1-4) is, for example, selected from glycidyl methacrylate, 3,4-epoxy cyclohexyl methacrylate, unsaturated glycidyl ether-containing compound, A group of epoxy-containing unsaturated compounds or any combination thereof. The aforementioned unsaturated group-containing glycidyl ether compound includes, but is not limited to, trade names Denacol EX-111, EX-121 Denacol, Denacol EX-141, Denacol EX-145, Denacol EX-146, Denacol EX-171, Denacol EX-192 And other compounds (the above are commercial products of Nagase Chemical Industries, Ltd.).

The first alkali-soluble resin (C-1) may be an epoxy compound (c-1-1) having at least two epoxy groups and at least one carboxylic acid group and at least one ethylenic compound having the formula (II-1). The saturated compound (c-1-2) is polymerized to form a reaction product containing a hydroxyl group, and then a carboxylic anhydride compound (c-1-3) is added and reacted. Based on the total hydroxyl equivalent of the hydroxyl-containing reaction product, the equivalent of the acid anhydride group contained in the carboxylic anhydride compound (c-1-3) is preferably from 0.4 to 1 equivalent, and more preferably from 0.75 to 1 equivalent. When a plurality of carboxylic anhydride compounds (c-1-3) are used, they can be added sequentially or simultaneously during the reaction. When the dicarboxylic acid anhydride compound and the tetracarboxylic acid anhydride compound are used as the carboxylic acid anhydride compound (c-1-3), the molar ratio of the dicarboxylic acid anhydride compound and the tetracarboxylic acid anhydride compound is preferably 1/99 to 90 / 10, more preferably 5/95 to 80/20. The operating temperature range of the reaction is, for example, a range of 50 ° C to 130 ° C.

The first alkali-soluble resin (C-1) may be an epoxy compound (c-1-1) having at least two epoxy groups and at least one carboxylic acid group and at least one ethylenic compound having the formula (II-2). The saturated compound (c-1-2) is reacted to form a hydroxyl-containing reaction product, and then a carboxylic anhydride compound (c-1-3) and / or an epoxy-containing compound (c-1) are added. -4) Obtained by polymerization. Based on the formula (II-2), the epoxy compound on the epoxy compound (c-1-1) having at least two epoxy groups has a total equivalent weight of 1 equivalent, and the above has at least one carboxylic acid group and at least one ethylenic compound. The acid value equivalent of the saturated compound (c-1-2) is preferably 0.8 to 1.5 equivalents, and more preferably 0.9 to 1.1 equivalents. The total amount of hydroxyl groups based on the above-mentioned hydroxyl-containing reaction product is 100 mole percent (mole%), and the usage amount of the carboxylic anhydride compound (c-1-3) is preferably 10 mole% to 100 Molar%, more preferably 20 Molar% to 100 Molar%, particularly preferably 30 Molar% to 100 Molar%.

When the first alkali-soluble resin (C-1) is prepared, in order to accelerate the reaction, a basic compound is usually added to the reaction solution as a reaction catalyst. The above reaction catalysts can be used alone or in combination, and the above reaction catalysts include but are not limited to: triphenyl phosphine, triphenyl stibine, triethylamine, triethanolamine , Tetramethyl ammonium chloride, benzyltriethyl ammonium chloride, and the like. The total amount of the epoxy compound (c-1-1) having at least two epoxy groups and the compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100. The use amount of the reaction catalyst is preferably 0.01 to 10 parts by weight, and more preferably 0.3 to 5 parts by weight.

In addition, in order to control the degree of polymerization, a polymerization inhibitor is usually added to the reaction solution. The above polymerization inhibitor may include, but is not limited to: methoxyphenol, methylhydroquinone, hydroquinone, 2,6-di-tert-butyl-p-cresol (2,6-di -t-butyl-p-cresol) or phenothiazine. In general, the above-mentioned polymerization inhibitors can be used alone or in combination. The total amount of the epoxy compound (c-1-1) having at least two epoxy groups and the compound (c-1-2) having at least one carboxylic acid group and at least one ethylenically unsaturated group is 100. The weight of the polymerization inhibitor is preferably from 0.01 to 10 parts by weight, and more preferably from 0.1 to 10 parts by weight. Parts to 5 parts by weight.

When preparing the first alkali-soluble resin (C-1), a polymerization reaction solvent may be used if necessary. Specific examples of the polymerization reaction solvent include alcohol compounds such as ethanol, propanol, isopropanol, butanol, isobutanol, 2-butanol, hexanol, or ethylene glycol; methyl ethyl ketone or cyclohexanone Other ketones; aromatic hydrocarbons such as toluene or xylene; cellosolve or butyl cellosolve; carbitol or butyl carbohydrate Carbitol compounds such as butyl carbitol; propylene glycol alkyl ether compounds such as propylene glycol monomethyl ether; polypropylene glycol alkyl ethers such as di (propylene glycol) methyl ether [poly (propylene glycol) alkyl ether] compounds; acetates such as ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, or propylene glycol methyl ether acetate Compounds; alkyl lactate compounds such as ethyl lactate or butyl lactate; or dialkyl glycol ethers; or ethyl 3-ethoxypropionate. The above-mentioned polymerization reaction solvents can be used singly or in combination. The acid value of the first alkali-soluble resin (C-1) is preferably 50 mgKOH / g to 200 mgKOH / g, and more preferably 60 mgKOH / g to 150 mgKOH / g.

In addition, the number-average molecular weight of the polystyrene-equivalent number of the first alkali-soluble resin (C-1) measured by a gel permeation chromatography (GPC) is generally 500 to 10,000. It is preferably 800 to 8,000, and more preferably 1,000 to 6,000.

In a specific example of the present invention, the total amount of the alkali-soluble resin (C) used is 100 parts by weight, and the amount of the first alkali-soluble resin (C-1) is used in a range of 10 to 100 parts by weight; 15 to 90 parts by weight; more preferably 20 to 80 parts by weight. When the first alkali-soluble resin (C-1) is used, the chemical resistance performance of the photosensitive resin composition is better.

Second alkali soluble resin (C-2)

The alkali-soluble resin (C) of the present invention may further include a second alkali-soluble resin (C-2), which is composed of an ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides. ) And other copolymerizable ethylenically unsaturated monomers (c-2-2) are copolymerized and reacted with the ethylenically unsaturated monomers (c-2-3) having epoxy groups.

In one embodiment, the second alkali-soluble resin (C-2) is an ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride and other copolymerizable The ethylenically unsaturated monomer (c-2-2) undergoes a double bond copolymerization reaction to form a polymer, wherein the side chain of the polymer has a carboxylic acid group. Then, the carboxylic acid group in the side chain of the polymer is subjected to an addition reaction with an ethylenically unsaturated monomer (c-2-3) having an epoxy group to obtain a second alkali-soluble resin (C-2) .

In another embodiment, the second alkali-soluble resin (C-2) is firstly other copolymerizable ethylenically unsaturated monomer (c-2-2) and an ethylenically unsaturated monomer having an epoxy group. The body (c-2-3) undergoes a double bond copolymerization reaction to form a polymer, wherein the side chain of the polymer has an epoxy group. Then, this The epoxy group in the side chain of the polymer is subjected to an addition reaction with an ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides to prepare the second alkali-soluble resin ( C-2).

In yet another embodiment, the second alkali-soluble resin (C-2) is a copolymerizable other ethylenically unsaturated monomer (c-2-2) and an ethylenically unsaturated monomer having an epoxy group. (c-2-3) Perform a double bond copolymerization reaction to form a polymer, wherein the side chain of the polymer has an epoxy group. Then, the epoxy group in the side chain of the polymer is subjected to addition reaction with an ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride, and then further carried out with an acid anhydride compound. The second ester-soluble resin (C-2) was obtained by a half-esterification reaction.

The aforementioned ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acids or carboxylic anhydrides, wherein the ethylenically unsaturated monomer having one or more carboxylic acids may include but is not limited to A saturated monocarboxylic acid compound, an unsaturated polycarboxylic acid compound, a polycyclic compound having an unsaturated group and one carboxylic acid group, or a polycyclic compound having an unsaturated group and a plurality of carboxylic acid groups.

The aforementioned unsaturated monocarboxylic acid compound may include, but is not limited to, (meth) acrylic acid, butenoic acid, α -chloroacrylic acid, ethacrylic acid, cinnamic acid, 2- (meth) acrylic acid ethoxysuccinate ( 2- (meth) acryloyloxy ethyl succinate monoester), 2- (meth) acryl ethoxy hexahydrophthalate, 2- (meth) acryl ethoxy phthalate or omega-carboxyl Acid-based polycaprolactone polyol monoacrylate and the like. The omega-carboxylic acid-based polycaprolactone polyol monoacrylate can be manufactured by East Asia Synthetic, and the model is ARONIX M-5300.

The aforementioned unsaturated polycarboxylic acid compound may include, but is not limited to, maleic acid, fumaric acid, methyl fumaric acid, itaconic acid, citraconic acid, and the like.

The aforementioned polycyclic compound having an unsaturated group and one carboxylic acid group may include, but is not limited to, 5-carboxylic acid bicyclo [2.2.1] hept-2-ene, 5-carboxylic acid-5-methylbicyclo [2.2. 1] hept-2-ene, 5-carboxylic acid-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxylic acid-6-methylbicyclo [2.2.1] hept-2-ene Ene or 5-carboxylic acid-6-ethylbicyclo [2.2.1] hept-2-ene and the like.

Examples of the polycyclic compound having an unsaturated group and a plurality of carboxylic acid groups include 5,6-dicarboxylic acid bicyclo [2.2.1] hept-2-ene and the like.

Preferably, the aforementioned ethylenically unsaturated monomer having one or more carboxylic acids is selected from the group consisting of acrylic acid, methacrylic acid, 2-methacrylic acid, ethoxysuccinate, and 2-methacrylic acid. Ethoxyhexahydrophthalate, or any combination of the above.

The aforementioned ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride, wherein the aforementioned ethylenically unsaturated monomer having one or more carboxylic anhydride may include, but is not limited to, unsaturated A carboxylic anhydride compound or a polycyclic compound having an unsaturated group and a carboxylic anhydride.

The aforementioned unsaturated carboxylic anhydride compound may include, but is not limited to, maleic anhydride, fumaric anhydride, methyl fumaric anhydride, itaconic anhydride, citraconic anhydride, and the like. The aforementioned polycyclic compound having an unsaturated group and a carboxylic anhydride may include, but is not limited to, 5,6-dicarboxylic anhydride bicyclo [2.2.1] hept-2-ene and the like.

Preferably, the aforementioned ethylenically unsaturated monomer having one or more carboxylic anhydrides is maleic anhydride.

The above mentioned ethyls having one or more carboxylic acids or carboxylic anhydrides The ethylenically unsaturated monomer (c-2-1) may be used alone or in combination.

In a specific example of the present invention, the ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride based on the second alkali-soluble resin (C-2) and other copolymerizable ones The total amount of the ethylenically unsaturated monomer (c-2-2) copolymerization monomer is 100 parts by weight, and the ethylenically unsaturated monomer (c-2-1) has one or more carboxylic acids or carboxylic anhydrides. ) Is used in an amount ranging from 10 parts by weight to 90 parts by weight; preferably 15 parts by weight to 85 parts by weight; more preferably 20 parts by weight to 80 parts by weight.

The aforementioned other copolymerizable ethylenically unsaturated monomer (c-2-2) may include, but is not limited to, alkyl (meth) acrylate, cycloaliphatic (meth) acrylate, and aryl (meth) acrylate Esters, unsaturated dicarboxylic acid esters, hydroxyalkyl (meth) acrylates, polyethers having a (meth) acrylate group, styrene compounds, or unsaturated compounds other than the above compounds.

The aforementioned 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 methacrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, and the like.

The aforementioned (meth) acrylic cycloaliphatic ester may include, but is not limited to, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and dicyclopentyl (meth) acrylate {or, Tricyclo [5.2.1.0 ^2,6 ] dec-8-yl (meth) acrylate}, dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate or (meth) acrylic acid Tetrahydrofuran ester.

The aryl (meth) acrylate may include, but is not limited to, Group) phenyl acrylate or benzyl methacrylate.

The aforementioned unsaturated dicarboxylic acid ester may include, but is not limited to, diethyl maleate, diethyl fumarate, diethyl itaconic acid, and the like.

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

The aforementioned polyether having a (meth) acrylate group may include, but is not limited to, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and the like.

The aforementioned styrene-based compound may include, but is not limited to, styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, or p-methoxystyrene, and the like.

Unsaturated compounds other than the above compounds may include, but are not limited to, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl ethyl ester, 1,3-butadiene, Isoprene, 2,3-dimethyl 1,3-butadiene, N-butanediimino-3-maleimide benzoate, N-butadiene imino- 4-maleimide iminobutyrate, N-butanediimide imino-6-maleimide iminohexanoate, N-butamidine imino-3-maleimide propionate , N- (9-acridyl) maleimide, N-octylmaleimide, N-cyclohexylmaleimide, or N-phenyl Maleimide (N-phenylmaleimide) and the like.

The aforementioned other copolymerizable ethylenically unsaturated monomers (c-2-2) may be used alone or in combination.

Preferably, the aforementioned other copolymerizable ethylenically unsaturated monomers The body (c-2-2) is selected from methyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, third butyl (meth) acrylate, Benzyl (meth) acrylate, dicyclopentyl (meth) acrylate, isobornyl methacrylate, dicyclopentyloxyethyl (meth) acrylate, styrene, p-methoxystyrene or the above Any combination of compounds.

In a specific example of the present invention, the ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride based on the second alkali-soluble resin (C-2) and other copolymerizable ones The total amount of the ethylenically unsaturated monomer (c-2-2) copolymerization monomer is 100 parts by weight, and the amount of other copolymerizable ethylenically unsaturated monomer (c-2-2) ranges from 10 to 90 parts by weight; preferably 15 to 85 parts by weight; more preferably 20 to 80 parts by weight.

The ethylenically unsaturated monomer (c-2-3) having an epoxy group may include, but is not limited to, a (meth) acrylate compound having an epoxy group, an α -alkylacrylate compound having an epoxy group, or a ring Oxypropyl ether compounds and the like.

The aforementioned (meth) acrylate compound having an epoxy group may include, but is not limited to, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, and (meth) acrylic acid 3,4 -Butylene oxide, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate or 3,4-epoxycyclohexyl methyl (meth) acrylate Wait.

The α -alkyl acrylate compound having an epoxy group may include, but is not limited to, α -ethyl acrylate, α -n-propyl acrylate, α -n-butyl acrylate, or α -Ethacrylic acid-6,7-epoxyheptyl etc.

Glycidyl ether compounds may include, but are not limited to, o-vinylbenzylglycidylether, m-vinylbenzylglycidylether, or p-vinylbenzyl P-vinylbenzylglycidylether and the like.

The ethylenically unsaturated monomer (c-2-3) having an epoxy group may be used alone or in combination.

Preferably, the aforementioned ethylenically unsaturated monomer (c-2-3) having an epoxy group is selected from the group consisting of glycidyl methacrylate, 2-methylglycidyl methacrylate, and methacrylic acid 3,4-epoxycyclohexyl methyl ester, 6,7-epoxyheptyl methacrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-ethylene Benzyl Glycidyl Ether or any combination thereof.

In a specific example of the present invention, the ethylenically unsaturated monomer (c-2-1) having one or more carboxylic acid or carboxylic anhydride based on the second alkali-soluble resin (C-2) and other copolymerizable ones The total amount of the ethylenically unsaturated monomer (c-2-2) copolymerization monomer is 100 parts by weight, and the amount of the ethylenically unsaturated monomer (c-2-3) having an epoxy group ranges It is 1 to 35 parts by weight; preferably 3 to 30 parts by weight; more preferably 5 to 25 parts by weight.

In addition, the above-mentioned second alkali-soluble resin (C-2) has a polystyrene-equivalent number average molecular weight measured by a gel permeation chromatography (GPC) of generally 1,000 to 35,000, preferably 3,000 to 30,000, More preferably, it is 5,000 to 25,000.

In the specific example of this invention, it is based on alkali-soluble resin (C) The sum of the used amounts is 100 parts by weight, and the used amount of the second alkali-soluble resin (C-2) is 0 to 90 parts by weight; preferably 10 to 85 parts by weight; more preferably 20 to 80 parts by weight Parts by weight.

Compounds containing ethylenically unsaturated groups (D)

The compound (D) having an ethylenically unsaturated group of the present invention may include an unsaturated compound having at least one ethylenically unsaturated group and an unsaturated compound having at least two ethylenically unsaturated groups.

Specific examples of the aforementioned unsaturated compound having at least one ethylenically unsaturated group may include, but are not limited to, acrylamide, acrylamidomorpholine, methacrylamidomorpholine, acrylic acid-7-amino-3,7-dimethyl Octyl ester, methacrylic acid 7-amino-3,7-dimethyloctyl ester, isobutoxymethacrylamide, isobutoxymethylmethacrylamide, isobornyl acrylate Ethyl ester, isobornyloxyethyl methacrylate, isobornyl acrylate, isobornyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, ethyldiethylene glycol Acrylate, Ethyl Diethylene Glycol Methacrylate, Third Octyl Acrylamidoxamine, Third Octyl Methacrylamidine, Diacetone Acrylamidine, Diacetone Methacrylamidine, Dimethylamine Acrylate Ester, dimethylamino methacrylate, dodecyl acrylate, dodecyl methacrylate, dicyclopentenyloxyethyl acrylate, dicyclopentenyl ethyl methacrylate, dicyclopentyl acrylate Pentenyl, dicyclopentenyl methacrylate, nitrogen, nitrogen-dimethylacrylamide, nitrogen, nitrogen-dimethylmethacrylamine , Tetrachlorophenyl acrylate, tetrachlorophenyl methacrylate, 2-tetrachlorophenoxyethyl acrylate, 2-tetrachlorophenoxyethyl methacrylate, tetrahydrofurfuryl acrylate, methacrylic acid Tetrahydrofurfuryl ester, tetrabromophenyl acrylate, Tetrabromophenyl methacrylate, 2-tetrabromophenoxyethyl acrylate, 2-tetrabromophenoxyethyl methacrylate, 2-trichlorophenoxyethyl acrylate, methacrylic acid- 2-trichlorophenoxyethyl, tribromophenyl acrylate, tribromophenyl methacrylate, 2-tribromophenoxyethyl acrylate, 2-tribromophenoxyethyl methacrylate, 2-Hydroxyethyl acrylate, 2-Hydroxyethyl methacrylate, 2-Hydroxypropyl acrylate, 2-Hydroxypropyl methacrylate, Vinyl caprolactam, Nitro-vinyl butyrate Ketones, phenoxyethyl acrylate, phenoxyethyl methacrylate, pentachlorophenyl acrylate, pentachlorophenyl methacrylate, pentabromophenyl acrylate, pentabromophenyl methacrylate, polyethyl acrylate Glycol esters, polyethylene glycol monomethacrylate, polypropylene glycol monoacrylate, polypropylene glycol monomethacrylate, bornyl acrylate, or bornyl methacrylate, and the like. The unsaturated compound having at least one ethylenically unsaturated group may be used alone or in combination.

Specific examples of the aforementioned unsaturated compound having at least two ethylenically unsaturated groups may include, but are not limited to, ethylene glycol diacrylate, ethylene glycol dimethacrylate, dicyclopentenyl diacrylate, and dimethacrylic acid. Dicyclopentenyl ester, triethylene glycol diacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, tris (2-hydroxyethyl) isocyanate diacrylate, tris (2-hydroxyethyl) Isocyanate dimethacrylate, tris (2-hydroxyethyl) isocyanate triacrylate, tris (2-hydroxyethyl) isocyanate trimethacrylate, caprolactone modified tris (2-hydroxyethyl) isocyanate Triacrylate, caprolactone modified tris (2-hydroxyethyl) isocyanate trimethacrylate, trimethylol propyl triacrylate, trimethylol propyl trimethacrylate, ethylene oxide ( (Hereinafter referred to as EO) modified trimethylol propyl triacrylate, modified EO trimethacrylate Methyl methyl propyl, propylene oxide (hereinafter referred to as PO) modified trimethylol propyl triacrylate, PO modified trimethylol propyl trimethacrylate, triethylene glycol diacrylate, triethylene glycol Alcohol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, 1 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, polyester di Acrylate, polyester dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate, di Pentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, caprolactone modified dipentaerythritol hexaacrylate, caprolactone modified dipentaerythritol hexamethyl Acrylate, dipentaerythritol pentaacrylate modified by caprolactone, dipentaerythritol pentamethacrylate modified by caprolactone, ditrimethylolpropane tetraacrylate, ditrimethylolpropane tetramethacrylate EO modified bisphenol A diacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol A diacrylate, PO modified bisphenol A dimethacrylate, EO Modified hydrogenated bisphenol A diacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A dimethacrylate PO modified glycerol tripropionate, EO modified bisphenol F diacrylate, EO modified bisphenol F dimethacrylate, novolac polyglycidyl ether acrylate, novolac polyglycidyl ether methyl Acrylate, manufactured by Toa Synthesis Co., Ltd., Japan Products of TO-1382, or products manufactured by Nippon Kayaku Co., Ltd. and whose models are KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, or KAYARAD DPCA-120. Among them, the unsaturated compound having at least two ethylenically unsaturated groups may be used alone or in combination.

Preferably, the compound (D) having an ethylenically unsaturated group is Selected from trimethylolpropyl triacrylate, trimethylolpropyl triacrylate modified by EO, trimethylolpropyl triacrylate modified by PO, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol Hexaacrylate, dipentaerythritol pentaacrylate, dipentaerythritol tetraacrylate, caprolactone modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, PO modified glycerol tripropionate, KAYARAD DPCA -20, KAYARAD DPCA-30, KAYARAD DPCA-60 or KAYARAD DPCA-120 or any combination of the above compounds.

The compound (D) having an ethylenically unsaturated group may be used alone or in combination.

Based on the total use amount of the alkali-soluble resin (C) is 100 parts by weight, the use amount of the compound (D) having an ethylenically unsaturated group is 20 to 200 parts by weight, preferably 30 to 180 parts by weight, And more preferably, it is 50 to 150 parts by weight.

Photoinitiator (E) Photoinitiator (E-1)

The photoinitiator (E) of the present invention may include a photoinitiator (E-1).

The photoinitiator (E-1) has a structure represented by the following formula (III):

In formula (III), E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE ₁₆ , OE ₁₇ , halogen, NO ₂ or ; Or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ respectively independently represent Alkenyl with 2 to 10 carbon atoms substituted; or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ respectively Local common representatives-(CH ₂ ) _p -W- (CH ₂ ) _q- ; or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are independently represented Wherein at least one of E ₁ and E _2, E _2, and E _3, E ₃ and E _4, E ₅ and E _6, E ₆ or E ₇ and E ₇ and E ₈ is E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having a carbon number of 1 to 20, and an alkyl group having a carbon number of 1 to 20 is an unsubstituted or at least one group as shown below Substituted and at least one group is selected from phenyl, halogen, CN, OH, SH, alkoxy having 1 to 4 carbon atoms, (CO) OH or (CO) O (R ₁ ), wherein R ₁ represents An alkyl group having 1 to 4 carbons; or E ₉ , E ₁₀ , E _11, and E ₁₂ each independently represents an unsubstituted phenyl group or a phenyl group substituted with at least one group as shown below, and at least one The group is selected from alkyl, halogen, CN, OE ₁₇ , SE _18, or NE ₁₉ E ₂₀ ; or E ₉ , E ₁₀ , E _11, and E ₁₂ each independently represent halogen, CN, OE ₁₇ , SE ₁₈ , SOE ₁₈ , SO ₂ E ₁₈ or NE ₁₉ E ₂₀ , wherein the substituents OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ are optionally via the groups E ₁₇ , E ₁₈ , E ₁₉ and / or E ₂₀ and a carbon atom of the naphthalene ring of formula (III) form a five-membered ring or a six-membered ring; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent , COE ₁₆ or NO ₂ ; W represents O, S, NE ₂₆ or single bond, p represents an integer from 0 to 3, q represents an integer from 1 to 3, Z ₁ represents CO or a single bond; E ₁₃ represents a carbon number of 1 Alkyl to 20, alkyl having 1 to 20 carbons are unsubstituted or substituted with at least one group as shown below, wherein at least one of the above groups is selected from halogen, E ₁₇ , COOE ₁₇ , OE ₁₇ , SE ₁₈ , CONE ₁₉ E ₂₀ , NE ₁₉ E ₂₀ , PO (OC _k H _{2k + 1} ) ₂ or ; Or E ₁₃ represents an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms is interspersed with one or more O, S, SO, SO ₂ , NE _26, or CO; or E ₁₃ represents a carbon number of Alkenyl radicals of 2 to 12, alkenyl radicals of 2 to 12 carbons are uninterspersed or interspersed with one or more O, CO or NE ₂₆ , of which interstitials and alkyls of 2 to 20 carbons and uninterspersed Or an alkenyl group having 2 to 12 carbon atoms is unsubstituted or substituted with at least one halogen; or E ₁₃ represents a cycloalkenyl group having 4 to 8 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or Unsaturated or insaturated one or more O, S, CO or NE ₂₆ cycloalkyl groups having 3 to 10 carbon atoms; or E ₁₃ represents phenyl or naphthyl, each of which is unsubstituted or as shown below At least one group is substituted, wherein the at least one group is selected from the group consisting of OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , , COE ₁₆ , CN, NO ₂ , halogen, alkyl with 1 to 20 carbons, haloalkyl with 1 to 4 carbons, interspersed with one or more O, S, CO or NE ₂₆ and carbons 2 to Alkyl groups of 20; or phenyl or naphthyl groups each substituted by a cycloalkyl group which is uninterstitial or interspersed with one or more O, S, CO or NE ₂₆ and 3 to 10 carbons; k represents 1 to 10 An integer; E ₁₄ represents a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an unsubstituted or at least as shown below One group substituted alkyl having 1 to 20 carbons, and at least one group is selected from halogen, phenyl, alkylphenyl having 1 to 20 carbons or CN; or E ₁₄ represents phenyl or naphthalene Group, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, halogen, CN , OE ₁₇ , SE ₁₈ and / or NE ₁₉ E ₂₀ ; or E ₁₄ represents a heteroaryl group having 3 to 20 carbons, an alkoxy group, benzyloxy or phenoxy group, 1 to 8 carbon atoms, benzyloxy And phenoxy are unsubstituted or substituted with at least one group as shown below, and at least One group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms and / or a halogen; E ₁₅ represents an aromatic group having 6 to 20 carbon atoms or 3 to 20 carbon atoms Heteroaryl, each unsubstituted or substituted with at least one group as shown below, and at least one group is selected from phenyl, halogen, haloalkyl having 1 to 4 carbons, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , an alkyl group bonded to SO with 1 to 10 carbons, an alkyl group bonded to SO ₂ with 1 to 10 carbons Radical, interspersed with one or more O, S or NE ₂₆ and an alkyl group having 2 to 20 carbons; or an aromatic group having 6 to 20 carbons or a heteroaryl group having 3 to 20 carbons each having a carbon number Is an alkyl substitution of 1 to 20, wherein the alkyl group having 1 to 20 carbons is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from halogen, COOE ₁₇ , CONE ₁₉ E ₂₀ , phenyl, cycloalkyl having 3 to 8 carbons, heteroaryl having 3 to 20 carbons, aryloxycarbonyl having 6 to 20 carbons, heteroaryloxy having 3 to 20 carbons carbonyl group, OE _17, SE _18, or NE ₁₉ E _20; E ₁₅ represents a hydrogen atom or the carbon atoms of the alkenyl group having 2 to 12, Or interrupted by intermingled with one or more O, CO, or NE ₂₆ carbon atoms and a cycloalkyl group of 3 to 8; or E ₁₅ represents a carbon atoms of an alkyl group having 1 to 20 carbon atoms of alkyl type from 1 to 20 Unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of halogen, OE ₁₇ , SE ₁₈ , a cycloalkyl group having 3 to 8 carbon atoms, and a hetero group having 3 to 20 carbon atoms. Aryl, aryloxycarbonyl with 6 to 20 carbons, heteroaryloxycarbonyl with 3 to 20 carbons, NE ₁₉ E ₂₀ , COOE ₁₇ , CONE ₁₉ E ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , Or phenyl, wherein the alkyl group having 1 to 20 carbon atoms is substituted by phenyl, and the phenyl group is halogen, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ represents an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms is interspersed with one or more O, SO or SO ₂ , interspersed with carbon The alkyl group of 2 to 20 is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of halogen, OE ₁₇ , COOE ₁₇ , CONE ₁₉ E ₂₀ , phenyl, or OE. ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ substituted phenyl; or E ₁₅ represents an alkyl or benzamyl group having 2 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below And at least one group is selected from alkyl, halogen, phenyl, OE ₁₇ , SE _18, or NE ₁₉ E _{20 with a} carbon number of 1 to 6, or E ₁₅ represents an unsubstituted or substituted with at least one OE ₁₇ A naphthylmethyl group or a heteroarylcarbonyl group having 3 to 14 carbon atoms; or E ₁₅ represents an alkoxycarbonyl group having 2 to 12 carbon atoms, and an alkoxycarbonyl group having 2 to 12 carbon atoms is not interspersed or Miscellaneous one or more O's Carbon atoms and an alkoxycarbonyl group having 2 to 12 lines of unsubstituted or substituted by at least one hydroxyl group; or E ₁₅ Representative phenoxycarbonyl, phenoxycarbonyl unsubstituted or system of at least one group shown by the following Substituted, and at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, OE ₁₇ , SE _18, or NE ₁₉ E ₂₀ ; or E ₁₅ represents CN, CONE ₁₉ E ₂₀ , NO ₂ , haloalkyl having 1 to 4 carbon atoms, S (O) _r -R ₂ , phenyl bonded to S (O) _r , of which S (O) _{r is} bonded Phenyl is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms or SO ₂ -R ₂ , and R ₂ represents an alkyl group having 1 to 6 carbon atoms; or E ₁₅ represents a bond with SO ₂ O Phenyl, wherein the phenyl bonded to SO ₂ O is unsubstituted or substituted with an alkyl group having 1 to 12 carbons; or E ₁₅ represents diphenylphosphinofluorenyl or bis (R ₃ ) -phosphinofluorene group, and R ₃ represents a carbon atoms of an alkoxy group having 1 to 4; R & lt represents an integer of 1 to 2; E _^'14 represents a one of those defined for the E _14; ^E' ₁₅ represents a ₁₅ for the definition of E one of those; Z ₂ Representative -O -, - S -, - SO- or -SO ₂ -; Z ₃ Representative -O -, - CO -, - S- or a single bond E ₁₆ represents a carbon atoms or an aromatic group of 6 to 20 carbon atoms of the 3 to 20 hetero aryl group, each of which is unsubstituted or substituted with at least one of the groups shown below, and at least one group selected from benzyl Radical, halogen, haloalkyl having 1 to 4 carbon atoms, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , alkane having one or more O, S or NE ₂₆ interspersed with 1 to 20 carbon atoms Or an alkyl group having 1 to 20 carbons, wherein the alkyl group having 1 to 20 carbons is unsubstituted or substituted with at least one group as shown below, wherein at least one group is selected from halogen, COOE ₁₇ , CONE ₁₉ E ₂₀ , phenyl, cycloalkyl with 3 to 8 carbons, heteroaryl with 3 to 20 carbons, aryloxycarbonyl with 6 to 20 carbons, 3 to 20 carbons Heteroaryloxycarbonyl, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₆ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or Substituted by at least one group as shown below, and at least one group is selected from halogen, phenyl, OH, SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (R ₁ ), O (CO)-(R ₁ ), O (CO) -phenyl or (CO) OH or (CO) O (R ₁ ); or E ₁₆ represents an alkyl group having 2 to 12 carbon atoms, and the alkyl group having 2 to 12 carbon atoms is interspersed with one or more O, S, or NE ₂₆ ; or E ₁₆ represents (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, wherein R ₄ represents An alkyl group having 1 to 8 carbons; or E ₁₆ represents a phenyl substituted with SE ₁₈ , where E ₁₈ represents a single bond bonded to the phenyl or naphthyl ring of the carbazole moiety to which COE _{16 is} attached; n represents an integer from 1 to 20; E ₁₇ represents a hydrogen atom, phenyl-R ₅ , and an alkyl group having 1 to 20 carbon atoms, which are unsubstituted or substituted with at least one group as shown below, and at least one The group is selected from halogen, OH, SH, CN, alkenyloxy groups having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (R ₁ ), O (CO)-(R ₁ ), O (CO)-(R ₆ ), phenyl bonded to O (CO), (CO) OH, (CO) O (R ₁ ), cycloalkyl with 3 to 20 carbon atoms, SO _2- (R ₇ ), O (R ₇ ) or a cycloalkyl group having one or more O and 3 to 20 carbon atoms, wherein R ₅ represents an alkyl group having 1 to 3 carbon atoms, and R ₆ represents a carbon number alkenyl group of 2 to 4, carbon atoms and R ₇ represents a haloalkyl group having from 1 to 4; or E ₁₇ substituting An alkyl group having a carbon number of 2 to 20, carbon atoms and an alkyl group of 2 to 20 based interrupted by one or more O, S or NE _26; E _17, or on behalf of _{(CH 2 CH 2 O) n} + 1 H, ( CH ₂ CH ₂ O) _n (CO)-(R ₄ ), alkylene group having 1 to 8 carbon atoms, alkenyl group having 2 to 12 carbon atoms, alkenyl group having 3 to 6 carbon atoms or carbon number A cycloalkyl group of 3 to 20, wherein a cycloalkyl group of 3 to 20 carbon atoms is not interspersed or interspersed with one or more O, S, CO or NE ₂₆ ; or E ₁₇ represents a carbon number of 1 to 8 A group formed by bonding an alkyl group to a cycloalkyl group having a carbon number of 3 to 10, and the above-mentioned groups are not interspersed or interspersed with one or more O's; or E ₁₇ represents benzamidine, benzamidine Is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of alkyl having 1 to 6 carbons, halogen, OH, or alkoxy having 1 to 3 carbons; or E ₁₇ represents a phenyl group, a naphthyl group or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from halogen, OH, carbon number is an alkyl group of 1 to 12 carbon atoms, alkoxy of 1 to 12, CN, NO _2, phenyl -R _8, a phenoxy group, an alkyl group having a carbon number of 1 to 12 Group, a phenyl group, N (R _{9) 2,} diphenyl - group or , Wherein R ₈ represents an alkoxy group having 1 to 3 carbon atoms, and R ₉ represents an alkyl group having 1 to 12 carbon atoms; or E ₁₇ and having or One of the carbon atoms of the phenyl or naphthyl ring forms a single bond; E ₁₈ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or phenyl-R ₅ , wherein An alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and phenyl-R ₅ are free of one or more O, S, CO, NE _26, or COOE ₁₇ ; or E; ₁₈ represents an alkyl group having a carbon number of 1 to 20, an alkyl group having a carbon number of 1 to 20 is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OH, SH, CN, Alkenyloxy groups having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (R ₁ ), O (CO)-(R ₆ ), O (CO)-(R ₁ ), O (CO) -phenyl or-(CO) OE ₁₇ ; or E ₁₈ represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is interspersed with one or more O, S, CO, NE ₂₆ or COOE ₁₇ ; or E ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), alkylalkyl or carbon number of 2 to 8 Is an alkenyl group of 3 to 6; or E ₁₈ represents benzyl group, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from carbon number 1 Alkyl, halogen, OH, carbon to 6 An alkoxy group having 1 to 4 or an alkylthio group having 1 to 4 carbons; or E ₁₈ represents a phenyl group, a naphthyl group or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or is as follows At least one of the groups shown is substituted, and at least one group is selected from the group consisting of halogen, alkyl having 1 to 12 carbons, haloalkyl having 1 to 4 carbons, alkoxy having 1 to 12 carbons, CN, NO ₂ , phenyl-R ₈ , phenoxy, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N (R ₉ ) ₂ , diphenylamino group, (CO) O ( R ₄ ), CO-R ₄ , (CO) N (R ₄ ) ₂ or ; E ₁₉ and E ₂₀ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a carbon number of Alkenyl groups of 2 to 5, cycloalkyl groups of 3 to 20 carbon atoms, phenyl-R ₅ , alkylfluorenyl groups of 1 to 8 carbon atoms, alkylalkyloxy groups of 1 to 8 carbon atoms, carbon number An alkenyl group, SO ₂ -R ₇ or benzamyl group of 3 to 12; or E ₁₉ and E ₂₀ represent a phenyl group, a naphthyl group or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or Substituted by at least one group as shown below, and the at least one group is selected from halogen, haloalkyl having 1 to 4 carbons, alkoxy having 1 to 20 carbons, and 1 to 12 carbons Alkyl, benzamyl, or alkoxy having 1 to 12 carbons; or E ₁₉ and E ₂₀ together with the nitrogen atom to which they are bonded form five members that are not interspersed or interspersed with O, S, or NE ₁₇ Or six-membered saturated or unsaturated ring, and the five- or six-membered saturated or unsaturated ring system is unsubstituted or substituted with at least one group as shown below, wherein at least one group system is selected from a carbon number of 1 to 20 Alkyl group, alkoxy group having 1 to 20 carbon atoms, = O, OE ₁₇ , SE ₁₈ , NE ₂₁ E ₂₂ , (CO) E _{2 3} , NO ₂ , halogen, haloalkyl having 1 to 4 carbon atoms, CN, phenyl, Or a cycloalkyl group with one or more O, S, CO, or NE ₁₇ and 3 or 20 carbon atoms without interstitial or interstitial; or E ₁₉ and E ₂₀ together with the attached nitrogen atom to form a heteroaromatic Ring system, the heteroaromatic ring system is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and 1 to 4 carbon atoms Haloalkyl, alkoxy having 1 to 20 carbon atoms, = O, OE ₁₇ , SE ₁₈ , NE ₂₁ E ₂₂ , (CO) E ₂₃ , , Halogen, NO ₂ , CN, phenyl, or cycloalkyl without one or more O, S, CO, or NE ₁₇ and 3 to 20 carbon atoms; E ₂₁ and E ₂₂ independently represent A hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group or phenyl group having 3 to 10 carbon atoms; E ₂₁ and E ₂₂ together with the nitrogen atom to which they are bonded Forms a five-membered or six-membered saturated or unsaturated ring without interspersed or interspersed O, S or NE ₂₆ , of which five or six-membered saturated or unsaturated ring systems are not fused or fused with benzene rings; E ₂₃ represents Hydrogen atom, OH, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, alkyl group having at least one O, CO or NE ₂₆ interspersed with 2 to 20 carbon atoms, uninterrupted or Cycloalkyl with O, S, CO or NE ₂₆ interspersed and 3 to 20 carbons; or E ₂₃ represents phenyl, naphthyl, phenyl-R ₁ , OE ₁₇ , SE ₁₈ or NE ₂₁ E ₂₂ ; E ₂₄ represents (CO) OE ₁₇ , CONE ₁₉ E ₂₀ , (CO) E ₁₇ or has one of the definitions for E ₁₉ and E ₂₀ ; E ₂₅ represents COOE ₁₇ , CONE ₁₉ E ₂₀ , (CO) E ₁₇ ; Or E ₂₅ has one of the definitions for E ₁₇ ; E ₂₆ represents a hydrogen atom, a carbon number An alkyl group having 1 to 20, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having one or more O or CO atoms and 2 to 20 carbon atoms; or E ₂₆ representing phenyl-R ₁ Or a cycloalkyl group having one or more O or CO and 3 to 8 carbon atoms; or E ₂₆ for (CO) E ₁₉ ; or E ₂₆ for phenyl, which is unsubstituted or as shown below At least one group is substituted and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a halogen, a halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or Provided that the photoinitiator (E-1) having a structure as shown in formula (III) has at least one or .

The photoinitiator (E-1) having a structure as shown in formula (III) is characterized in that the carbazole portion thereof includes at least one annelated unsaturated ring. In other words, at least one pair of E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ .

The aforementioned alkyl group having a carbon number of 1 to 20 is a straight or branched chain and is, for example, a carbon number of 1 to 18, a carbon number of 1 to 4, a carbon number of 1 to 12, a carbon number An alkyl group having 1 to 8 carbon numbers 1 to 8 or 1 to 4 carbon atoms or an alkyl group having 4 to 12 carbon numbers or 4 to 8 carbon numbers; Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, isobutyl, third butyl, pentyl, hexyl, heptyl, 2,4,4-trimethyl Pentyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl and icosyl. An alkyl group having 1 to 6 carbons has the same definition as the above-mentioned alkyl group having 1 to 20 carbons and has the highest corresponding number of carbon atoms.

An unsubstituted or substituted alkyl group having 1 to 20 carbon atoms containing at least one carbon-carbon multiple bond is an alkenyl group described later.

The halogenated alkyl group having 1 to 4 carbons is an alkyl group substituted with halogen as defined later and having 1 to 4 carbon atoms as defined above. Alkyl group may be, for example, mono - or polyhalogenated, until all of the hydrogen atoms replaced by halogen, and may, for example, C _j H _w X _y, where w + y = 2j + 1 and X is halogen, preferably fluorine atom . Specific examples are chloromethyl, trichloromethyl, trifluoromethyl or 2-bromopropyl, especially trifluoromethyl or trichloromethyl.

A hydroxyalkyl group having 2 to 4 carbons means an alkyl group having 2 to 4 carbons substituted with one or two oxygen atoms. The alkyl group may be straight or branched. Specific examples are 2-hydroxyethyl, 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 4-hydroxybutyl, 2-hydroxybutyl , 3-hydroxybutyl, 2,3-dihydroxypropyl or 2,4-dihydroxybutyl.

The alkoxyalkyl group having 2 to 10 carbon atoms is an alkyl group having 2 to 10 carbon atoms through mono-O-heterocycle. An alkyl group having 2 to 10 carbons has the same definition as the aforementioned alkyl group having 1 to 20 carbons and has the highest corresponding number of carbon atoms. Specific examples such as methoxymethyl, methoxyethyl, methoxypropyl, ethoxymethyl Group, ethoxyethyl, ethoxypropyl, propoxymethyl, propoxyethyl, propoxypropyl.

Alkyl groups having 2 to 20 carbon atoms interspersed with one or more O, S, NE ₂₆ or CO are, for example, interspersed with O, S, NE ₂₆ or CO 1 to 9 times, 1 to 5 times, 1 to 3 times, 1 or 2 times. If more than one hetero group is present, they are the same kind or different. The two oxygen atoms are separated by at least one methylene group, preferably at least two methylene groups (ie, ethylidene). These alkyl groups are straight or branched. For example, the following structural units will exist: -CH ₂ -CH ₂ -O-CH ₂ CH ₃ ,-[CH ₂ CH ₂ O] _y -CH ₃ (where y = 1 to 9),-(CH _{2- CH 2 O) 7 -CH 2 CH} 3, -CH 2 -CH (CH 3) -O-CH 2 -CH 2 CH 3, -CH 2 -CH (CH 3) -O-CH 2 -CH 3, - CH ₂ -CH ₂ -S-CH ₂ CH ₃ , -CH ₂ -CH (CH ₃ ) -NE ₂₆ -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -COO-CH ₂ CH ₃ or -CH _2- CH (CH ₃ ) -OCO-CH ₂ -CH ₂ CH ₃ .

In the present invention, a cycloalkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms can be understood as an alkyl group containing at least one ring. Specific examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, pentylcyclopentyl and cyclohexyl. In the present invention, a cycloalkyl group having 3 to 10 carbon atoms also covers an example of a bicyclic ring, that is, a bridged ring, and a specific example may be , , , And other corresponding rings. Other specific examples can be, for example, , , (E.g )or And other structures, as well as bridged or fused ring systems, for example, the definition here also includes or And other structures in which R ₁₀ represents an alkylene group and R ₁₁ represents an alkyl group.

A cycloalkyl group having a carbon number of 3 to 20 interspersed with O, S, NE ₂₆ or CO has the same definition as above, wherein at least one -CH ₂ -group of the alkyl group is replaced with O, S, NE ₂₆ or CO . Specific examples such as , , (E.g ), , , , , or And other structures.

The group formed by the bonding of an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms refers to a carbon number as defined above substituted with at least one alkyl group having up to 8 carbon atoms 3 to 10 cycloalkyl. The specific example is or Wait.

A group formed by bonding an alkyl group having 1 to 8 carbon atoms with one or more O and a cycloalkyl group having 3 to 10 carbon atoms refers to a group substituted with at least one alkyl group having up to 8 carbon atoms. As defined before, one or more cycloalkyl groups having a carbon number of 3 to 10 are intermingled. Specific examples such as or Wait.

An alkoxy group having 1 to 12 carbons is an alkyl group having 1 to 12 carbons substituted with one oxygen atom. An alkyl group having 1 to 12 carbons has the same definition as the aforementioned alkyl group having 1 to 20 carbons and has the highest corresponding number of carbon atoms. Alkoxy groups having 1 to 4 carbon atoms are straight or branched, such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy Or third butoxy. The alkoxy group having 1 to 8 carbons and the alkoxy group having 1 to 4 carbons are the same as defined above and have the highest corresponding number of carbon atoms.

The alkylthio group having 1 to 12 carbons is an alkyl group having 1 to 12 carbons substituted with one sulfur atom. An alkyl group having 1 to 12 carbons has the same definition as the aforementioned alkyl group having 1 to 20 carbons and has the highest corresponding number of carbon atoms. Alkylthio groups having 1 to 4 carbons are straight or branched, such as methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, second butyl Thio, isobutylthio, and third butylthio.

Phenyl-R ₅ may be, for example, benzyl, phenylethyl, α -methylbenzyl or α , α -dimethyl-benzyl, especially benzyl.

Phenyl-R ₈ may be, for example, benzyloxy, phenylethoxy, α -methylbenzyloxy or α , α -dimethylbenzyloxy, especially benzyloxy.

Alkenyl groups having 2 to 12 carbon atoms are mono- or polyunsaturated and are, for example, alkenyl groups having 2 to 10 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, and 2 to 5 carbon atoms The alkenyl. Specific examples such as vinyl, allyl, methallyl, 1,1-dimethylallyl, 1-butenyl, 3-butenyl, 2-butenyl, 1,3-pentyl Dienyl, 5-hexenyl, 7-octenyl or dodecenyl, especially allyl. The alkenyl group having 2 to 5 carbon atoms has the same definition as the aforementioned alkenyl group having 2 to 12 carbon atoms and has the highest corresponding number of carbon atoms.

Alkenyl systems with one or more O, S, NE _26, or CO atoms having 2 to 12 carbon atoms, for example, 1 to 9 times, 1 to 5 times, 1 to 3 times through O, S, NE _26, or CO 1 or 2 times. If more than one hetero group is present, they are the same kind or different. The two oxygen atoms are separated by at least one methylene group, preferably at least two methylene groups (ie, ethylidene). Alkenyl is straight or branched and is as defined previously. For example, the following structural units may be formed: -CH = CH-O-CH ₂ CH ₃ , -CH = CH-O-CH = CH ₂ and the like.

A cycloalkenyl group having 4 to 8 carbon atoms has at least one double bond, and may be, for example, a cycloalkenyl group having 4 to 6 carbon atoms or a cycloalkenyl group having 6 to 8 carbon atoms. Specific examples are cyclobutenyl, cyclopentenyl, cyclohexenyl or cyclooctenyl, especially cyclopentenyl and cyclohexenyl, and cyclohexenyl is preferred.

The alkenyloxy group having 3 to 6 carbon atoms is mono- or polyunsaturated, and has one of the definitions of the aforementioned alkenyl groups, and the attached oxygen group has the highest corresponding number of carbon atoms. Specific examples are allyloxy, methallyloxy, butenyloxy, pentenyloxy, 1,3-pentadienyloxy, 5-hexenyloxy.

The alkynyl group having 2 to 12 carbon atoms is a mono- or polyunsaturated straight or branched chain, and may be, for example, an alkynyl group having 2 to 8 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or a carbon number of 2 to 4-alkynyl. Specific examples such as ethynyl, propynyl, butynyl, 1-butynyl, 3-butynyl, 2-butynyl, pentynylhexynyl, 2-hexynyl, 5-hexynyl, octynyl, and the like.

Alkyl groups having 2 to 20 carbons are straight or branched, and may be, for example, 2 to 18 carbons, 2 to 14 carbons, 2 to 12 carbons, 2 to 8 carbons, carbon Alkyl groups having 2 to 6 or 2 to 4 carbons or alkyl groups having 4 to 12 carbons or 4 to 8 carbons. Specific examples such as ethenyl, propionyl, butyryl, isobutyryl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, fifteen Fluorenyl, hexadecyl, octadecyl, and icosyl, preferably ethenyl. Alkyl groups having 1 to 8 carbons have the same definition as the aforementioned alkyl groups having 2 to 20 carbon numbers and have the highest corresponding number of carbon atoms.

Alkoxycarbonyl groups having 2 to 12 carbons are straight or branched, and are, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, 1, 1-dimethylpropoxycarbonyl, pentoxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonoxycarbonyl, decoxycarbonyl or dodecyloxycarbonyl, especially methoxy A carbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an n-butoxycarbonyl group, or an isobutoxycarbonyl group, preferably a methoxycarbonyl group.

The alkoxycarbonyl group having 2 to 12 carbon atoms interspersed with one or more O may be straight or branched. The two oxygen atoms are separated by at least two methylene (ie, ethylene). The meta heteroalkoxycarbonyl group is unsubstituted or substituted with one or more hydroxyl groups. The aryloxycarbonyl group having 6 to 20 carbon atoms may be, for example, a phenyloxycarbonyl group (= phenyl-O- (CO) O-), a naphthyloxycarbonyl group, an anthracenoxycarbonyl group, and the like. Carbon number is The heteroarylcarbonyl group of 5 to 20 may be a heteroaryl group having 5 to 20 carbon atoms bonded to -O-CO-.

The cycloalkylcarbonyl group having 3 to 10 carbon atoms may be a cycloalkyl group having 3 to 10 carbon atoms bonded to CO, wherein the cycloalkyl group has the same definition as the foregoing and has the highest corresponding number of carbon atoms. A cycloalkylcarbonyl group having 3 to 10 carbon atoms interspersed with one or more O, S, NE _26, or CO refers to a cycloalkyl group bonded to CO, wherein the cycloalkyl group having the same heterocyclic group is the same as described above. Definition.

The cycloalkoxycarbonyl group having 3 to 10 carbon atoms may be a cycloalkyl group having 3 to 10 carbon atoms bonded to -O- (CO)-, wherein the cycloalkyl group has the same definition as the foregoing and has the highest definition Corresponding number of carbon atoms. A cycloalkoxycarbonyl group having 3 to 10 carbon atoms interspersed with one or more O, S, NE ₂₆ or CO refers to a cycloalkyl group bonded to -O- (CO)- Cycloalkyl has the same definition as before.

An alkylphenyl group having a carbon number of 1 to 20 refers to a phenyl group substituted with at least one alkyl group, in which the total of carbon atoms is at most 20.

An aryl group having 6 to 20 carbon atoms may be, for example, phenyl, naphthyl, anthracenyl, phenanthryl, fluorenyl, 1,2-benzophenanthryl, tetraphenyl, diphenyltriphenyl, etc., especially benzene Or naphthyl, preferably phenyl. Naphthyl is 1-naphthyl or 2-naphthyl.

In the content of the photoinitiator (E-1) of the present invention, the heteroaryl group having 3 to 20 carbon atoms includes a monocyclic or polycyclic system, such as a fused ring system. Specific examples may be thienyl, benzo [b] thienyl, naphtho [2,3-b] thienyl, thienthyl, furanyl, dibenzofuranyl, Fluorenyl, xanthenyl, thioxanthenyl, phenoxathiol, pyrrolyl, imidazolyl, pyrazolyl, pyrazinyl, pyrimidinyl, pyridazinyl, midazoinyl, isoindolyl, indolyl , Indazolyl, purinyl, quinazinyl, isoquinolinyl, quinolinyl, phthalazinyl, naphthyridinyl, quinoxalinyl, quinazolinyl, Porphyrinyl, pyridinyl, carbazolyl, β -fluorinyl, phenanthridyl, acridinyl, naphthylazine, phenanthroline, phenothiyl, isothiazolyl, phenothiazinyl , Isoxazolyl, furfuryl, phenoxal, 7-phenanthryl, anthraquinone-2-yl (= 9,10-dioxo-9,10-dihydroanthracen-2-yl), 3 -Benzo [b] thienyl, 5-benzo [b] thienyl, 2-benzo [b] thienyl, 4-dibenzofuryl, 4,7-dibenzofuryl, 4-methyl -7-dibenzofuranyl, 2-xanthenyl, 8-methyl-2-xanthenyl, 3-xanthenyl, 2-phenoxanthenyl, 2,7-phenoxanthenyl, 2 -Pyrrolyl, 3-pyrrolyl, 5-methyl-3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-methyl-4-imidazolyl, 2-ethyl-4 -Imidazolyl, 2-ethyl-5-imidazolyl, 1H-tetrazol-5-yl, 3-pyrazolyl, 1-methyl-3-pyrazolyl, 1-propyl-4-pyrazolyl , 2-pyrazinyl, 5,6-dimethyl-2-pyrazinyl, 2-indolizinyl, 2-methyl-3-isoindolyl, 2-methyl-1-isoindole , 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-purine , 2-quinazinyl, 3-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl, 3-methoxy-6-isoquinolinyl, 2-quinolinyl, 6- Quinolinyl, 7-quinolinyl, 2-methoxy-3-quinolinyl, 2-methoxy-6-quinolinyl, 6-phthalazinyl, 7-phthalazinyl, 1-methoxy -6-phthalazinyl, 1,4-dimethoxy-6-phthalazinyl, 1,8-naphthyridin-2-yl, 2-quinoxalinyl, 6-quinoxalinyl, 2, 3-dimethyl-6-quinoxaline group, 2,3-dimethoxy-6-quinoxaline group, 2-quinazolinyl group, 7-quinazolinyl group, 2-dimethylamino group -6-quinazolinyl, 3- Phenyl, 6- Phenyl, 7- Phenyl, 3-methoxy-7- Phenyl, 2-pyridinyl, 6-pyridinyl, 7-pyridinyl, 6,7-dimethoxy-2-pyridinyl, 2-carbazolyl, 3-carbazolyl, 9- Methyl-2-carbazolyl, 9-methyl-3-carbazolyl, β -fluorin-3-yl, 1-methyl-β-fluorin-3-yl, 1-methyl-β- Perylene-6-yl, 3-phenanthridyl, 2-acridyl, 3-acridyl, 2-naphthylazine, 1-methyl-5-naphthylazine, 5-phenanthroline, 6-phenanthroline, 1-phenazinyl, 2-phenazinyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-phenthiazinyl , 3-phenothiazinyl, 10-methyl-3-phenothiazinyl, 3-isooxazolyl, 4-isooxazolyl, 5-isooxazolyl, 4-methyl-3-furanyl Group, 2-phenoxa group, 10-methyl-2-phenoxa group and the like.

Preferably, the heteroaryl group having a carbon number of 3 to 20 may be a thienyl group, a benzo [b] thienyl group, a thienyl group, a thienyl group, a 1-methyl-2-indolyl group, or a 1-methyl group. -3-indolyl. More preferably, a heteroaryl group having 3 to 20 carbon atoms may be a thienyl group.

A heteroarylcarbonyl group having 4 to 20 carbon atoms is a heteroaryl group having 3 to 20 carbon atoms as defined above, which is connected to the rest of the molecule via a CO group.

Substituted aryl (phenyl, naphthyl, aryl having 6 to 20 carbons or heteroaryl having 5 to 20 carbons) is 1 to 7 times, 1 to 6 times, or 1 to 4 times, respectively. , Preferably by 1, 2, or 3 substitutions. An aryl group must not have more substituents than there are free positions on the aryl ring.

The substituent on the phenyl ring is preferably in position 4 on the phenyl ring or in a 3,4-, 3,4,5-, 2,6-, 2,4-, or 2,4,6-configuration .

Groups that have been interspersed at least once are, for example, 1 to 19 times, 1 to 15 times, 1 to 12 times, 1 to 9 times, 1 to 7 times, 1 to 5 times, 1 to 4 Times, 1 to 3 times, or 1 or 2 times (the number of interstitial atoms depends on the number of carbon atoms to be interstitial). Substituted groups at least once have, for example, 1 to 7, 1 to 5, 1 to 4, 1 to 3, or 1 or 2 identical or different substituents.

A group substituted with at least one substituent as defined above means having at least one substituent that is the same or different. Halogen is fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine, and more preferably fluorine and chlorine.

For example, if E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ or E ₅ and R ₆ , E ₆ and E ₇ , E ₇ and E ₈ are independently , Then a structure such as the following formula (IIIa) to formula (IIIi) is formed: Among them, the structure of formula (IIIa) is preferred.

The compound of formula (III) 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 structures of the above formula (IIIa) to (IIIi) is shown according to formula (III).

If E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ or E ₅ and R ₆ , E ₆ and E ₇ , E ₇ and E ₈ are independently-(CH ₂ ) _p -W- ( CH ₂ ) _q- , then for example or And other structures.

If the substituent OE on the phenyl or naphthyl ring ₁₇ , SE ₁₈ SOE ₁₈ , SO ₂ E ₁₈ Or NE ₁₉ E ₂₀ Via group E ₁₇ , E ₁₈ , E ₁₉ And / or E ₂₀ By forming a five-membered or six-membered ring with one carbon atom of the naphthyl ring, a structure including 3 or more rings (including the naphthyl ring) is obtained. Specific examples can be, for example, or Wait.

If E ₁₇ has or A single bond on one of the carbon atoms of the phenyl or naphthyl ring of the group forms, for example or And other structures.

If E ₁₆ is a phenyl substituted with SE ₁₈ , where E ₁₈ represents a single bond bonded to a phenyl or naphthyl ring having a carbazole moiety of COE ₁₆ , the structure formed may be, for example, , . That is, if E ₁₆ is a phenyl substituted with SE ₁₈ , where the group E ₁₈ represents a single bond bonded to a phenyl or naphthyl ring having a carbazole moiety of COE ₁₆ to form a thioxanthyl moiety A phenyl or naphthyl ring with a carbazole moiety.

If E ₁₉ and E ₂₀ together with the bonded nitrogen atom form a five- or six-membered saturated or unsaturated ring that is not interspersed or interspersed with O, S, or NE ₁₇ , the saturated or unsaturated ring formed may Examples are aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydropyridine or morpholine. Preferably, if E ₁₉ and E ₂₀ together with the bonded nitrogen atom form a five-membered or six-membered saturated or unsaturated ring which is not interspersed or interspersed with O, S or NE ₁₇ , then an unsaturated or interstitial ring is formed. There are O or NE _{17 in between} , especially five or six member O saturated rings.

If E ₂₁ and E ₂₂ together with the bonded nitrogen atom form a five- or six-membered saturated or unsaturated ring that is not interspersed or interspersed with O, S, or NE ₂₆ , and the benzene ring is selectively The unsaturated ring is fused, and the saturated or unsaturated ring formed may be, for example, aziridine, pyrrole, thiazole, pyrrolidine, oxazole, pyridine, 1,3-diazine, 1,2-diazine, hexahydro Pyridine or morpholine or the corresponding ring (e.g. ).

If E ₁₉ and E ₂₀ form a heteroaromatic ring system together with the nitrogen atom to which they are bonded, the heteroaromatic ring system means that it contains more than one ring (for example, 2 or 3 rings) and is from the same species or different One or more kinds of heteroatoms. Suitable heteroatoms may be, for example, N, S, O or P, especially N, S or O. Specific examples include carbazole, indole, isoindole, indazole, purine, isoquinoline, quinoline, oxoline, phenothiazine, and the like.

The term "and / or" or "or / and" in the context of the present invention means that not only one of the defined substituents may exist, but also a total of several defined substituents, that is, different substitutes ( Substituents).

The "at least" is defined as one or more than one, such as one or two or three, preferably one or both.

Throughout this specification and the scope of patent applications below, unless the context requires otherwise, the word "comprise" or variations (e.g., "comprises" or "comprising") shall be understood to imply the inclusion of the stated integer or Step or integer group or step group, but does not exclude any other integer or step or integer group or step group. The "(meth) acrylate" in the context of the present invention is intended to mean an acrylate and the corresponding methacrylate.

The preferred ones shown in the text used for the compounds of the present invention in the context of the present invention are intended to refer to all categories of patent application scope, that is, to the patent application scope of compositions, uses, methods, color filters, and the like.

The oxime ester represented by formula (III) is prepared by a conventional method, for example, by reacting the corresponding oxime with a halogen, especially a chloride or an acid anhydride, under the following conditions: Ether, tetrahydrofuran (THF) or dimethylformamide), in the presence of a base such as triethylamine or pyridine, or in a basic solvent such as pyridine. In one embodiment of the present invention, the compound of formula (IIIa) is prepared by the following formula (i), wherein E ₇ is an oxime ester group ( ) And Z ₁ is a single bond. The compounds represented by formulae (IIIb) to (IIIh) are prepared in the same way, but are carried out by using a suitable oxime.

In formula (i), E ₁ , E ₂ , E ₅ , E ₆ , E ₈ , E ₁₃ , E ₁₄ and E ₁₅ are as defined above, and X means a halogen atom, especially a chlorine atom.

Preferably, E ₁₄ is methyl.

The above reaction shown by formula (i) is well known to those having ordinary knowledge in the technical field, and is usually carried out at a temperature of -15 ° C to + 50 ° C, preferably at a temperature of 0 ° C to 25 ° C. .

When Z ₁ is CO, the corresponding oxime is obtained by using alkyl nitrite (such as methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite, or isoamyl nitrite). Synthesized by methyl nitrosation. Then, the esterification is performed under the same conditions as described above, and the detailed preparation method is as shown in formula (ii).

Therefore, the corresponding oxime compound can be obtained by, for example, Zhi Ling or as The acid anhydride is reacted to prepare a compound of formula (III) as defined above, wherein X is a halogen atom, and especially a chlorine atom, and the definition of E ₁₄ is as described above.

The oxime required as a starting material can be obtained from standard chemistry textbooks (such as J. March, Advanced Organic Chemistry, 4th Edition, Wiley Interscience, 1992) or monographs (such as S.R. Sandler & W. Karo, Organic functional group preparations, 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 the base can be added continuously at the beginning or during the reaction. It is also possible to use a basic solvent such as pyridine as the base and / or solvent or co-solvent. The reaction temperature is usually from room temperature to the reflux temperature of the mixture, and is generally about 20 ° C to 120 ° C.

The corresponding ketone intermediates are prepared, for example, by methods described in the literature (e.g. standard chemistry textbooks, e.g. J. March, Advanced Organic Chemistry, 4th edition, Wiley Interscience, 1992). In addition, the continuous Friedel-Crafts reaction can be effectively used for the synthesis of intermediates. These reactions are well known to those skilled in the art.

Another convenient synthesis of oximes is the use of nitrous acid or alkyl nitrite to "active" methylene nitrite. 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, for example, Organic Synthesis coll (Vol. V, pages 32 and 373, coll. Vol. III, pages 191 and 513, coll. Vol. II, pages 202, 204 and 363) Suitable for the preparation of oximes used as starting materials in the present invention. Nitrite is generally produced from sodium nitrite. Nitrite The alkyl ester may be, for example, methyl nitrite, ethyl nitrite, propyl nitrite, butyl nitrite, or isoamyl nitrite.

In another embodiment, the photoinitiator (E-1) is a free oxime compound and has a structure represented by the following formula (IIIA):

In formula (IIIA), E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE ₁₆ , OE ₁₇ , halogen atom, NO ₂ or ; Or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ respectively independently represent Alkenyl with 2 to 10 carbon atoms substituted, or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are independent Local common representatives-(CH ₂ ) _p -W- (CH ₂ ) _q- ; or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ are independently and jointly represented Wherein at least one of E ₁ and E _2, E _2, and E _3, E ₃ and E _4, E ₅ and E _6, E ₆ or E ₇ and E ₇ and E ₈ is ; E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 20 carbon atoms is unsubstituted or at least one group as shown below Group substitution and at least one group is selected from phenyl, halogen atom, CN, OH, SH, alkoxy group having 1 to 4 carbon atoms, (CO) OH or (CO) O (R ₁ ), where R ₁ represents an alkyl group having 1 to 4 carbons; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represents an unsubstituted phenyl group or a phenyl group substituted with at least one group as shown below, the At least one group is selected from the group consisting of an alkyl group having a carbon number of 1 to 6, a halogen atom, CN, OE ₁₇ , SE _18, or NE ₁₉ E ₂₀ ; or E ₉ , E ₁₀ , E _11, and E ₁₂ each independently represent a halogen Atom, CN, OE ₁₇ , SE ₁₈ , SOE ₁₈ , SO ₂ E ₁₈ or NE ₁₉ E ₂₀ , wherein the substituents OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ are optionally via the groups E ₁₇ , E ₁₈ , E ₁₉ and / or E ₂₀ and a carbon atom of the naphthalene ring in formula (IIIA) form a five-membered ring or a six-membered ring; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent , COE ₁₆ or NO ₂ ; W represents O, S, NE ₂₆ or single bond, p represents an integer from 0 to 3, q represents an integer from 1 to 3, Z ₁ represents CO or a single bond; E ₁₃ represents a carbon number of 1 Alkyl to 20, alkyl having 1 to 20 carbons are unsubstituted or substituted with at least one group as shown below, wherein at least one of the above groups is selected from halogen atoms, E ₁₇ , COOE ₁₇ , OE ₁₇ , SE ₁₈ , CONE ₁₉ E ₂₀ , NE ₁₉ E ₂₀ , PO (OC _k H _{2k + 1} ) ₂ or ; Or E ₁₃ represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is interspersed with one or more O, S, SO, SO ₂ , NE _26, or CO; or E ₁₃ represents a carbon number An alkenyl group of 2 to 12 and an alkenyl group of 2 to 12 carbons are interspersed or interspersed with one or more O, CO or NE ₂₆ , wherein the interstitialed and alkyl groups of 2 to 20 and Interstitial or interstitial alkenyl having 2 to 12 carbons is unsubstituted or substituted with at least one halogen atom; or E ₁₃ represents a cycloalkenyl having 4 to 8 carbons and an alkynyl having 2 to 12 carbons , Or without or with one or more O, S, CO or NE ₂₆ cycloalkyl groups having a carbon number of 3 to 10; or E ₁₃ represents phenyl or naphthyl, each of which is unsubstituted or is as follows The at least one group shown is substituted, wherein the at least one group is selected from the group consisting of OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , , COE ₁₆ , CN, NO ₂ , halogen atom, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, interspersed with one or more O, S, CO or NE ₂₆ and carbon number 2 Alkyl groups of 20 to 20; or each substituted by a cycloalkyl group which is unsubstituted or interspersed with one or more O, S, CO, or NE ₂₆ and has a carbon number of 3 to 10; k represents an integer of 1 to 10; E ₁₅ Representing an aromatic group having 6 to 20 carbon atoms or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from phenyl, Halogen atom, haloalkyl having 1 to 4 carbon atoms, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , bonded to SO and having 1 to 4 carbon atoms An alkyl group having 10, an alkyl group having 1 to 10 carbon atoms bonded to SO ₂ , an alkyl group having one or more O, S or NE ₂₆ interspersed with 2 to 20 carbon atoms; or each having a carbon number of 1 to 20 alkyl substitutions, in which the alkyl group having 1 to 20 carbons is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from halogen atoms, COOE ₁₇ , CONE ₁₉ E _20, a phenyl group, a cycloalkyl group having a carbon number of 3 to 8 carbon atoms, a heteroaryl group of 3-20 Carbon atoms, an aryloxycarbonyl group of 6 to 20 of carbon atoms heteroaryl aryloxycarbonyl group 3 to 20 of, OE _17, SE _18, or NE ₁₉ E _20; or E ₁₅ represents a hydrogen atom, a carbon number of 2 to 12 of Alkenyl, cycloalkyl without one or more O, CO or NE ₂₆ and 3 to 8 carbons; or E ₁₅ representing an alkyl with 1 to 20 carbons and 1 to 20 carbons The alkyl group is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OE ₁₇ , SE ₁₈ , a cycloalkyl group having 3 to 8 carbon atoms, and a carbon number of Heteroaryl groups of 3 to 20, aryloxycarbonyl groups of 6 to 20 carbons, heteroaryloxycarbonyl groups of 3 to 20 carbons, NE ₁₉ E ₂₀ , COOE ₁₇ , CONE ₁₉ E ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , , Or phenyl, in which the alkyl group having 1 to 20 carbon atoms is substituted by phenyl, and the phenyl group is halogen atom, alkyl group having 1 to 20 carbon atoms, haloalkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₅ represents an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms is interspersed with one or more O, SO or SO ₂ , interspersed with carbon The alkyl group of 2 to 20 is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OE ₁₇ , COOE ₁₇ , CONE ₁₉ E ₂₀ , phenyl or OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ substituted phenyl; or E ₁₅ represents an alkyl or benzamyl group having 2 to 20 carbon atoms, which is unsubstituted or at least one group as shown below Substituted, and at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a phenyl group, OE ₁₇ , SE _18, or NE ₁₉ E ₂₀ ; or E ₁₅ represents an unsubstituted group or at least one OE ₁₇ A substituted naphthylmethyl group or a heteroarylcarbonyl group having 3 to 14 carbons; or E ₁₅ represents an alkoxycarbonyl group having 2 to 12 carbons, and an alkoxycarbonyl group having 2 to 12 carbons is not Miscellaneous or miscellaneous one or more O, where And intermingled with or without a carbon number of alkoxycarbonyl group of 2 to 12 based unsubstituted or substituted with at least one hydroxyl group; or E ₁₅ Representative phenoxycarbonyl, phenoxycarbonyl unsubstituted or system as shown by the following At least one group is substituted and at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, a phenyl group, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; Or E ₁₅ represents CN, CONE ₁₉ E ₂₀ , NO ₂ , a halogenated alkyl group having 1 to 4 carbon atoms, S (O) _r -R ₂ , a phenyl group bonded to S (O) _r , wherein S (O) O) _R- bonded phenyl is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms or SO ₂ -R ₂ , and R ₂ represents an alkyl group having 1 to 6 carbon atoms; or E ₁₅ represents an alkyl group with SO ₂ O bonded phenyl, diphenylphosphinofluorenyl, or bis (R ₃ ) -phosphinofluorenyl, wherein the phenyl bonded to SO ₂ O is an unsubstituted or alkane having 1 to 12 carbon atoms substituent group, and R ₃ represents a carbon atoms of an alkoxy group having 1 to 4; R & lt represents an integer of 1 to 2; E _^'15 represents a one of those defined for E, _15; Z ₂ representative of O, S, SO, or SO _2; Z ₃ representative of O, CO, S or a single bond; E ₁₆ represents a carbon atoms or an aryl group of 6 to 20 carbon atoms of the 3 to 20 An aryl group, each of which is unsubstituted or substituted with at least one of the groups shown below, and at least one group selected from a phenyl group, a halogen atom, a haloalkyl group having a carbon number of 1 to 4, CN, NO _2, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , an alkyl group having one or more O, S, or NE ₂₆ and a carbon number of 1 to 20, or an alkyl group of 1 to 20 carbon, wherein the carbon number is 1 to 20 The alkyl group is unsubstituted or substituted with at least one group shown below, wherein at least one group is selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , phenyl, and a cycloalkane having 3 to 8 carbon atoms. A heteroaryl group having 3 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 20 carbon atoms, a heteroaryloxycarbonyl group having 3 to 20 carbon atoms, OE ₁₇ , SE _18, or NE ₁₉ E ₂₀ ; or E ₁₆ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, wherein the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from Halogen atom, phenyl, OH, SH, CN, alkenyloxy group having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (R ₁ ), O (CO)-(R ₁ ), O (CO) phenyl or (CO) OH or _{(CO) O (R 1)} ; or E ₁₆ represents a carbon number of 2 to 12 alkoxy , An alkyl group having a carbon number of 2 to 12 based interrupted by one or more O, S or NE _26; E _16, or on behalf of _{(CH 2 CH 2 O) n} + 1 H, (CH 2 CH 2 O) n (CO) -(R ₄ ), an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, wherein R ₄ represents an alkyl group having 1 to 8 carbon atoms; or E ₁₆ represents substitution with SE ₁₈ Phenyl, where E ₁₈ represents a single bond bonded to the phenyl or naphthyl ring of the carbazole moiety to which COE _{16 is} attached; n represents an integer from 1 to 20; E ₁₇ represents a hydrogen atom, phenyl-R _5. An alkyl group having a carbon number of 1 to 20, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OH, SH, CN, and a carbon number of 3 Alkenyloxy to 6, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (R ₁ ), O (CO)-(R ₁ ), O (CO)-(R ₆ ), and O (CO ) Bonded phenyl, (CO) OH, (CO) O (R ₁ ), cycloalkyl with 3 to 20 carbon atoms, SO _2- (R ₇ ), O (R ₇ ) or one or more interspersed O and a cycloalkyl group having 3 to 20 carbon atoms, wherein R ₅ represents an alkyl group having 1 to 3 carbon atoms, R ₆ represents an alkenyl group having 2 to 4 carbon atoms, and R ₇ represents 1 to 3 carbon atoms A halogenated alkyl group of 4; or E ₁₇ represents an alkyl group having 2 to 20 carbon atoms, and the carbon number is 2 to 20 alkyl groups are interspersed with one or more O, S or NE ₂₆ ; or E ₁₇ represents (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), Alkyl groups of 1 to 8 carbons, alkenyl groups of 2 to 12 carbons, alkenyl groups of 3 to 6 carbons or cycloalkyl groups of 3 to 20 carbons, which are not interspersed Or interspersed with one or more O, S, CO or NE ₂₆ ; or E ₁₇ represents a group formed by bonding an alkyl group having 1 to 8 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms, and the above-mentioned groups One or more O's are unattached or anodic; or E ₁₇ represents benzamyl, which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected From an alkyl group having 1 to 6 carbon atoms, a halogen atom, OH or an alkoxy group having 1 to 3 carbon atoms; or E ₁₇ represents a phenyl group, a naphthyl group or a heteroaryl group having 3 to 20 carbon atoms, each of which Unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of a halogen atom, OH, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, CN , NO ₂ , phenyl-R ₈ , phenoxy, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N (R ₉ ) ₂ , diphenyl-amine group or , Wherein R ₈ represents an alkoxy group having 1 to 3 carbon atoms, and R ₉ represents an alkyl group having 1 to 12 carbon atoms; or E ₁₇ and having or One of the carbon atoms of the phenyl or naphthyl ring forms a single bond; E ₁₈ represents a hydrogen atom, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms or phenyl-R ₅ , wherein An alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and phenyl-R ₅ are free of one or more O, S, CO, NE _26, or COOE ₁₇ ; or E; ₁₈ represents an alkyl group having a carbon number of 1 to 20, and the alkyl group having a carbon number of 1 to 20 is unsubstituted or substituted with at least one group of the following formula, and at least one group is selected from OH, SH, CN, Alkenyloxy groups having 3 to 6 carbon atoms, OCH ₂ CH ₂ CN, OCH ₂ CH ₂ (CO) O (R ₁ ), O (CO)-(R ₆ ), O (CO)-(R ₁ ), O (CO) -phenyl or (CO) OE ₁₇ ; or E ₁₈ represents an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms is interspersed with one or more O, S, CO, NE ₂₆ or COOE ₁₇ ; or E ₁₈ represents (CH ₂ CH ₂ O) _n H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), an alkyl group having 2 to 8 carbon atoms, or a carbon number of An alkenyl group of 3 to 6; or E ₁₈ represents a benzamyl group, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a carbon number of 1 to 6 alkyl, halogen atom, OH Carbon atoms, alkoxy having 1 to 4 carbon atoms or an alkyl group of 1 to 4; or E ₁₈ represents phenyl, naphthyl or heteroaryl having a carbon number of 3 to 20 aryl group, each of which is unsubstituted or At least one group substituted as shown below, and at least one group is selected from the group consisting of a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. Group, CN, NO ₂ , phenyl-R ₈ , phenoxy, alkylthio group having 1 to 12 carbon atoms, phenylthio group, N (R ₉ ) ₂ , diphenylamino group, (CO) O (R ₄ ), CO-R ₄ , (CO) N (R ₄ ) ₂ or ; E ₁₉ and E ₂₀ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, an alkoxyalkyl group having 2 to 10 carbon atoms, and a carbon number of Alkenyl groups of 2 to 5, cycloalkyl groups of 3 to 20 carbon atoms, phenyl-R ₅ , alkylfluorenyl groups of 1 to 8 carbon atoms, alkylalkyloxy groups of 1 to 8 carbon atoms, carbon number An alkenyl group, SO ₂ -R ₇ or benzamyl group of 3 to 12; or E ₁₉ and E ₂₀ represent a phenyl group, a naphthyl group or a heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or Substituted by at least one group as shown below, and the at least one group is selected from a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 1 to 12 carbon atoms Alkyl, benzamidine, or alkoxy groups having 1 to 12 carbons; or E ₁₉ and E ₂₀ together with the nitrogen atom to which they are bonded are not interspersed or interspersed with O, S or NE ₁₇ five -Membered or six-membered saturated or unsaturated ring, and the five-membered or six-membered saturated or unsaturated ring system is unsubstituted or substituted with at least one group as shown below, wherein at least one group system is selected from a carbon number of 1 to 20 alkyl group, alkoxy group having 1 to 20 carbon atoms, = O, OE ₁₇ , SE ₁₈ , NE ₂₁ E ₂₂ , ( CO) E ₂₃ , NO ₂ , halogen atom, haloalkyl having 1 to 4 carbon atoms, CN, phenyl, Or a cycloalkyl group that is not interspersed or interspersed with at least one O, S, CO, or NE ₁₇ and has a carbon number of 3 to 20; or E ₁₉ and E ₂₀ together with the attached nitrogen atom form a heteroaromatic ring System, the heteroaromatic ring system is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and 1 to 4 carbon atoms Haloalkyl, alkoxy having 1 to 20 carbon atoms, = O, OE ₁₇ , SE ₁₈ , NE ₂₁ E ₂₂ , (CO) E ₂₃ , , A halogen atom, NO ₂ , CN, phenyl, or a cycloalkyl group having one or more O, S, CO, or NE ₁₇ and 3 to 20 carbon atoms without being interspersed or interspersed; E ₂₁ and E ₂₂ are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a cycloalkyl group or phenyl group having 3 to 10 carbon atoms; E ₂₁ and E _{22 are} nitrogen atoms to which they are bonded. Together form a five- or six-membered saturated or unsaturated ring that is not interspersed or interspersed with O, S or NE ₂₆ , wherein the five- or six-membered saturated or unsaturated ring system is not fused or fused with a benzene ring; E ₂₃ represents a hydrogen atom, OH, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O, CO or NE ₂₆ interspersed with 2 to 20 carbon atoms, Interspersed or interspersed O, S, CO or NE ₂₆ and a cycloalkyl group having 3 to 20 carbons; or E ₂₃ represents phenyl, naphthyl, phenyl-R ₁ , OE ₁₇ , SE ₁₈ or NE ₂₁ E ₂₂ ; E ₂₄ represents (CO) OE ₁₇ , CONE ₁₉ E ₂₀ , (CO) E ₁₇ or has one of the definitions for E ₁₉ and E ₂₀ ; E ₂₅ represents COOE ₁₇ , CONE ₁₉ E ₂₀ , (CO) E _17; or for those having one of the definitions E _17; E ₂₆ represents a hydrogen atom, Alkyl having from 1 to 20, the haloalkyl group having a carbon number of 1 to 4, intermingled with at least one O or CO and alkyl having 2 to 20; or E ₂₆ represents phenyl -R _1, not intermingled Or a cycloalkyl group with one or more O or CO and 3 to 8 carbon atoms; or E ₂₆ for (CO) E ₁₉ ; or E ₂₆ for phenyl, E ₂₆ is unsubstituted or as shown below At least one group is substituted, and the at least one group is selected from an alkyl group having 1 to 20 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or Provided that the photoinitiator (E-1) having a structure as shown in formula (IIIA) has at least one or .

For the group defined for the compound represented by the formula (IIIA), it preferably corresponds to the group defined for the compound of the formula (III) as follows, but only the defined oxime ester group (for example ) Are replaced by the corresponding free oxime group .

Each oxime ester group can exist in two configurations (Z) or (E). Isomers can be separated by conventional methods, but it is also possible to use a mixture of isomers as, for example, a photoinitiator. Therefore, the photoinitiator (E-1) of the present invention, such as the compound represented by the formula (III), contains a mixture of configurational isomers.

In a preferred embodiment, the photoinitiator (C) includes a photoinitiator (E-1) having a structure shown in formula (III), wherein E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, , COE ₁₆ or NO ₂ ; or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ respectively and jointly represent Wherein at least one of E ₁ and E _2, E _2, and E _3, E ₃ and E _4, E ₅ and E _6, E ₆ or E ₇ and E ₇ and E ₈ is Z ₁ represents CO or a single bond; E ₁₃ represents an alkyl group having 1 to 20 carbons, and an alkyl group having 1 to 20 carbons is unsubstituted or substituted with at least one group as shown below, and at least one group The group is selected from a halogen atom, OE ₁₇ , SE ₁₈ , COOE ₁₇ , CONE ₁₉ E _20, or PO (OC _k H _{2k + 1} ) ₂ ; or E ₁₃ represents an alkyl group having 2 to 20 carbon atoms, interspersed with an Or more O, S, NE ₂₆ or CO; or E ₁₃ represents phenyl or naphthyl, both of which are unsubstituted or at least one Or COE ₁₆ substitution; E ₁₄ represents an alkyl, phenyl or alkoxy group having 1 to 20 carbons; E ₁₅ represents a phenyl, naphthyl, or hetero aromatic group having 3 to 20 carbons Group, each of which is unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from the group consisting of a phenyl group, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ , An alkyl group having at least one O or S and a carbon number of 2 to 20, or each of which is substituted with one or more alkyl groups having a carbon number of 1 to 20, and the alkyl group having a carbon number of 1 to 20 is not Substituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , phenyl, a cycloalkyl group having 3 to 8 carbon atoms, and a carbon number of Heteroaryl groups of 3 to 20, aryloxycarbonyl groups of 6 to 20 carbons, heteroaryloxycarbonyl groups of 4 to 20 carbons, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or PO (OC _k H _{2k +1} ) ₂ ; or E ₁₅ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OE ₁₇ , SE ₁₈ , Cycloalkyl with 3 to 8 carbons, Heteroaryl with 3 to 20 carbons, NE ₁₉ E ₂₀ , COOE ₁₇ , CONE ₁₉ E ₂₀ or PO (OC _k H _{2k + 1} ) ₂ ; E _'14 represents one of the definitions for E ₁₄ ; E' ₁₅ represents one of the definitions for E ₁₅ ; E ₁₆ represents phenyl, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , and at least one O, S or NE ₂₆ and an alkyl group having a carbon number of 2 to 20; or E ₁₆ represents a phenyl group which is substituted with at least one alkyl group having a carbon number of 1 to 20, wherein the alkyl group having a carbon number of 1 to 20 is unsubstituted or Substituted by at least one group as shown below, and at least one group is selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , a phenyl group, a cycloalkyl group having 3 to 8 carbon atoms, and a carbon number of 3 to 20 Heteroaryl, aryloxycarbonyl having 6 to 20 carbons, heteroaryloxycarbonyl having 4 to 20 carbons, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₆ represents a carbon number of 1 to Alkyl group of 20, E ₁₆ is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from halogen atom, phenyl, OH, SH, CN, and carbon number of 3 to 6 Alkenyloxy, OCH ₂ CH ₂ (CO) O (R ₁ ), O (CO)-(R ₁ ) Or (CO) O (R ₁ ); E ₁₇ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from halogen Atom, OCH ₂ CH ₂ (CO) O (R ₁ ), O (R ₁ ), (CO) O (R ₁ ), cycloalkyl group having 3 to 20 carbon atoms, in which the ring having 3 to 20 carbon atoms Alkyl is unsubstituted or at least one O; or E ₁₇ represents an alkyl having 2 to 20 carbons, and alkyl is at least one O having 2 to 20 carbons; E ₁₈ represents substituted with (CO) OE ₁₇ E ₁₉ and E ₂₀ each independently represent a hydrogen atom, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 1 to 8 carbon atoms, or an alkyl group oxygen having 1 to 8 carbon atoms Or E ₁₉ and E ₂₀ together with the bonded nitrogen atom to form a heteroaromatic ring system, the heteroaromatic ring system is unsubstituted or Substitution, provided that the photoinitiator (E-1) has a structure as shown in formula (III) has at least one or .

Attention must be paid to compounds of formula (III) as defined above, wherein E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom, , COE ₁₆ or NO ₂ ; E ₃ and E ₄ together are E ₉ , E ₁₀ , E ₁₁ and E ₁₂ are hydrogen atoms; Z ₁ is a single bond; E ₁₃ is an alkyl group having 1 to 20 carbons; E ₁₄ is an alkyl group having 1 to 20 carbons; E ₁₅ It is an alkyl group having 1 to 20 carbons or a phenyl group substituted with at least one of the following groups, at least one of which may be OE ₁₇ or an alkyl group having 1 to 20 carbons; E ₁₆ is a phenyl group and benzene The group is substituted with at least one of the following groups, wherein at least one group may be OE ₁₇ or an alkyl group having 1 to 20 carbon atoms; E ₁₇ is unsubstituted or substituted with at least one halogen atom and 1 or A 20 alkyl group or an alkyl group having 1 to 20 carbon atoms interspersed with at least one oxygen atom.

Provided that at least one of the compounds of the structural formula shown by formula (III) .

In a more preferred embodiment, the photoinitiator (C) comprises a photoinitiator (E-1) having a structure shown in formula (III), wherein E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom; or E ₁ and E ₂ , E ₃ and E ₄ or E ₅ and E ₆ each independently represent each other And at least one of E ₁ and E ₂ , E ₃ and E ₄ or E ₅ and E ₆ is Or E ₂ stands for , COE ₁₆ , NO ₂ or ; Or E ₇ representative Or COE ₁₆ ; E ₉ , E ₁₁ and E ₁₂ represent hydrogen atoms; E ₁₀ represents a hydrogen atom, OE ₁₇ or COE ₁₆ ; Z ₁ represents CO or a single bond; E ₁₃ represents an alkyl group having 1 to 20 carbon atoms, which Is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, E ₁₇ , OE ₁₇ , SE ₁₈ or PO (OC _k H _{2k + 1} ) ₂ ; or E ₁₃ Represents an alkyl group having a carbon number of 2 to 20, and is interspersed with at least one O; or E ₁₃ represents a phenyl group; k represents an integer 2; E ₁₄ represents an alkyl group or thienyl group having a carbon number of 1 to 20; E ₁₅ represents benzene Or naphthyl, each of which is unsubstituted or substituted with at least one OE ₁₇ or alkyl having 1 to 20 carbons; or E ₁₅ represents a thienyl, hydrogen atom, or alkyl having 1 to 20 carbons, wherein An alkyl group having 1 to 20 carbons is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OE ₁₇ , SE ₁₈ , a cycloalkyl group having 3 to 8 carbons, NE ₁₉ E ₂₀ or COOE ₁₇ ; or E ₁₅ represents an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms is mixed with SO ₂ ; E ₁₆ represents a phenyl group or a naphthyl group, each of which is not Substituted or substituted with at least one group as shown below, and at least one Group selected from _{OE 17, SE 18, NE 19} E 20 carbon atoms or an alkyl group of 1 to 20; E _16, or on behalf of thienyl; E ₁₇ represents a hydrogen atom, an alkyl carbon atoms or acyl of 1 to 8 carbon Alkyl groups of 1 to 20, alkyl groups of 1 to 20 carbons are unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from halogen atoms, O (CO) -(R ₁ ), O (CO)-(R ₆ ), or a cycloalkyl group interspersed with at least one O and a carbon number of 3 to 20; or E ₁₇ represents an alkyl group having a carbon number of 2 to 20 and the carbon number It is 2 to 20 alkyl groups with at least one O; E ₁₈ represents a cycloalkyl group having 3 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms, which are unsubstituted or undergo at least one OH, O (CO )-(R ₆ ) or (CO) OE ₁₇ substitution; or E ₁₈ represents phenyl, which is unsubstituted or substituted with at least one halogen atom; E ₁₉ and E ₂₀ each independently represent a carbon number of 1 to 8 An alkyl fluorenyl group or an alkyl alkoxy group having 1 to 8 carbon atoms; or E ₁₉ and E ₂₀ together with the bonded nitrogen atom to form a five-membered or six-membered saturated ring with O, provided that the formula is The photoinitiator (E-1) having the structure shown in (III) has at least one .

Specific examples of the photoinitiator (E-1) of the present invention are compounds of formulae (IIIa) to (IIIg) as defined above, formulae (IIIa), (IIIb), (IIIc), and especially formula ( IIIa) or formula (IIIc), or formula (IIIa), formula (IIIc) or formula (IIId), especially compounds of formula (IIIa) are of interest.

In an example, E ₁ , E ₂ , E ₃ , E ₄ , E ₅ , E ₆ , E ₇ and E ₈ each independently represent a hydrogen atom, Or COE ₁₆ or E ₁ and E ₂ , E ₂ and E ₃ , E ₃ and E ₄ , E ₅ and E ₆ , E ₆ and E ₇ or E ₇ and E ₈ .

In one example, E ₁ and E ₂ or E ₃ and E _{4 are} collectively , Or E ₃ and E ₄ , E ₅ and E ₆ together ; E ₃ and E _{4 are} particularly common .

In one example, E ₁ , E ₅ , E ₆ and E ₈ represent hydrogen atoms. Preferably, E ₇ represents a hydrogen atom, Or COE ₁₆ or E ₇ Or COE ₁₆ but E ₇ For the better. Preferably, E ₂ represents , COE ₁₆ or Or E ₁ and E ₂ together for the Of course, it is better to use E ₂ for COE ₁₆ . Z _{1 is} preferably a single bond.

In an example, E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group, or substituted with at least one group as shown below. Phenyl, and at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE ₁₇ or SE ₁₈ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a halogen atom, OE ₁₇ , SE ₁₈ , or NE ₁₉ E ₂₀ , wherein the substituents OE ₁₇ , SE _18, or NE ₁₉ E ₂₀ are optionally via the groups E ₁₇ , E ₁₈ , E ₁₉ and / or E ₂₀ and formula (III) A carbon atom of the naphthalene ring in the five- or six-membered ring; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent Or COE ₁₆ .

In a specific example, E ₉ , E ₁₀ , E _11, and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group, or at least one group as shown below. A substituted phenyl group, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE ₁₇ or SE ₁₈ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a halogen Atomic, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent Or COE ₁₆ .

In an example, E ₉ , E ₁₀ , E _11, and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group, or 1 to 2 carbon atoms 6 alkyl-substituted phenyl groups; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent Or COE ₁₆ .

In another example, E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group or substituted with at least one group as shown below Phenyl, and at least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE ₁₇ or SE ₁₈ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a halogen atom, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ , wherein the substituents OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ are optionally via the groups E ₁₇ , E ₁₈ , E ₁₉ and / or E ₂₀ and any of formula (III) One carbon atom of the naphthalene ring forms a five-membered ring or a six-membered ring.

In addition, in one example, E ₉ , E ₁₀ , E _11, and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group, or at least one group as shown below. At least one of the substituted phenyl groups is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OE ₁₇ or SE ₁₈ ; or E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a halogen atom, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or COE ₁₆ .

Alternatively, in an example, E ₉ , E ₁₀ , E ₁₁ and E ₁₂ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an unsubstituted phenyl group, or at least one group as shown below the substituted phenyl group, at least one group selected from an alkyl group having a carbon number of 1-6, a halogen atom, _{OE. 17} or SE _18; or E _9, E _10, E ₁₁ and E ₁₂ each independently represents a halogen atom, OE ₁₇ , COE ₁₆ or NE ₁₉ E ₂₀ .

Preferably, E ₉ , E ₁₁ and E ₁₂ are hydrogen atoms, and E ₁₀ is a hydrogen atom, OE ₁₇ or COE ₁₆ .

E _{13 is} , for example, an alkyl group having a carbon number of 1 to 20, which is unsubstituted or substituted with at least one group as shown below, wherein the at least one group described above is selected from a halogen atom, COOE ₁₇ or CONE ₁₉ E ₂₀ ; or E ₁₃ represents an alkyl group having 2 to 20 carbon atoms, and the alkyl group having 2 to 20 carbon atoms is interspersed with one or more O, S, SO, SO ₂ , NE _26, or CO; E ₁₃ represents carbon Alkenyl groups having 2 to 12 carbon atoms, and alkenyl groups having 2 to 12 carbon atoms are not heterocyclic or interspersed with one or more O, CO or NE ₂₆ ; or E ₁₃ represents a cycloalkyl group having 3 to 10 carbon atoms. Alkyl is unsubstituted or one or more O, S, CO or NE ₂₆ ; or E ₁₃ represents phenyl or naphthyl, each of which is unsubstituted or substituted with at least one group as shown below, wherein At least one group is selected from OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , , COE ₁₆ , NO ₂ , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkyl group having at least one O heterocycle and 2 to 20 carbon atoms; or representing a carbon number An alkyl group of 1 to 20, which is unsubstituted or substituted with at least one group as shown below, wherein the at least one group is selected from the group consisting of a halogen atom, E ₁₇ , COOE ₁₇ , OE ₁₇ , SE ₁₈ , CONE ₁₉ E ₂₀ or PO (OC _k H _{2k + 1} ) ₂ ; or an alkyl group having 2 to 20 carbon atoms, interspersed with one or more O.

In addition, E ₁₃ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, wherein the at least one group is selected from the group consisting of a halogen atom, E ₁₇ , COOE ₁₇ , OE ₁₇ , SE ₁₈ , CONE ₁₉ E ₂₀ or PO (OC _k H _{2k + 1} ) ₂ ; or represents an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms is mixed with an O; Or represents an alkenyl group having 2 to 12 carbon atoms and a cycloalkyl group having 3 to 10 carbon atoms; or E ₁₃ represents a phenyl group or a naphthyl group, each of which is an unsubstituted or at least one group as shown below Substitution, wherein at least one group is selected from OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , COE ₁₆ , NO ₂ , a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and an alkyl group having 2 to 20 carbon atoms interspersed with one or more O atoms.

In another embodiment, E ₁₃ represents an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, wherein the at least one group described above is selected from halogen atoms, E ₁₇ , OE ₁₇ , SE ₁₈ , or PO (OC _k H _{2k + 1} ) ₂ ; or represents an alkyl group having one or more O interspersed with 2 to 20 carbons; or an olefin having 2 to 12 carbons Radical, cycloalkyl, phenyl or naphthyl having 3 to 10 carbon atoms.

Alternatively, E ₁₃ may represent, for example, an alkyl group having a carbon number of 1 to 20, which is unsubstituted or substituted with at least one group as shown below, wherein the at least one group described above is selected from a halogen atom, E ₁₇ , OE ₁₇ , SE ₁₈ or PO (OC _k H _{2k + 1} ) ₂ ; or represents at least one O hetero and alkyl group having 2 to 20 carbon atoms; or represents phenyl, alkenyl group or carbon having 2 to 12 carbon atoms The number is 3 to 10 cycloalkyl.

Alternatively, E ₁₃ may represent an alkyl group having 1 to 20 carbon atoms, a phenyl group, an alkenyl group having 2 to 12 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. Or E ₁₃ is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. Preferably, E ₁₃ may represent an alkyl group having 1 to 20 carbon atoms, especially an alkyl group having 1 to 8 carbon atoms, such as 2-ethylhexyl.

E ₁₄ may, for example, represent a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, It is unsubstituted or substituted with at least one halogen atom or phenyl; or E ₁₄ represents phenyl or naphthyl, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is Selected from an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a halogen atom, OE ₁₇ , SE _18, and / or NE ₁₉ E ₂₀ ; or E ₁₄ represents a hetero atom having 3 to 5 carbon atoms Aryl, such as thienyl, or an alkoxy, benzyloxy or phenoxy group having 1 to 8 carbons.

Alternatively, E ₁₄ represents a carbon atoms may be, for example, an alkyl group of 1 to 20, carbon atoms and at least one halogen atom or a phenyl group substituted with an alkyl group of 1 to 20 by line; E ₁₄ represents a carbon or hetero atoms of 3 to 5 Aryl (e.g. thienyl) or represents a phenyl group which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from an alkyl group having 1 to 6 carbon atoms and a carbon number of 1 to A halogenated alkyl group, a halogen atom, OE ₁₇ , SE _18, and / or NE ₁₉ E ₂₀ ; or E ₁₄ represents an alkoxy group, a benzyloxy group, or a phenoxy group having a carbon number of 1 to 8.

In another embodiment, E ₁₄ represents an alkyl group having 1 to 20 carbon atoms, and the alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with a phenyl group; or E ₁₄ is phenyl group and the phenyl group is not Substituted or substituted with at least one alkyl group having 1 to 6 carbons.

Preferably, E ₁₄ is an alkyl group having 1 to 20 carbon atoms, a heteroaryl group having 3 to 5 carbon atoms (such as thienyl), or a phenyl group, especially an alkyl group having 1 to 20 carbon atoms or The thienyl group is more preferably an alkyl group having 1 to 8 carbon atoms.

E ₁₅ may be, for example, an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 5 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected From a phenyl group, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ , an alkyl group having 1 to 20 carbon atoms; or an E ₁₅ series hydrogen atom 3, a cycloalkyl group having 3 to 8 carbon atoms, wherein the cycloalkyl group having 3 to 8 carbon atoms is not interspersed or interspersed with one or more O, CO or NE ₂₆ ; or E ₁₅ series is 1 to 20 Alkyl group, an alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, OE ₁₇ , and a carbon number of 3 to 8 Cycloalkyl, heteroaryl with 5 to 20 carbons, phenoxycarbonyl with 8 to 20 carbons, heteroaryloxy-carbonyl with 5 to 20 carbons, NE ₁₉ E ₂₀ , COOE ₁₇ , CONE ₁₉ E ₂₀ , PO (OC _k H _{2k + 1} ) ₂ , , Phenyl or phenyl substituted with a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ or NE ₁₉ E ₂₀ ; Or E ₁₅ is an alkyl group having 2 to 20 carbons, and the alkyl group having 2 to 20 carbons is mixed with at least one O, S or SO ₂ , or E ₁₅ is an alkyl group having 2 to 20 carbons , Benzamidine, alkoxycarbonyl having 2 to 12 carbons, phenoxycarbonyl, CONE ₁₉ E ₂₀ , NO ₂ or haloalkyl having 1 to 4 carbons.

In addition, E ₁₅ may be, for example, a hydrogen atom, an aryl group having 6 to 20 carbon atoms, especially a phenyl or naphthyl group, each of which is unsubstituted or substituted with an alkyl group having 1 to 12 carbon atoms. ; Or a heteroaryl group having 3 to 5 carbons, such as thienyl; or a cycloalkyl group having 3 to 8 carbons, and an alkyl group having 1 to 20 carbons, which are unsubstituted or are as follows And at least one group is selected from the group consisting of OE ₁₇ , SE ₁₇ , a cycloalkyl group having 3 to 8 carbon atoms, NE ₁₉ E ₂₀ or COOE ₁₇ ; or E _{15 having} a carbon number of 2 To 20 alkyl groups, and alkyl groups having 2 to 20 carbon atoms are mixed with at least one O or SO ₂ .

In the compound represented by formula (III), E ₁₅ may be, for example, a hydrogen atom, a phenyl group, or a naphthyl group, each of which is unsubstituted or substituted with an alkyl group having 1 to 8 carbon atoms; or E ₁₅ is a thienyl group Alkyl group having 1 to 20 carbons, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from the group consisting of OE ₁₇ , SE ₁₇ , and 3 to 8 carbon rings Alkyl, NE ₁₉ E ₂₀ or COOE ₁₇ ; or E ₁₅ is an alkyl group having 2 to 20 carbon atoms, and an alkyl group having 2 to 20 carbon atoms is mixed with at least one O or SO ₂ .

E ₁₅ is, for example, a cycloalkyl group having 3 to 8 carbon atoms or an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Of alkyl.

The better of E _'14 and E' ₁₅ respectively have one of the definitions for E ₁₄ and E ₁₅ above.

Z ₂ is, for example, O, S or SO, such as O or S, and especially O.

E ₁₆ may be, for example, an aryl group (especially phenyl or naphthyl, especially phenyl) having 6 to 20 carbon atoms or a heteroaryl group (especially thienyl) having 5 to 20 carbon atoms, each of which is unsubstituted or At least one group substituted as shown below, and at least one group is selected from the group consisting of phenyl, halogen atom, haloalkyl having 1 to 4 carbon atoms, CN, NO ₂ , OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ Or at least one O with 1 to 20 carbons; or each substituted with at least one 1 to 20 carbons, the 1 to 20 carbons are unsubstituted or At least one group is substituted, and at least one group is selected from the group consisting of a halogen atom, COOE ₁₇ , CONE ₁₉ E ₂₀ , a phenyl group, a cycloalkyl group having 3 to 8 carbon atoms, and a heteroaromatic group having 5 to 20 carbon atoms Group, aryloxycarbonyl group having 6 to 20 carbons, heteroaryloxycarbonyl group having 5 to 20 carbons, OE ₁₇ , SE ₁₈ or NE ₁₉ E ₂₀ ; or E ₁₆ series hydrogen atom, carbon number 1 to An alkyl group of 20 and an alkyl group having 1 to 20 carbon atoms is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from halogen atom, phenyl group, OH, SH, carbon Alkenyloxy groups of 3 to 6, OCH ₂ CH ₂ (CO) O (R ₁ ), O (CO)-(R ₁ ), O (CO) -phenyl, (CO) OH or (CO) O (R ₁ ); or E ₁₆ is an alkyl group having 2 to 12 carbon atoms, and the carbon number is 2 There is at least one O between alkyl groups to 12; or E ₁₆ series (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), and carbon number is 2 to 12 Alkenyl or cycloalkyl having 3 to 8 carbons, and n is 1 to 20, such as 1 to 12 or 1 to 8, especially 1 or 2.

In addition, E ₁₆ may be, for example, phenyl or naphthyl, especially phenyl, thienyl, or carbazole, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from Phenyl, halogen atom, halogenated alkyl group having 1 to 4 carbon atoms, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or alkyl group having 1 to 20 carbon atoms; or E ₁₆ series alkyl group having 1 to 20 carbon atoms , An alkyl group having a carbon number of 1 to 20 is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a halogen atom, a phenyl group, OH, SH, and a carbon number of 3 to 6 Alkenyloxy, OCH ₂ CH ₂ (CO) O (R ₁ ), O (CO)-(R ₁ ), O (CO) -phenyl, (CO) OH or (CO) O (R ₁ ); Or E ₁₆ is an alkyl group having 2 to 12 carbons, and the alkyl group having 2 to 12 carbons is mixed with at least one O; or E ₁₆ is (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ), an alkenyl group having 2 to 12 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms, and n is 1 to 20, such as 1 to 12 or 1 to 8 , Especially 1 or 2.

In addition, E ₁₆ may be, for example, phenyl or naphthyl, especially phenyl, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a phenyl group, a halogen atom, Haloalkyl having 1 to 4 carbons, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ or alkyl having 1 to 20 carbons; or E ₁₆ is a heteroaryl group having 3 to 5 carbons, especially thienyl .

E ₁₆ is, for example, phenyl, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from OE ₁₇ , SE ₁₈ , NE ₁₉ E _20, or a carbon number of Alkyl of 1 to 20, or E _16- based thienyl.

Preferably, E ₁₆ is, for example, phenyl or naphthyl, each of which is unsubstituted or substituted with at least one alkyl group having 1 to 20 carbon atoms.

E _{16 is} especially phenyl, and phenyl is substituted with at least one alkyl group having 1 to 20 carbons.

E ₁₇ may be, for example, a hydrogen atom, phenyl-R ₅ , an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from Halogen atom, OH, OCH ₂ CH ₂ (CO) O (R ₁ ), O (CO)-(R ₁ ), O (CO)-(R ₆ ), O (CO) -phenyl, (CO) OH , (CO) O (R ₁ ), a cycloalkyl group having 3 to 20 carbon atoms or a cycloalkyl group having 3 to 20 carbon atoms interspersed with at least one O; or an E _17- based alkane having 2 to 20 carbon atoms And at least one O between alkyl groups having 2 to 20 carbon atoms; or E ₁₇ series (CH ₂ CH ₂ O) _{n + 1} H, (CH ₂ CH ₂ O) _n (CO)-(R ₄ ) Alkyl groups having 1 to 8 carbons, alkenyl groups having 2 to 12 carbons, alkenyl groups having 3 to 6 carbons or cycloalkyl groups having 3 to 20 carbons, which are not interspersed or Interspersed with at least one O; or E ₁₇ is benzamidine, and the benzamidine is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from a carbon number of 1 to 6 alkyl group, halogen atom, OH or alkoxy group having 1 to 3 carbon atoms; or E ₁₇ phenyl group, naphthyl group or heteroaryl group having 5 to 20 carbon atoms, each of which is unsubstituted or substituted Substituted with at least one group as shown below, and Less in a group selected from a halogen atom, OH, an alkyl group having a carbon number of 1-12, an alkoxy group having a carbon number of 1 to 12, CN, NO _2, phenyl -R _8, a phenoxy group, C Alkylthio, phenylthio, N (R ₉ ) ₂ , diphenyl-amino or .

In another embodiment, E ₁₇ is, for example, a hydrogen atom, phenyl-R ₅ , an alkyl group having 1 to 20 carbon atoms, which is unsubstituted or substituted with at least one group as shown below, and At least one group is selected from the group consisting of a halogen atom, O (CO)-(R ₁ ), O (CO)-(R ₆ ), or an alkyl group having a carbon number of 2 to 20 interspersed with at least one O; or E ₁₇ Alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, alkenyl groups having 3 to 6 carbon atoms, alkyl groups having 2 to 20 carbon atoms interspersed with at least one O, and Via a heterocycle or a heterocycle containing at least one O, a cycloalkyl group having a carbon number of 3 to 20; or E ₁₇ is benzamidine, which is unsubstituted or substituted with at least one group as shown below, and At least one group is selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, OH or an alkoxy group having 1 to 3 carbon atoms; or an E _17- based phenyl or naphthyl group, each of which is unsubstituted or Substituted by at least one group as shown below, and at least one group is selected from a halogen atom, an alkyl group having 1 to 12 carbons or an alkoxy group having 1 to 12 carbons.

E ₁₇ is also, for example, a hydrogen atom, phenyl-R ₅ , an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 20 carbon atoms, which are unsubstituted or at least one Group substituted, and at least one group is selected from the group consisting of a halogen atom, a cycloalkyl group having 3 to 20 carbon atoms, O (CO)-(R ₁ ), O (CO)-(R ₆ ), or An O is an alkyl group having 2 to 20 carbons, or an E _17- based alkyl group having 2 to 20 carbons, with at least one O interposed therebetween.

E _{17 is} especially a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, and an alkyl group having 1 to 20 carbon atoms, which are unsubstituted or substituted with at least one group as shown below, and at least one group It is selected from the group consisting of O (CO)-(R ₁ ), O (CO)-(R ₆ ) or an alkyl group having 2 to 20 carbon atoms, or E ₁₇ series having 2 to 20 carbon atoms. The alkyl group is mixed with at least one O in between.

E ₁₈ is, for example, a cycloalkyl group having 3 to 20 carbon atoms, which is not interspersed or interspersed with at least one O; or E ₁₈ is an alkyl group, which is 1 to 20 carbons, which is unsubstituted or modified as follows And at least one group is selected from the group consisting of OH, O (CO)-(R ₆ ), O (CO)-(R ₁ ), or (CO) OE ₁₇ ; or E ₁₈ series carbon. Alkyl groups of 2 to 20, intermixed with at least one O, S, CO, NE ₂₆ or COOE ₁₇ ; or E ₁₈ is an alkylalkyl group having 2 to 8 carbon atoms or an alkylene group having 3 to 6 carbon atoms Group, benzamyl group; or E _18- based phenyl, naphthyl or heteroaryl group having 3 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and at least one group It is selected from a halogen atom, an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or NO ₂ .

In another embodiment, E ₁₈ is, for example, a cycloalkyl group having 3 to 20 carbon atoms and an alkyl group having 1 to 20 carbon atoms, which are unsubstituted or substituted with at least one group as shown below And at least one group is selected from OH, O (CO)-(R ₆ ), O (CO)-(R ₁ ), or (CO) OE ₁₇ ; or E ₁₈ is phenyl or naphthyl, each Unsubstituted or substituted with at least one halogen atom or an alkyl group having 1 to 12 carbon atoms, especially a halogen atom.

E ₁₈ is, for example, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, phenyl-R ₅ , and 2 to 8 carbon atoms Alkyl, benzamyl, phenyl or naphthyl.

For example, E ₁₈ is an alkyl group having 1 to 20 carbon atoms, which is substituted with at least one group as shown below, and at least one group is selected from OH, O (CO)-(R ₆ ), O (CO)-(R ₁ ) or (CO) OE ₁₇ , or E _18- based phenyl, which is substituted with at least one halogen atom.

Preferably, E ₁₈ is an alkyl group having 1 to 8 carbons, which is substituted as defined above.

For example, E ₁₉ and E ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl group. -R ₅ , phenyl or naphthyl, an alkylfluorenyl group having 1 to 8 carbon atoms, an alkylfluorenyloxy group having 1 to 8 carbon atoms, and an alkenyl group or benzamyl group having 3 to 12 carbon atoms; Or E ₁₉ and E ₂₀ together with the bonded nitrogen atom form a five- or six-membered saturated or unsaturated ring that is not interspersed or interspersed with O, S or NE ₁₇ ; or E ₁₉ and E ₂₀ are bonded to the bonded nitrogen atom The bound nitrogen atoms together form a heteroaromatic ring system. The heteroaromatic ring system is unsubstituted or substituted with at least one group as shown below, and at least one group is selected from an alkyl group having 1 to 20 carbon atoms. , A halogenated alkyl group having 1 to 4 carbon atoms, or .

In addition, for example, E ₁₉ and E ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, Phenyl-R ₅ , an alkylfluorenyl group having 1 to 8 carbon atoms, an alkylfluorenyloxy group having 1 to 8 carbon atoms, an alkenyl group or benzamyl group having 3 to 12 carbon atoms; or E ₁₉ and E ₂₀ forms a five- or six-membered saturated ring without nitrogen or O or NE ₁₇ together with the bonded nitrogen atom; or E ₁₉ and E ₂₀ together with the bonded nitrogen atom to form a carbazole ring .

For example, E ₁₉ and E ₂₀ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 2 to 4 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a phenyl group. -R ₅ , an alkylfluorenyl group having 1 to 8 carbon atoms, an alkylfluorenyloxy group having 1 to 8 carbon atoms, an alkenyl group or benzamyl group having 3 to 12 carbon atoms; or E ₁₉ and E ₂₀ It forms a five- or six-membered saturated ring with or without O or NE ₁₇ together with the bonded nitrogen atom.

Preferably, E ₁₉ and E ₂₀ are each independently an alkylfluorenyl group having 1 to 8 carbon atoms, and an alkylfluorenyloxy group having 1 to 8 carbon atoms; or E ₁₉ and E ₂₀ are nitrogen bonded to each other The atoms form a morpholine ring.

For example, E ₂₁ and E ₂₂ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group or phenyl group having 3 to 10 carbon atoms; Or E ₂₁ and E ₂₂ form a morpholine ring with the nitrogen atom to which they are bonded. E ₂₁ and E ₂₂ are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.

E ₂₃ is, for example, a hydrogen atom, OH, phenyl, or an alkyl group having 1 to 20 carbon atoms. E _{23 is} especially a hydrogen atom, OH or an alkyl group having 1 to 4 carbon atoms.

The better of E ₂₄ is one of those defined for E ₁₉ and E ₂₀ . The better of E ₂₅ is one of those defined for E ₁₇ .

E ₂₆ is, for example, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, and an alkyl group having 2 to 20 carbon atoms, intermixed with at least one O or CO; or E _26- series phenyl-R ₁ , a cycloalkyl group having 3 to 8 carbon atoms, and a cycloalkyl group having 3 to 8 carbon atoms are not interspersed or interspersed with one or more O or CO; or E _26- series (CO ) E ₁₉ or phenyl, and the phenyl is unsubstituted or substituted with at least one of the following groups, at least one of which may be an alkyl group having 1 to 20 carbon atoms, a halogen atom, and a halogenated alkyl group having 1 to 4 carbon atoms Base, OE ₁₇ , SE ₁₈ , NE ₁₉ E ₂₀ .

Or E ₂₆ represents, for example, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms; a phenyl-R ₁ group, a cycloalkyl group having 3 to 8 carbon atoms, (CO E ₁₉ or phenyl, and phenyl is unsubstituted or substituted with at least one alkyl group having 1 to 20 carbons. In addition, E ₂₆ is, for example, hydrogen or an alkyl group having 1 to 20 carbon atoms, and particularly an alkyl group having 1 to 4 carbon atoms.

Specific examples of the aforementioned photoinitiator (E-1) having a structure represented by formula (III) may include photoinitiators having a structure represented by the following formula (III-1) to formula (III-86) .

Based on 100 parts by weight of the alkali-soluble resin (C) and 0.1 to 15 parts by weight of the photoinitiator (E-1), preferably 1 to 12 parts by weight, and more preferably It is 3 to 10 parts by weight. If the photosensitive resin composition contains a photoinitiator (E-1), it can have favorable chemical resistance.

Other radical photoinitiators (E-2)

The photoinitiator (E) of the present invention may further contain other free-radical photoinitiators (E-2).

The other radical-type photoinitiator (E-2) may be selected from acetophenone, biimidazole, acyl oxime, or a combination thereof.

The aforementioned acetophenone-based compound is selected from the group consisting of p-dimethylamino-acetophenone, α , α'-dimethoxyazoxy-acetophenone ), 2,2'-dimethyl-2-phenyl-acetophenone (2,2'-dimethyl-2-phenyl-acetophenone), p-methoxy-acetophenone, 2- Methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone [2-methyl-1- (4-methylthio phenyl) -2-morpholino-1-propanone], 2- Benzyl-2-nitro, nitro-dimethylamine-1- (4-morpholinophenyl) -1-butanone [2-benzyl-2-N, N-di-methylamino-1- (4-morpholinophenyl ) -1-butanone].

The above diimidazole-based compound is selected from 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyldiimidazole [2,2'-bis (o-chlorophenyl ) -4,4 ', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (o-fluorophenyl) -4,4,5,5'-tetraphenyldiimidazole [2,2' -bis (o-fluorophenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (o-methylphenyl) -4,4', 5,5'-tetraphenyl Diimidazole [2,2'-bis (o-methyl phenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (o-methoxyphenyl) -4, 4 ', 5,5'-tetrabenzene Diimidazole [2,2'-bis (o-methoxyphenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (o-ethylphenyl) -4,4' , 5,5'-tetraphenyldiimidazole [2,2'-bis (o-ethylphenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (p-methoxy (Phenyl) -4,4 ', 5,5'-tetraphenyldiimidazole [2,2'-bis (p-methoxyphenyl) -4,4', 5,5'-tetraphenyl-biimidazole], 2,2 '-Bis (2,2', 4,4'-tetramethoxyphenyl) -4,4 ', 5,5'-tetraphenyldiimidazole [2,2'-bis (2,2', 4,4'-tetramethoxyphenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl Diimidazole [2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-biimidazole], 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyldiimidazole [2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-biimidazole].

The above-mentioned oxime-based compound is selected from acetone, 1- [9-ethyl-6- (2-methylbenzylidene) -9hydro-carbazole-3-substituent]-, 1- (Oxy-acetamoxime) [Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyl oxime), for example, manufactured by Ciba Specialty Chemicals The product name is CGI-242, and its structure is shown by the following formula (E-2-1)], 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O -Benzyl oxime) [1- [4- (phenylthio) phenyl] -octane-1,2-dione2- (O-benzoyloxime), for example, a product manufactured by Ciba Specialty Chemicals under the trade name CGI-124, and its structure is as follows Represented by the formula (E-2-2)], acetone, 1- [9-ethyl-6- (2-chloro-4-benzyl-thio-benzylidene) -9hydro-carb Azole-3-substituent]-, 1- (oxy-acetamoxime) [Ethanone, 1- [9-ethyl-6- (2-cholro-4-benzyl-thio-benzoyl) -9H-carbazole-3- yl]-, 1- (O-acetyl oxime), for example, manufactured by Asahi Kasei Corporation, its structure is shown by the following formula (E-2-3)]:

Preferably, the other radical-type photoinitiator (E-2) is 2-methyl-1- (4-methylthiophenyl) -2-morpholino-1-acetone, 2-benzyl Methyl-2-nitro, nitro-dimethylamine-1- (4-morpholinophenyl) -1-butanone, 2,2'-bis (o-chlorophenyl) -4,4 ', 5, 5'-tetraphenyldiimidazole, acetone, 1- [9-ethyl-6- (2-methylbenzylidene) -9hydro-carbazole-3-substituent]-, 1- ( Oxygen-acetamoxime) or one of these combinations.

The other free radical photoinitiator (E-2) of the present invention can be further Add the following compounds: thioxanthone, 2,4-diethyl-thioxanthanone, thioxanthone-4-sulfone, diphenyl Benzophenone, 4,4'-bis (dimethylamino) benzophenone [4,4'-bis (dimethylamino) benzophenone], 4,4'-bis (diethylamine) benzophenone [ 4,4'-bis (diethylamino) benzophenone] and other benzophenone compounds; benzil, acetyl and other α-diketone compounds; Acyloin compounds such as benzoin; benzoin methylether, benzoin ethylether, benzoin isopropyl ether And other acyloin ether compounds; 2,4,6-trimethyl-benzoyl-diphenyl-phosphine oxide, bis- (2, 6-dimethoxyphenylhydrazone) -2,4,4-trimethylphenylphosphine oxide [bis- (2,6-dimethoxy-benzoyl) -2,4,4-trimethyl-benzyl-phosphineoxide], etc. Acylphosphineoxide; anthraquinone quinone), 1,4-naphthoquinone and other quinone compounds; phenacyl chloride, tribromomethyl-phenylsulfone, tris (tri Halides such as tris (trichloromethyl) -s-triazine; and peroxides such as di-tertbutylperoxide. Among them, benzophenone compounds are preferred, and 4,4'-bis (diethylamine) benzophenone is most preferred.

The other radical-type photoinitiators (E-2) may be used alone or in combination.

In a specific example of the present invention, the total amount of the alkali-soluble resin (C) used is 100 parts by weight, and the used amount of the other radical photoinitiator (E-2) ranges from 9.9 parts by weight to 85 parts by weight ; Preferably 14 to 78 parts by weight; more preferably 17 to 70 parts by weight.

Based on the total use amount of the alkali-soluble resin (C) being 100 parts by weight, the use amount of the photoinitiator (E) is 10 parts by weight to 100 parts by weight; preferably 15 parts by weight to 90 parts by weight; more preferably 20 Part by weight to 80 parts by weight.

Unsaturated benzophenone compound (F)

The photosensitive resin composition of the present invention may include an unsaturated group-containing benzophenone compound (F), wherein the unsaturated group has a structure represented by the formula (IV-1):

In formula (IV-1), b represents an integer of 0 or 1.

In one embodiment, the unsaturated benzophenone compound (F) of the present invention may have a structure represented by the following formula (IV):

In the formula (IV), R ^1f may represent a hydrogen atom or an unsaturated group represented by the above formula (IV-1), and R ^2f may represent an unsaturated group, a benzyl group, or a carbon represented by the formula (IV-1) An alkyl group having a number of 1 to 8, wherein at least one of R ^1f and R ^2f is an unsaturated group represented by formula (IV-1).

Specific examples of the unsaturated group-containing benzophenone compound (F) include, for example, 2-hydroxy-4-allyloxy benzophenone, 2-hydroxy-4-allyloxy benzophenone, and 2-hydroxy-4-allyloxy benzophenone. 2-hydroxy-4-vinyloxy benzophenone, 2-hydroxy-3-allyl-4-ethoxybenzophenone, 2-hydroxy-3-allyl-4- Propoxybenzophenone, 2-hydroxy-3-allyl-4-hexyloxybenzophenone, 2-hydroxy-3-allyl-4-octyloxybenzophenone (2- hydroxy-3-allyl-4-octyloxy benzophenone), 2-hydroxy-3-allyl-4-benzyloxy benzophenone, or a combination thereof.

Based on the total amount of the alkali-soluble resin (C) used being 100 parts by weight, the amount of the unsaturated group-containing benzophenone compound (F) used is 0.1 to 30 parts by weight; preferably 0.6 to 27 parts by weight Parts; more preferably 1 to 24 parts by weight.

If the unsaturated group-containing benzophenone compound (F) is not used, the photosensitive resin composition has a problem of poor chemical resistance.

Solvent (G)

In the preparation of the photosensitive resin composition of the present invention, generally, components other than the pigment (A) are first dissolved in a solvent (G) to prepare a liquid composition, and then the pigment (A) is added and mixed uniformly. Solvent (G) needs to select soluble dye (B), alkali-soluble resin (C), compounds containing ethylenic unsaturated groups (D), a photoinitiator (E), and an unsaturated group-containing benzophenone compound (F), and those which do not react with these components and have appropriate volatility.

Based on the total amount of the alkali-soluble resin (C) used being 100 parts by weight, the amount of the solvent (G) used is in the range of 500 parts by weight to 5000 parts by weight; preferably 800 parts by weight to 4500 parts by weight; more preferably 1000 parts by weight To 4000 parts by weight.

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

Additive (H)

In a preferred embodiment of the present invention, the photosensitive resin composition further includes an additive (H), for example, a filler, a polymer compound other than the alkali-soluble resin (C), an adhesion promoter, an antioxidant, and ultraviolet absorption. Agent, anti-aggregation agent, etc.

Additives (H) can be used alone or in combination, and the additives (H) include, but are not limited to, fillers such as glass and aluminum; polyvinyl alcohol, polyethylene glycol monoalkyl ether, and polyfluoroacrylates such as alkali-soluble resins ( C) Other polymer compounds; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, nitrogen- (2-aminoethyl) -3- Aminopropylmethyldimethoxysilane, nitrogen- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-epoxy Propanolpropyltrimethoxysilane, 3-glycidylpropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloro Adhesion promoters such as propyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-thiolpropyltrimethoxysilane; 2,2-thiobis (4-methyl -6-Third-butylphenol), 2,6-di-Third-butylphenol and other antioxidants; 2- (3-Third-butyl-5-methyl-2-hydroxyphenyl) -5-chloro UV absorbers such as phenyl azide and alkoxy phenone; and anti-aggregation agents such as sodium polyacrylate.

Based on the total amount of the alkali-soluble resin (C) used being 100 parts by weight, the amount of the additive (H) used is in the range of 0.1 to 10 parts by weight; preferably 0.3 to 7 parts by weight; more preferably 0.5 part by weight To 4 parts by weight.

Preparation of color filters

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

The present invention also provides a color filter, which is prepared by the aforementioned method.

The manufacturing method of the color filter of the present invention is mainly a method of mixing the solution into a solution by spin coating, cast coating, ink-jet coating, or roll coating. A photosensitive composition for a color filter is coated on a substrate. After coating, first remove most of the solvent by drying under reduced pressure, and then remove the solvent by pre-bake to form a pre-bake coating film. Among them, the conditions of reduced pressure drying and pre-baking vary according to the type of each component and the blending ratio. Generally, the reduced pressure drying is performed at a pressure of 0 to 200 mmHg for 1 second to 60 seconds, while pre-baking is It is performed at a temperature of 70 to 110 ° C for 1 minute to 15 minutes. After pre-baking, the pre-baking film is applied to the designated mask (mask) exposure, immersed in a developing solution for 15 seconds to 5 minutes at a temperature of 23 ± 2 ° C., and developed an unnecessary portion to form a pattern. The light used for exposure is preferably ultraviolet rays such as g-line, h-line, i-line, etc., and the ultraviolet device can be a (super) high-pressure mercury lamp or a metal halide lamp.

Specific examples of the aforementioned substrate include: alkali-free glass, soda-lime glass, hard glass (Pales glass), quartz glass, soda glass, and transparent conductive films attached to these glasses for liquid crystal display devices; or Photoelectric conversion device substrates (such as silicon substrates) for solid-state imaging devices and the like. These substrates are generally formed with a black matrix that isolates each pixel color layer.

Moreover, specific examples of the developing solution include: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium silicate, sodium methylsilicate, ammonia, ethylamine, diethylamine, Dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, pyridine, 1,8-diazabicyclo- (5,4,0) -7-undecene and other bases The concentration of the alkaline aqueous solution composed of a neutral compound is generally 0.001 to 10% by weight, preferably 0.005 to 5% by weight, and more preferably 0.01 to 1% by weight.

When using a developing solution composed of the aforementioned alkaline aqueous solution, it is generally washed with water after development, and then the pattern is air-dried with compressed air or compressed nitrogen.

After air-drying, the substrate with the light-hardened coating film layer is heated at a temperature of 100 to 280 ° C for 1 to 15 minutes using a heating device such as a hot plate or an oven to remove the volatile components in the coating film and make the coating film The reacted ethylenically unsaturated double bond undergoes a thermosetting reaction. Use various colors (mainly including red, The green, blue, and blue photosensitive resin composition is repeated three times in the same steps on a predetermined pixel to obtain a red, green, and blue pixel colored layer.

Next, an ITO (indium tin oxide) vapor-deposited film is formed on the pixel color layer under a vacuum at a temperature of 220 ° C to 250 ° C. If necessary, the ITO vapor-deposited film is subjected to etching and wiring, and then a polycrystalline silicon alignment film is coated. Perylene imine, which can be further fired, can be used as a color filter for liquid crystal displays.

In addition, the liquid crystal alignment film used in the foregoing is used to restrict the alignment of liquid crystal molecules, which is not particularly limited here, and any inorganic or organic substance may be used. As for the technology for forming a liquid crystal alignment film, it is well known to anyone with ordinary knowledge in the technical field to which the present invention pertains and is not the focus of the present invention, so it will not be described in detail.

Preparation of liquid crystal display element

Another object of the present invention is to provide a liquid crystal display element including the aforementioned color filter.

The liquid crystal display element of the present invention is mainly composed of a color filter substrate formed by the above-mentioned color filter forming method, and a driving substrate provided with a thin film transistor (TFT, Thin Film Transistor). The interposition gap (cell gap; cell gap) between the substrates is oppositely arranged, and the peripheral parts of the two substrates are bonded with a sealing agent. The liquid crystal is filled into the gap separated by the substrate surface and the sealing agent, and the injection is sealed. Holes to form a liquid crystal cell. Then, on the outer surface of the liquid crystal cell, that is, on the other side of each substrate constituting the liquid crystal cell, a polarizing plate is bonded to prepare a liquid crystal display element.

As for the liquid crystal used above, that is, a liquid crystal compound or a liquid crystal composition, it is not particularly limited here, but any liquid crystal compound and liquid crystal composition may be used.

By applying the photosensitive resin composition of the present invention, a color filter, a manufacturing method thereof, and its application, the prepared color filter and a liquid crystal display device including the color filter can have good chemical resistance and contrast .

1‧‧‧ photosensitive resin layer

2, 3‧‧‧ polarizing plate

4‧‧‧ light source

5‧‧‧ Luminance Meter

In order to make the above and other objects, features, advantages, and embodiments of the present invention more comprehensible, the detailed description of the drawings is as follows: [FIG. 1] is a schematic diagram of the state (a) of the comparative measurement of the photosensitive resin layer; and [Fig. 2] Fig. 2 is a schematic diagram of a comparative measurement state (2) of a photosensitive resin layer.

The following examples are used to explain the present invention in detail, but it is not meant to limit the present invention to the contents disclosed in these examples.

Preparation of the first alkali-soluble resin (C-1)

Synthesis Example C-1-1

100 parts by weight of a rhenium epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, and 0.1 parts by weight of 2,6-Di-tert-butyl-p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feed rate was controlled at 25 parts by weight The temperature is maintained in the range of 100 ° C. to 110 ° C. per minute, and after a reaction for 15 hours, a light yellow transparent mixed solution having a solid content concentration of 50% by weight can be obtained.

Next, 100 parts by weight of the mixed solution was dissolved in 25 parts by weight of ethylene glycol 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 ° C to 115 ° C. After reacting for 2 hours, a first alkali-soluble resin (C-1-1) having an acid value of 98.0 mgKOH / g and a number average molecular weight of 1,623 can be obtained.

Synthesis Example C-1-2

100 parts by weight of a rhenium epoxy compound (model ESF-300, manufactured by Nippon Steel Chemical; epoxy equivalent 231), 30 parts by weight of acrylic acid, 0.3 parts by weight of benzyltriethylammonium chloride, and 0.1 parts by weight of 2,6-Di-tert-butyl p-cresol and 130 parts by weight of propylene glycol methyl ether acetate were continuously added to a 500 mL four-necked flask, and the feeding speed was controlled at 25 parts by weight / minute, and the temperature was maintained at 100 ° C. Within the range of 110 ° C, a light yellow transparent mixed solution having a solid content concentration of 50% by weight can be obtained after 15 hours of reaction.

Next, 100 parts by weight of the above mixed solution was dissolved in 25 parts by weight of ethylene glycol ether acetate, and 13 parts by weight of benzophenonetetracarboxylic dianhydride was added at the same time, and the reaction was performed at 90 ° C to 95 ° C for 2 hours. Next, by adding 6 parts by weight of tetrahydrophthalic anhydride and reacting at 90 ° C to 95 ° C for 4 hours, a first alkali-soluble resin having an acid value of 99.0 mgKOH / g and a number average molecular weight of 2,162 can be obtained. (C-1-2).

Synthesis Example C-1-3

400 parts by weight of an epoxy compound (model NC-3000, manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent 288), 102 parts by weight of acrylic acid, 0.3 parts by weight of methoxyphenol, and 5 parts by weight of Triphenylphosphine and 264 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature was maintained at 95 ° C. After 9 hours of reaction, an intermediate product having an acid value of 2.2 mgKOH / g was obtained. Next, 151 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain a first alkali-soluble resin having an acid value of 102 mgKOH / g and a number average molecular weight of 2,589 ( C-1-3).

Synthesis Example C-1-4

200 parts by weight of an epoxy compound (model NC-3000, manufactured by Nippon Kayaku Co., Ltd .; epoxy equivalent 288), 60 parts by weight of acrylic acid, 0.15 parts by weight of methoxyphenol, and 2.5 parts by weight of Triphenylphosphine and 200 parts by weight of propylene glycol methyl ether acetate were placed in a reaction flask, and the temperature was maintained at 95 ° C. After 9 hours of reaction, an intermediate product having an acid value of 2.5 mgKOH / g was obtained. Next, 85 parts by weight of tetrahydrophthalic anhydride was added and reacted at 95 ° C for 4 hours to obtain a first alkali-soluble resin having an acid value of 105 mgKOH / g and a number average molecular weight of 3,410 ( C-1-4).

Preparation of the second alkali-soluble resin (C-2)

Synthesis Example C-2-1

A four-necked conical flask was provided with a stirrer, a thermometer, a condenser tube, and a nitrogen inlet, and nitrogen was introduced. Then, 100 parts by weight of propylene glycol was added Methyl ether acetate (abbreviated as PGMEA), and the temperature was raised to 100 ° C. Next, 25 parts by weight of 2-methacrylic acid ethoxysuccinate (abbreviated as HOMS), 70 parts by weight of 2-hydroxyethyl methacrylate (abbreviated as HEMA), and 15 parts by weight of methyl 3,4-epoxycyclohexyl methyl acrylate (ECMMA), 10 parts by weight of o-vinylbenzyl glycidyl ether (VBGE for short), and 4.5 parts by weight of 2,2'-azobis- 2-Methylbutyronitrile (abbreviated as AMBN) was dissolved in 100 parts by weight of propylene glycol methyl ether acetate, and the mixed solution was dropped into the four-necked conical flask dropwise within 2 hours. After reacting at 100 ° C for 6.5 hours, 5 parts by weight of acrylic acid (referred to as AA) was added to a four-necked conical flask filled with nitrogen, and the temperature was raised to 110 ° C. After 6 hours of reaction, the second alkali-soluble resin of Synthesis Example C-2-1 was obtained.

Production method of Synthesis Examples C-2-2 to C-2-6

Synthesis Examples C-2-2 to C-2-6 were prepared using the same procedure as Synthesis Example C-2-1 to prepare the second alkali-soluble resin (C-2), except that the type and use of the ingredients were changed.量, and details are shown in Table 1.

Preparation of photosensitive resin

Example 1

100 parts by weight of the second alkali-soluble resin (C-2-1) obtained in the aforementioned Synthesis Example, 50 parts by weight of CI Pigment Red 254 (hereinafter referred to as A-1), and 15 parts by weight of CI Acid Red 37 (hereinafter referred to as B-2-1), 30 parts by weight of dipentaerythritol hexaacrylate (hereinafter referred to as D-2), 50 parts by weight of 1- [4- (phenylthio) phenyl] -octane-1,2- Diketone 2- (O-phenylfluorenyl oxime) (hereinafter referred to as E-2-1), 5 parts by weight of 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5, 5'-tetraphenyldiimidazole (hereinafter referred to as E-2-2), 3 parts by weight 2-Hydroxy-3-allyl-4-benzylbenzophenone (F-1) was added with 1500 parts by weight of ethyl 3-ethoxypropionate (hereinafter referred to as G-1), and then the A stirrer can be prepared by dissolving and mixing to obtain a photosensitive resin composition. The photosensitive resin composition is evaluated by the following measurement and evaluation methods. The results are shown in Table 2.

Examples 2 to 12 and Comparative Examples 1 to 7

The photosensitive resin compositions of Examples 2 to 12 and Comparative Examples 1 to 7 were prepared by the same method as in Example 1. The difference is that the types of composition used or the amounts used in Examples 2 to 12 and Comparative Examples 1 to 7 were changed. The detailed conditions and evaluation results are shown in Table 2, and will not be repeated here.

Evaluation method

Chemical resistance

The photosensitive resin composition described above is spin-coated on the surface of a soda glass substrate, wherein the soda glass substrate has a silicon dioxide film that prevents sodium precipitation. Next, a pre-baking treatment was performed on a hot plate at 90 ° C. for 2 minutes to form a coating film having a film thickness of 2.5 μm.

Then, the pre-baked substrate was cooled to room temperature, a photomask was placed between the substrate and a high-pressure mercury lamp, and the substrate was exposed with radiation having a wavelength of 365 nm, 405 nm, and 436 nm and an exposure amount of 400 J / m ² , respectively. After that, the exposed substrate was spray-developed with a potassium hydroxide aqueous solution having a concentration of 0.04 weight percent at 23 ° C., wherein the diameter of the nozzle was 1 mm and the developing pressure was 1 kgf / cm ² .

Then, after washing with ultrapure water and air blasting, a post-bake treatment was performed at 230 ° C. for 30 minutes to form pattern dots on the substrate. Next, the patterned substrate was immersed in propylene glycol methyl ether acetate (PGMEA) at 80 ° C for 40 minutes.

The substrate before immersion has a color saturation coordinate value of (x, y) and saturation Y, and the color difference ΔE * ab of the substrate before and after immersion is measured as an evaluation standard. The evaluation method is as follows:

◎: △ E * ab ≦ 1

○: 1 <△ E * ab ≦ 2

△: 2 <△ E * ab ≦ 3

╳: 3 <△ E * ab

2.Contrast

The photosensitive resin composition was spin-coated on a 100 mm × 100 mm glass substrate, and then dried under reduced pressure, under a pressure of 100 mmHg for 30 seconds, and then pre-baked at a temperature of 80 ° C. and a time of 2 In a minute, a pre-baking coating film with a film thickness of 2.5 μm can be formed. After the pre-bake coating film was irradiated with a light amount of 100 mJ / cm ² of ultraviolet light (Canon PLA-501F), the pre-bake coating film was immersed in a developing solution at 23 ° C. for 1 minute and washed with pure water.

Next, after baking at 235 ° C for 30 minutes, a photosensitive resin layer with a thickness of 2.0 μm can be formed on the glass substrate.

The obtained photosensitive resin layer was subjected to the measurement methods shown in FIG. 1 and FIG. 2 and calculated based on the measured brightness. Among them, the obtained photosensitive resin layer 1 was placed between two polarizing plates 2 and 3. between, out of the irradiated light sequentially from the light source 4 through the polarizing plate 2, the photosensitive resin layer 1, the polarizing plate 3, and finally through the polarizing plate 3 of luminance (cd / cm ²⁾ 5 places luminance meter (Topcon Corporation of Japan Measurement, model BM-5A).

As shown in FIG. 1, when the polarization direction of the polarizing plate 3 and the polarization direction of the polarizing plate 2 are parallel to each other (measurement state (a)), the measured luminance is A (cd / cm2); in addition, as shown in FIG. 2 It is shown that when the polarization direction of the polarizing plate 3 and the polarization direction of the polarizing plate 2 are perpendicular to each other (measurement state (two)), the measured luminance is B (cd / cm2); then the contrast can be determined by the luminance A and the luminance B The ratio (brightness A / brightness) is obtained, and the evaluation criteria are as follows.

◎: (Brightness A / Brightness) ≧ 3500

○: 3300 ≦ (Brightness A / Brightness) <3500

△: 3000 ≦ (Brightness A / Brightness) <3300

╳: (Brightness A / Brightness) <3000

According to the evaluation results in Table 2 below, when the photosensitive resin composition of the present invention includes the dye (B-1), its contrast performance is better. When the photosensitive resin composition includes the first alkali-soluble resin (C-1) and / or the photoinitiator (E-1), its chemical resistance is better. When the photosensitive resin composition does not contain an unsaturated benzophenone compound (F), the chemical resistance is not good.

Therefore, the photosensitive resin composition, the color filter, and the manufacturing method and application thereof of the present invention can effectively improve the chemical resistance and poor contrast of the color filter prepared by the conventional photosensitive resin composition. Disadvantages.

Although the present invention has been disclosed as above in the embodiments, it is not intended to limit the present invention, and any person having ordinary knowledge in the technical field to which the present invention belongs Experts, without departing from the spirit and scope of the present invention, can make various modifications and retouching. Therefore, the protection scope of the present invention shall be determined by the scope of the appended patent application.

MAA methacrylic

HOMS 2-Methacrylic Acetate Ethoxy Succinate

AA acrylic

N-PMI N-phenylmaleimide

HEMA 2-hydroxyethyl methacrylate

BzMA benzyl methacrylate

ECMMA 3,4-epoxycyclohexyl methyl methacrylate

MGMA 2-methyl glycidyl methacrylate

VBGE o-vinyl benzyl glycidyl ether

AMBN 2,2’-Azobis-2-methylbutanil

ADVN 2,2-Azo-bis- (2,4-dimethylvalerine)

PGMEA propylene glycol methyl ether acetate

EEP ethyl 3-ethoxypropionate

A-1 C.I.Pigment Red 254

A-2 C.I.Pigment Green 36

A-3 C.I. Pigment Blue 15: 6

A-4 C.I.Pigment Blue 66

A-5 C.I.Pigment Red 177

B-1-1 Compound represented by formula (1) (R ^c and R ^d are -SO ₃ ^- and a is 0)

B-1-2 Compound represented by formula (22)

B-1-3 Compound represented by formula (28)

B-2-1 C.I. Acid Red 37

B-2-2 C.I. Disperse Red 60

B-2-3 C.I. Disperse Blue 60

D-1 EO modified trimethylolpropyl triacrylate

D-2 Dipentaerythritol hexaacrylate

D-3 Caprolactone Modified Dipentaerythritol Hexacrylate

E-1-1 Compound represented by formula (III-1)

E-1-2 A compound represented by formula (III-8)

E-1-3 A compound represented by formula (III-27)

E-2-1 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-phenylamidoxime)

E-2-2 2,2’-bis (2,4-dichlorophenyl) -4,4 ’, 5,5’-tetraphenyldiimidazole

E-2-3 4,4’-bis (diethylamine) benzophenone

E-2-4 2-Benzyl-2-nitro, nitro-dimethylamine-1- (4-morpholinophenyl) -1-butanone

F-1 2-hydroxy-3-allyl-4-benzylbenzophenone

F-2 2-hydroxy-4-vinyloxybenzophenone

F-3 2-hydroxy-4-allyloxybenzophenone

G-1 ethyl 3-ethoxypropionate

G-2 Propylene glycol methyl ether acetate

G-3 cyclohexanone

H-1 3-Mercaptopropyltrimethoxysilane

H-2 2,2-thiobis (4-methyl-6-tert-butylphenol)

H-3 2-hydroxy-4-methoxybenzophenone

Claims (12)

A photosensitive resin composition comprising: a pigment (A); a dye (B); an alkali-soluble resin (C); an ethylenically unsaturated group-containing compound (D); and a photoinitiator (E) ; An unsaturated group-containing benzophenone compound (F), wherein the unsaturated group has a structure represented by formula (IV-1), and the unsaturated group-containing benzophenone compound (F) has A structure shown by formula (IV); and a solvent (G), In the formula (IV-1), b represents an integer of 0 or 1; and In the formula (IV), R ^1f represents a hydrogen atom or an unsaturated group represented by the formula (IV-1), and R ^2f represents an unsaturated group, benzyl represented by the formula (IV-1) Or an alkyl group having 1 to 8 carbon atoms, and at least one of the R ^1f and the R ^2f is an unsaturated group represented by the formula (IV-1). The photosensitive resin composition according to item 1 of the scope of patent application, wherein the dye (B) comprises a dye (B-1) having one of the formula (I): In the formula (I), each of L ₁ to L ₄ independently represents hydrogen, -L ₆ , an aromatic hydrocarbon group having 6 to 10 carbon atoms, or a halogen atom, -L ₆ , -OH, -OL ₆ , _{^{-SO 3 -, -SO 3 H,}} -SO 3 M, -COOH, -COOL 6, -SO 3 L 6, -SO 2 NHL 8 or -SO ₂ NL ₈ L ₉ substituent of from 6 to 10 carbon atoms of aromatic hydrocarbon group; L ₅ represents the _{^{-SO 3 -, -SO 3 H,}} -SO 3 M, -COOH, -COOL 6, -SO 3 L 6, -SO 2 NHL 8 or -SO ₂ NL ₈ L _9; the u represents an integer from 0 to 5; when u represents 2 to 5, a plurality of L ₅ are the same or different; X ^b represents a halogen atom; the a represents 0 or 1; the L ₆ represents a carbon number of 1 to 10 Alkyl groups or alkyl groups having 1 to 10 carbon atoms substituted with halogen atoms, wherein -CH _{2 in} the alkyl groups having 1 to 10 carbon atoms or alkyl groups having 1 to 10 carbon atoms substituted with a halogen atom -Is unsubstituted or substituted with -O-, carbonyl or -NL _7- ; the L ₇ represents an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms substituted with a halogen atom; L ₈ and L ₉ each independently represent a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q; wherein, Carbon number is 1 The hydrogen atom in a linear alkyl group of 10, a branched alkyl group having 3 to 10 carbon atoms, or a cycloalkyl group having 3 to 30 carbon atoms is unsubstituted or substituted with a substituent, and the substituent is selected Group consisting of free hydroxyl, halogen atom, -Q, -CH = CH ₂ and -CH = CH-L ₆ ; linear alkyl group having 1 to 10 carbon atoms, branched alkyl group having 3 to 10 carbon atoms Or -CH ₂ -in a cycloalkyl group having a carbon number of 3 to 30 is unsubstituted or substituted with -O-, carbonyl, or -NL _7- ; or the L ₈ and the L _{9 are} combined to form a carbon number of 2 To 10 heterocyclic group, wherein the hydrogen atom in the heterocyclic group having 2 to 10 carbon atoms is unsubstituted or substituted with L ₆ , -OH, or -Q; the Q represents 6 to 10 carbon atoms Aromatic radical, heteroaromatic group with 5 to 10 carbons, carbon substituted with halogen atom, -L ₆ , -OH, -OL ₆ , -NO ₂ , -CH = CH ₂ or -CH = CH-L ₆ Aromatic hydrocarbon groups of 6 to 10 or 5 to 10 carbon atoms substituted with halogen atoms, -L ₆ , -OH, -OL ₆ , -NO ₂ , -CH = CH ₂ and -CH = CH-L ₆ A heteroaromatic group; and the M represents potassium or sodium. The photosensitive resin composition according to item 1 of the patent application range, wherein the alkali-soluble resin (C) comprises a first alkali-soluble resin (C-1), and the first alkali-soluble resin (C-1) is composed of A mixture prepared by polymerization reaction, and the mixture comprises an epoxy compound (c-1-1) having at least two epoxy groups and a compound having at least one carboxylic acid group and at least one ethylenically unsaturated group (c-1-2). The photosensitive resin composition according to item 3 of the scope of patent application, wherein the epoxy compound (c-1-1) having at least two epoxy groups has a formula (II-1) or a formula (II-2) ) Structure shown; In the formula (II-1), the R ^1c , the R ^2c , the R ^3c, and the R ^4c are the same or different, and represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbons, and a carbon atom. An alkoxy group having 1 to 5, an aromatic group having 6 to 12 carbons or an aralkyl group having 6 to 12 carbons; In the formula (II-2), each of R ^5c to R ^18c independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbons or an aromatic group having 6 to 15 carbons; and the g represents An integer from 0 to 10. The photosensitive resin composition according to item 1 of the scope of patent application, wherein the photoinitiator (E) comprises a photoinitiator (E-1) having one of the formula (III): In the formula (III), at least one of the E ₃ and E ₄ or the E ₅ and E ₆ are independently and jointly represented. , And the E ₃ , the E ₄ , the E _5, and the E ₆ are not formed , The E ₁ , the E ₂ , the E ₇ and the E ₈ each independently represent a hydrogen atom, , COE ₁₆ or NO ₂ ; the E ₉ , the E ₁₀ , the E ₁₁ and the E ₁₂ each independently represent a hydrogen atom; the Z ₁ represents a single bond; the E ₁₃ represents an alkyl group having 1 to 20 carbon atoms; the E ₁₄ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms; the E ₁₅ represents an aromatic group having 6 to 20 carbon atoms, each of which is unsubstituted or substituted with at least one group as shown below, and the at least One group is selected from OE ₁₇ or an alkyl group having 1 to 20 carbons; or E ₁₅ represents an alkyl group having 1 to 20 carbons; E ₁₆ represents an aromatic group having 6 to 20 carbons, each Unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from alkyl groups having 1 to 20 carbon atoms; the E ₁₇ represents an alkyl group having 1 to 20 carbon atoms, which is Unsubstituted or substituted with at least one group as shown below, and the at least one group is selected from a halogen atom; or the E ₁₇ represents an alkyl group having 2 to 20 carbons, and the carbon number is 2 to 20 The alkyl group is mixed with one or more O, provided that the photoinitiator (E-1) having a structure as shown in the formula (III) has at least one . The photosensitive resin composition according to item 1 of the scope of patent application, wherein the amount of use of the alkali-soluble resin (C) is 100 parts by weight, and the amount of use of the pigment (A) is 30 to 300 parts by weight, The dye (B) is used in an amount of 5 to 50 parts by weight, the ethylenically unsaturated group-containing compound (D) is used in an amount of 20 to 200 parts by weight, and the photoinitiator (E) is used in The used amount is 10 to 100 parts by weight, the unsaturated group-containing benzophenone compound (F) is used in an amount of 0.1 to 30 parts by weight, and the solvent (G) is used in an amount of 500 parts by weight To 5000 parts by weight. The photosensitive resin composition according to item 2 of the scope of the patent application, wherein the use amount of the alkali-soluble resin (C) is 100 parts by weight, and the use amount of the dye (B-1) is 3 to 50 parts by weight Serving. The photosensitive resin composition according to item 3 of the scope of patent application, wherein the amount of use of the alkali-soluble resin (C) is 100 parts by weight, and the amount of use of the first alkali-soluble resin (C-1) is 10 weight Parts to 100 parts by weight. The photosensitive resin composition according to item 5 of the scope of the patent application, wherein the use amount of the alkali-soluble resin (C) is 100 parts by weight, and the use amount of the photoinitiator (E-1) is 0.1 part by weight To 15 parts by weight. A method for manufacturing a color filter, which uses the photosensitive resin composition according to any one of claims 1 to 9 of the scope of patent application to form a pixel layer on a substrate. A color filter is manufactured according to the method for manufacturing a color filter described in item 10 of the scope of patent application. A liquid crystal display device includes the color filter described in item 11 of the scope of patent application.