TW201140240A - Photopolymerization initiator, photocurable composition, pattern forming method, color filter, liquid crystal display device, and method for producing photopolymerization initiator - Google Patents

Abstract

The present invention provides a photopolymerization initiator, which has excellent phase-solubility to a compound having ethylenic unsaturatured bond, a compound having ether bond and/or ester bond and being liquid at 25 DEG C, in a photocurable composition, and the solubility to solvent is high, sensitivity to light (especially, the light with short wave length of 450nm and less) is high, no pollution caused by produced resolvent by light during exposure in polymer or in equipment. It is provided a photopolymerization initiator capable of forming a photocurable composition that has excellent resolution, development, deep part hardness and cohesion to substrate, having the following structure. Further, it is provided a photocurable composition containing the said photopolymerization initiator, a pattern forming method using the said photocurable composition, a color filter using the said photocurable composition, and a liquid crystal display device having the said color filter. Moreover, it is provided a simple and easy method for producing the photopolymerization initiator in low cost. (wherein R1 to R11 represent hydrogen atom, alkyl and the like; R3 is optionally together with R4 or R5 to form a ring; R4 is optionally together with R5 to form a ring; Ar represents aryl or heteroaryl; W represents a single bond or oxygen atom; Z represents a single bond, oxygen or > NR3' (R3' represents alkyl, or R3' links to R3 and is together with nitrogen oxygen to form a ring); n represents an integer of 1 to 10; plural R4 or R5 are optionally same or different each other).

Description

[Technical Field] The present invention relates to a method of producing a liquid crystal using the pattern forming sheet of the composition and a liquid material having the color filter. More specifically, the solubility in the photocurable composition having an ether bond and/or an ester bond at 25 ° C for a solvent (including a compound having an ether described above) is high, and the following short wavelength light is used. a sensitizing decomposition product which causes a polymer stain, which can be used to provide a photocurable composition in which the adhesion of the resolution plate becomes a good photohardening agent; a method of making: using the photocurable group color Filter liquid crystal display device; method. [Prior Art] The photocurable resin composition is a monomer and a photopolymerization initiator, and an emissive initiator for the use of a curable ink or a photosensitive printing plate from the ease of use or sensitivity, such as an electromagnetic wave of radiation such as a line. , a photocurable composition, a method, a color filter crystal display device using the composition, and a photopolymerization initiator for a photopolymerization initiator, which is a compound of an ethylenically unsaturated bond, and a phase of a compound having a liquid Solubility, and bond and/or ester bond, at 25 ° C for liquid versus light (especially at a wavelength of 450 nm, no photopolymerization caused by light exposure or device contamination, developability, deep a curable and base composition; a color filter comprising the photopolymerizable pattern former of the photocurable composition: having the color and the photopolymerization initiator produced, for example, a binder resin or a polymerization It is possible to use light to irradiate light (containing particles to cure it by polymerization), and therefore it is used for light, color filters, various photoresists, etc. Point, photocurable resin composition 201140240 Most of the light is based on wavelengths below 450 nm. The light source is a high-pressure mercury lamp with strong luminescence at 365 nm and 405 nm, or a quasi-laser laser with KrF (ArF). Further, in the case of forming a pattern, it is possible to review a radiation having a short wavelength such as an electron beam or an ultraviolet light (Extreme Ultra Violet). The curing by light is due to the fact that it is thermally hardened or separated by light. The irradiation with the cover makes the demand for the hard-use field of the desired pattern high, and in particular, the high-sensitivity photopolymerization initiation for increasing the amount of the production photopolymerization initiator is increasing. Further, the pigment dispersion method is used. The color filter is usually coated with a photo-curable composition obtained by dispersing a pigment as a dispersant or the like, and then dried, and then developed using a photomask to form a colored pattern, and the pattern is fixed by heating. The step is repeated for each color to form a color filter. The photo-curable group formed by the image of such a color filter has sufficient resolution and adhesion to the substrate. In addition, in recent years, it has been developed to achieve a black color such as a coloring pigment or a carbon black in a photohardenable composition for a black matrix which exhibits a high optical density of a light-shielding layer by using a paint having a high color density. The light transmittance of the composition is reduced, and the light from the exposure source cannot reach the photocurable light (ultraviolet rays, 436 nm of cesium fluoride) and is used for finer EUV (extreme electromagnetic waves or energy saving, etc. In each, and the reducing agent needs to be in the glass base dispersion and exposed to form a pixel sheet. The use of the product is required to have characteristics such as the element or its own photoresist, so that the content of the material increases In the deep portion of 201140240 of the resin coating film, there is a problem that the resolution, the adhesion to the substrate, and the developability are deteriorated, so that the productivity, accuracy, and reliability required for the color filter are lowered. Further, since the glass substrate for forming a color filter has been enlarged in size year by year and has been exposed to a large area, there is a tendency that the exposure illuminance is small, or that it is required to shorten the exposure time in order to further improve productivity, and thus has progressed to There is a need for a photopolymerization initiator having a higher sensitivity. Therefore, in order to obtain a photocurable composition which can achieve high sensitivity and high resolution, a proposal has been made to use an oxime ester compound as a photopolymerization initiator (see Patent Documents 1 to 5). [Previous Technical Document] (Invention Patent Document) (Invention Patent Document 1) Invention Patent No. 3 8 6 0 1 7 No. (Invention Patent Document 2) Japanese Laid-Open Patent Publication No. 2006-036750 (Invention Patent Document 3) Japanese Patent Laid-Open Publication No. 2010-037542 (Invention Patent Document 5) Korean Laid-Open Patent Publication No. 2009-0046108 [Summary of the Invention] Technical Problem] The photopolymerization initiators disclosed in 'Patent Documents 1 to 5' have sensitivity, resolution, developability, and compatibility or solubility, particularly with the olefinic bond in the 201140240 photocurable composition. The compatibility of a compound having an unsaturated bond (particularly a compound having a (meth) propylene methoxy group) or solubility in a solvent is insufficient, the use conditions are limited, and there is still room for further improvement. Further, in Patent Documents 1 to 5, the photopolymerization initiator disclosed in the photopolymerization initiator adheres to the mask due to light at the time of exposure, and as a result, pattern formation is poor at the time of branding, resulting in a yield. reduce. Therefore, it has been desired to produce a decomposition initiator which does not contaminate a photopolymerization initiator such as a polymer or a device. Therefore, the technical problem of the present invention is to provide a photopolymerization initiator which is a compound having an ethylenically unsaturated bond in a photocurable composition (particularly a compound having a (meth)acryloxy group), The solubility of a compound having an ether bond and/or an ester bond and being a liquid at 25 ° C, and the solubility of a solvent (including a compound having an ether bond and/or an ester bond as described above and being a liquid at 25 t) is high. A photopolymerization initiator which has a high sensitivity to light (especially a short-wavelength light having a wavelength of 450 nm or less) and which does not cause contamination of a polymer or contamination of a device due to decomposition products generated by light upon exposure. Further, it is possible to provide a photocurable composition which is excellent in resolution, developability, deep hardenability, and adhesion to a substrate. Further, a photocurable composition containing the photopolymerization initiator, a pattern forming method using the photocurable composition, a color filter using the photocurable composition, and a color filter are provided. Liquid crystal display device. Further, a method of easily producing the photopolymerization initiator at a low cost is provided. [Technical method for solving the problem] The inventors of the present invention have focused on the above-mentioned technical problems, and have found that it is a thin photopolymerization initiator which is a specific junction f represented by the following formula (Ia). The aforementioned technical problem can be solved. That is, the present invention relates to the following items [1] to [23]. [1] A photopolymerization initiator represented by the following formula (I):

(wherein R1 to R11 are independently a hydrogen atom, an atom, a substituted or unsubstituted carbon number of 1 to 20, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms; a substituted or unsubstituted ring-forming atom having a number of 3 to 10 alkyl groups, a substituted or unsubstituted carbon number of 4 to 20, a hydroxyl group, a substituted or unsubstituted carbon number 1 to 20 $ alkoxy, substituted or unsubstituted carbon number 2 to 20 oxy, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or not Substituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted ring-forming aryl group having 6 to 14 carbon atoms or substituted or unsubstituted ring-forming atom a heterocyclic group of 3 to 14; R3 may form a ring together with R4 or R5, and R4 may form a ring together with R5-10-201140240; and 'Ar is a substituted or unsubstituted monument The number of 6 to 14 aryl groups or substituted or uncarbonated heteroaryl groups having 5 to 14 atomic numbers; V ring W is a single bond or an oxygen atom; Z is a single bond, oxygen > NR 3' (R3' is a substituted or unsubstituted alkyl group having a carbon number of \ to 20' or R is bonded to r3 and forms a ring with a nitrogen atom; represents 1 main, and η is 2 to 丨In the case of an integer of 0 [2], a plurality of R4 and R5 may each be the same or different). The photopolymerization initiator according to item [1], which can be represented by the following formula (I-a): η

Atom, substituted or unsubstituted alkyl having 1 to 20 carbon atoms, substituted or unsubstituted, having 2 to 20 carbon atoms, substituted or unsubstituted ring forming atoms a ring of 3 to 10, a substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, a substituted or unsubstituted carbon number of 1 to 2 0 - 201140240 alkoxy a substituted, unsubstituted or unsubstituted alkenyloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted alkyl alkano group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number of 2 to 20 olefinic group, substituted or unsubstituted ring-forming aryl group having 6 to 14 carbon atoms or substituted or unsubstituted heterocyclic group having 3 to 14 ring atoms; R3 It may form a ring together with R4 or R5, and R4 may form a ring together with R5; further, Ar is a substituted or unsubstituted ring-forming aryl group having 6 to 14 carbon atoms or substituted or not The substituted heteroaryl group having a ring number of 5 to 14; η is an integer representing 1 to 10, and η is an integer of 2 to 1 ,, and a plurality of R4 and R5 may each be the same or different) . [3] The photopolymerization initiator according to [2], wherein in the formula (i-a), 'R1, R2 and R3 are each independently substituted or unsubstituted, having a carbon number of 1 to 20 a group, η is 2, and a plurality of R 4 and R 5 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and Ar is a substituted or unsubstituted ring-forming carbon number. It is an aryl group of 6 to 14. [4] The photopolymerization initiator according to [2], wherein in the formula ( ), R1, R2 and R3 are each independently substituted or unsubstituted carbon number of 1 to 2 Å. The base 'η is 2, and the plurality of r4 and R5 are each independently a hydrogen atom or a substituted or unsubstituted carbon number of 1 to 20'. Ar is a substituted or unsubstituted ring-forming atom. The number is a heteroaryl group of 5 to 14. -12- 201140240 [5] The photopolymerization initiator of item [3] or [4] is not more than 5 1 5 . [6] The photopolymerization initiator according to item [2], wherein

In the general formula (I), 'N and R2 are each independently substituted or unsubstituted 3, and the carbon number is from 1 to 20'. The R3 is substituted or unsubstituted, and the carbon number is 3 to The cycloalkyl group 'n of 18 is 2, and the plurality of r5 are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. [7] The photopolymerization initiator according to [2], wherein in the formula a), 'R1 and R2 are each independently substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, R3 Is a hospital group having a carbon number of 1 to 2 取代 substituted by a cyclic ether group having 3 to 6 atomic groups forming a ring, η is 2, and a plurality of R/ and R 5 are each independently a hydrogen atom or substituted Or unsubstituted carbon bases of 1 to 2 inches. [8] The photopolymerization initiator according to item [6] or [7], which has a molecular weight of 550 or less. [9] The photopolymerization initiator according to item [1], which can be represented by the following formula (I - b): • 13- 201140240 丫1 η 〇, Μ

(wherein R1 to R11 are each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted carbon group having a carbon number of 1 to 20', and the substituted or unsubstituted carbon number is 2 to 20 Alkenyl, substituted or unsubstituted cycloalkyl group having 3 to 10 ring atoms, substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, hydroxy group, substituted or unsubstituted Alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyloxy groups having 2 to 20 carbon atoms, substituted or unsubstituted alkyl alkano groups having 1 to 20 carbon atoms, a substituted or unsubstituted olefin group having 2 to 20 carbon atoms, a substituted or unsubstituted ring-forming aryl group having 6 to 14 carbon atoms or a substituted or unsubstituted ring-forming atomic number a heterocyclic group of 3 to 14;

Ar is a substituted or unsubstituted ring-forming aryl group having 6 to 14 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms; W is a single bond or Oxygen atom; Z represents a single bond, an oxygen atom or > NR3 (R3 represents a substituted or unsubstituted carbon number of 1 -14 - 201140240

An alkyl group to 2 Å, or R3' is bonded to R3 and a nitrogen atom to form a ring)). I In the case of I Ib), R1 and R3 are each independently substituted or unsubstituted alkyl having a carbon number of 1 to 20, which is an oxygen atom, a single bond or an oxygen atom. Ar is a substituted or unsubstituted aryl group having a carbon number of 6 to 14. [1 1] The photopolymerization initiator according to item [10], wherein the further step V is a carbon number having a hospital base or a ring formed by an OCOR13 (R丨3 is a carbon number of ≤2) The carbon number of the ester group represented by an aryl group of 6 to 14 or C 〇〇 R 2 〇 (which is an alkyl group having a carbon number of 1 to 2 Å or an aryl group having a carbon number of 6 to 14 forming a ring) is An alkyl group of 1 to 20. [12] The photopolymerization initiator according to item [9], wherein in the formula (H), 'R1 and R3 are each independently substituted or unsubstituted, and the number of carbon atoms is from 1 to 20, w is a single bond, z is >NR3' (R3' is as defined above), and Ar is a substituted or unsubstituted aryl group having a carbon number of 6 to 14. [13] The photopolymerization initiator according to item [12], wherein the further step R2 is one having a ruthenium COR13 (R13 is an alkyl group having a carbon number of 1 to 20 or a ring forming carbon number of 6 to 14) The aryl group) or -CO〇R2Q (R2Q is an alkyl group having a carbon number of -20 or an aryl group having a carbon number of 6 to 14 forming a ring), and the number of carbon atoms of the ester group is 1 to 20 base. -15- 201140240 [14] A photocurable composition comprising a binder resin and/or a compound having an ethylenically unsaturated bond, and any one of the items [1] to [.13] Photopolymerization initiator. [15] The photocurable composition according to item [14], wherein the content of the photopolymerization initiator is from 2 to 50% by mass based on the solid content of the photocurable composition. [16] The photocurable composition according to item [14] or [15], which further contains a color material. [17] The photocurable composition according to any one of [1] to [6], further comprising 5 to 100 parts by mass of an ether bond with respect to 1 part by mass of the photopolymerization initiator And/or an ester bond and a liquid compound at 25 ° C. [1] The photocurable composition according to any one of [1] to [6] wherein the compound having an ethylenically unsaturated bond is at least one having an ether bond and/or an ester bond. A compound having an ethylenically unsaturated bond, and the solvent contained therein is only 10% by mass or less based on the total amount of the photocurable composition. [19] The photocurable composition according to any one of [6] to [18], which is used for a color filter. [20] A color filter comprising the photocurable composition according to any one of [16] to [18]. [21] A liquid crystal display device comprising the color filter and the counter substrate of the item [20], and a liquid crystal layer formed between the color filter and the counter substrate. -16- 201140240 [22] A pattern forming method by applying a photocurable composition according to any one of items [16] to [18] on a substrate, and drying it, using a photomask Exposure followed by development. [23] A process for producing a photopolymerization initiator which is obtained by the following steps to obtain a photopolymerization initiator represented by the following formula (I - a 1 ):

R3 (wherein R1 to R3, R4', r5', 1^6 to Rii and Al• are as defined below), the step comprising: carbazole represented by the following formula (1) Carbazole derivatives: R6 R11

(wherein R6 to R11 are each independently represent a hydrogen atom, a halogen stomach, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and the substituted or unsubstituted carbon number is 2 to 20 Alkenyl, ring-substituted or unsubstituted ring-forming atoms having a ring number of 3 to 10 & ® 'substituted or unsubstituted ring olefins having a carbon number of 4 to 20 • 17- 201140240, hydroxy, Substituted or unsubstituted C 1 to 20 alkoxy, substituted or unsubstituted C 2 to 20 oxy group, substituted or unsubstituted C 1 to 20 alkyl group , substituted or unsubstituted olefin having 2 to 20 carbon atoms, substituted or unsubstituted ring-forming carbon number of 6 to 14 aryl or substituted or unsubstituted ring-forming atomic number Is a 3 14 heterocyclic group), and an acrylate derivative represented by the following formula (2〇: r4-^A〇^R3 (2a) R5· (wherein R3, R4' and R5' are each A halogen atom independently representing a hydrogen atom, a substituted or unsubstituted carbon number of 1 to 20 alkyl groups, a substituted or unsubstituted olefin having 2 to 20 carbon atoms, a substituted or unsubstituted ring-forming ring original a cycloalkyl group of 3 to 4, a substituted or unsubstituted carbon number of 4 to 20 cycloalkenyl groups, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted Or unsubstituted carbon number 2 to alkenyloxy, substituted or unsubstituted carbon number 1 to 20 alkyl alkano group, substituted or unsubstituted carbon number 2 to 20 fluorenyl group The substituted or unsubstituted aryl group having a carbon number of 6 14 or a substituted or unsubstituted ring-forming atom is a heterocyclic group of 3 to 14, and R 3 is formed together with r 5 '. Ring) The reaction is carried out in the presence of a test to obtain a carbonyl alkyl group-introducing body represented by the following formula (3 a, the olefin group of the group 10 to 20 olefin to the number I) -18- 201140240 R6 R11

Shown; R11 is as defined above, the obtained carbonyl alkyl group is introduced (4)

The two deuteration agents represented by the following formula: 0

R2 Λ X, (5) (wherein X represents a halogen atomic sphere -~〇C( = 〇)Ar , X, represents a dentate atom or —〇C( = . The number of carbon atoms forming the ring is 6 generations Ring forming atom

Ar is a substituted or unsubstituted aryl group of from 14 to 14 or a substituted or unsubstituted heteroaryl group of 5 to 14; R 疋 represents a hydrogen atom 'halogen atom, substituted or unsubstituted carbon number a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted ring-forming ring having 3 to 10 atomic number, substituted or Unsubstituted carbon 4 to 20 cycloalkenyl, hydroxy' substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted -19-201140240 carbon number 2 to 20 alkenyloxy group, substituted or unsubstituted alkyl halo group having 1 to 20 carbon atoms, substituted or unsubstituted olefin group having 2 to 20 carbon atoms, substituted or unsubstituted The aryl group having a carbon number of 6 to 14 formed by a ring or a substituted or unsubstituted heterocyclic group having a ring number of 3 to 14) is obtained by conducting a reaction in the presence of a Lewis acid (Lewis acid) a diketone body represented by the following general formula (6a')

• 20-201140240 and reacting the obtained carcass with a cooling agent represented by the following general formula (8) to obtain a photopolymerization bow represented by the general formula (I_a 1 ): People (8)

R1 Y (wherein Y represents a halogen atom or an OChCOR1; further, R1 represents a gas atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted An alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring atoms, a substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted carbon number of 1 An alkylene group of 20 to 20, a substituted or unsubstituted olefin group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having a carbon number of 6 to 14 or substituted or unsubstituted The substituted heterocyclic group having a ring number of 3 to 14). [Effect of the Invention] The photopolymerization initiator of the present invention has a high sensitivity to light (especially a short-wavelength light of 45 nm or less, for example, a light having a wavelength of 365 nm or a wavelength of 405 nm), and can be thinned, Forming a low-cost and high-quality pattern and compatibility with a compound having an ethylenically unsaturated double bond, a compound having an ether bond and/or an ester bond and being liquid at 25 ° C, and a solvent (including the foregoing The solubility of a compound having an ether bond and/or an ester bond and being a liquid at 25 t is high, and a solvent-free photocurable composition can also be prepared - 21-201140240, and light for a color filter is used. In terms of the curable composition, the selection amount of the photopolymerization initiator is broad, and as a result, the sensitivity, the resolution, the developability, and the deep hardenability can be improved. In the present invention, the photopolymerization initiator of the present invention has a relatively small molecular weight and can reduce the amount of the photocurable composition by increasing the molecular weight while imparting various substituents to the photopolymerization initiator. In addition, the photopolymerization initiator is compatible with a compound having an ethylenically unsaturated double bond, a compound having an ether bond and/or an ester bond and being a liquid at 25 ° C, and a solvent (including the foregoing) The compound having an ether bond and/or an ester bond and being a liquid at 25 ° C has high solubility, and has excellent sensitivity, resolution, developability, and adhesion to a substrate. [Embodiment] [Formation for carrying out the invention] [Photopolymerization initiator] The photopolymerization initiator of the invention can be represented by the following formula (I) 〇x/R1

(wherein R1 to R11 are each independently represent a hydrogen atom, a halogen atom, -22- 201140240 substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted carbon number 2 Alkenyl group to 20, substituted or unsubstituted cycloalkyl group having 3 to 1 ring atomic number, substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, s. A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyloxy group having 2 to 2 carbon atoms, a substituted or unsubstituted carbon number of 1 to 2 Alkyl, substituted or unsubstituted olefinic group having 2 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 4 carbon atoms forming a ring or substituted or unsubstituted The substituted heterocyclic group having a ring number of 3 to M may form a ring together with R or R5, and R4 may form a ring together with R5; further, Ar represents a substituted or unsubstituted ring. a carbon number of 6 to 14 or a substituted or unsubstituted heteroaryl group forming a ring having 5 to 14 atoms; 'W is a single bond or an oxygen atom; z is a single bond, an oxygenogen Or > NR3 (R3 represents an alkyl group having 1 to 2 carbon atoms substituted or unsubstituted, or R3 is bonded to R3 and forms a ring with a nitrogen atom), and η represents 1 to 10 In the case of the integer of 2 to 1 ', the plural R4 and R5 may each be the same or different. Further, in the photopolymerization initiator of the present invention represented by the general formula (I), The viewpoint of the effect of the invention is preferably a photopolymerization initiator represented by the following formula (^ which is equivalent to a single bond, a hydrazine: an oxygen atom) and represented by the following formula (1-b) Photopolymerization initiator (corresponding to the case where η is 1). • 23- 201140240

(I - a ) ( I - b ) In the above formula, R 1 to R 11 are each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or not a substituted alkenyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring atoms, a substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted carbon number of 1 An alkanoyl group to 20, an olefin group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having a carbon number of 6 to 14 or a substituted or unsubstituted ring-forming atom Further, in the formula (Ia), R3 may form a ring together with R4 or R5, and further, R4 may form a ring together with R5. Further, Ar is a substituted or unsubstituted aryl group having 6 to 14 carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms. W in the formula (Ib) represents a single bond or an oxygen atom: Further, Z in the formula (Ib) represents a single bond, and the substituted or unsubstituted carbon number is V-bonded with nitrogen. The atom ～ is formed into a ring, an oxygen atom or > NR3' (R3' is an alkyl group of 1 to 20, or R3' is an integer of 1 〇 in the formula (Ia), and the complex η represents 丨 to The integer, n is 2 to several R4 and R5 are each the same or different from the viewpoint of becoming a low molecular weight, and are compatible with a compound having an ethylenically unsaturated double bond (hereinafter, simply referred to as "Compatibility" or a viewpoint of solubility in a solvent (hereinafter, simply referred to as "solubility") and ease of production, η is preferably an integer of 2 to 8' more preferably 2 to An integer of 4, more preferably 2. In terms of a halogen atom independently represented by R1 to R11, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., the carbon independently represented by R1 to R11 For the alkyl group having 1 to 20, a linear or branched chain such as methyl, ethyl or n-propyl may be exemplified. , isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-octyl, 2-ethyl-n-octyl, n-decyl, n-dodecane Among these, from the viewpoint of low molecular weight, compatibility, solubility, and ease of production, an alkyl group having 1 to 10 carbon atoms, more preferably 1 carbon number is preferred. The alkyl group of 5 to 5. The alkenyl group having 2 to 20 carbon atoms independently represented by R1 to R11 may, for example, be a linear or branched chain such as a vinyl group, a propyl group, or a 7-octyl group. Alkenyl group, etc. Among these, 'from the viewpoint of being a low molecular weight, the viewpoint of compatibility -2540 to 201140240, solubility and solubility, and ease of production' are preferably alkenyl groups having a carbon number of 2 to 10, more The alkenyl group having 2 to 6 carbon atoms is preferable. The cyclopropyl group, the cyclopentyl group and the cyclohexyl group are exemplified as the cycloalkyl group having 3 to 10 atoms forming a ring independently represented by R1 to R11. Cyclooctyl group, etc. Among these, from the viewpoint of low molecular weight, compatibility, solubility, and ease of production, it is preferred that the number of atoms forming the ring is 3 a cycloalkyl group of 6. A cyclopentenyl group, a cyclohexenyl group, a cyclohexadienyl group, a cyclooctene group can be exemplified as the cycloalkenyl group having 4 to 20 carbon atoms independently represented by R1 to R11. Among these, a cycloalkenyl group having a carbon number of 4 to 1 Å, more preferably a carbon number, is preferred from the viewpoints of low molecular weight, compatibility, solubility, and ease of production. The cycloalkenyl group is 4 to 6. In the case of the alkoxy group having 1 to 20 carbon atoms independently represented by R1 to R11, the alkyl moiety is exemplified by the above-mentioned alkyl group having 1 to 20 carbon atoms. Among these, from the viewpoints of low molecular weight, compatibility, solubility, and ease of production, an alkoxy group having a carbon number of 1 to 1 Torr is preferable, and a carbon number is preferably 1 to 1. 5 alkoxy groups. With respect to the alkoxy group having 2 to 20 carbon atoms independently represented by R1 to R11, the alkenyl group may be exemplified by the above-mentioned alkenyl group having 2 to 20 carbon atoms. Among these, from the viewpoints of low molecular weight, compatibility, solubility, and ease of production, an alkenyl group having a carbon number of 2 to 10 is preferred, and a carbon number of 2 is more preferred. 6 alkenyloxy. With respect to the alkyl fluorenyl group having 1 to 20 carbon atoms independently represented by R1 to R11, a linear or branched chain such as methane fluorenyl group, ethyl -26-201140240 alkyl fluorenyl group, n-propane group can be exemplified. Anthracenyl, isopropane fluorenyl, n-butane fluorenyl, tertiary butane fluorenyl, n-hexane fluorenyl, n-octane fluorenyl, n-decyl fluorenyl, n-dodecyl fluorenyl, and the like. Among these, from the viewpoints of low molecular weight, compatibility, solubility, and ease of production, an alkane group having a carbon number of 1 to 10 is preferred, and a carbon number of 1 to 5 is more preferred. Alkyl group. The olefinic group having 2 to 20 carbon atoms independently represented by R1 to R11 may, for example, be a linear or branched chain, for example, an ethylene fluorenyl group, a n-propenyl fluorenyl group, an isopropylene fluorenyl group, or a positive Butenyl group, tertiary butenyl group, n-hexenylene group, n-octene fluorenyl group, n-decene fluorenyl group, n-dodecenyl group, and the like. Among these, from the viewpoints of low molecular weight, compatibility, solubility, and ease of production, an ene group having a carbon number of 2 to 10 is preferable, and a carbon number of 2 is more preferable. 6 olefinic group. With respect to the aryl group having 6 to 14 carbon atoms which are independently represented by R1 to R11, for example, a phenyl group, a naphthyl group or an anthracenyl group can be exemplified. With respect to the heterocyclic group in which R1 to R11 are each independently represented to form a ring having 3 to 14 atomic atoms, for example, 2-furyl group, 2-phenylthio group, 2-pyridyl group, and the following formula (A) are exemplified. The base represented (hereinafter, referred to as "substituent (A)")

1ί

An unsaturated heterocyclic group having a ring number of 5 to 14 formed by S; etc.; 2•tetrahydrofuranyl, 3-tetrahydrofuranyl, pyrrolidinyl, piperidinyl, 2,2,6,6-trimethylpiperidine The -4- group or the like forms a saturated heterocyclic group having 3 to 1 atomic number of atoms. Among these, from the viewpoint of the viewpoint of low molecular weight, compatibility or solubility, and the ease of production, it is preferred to form an unsaturated heterocyclic group having 5 to 6 atoms in the ring. A saturated heterocyclic group having a ring number of 3 to 6 is formed. Further, the above-mentioned "R3 and R4 or R5 together form a ring", for example, when η = 2, W is a single bond, and Z is an oxygen atom, it can be explained by the following formula, which is exemplified on the right side. The ring is a concrete example.

The ring formed by R4 and R5 may, for example, be a ring having a carbon number of 3 to 10 (preferably 3 to 6) which forms a ring of a cyclopentyl ring, a cyclooctyl ring or the like. Further, R1 to R11 each independently represent the aforementioned alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, alkoxy 'alkenyloxy group, alkanoyl group, olefin group, aryl group and heterocyclic group. Has a substituent. The substituent of the alkyl group or the alkenyl group which each independently represents R1 to R11 may, for example, be a hydroxyl group: a carboxyl group: a linear or branched chain carbon such as a methoxy group, an ethoxy group or a propoxy group. The number of alkoxy groups is from 1 to 18 (preferably from 1 to 1 Torr, further preferably from 1 to 5); the linear or branched chain has a carbon number of from 2 to 18 (preferably from 2 to 10, Further preferably, the oxy group of 2 to 6) is a thiol group having a carbon number of 2 to 18 (preferably 2 to 10, more preferably 2 to 6) in a straight bond or a branched bond; The chain or branched chain has a carbon number of from 1 to 18 (preferably from 1 to 1 Torr, further preferably from 1 to 5); the carbon number is from 5 to 18 (preferably from 5 to 10). Cyclohexane -28- 201140240 A cycloalkyl group having a carbon number of 3 to 18 (preferably 3 to 10' and further preferably 3 to 6) of cyclopropyl, cyclopentyl or cyclohexyl: phenoxy The carbon group forming the ring is an aryloxy group having a ό to 10; a halogen atom such as a fluorine atom, a chlorine atom, a desert atom or an iodine atom; an oxygen atom (=〇); a sulfur atom (=s:); a cyano group; ; nitro; trimethyl sand yards and other three hospital bases; trimethoxy sand yards and other three courtyards a phenyl group, a naphthyl group, a fluorenyl group or the like which forms a ring having 6 to 14 (preferably 6 to 10) carbon atoms; _c〇r12; 〜NHCOOR1 -OCOR13; — NR14R15 ; — NHCOR1 CONR18R19 : - COOR20 ; —S03NR21R22 ; a s〇3r23 : a cyclic acid group having a ring number of 3 to 6 formed by an epoxy group or a tetrahydrofuranyl group, a 2-thiophenyl group '2-pyridyl group, a furyl group, a thiazolyl group, a benzo group The thioxyl group, the morphyl group, the saturated or unsaturated group of the substituent (A) or the like, which forms a ring, has a number of atoms of 3 to 10 (preferably 3 to 6), and the like. In the above formula, R12 to R2 3 are an aryl group each independently representing a linear or branched chain alkyl group having a carbon number of 1 to 20 and a ring having 6 to 14 carbon atoms. The alkyl group and the aryl group are the same as those in the case of R1 to R11. The substituent of the alkoxy group, the alkenyloxy group, the alkanoyl group or the olefin group which each independently represents R1 to R11 may, for example, be a hydroxyl group; a carboxyl group; a methoxy group, an ethoxy group, a propoxy group or the like. a linear or branched chain alkoxy group having a carbon number of 1 to 18 (preferably 1 to 10, further preferably 1 to 5): a linear or branched chain having a carbon number of 2 to 18 (preferably 2 to 10' is further preferably 2 to 6) an alkenyloxy group; the linear or branched chain has a carbon number of 2 to 18 (preferably 2 to 10, further preferably 2) To 6) alkylthio-29- 201140240; linear or branched chain carbon number of 1 to 18 (preferably 1 to 10, further preferably 1 to 5) alkyl group; carbon number a cycloalkenyl group of 5 to 18 (preferably 5 to 10); a cyclopropyl group, a cyclopentyl group, a cyclohexyl group or the like having 3 to 18 carbon atoms (preferably 3 to 10, further preferably 3 to 6) a cycloalkyl group; an aryloxy group having a carbon number of 6 to 10 forming a ring such as a phenoxy group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; an oxygen atom (=〇); a sulfur atom; (=S): cyano group: nitro: trialkyl decyl group such as trimethyl decyl group: trimethoxy decyl group, etc. Alkoxyalkylene; phenyl, naphthyl, anthracenyl or the like which forms a ring having 6 to 14 (preferably 6 to 10) carbon atoms; a COR12; - OCOR13; - NRI4R15; - NHCOR丨6 - NHCOOR17; - CONRI8R19; - COOR20; - S03NR21R22; _S03R23; a cyclic ether group having a ring number of 3 to 6 formed by an epoxy group or a tetrahydrofuranyl group, a 2-thienyl group, a 2-pyridyl group, a furyl group a sulfazolyl group, a benzothiazolyl group, a morpholinyl group, a saturated or unsaturated group of the above substituent (A), etc., which forms a ring having 3 to 10 (preferably 3 to 6) atomic groups, etc. In the above, R12 to R23 are as defined above.) 0. The substituents of the cycloalkyl or cycloalkenyl group which are independently represented by R1 to R11, respectively, may be exemplified by a hydroxyl group; a carboxyl group; a methyl group, an ethyl group or the like. a linear or branched chain having an alkyl group having 1 to 18 (preferably 1 to 10, and more preferably 1 to 5) carbon atoms; a linear chain such as a methoxy group, an ethoxy group or a propoxy group; a branched or branched chain having an alkoxy group having 1 to 18 (preferably 1 to 10, further preferably 1 to 5) carbon atoms; and a linear or branched chain having 2 to 18 carbon atoms ( Preferably 2 to 10, further Preferred are 2 to 6) alkenyloxy-30-201140240; linear or branched chain carbon number of 2 to 18 (preferably 2 to 10, further preferably 2 to 6) olefin sulfur a linear or branched chain alkenyl group having a carbon number of 2 to 18 (preferably 2 to 10, more preferably 2 to 6); a linear or a branched chain; a branched chain having a carbon number of from 1 to 18 (preferably from 1 to 10, further preferably from 1 to 5); a cycloalkenyl group having from 5 to 18 (preferably from 5 to 10) carbon atoms: An aryloxy group having a carbon number of 6 to 10 which forms a ring such as a phenoxy group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom: an oxygen atom (=〇); a sulfur atom (=S); cyanide a trialkylalkylene group such as a nitro group; a trimethyl decyl group; a trialkoxy fluorenyl group such as a trimethoxy decyl group; a carbon number of the phenyl group, a naphthyl group, an anthryl group or the like which forms a ring of 6 to 14 (preferably 6 to 10) aryl; -COR12; - OCOR13; - NRI4R15; - NHCOR16; - NHCOOR17; - CONR18R19; - COOR20; - S03NR21R22; -S03R2 3 ; formation of epoxy or tetrahydrofuranyl a cyclic ether group having 3 to 6 atoms in the ring, 2 -thinyl, The number of atoms forming a ring of 2-pyridyl, furyl, thiazolyl, benzothiazolyl, morpholinyl, the above-mentioned substituent (A) or the like is from 3 to 10 (preferably from 3 to 6). A heterocyclic group or the like (wherein RU to R23 are as defined above). The substituent of the aryl group or the heterocyclic group independently represented by R1 to R11 may, for example, be a hydroxyl group; a carboxyl group; a linear or branched chain having a carbon number of 1 to 18 such as a methyl group or an ethyl group; An alkyl group (preferably 1 to 1 Torr, further preferably 1 to 5); a linear or branched chain of methoxy, ethoxy, propoxy or the like having a carbon number of 1 to 18 ( Preferably, it is an alkoxy group of 1 to 10, more preferably 1 to 5); the linear or branched chain carbon number is 2 to -31 to 201140240 18 (preferably 2 to 10, further preferably An alkenyloxy group of 2 to 6); a linear or branched chain having a carbon number of 2 to 18 (preferably 2 to 10, further preferably 2 to 6); linear or a branched chain having a carbon number of 1 to 18 (preferably 1 to 10' and further preferably 1 to 5); a linear or branched chain carbon such as a vinyl group or an allyl group; An alkenyl group having 2 to 18 (preferably 2 to 10, further preferably 2 to 6); a cycloalkenyl group having 5 to 18 (preferably 5 to 10) carbon atoms; a cyclopropyl group; a cycloalkyl group having a carbon number of 3 to 18 (preferably 3 to 10, more preferably 3 to 6); a phenoxy group or the like forming a ring An aryloxy group having 6 to 10 carbon atoms; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; a cyano group; a nitro group; a trialkylsulfonyl group such as a trimethylsulfanyl group; Alkyloxyalkylene group; a COR12; —OCOR1 3 ; -NR14R15 ; -NHCOR16 ; -NHCOOR1 7 ;- CONR18R19 ; - COOR20 ; — so3nr2Ir22 : — S03R23 ; an epoxy group or a tetrahydrofuranyl group a saturated or unsaturated group of a cyclic ether group having 3 to 6 atoms, a 2-thiophenyl group, a 2-pyridyl group, a furyl group, a succinazolyl group, a benzothiazolyl group, a morpholinyl group, the aforementioned substituent (A), or the like The heterocyclic group or the like having a ring number of 3 to 10 (preferably 3 to 6) is formed (wherein R12 to R23 are as defined above). Further, as the aryl group represented by Ar which forms a ring having 6 to 14 carbon atoms, for example, a phenyl group, a naphthyl group, an anthracenyl group, a chrysenyl group, a phenanthryl group, a methenyl group, a fluorenyl group can be exemplified. Wait. Among these, from the viewpoints of low molecular weight, compatibility, solubility, and ease of production, it is preferred to form an aryl group having a carbon number of 6 to 10, more preferably a phenyl-32 group. - 201140240 °Ar represents a heteroaryl group having 5 to 14 ring atoms, and includes, for example, a 2-furyl group, a 2-phenylthio group, a 2-pyridyl group and the like. Among these, from the viewpoints of low molecular weight, compatibility, solubility, and ease of production, a heteroaryl group having 5 to 6 atoms in the ring is formed, and more preferably 2-furan. Base, 2-phenylthio group. These aryl and heteroaryl groups may have a substituent. With respect to the substituent, the substituents of the aryl group independently represented by each of R1 to R11 described above are the same, and preferably the carbon number is from 1 to 18 (preferably from 1 to 10, further An alkyl group of preferably 1 to 5) is further preferably a methyl group. Further, when the substituent is an alkyl group or an alkenyl group, a condensed ring may be formed with Ar to form, for example, an anthracene ring or an anthracene ring may be formed. R3' represented by Z> NR3' is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms as described above, or R3' is bonded to R3 to form a ring together with a nitrogen atom. The alkyl group having 1 to 20 carbon atoms is the same as those in the case of R1 to R11 and is preferably the same, and particularly preferably a methyl group. Further, a specific example of the ring in which 'R3' is bonded to R3 and formed together with a nitrogen atom includes a morpholine ring, a pyrrolidine ring, a piperidine ring, a meperidine ring, a piperazine ring and the like. Among these, a morpholine ring is preferred. The combination of w and z includes: in the case where W is a single bond, Z is preferably an oxygen atom or > N r3 ', and in the case where W is an oxygen atom, Z is preferably a single bond or an oxygen atom. . And 'About the general formula (I-a)' (a)!^1, ! ^2 and R3 are each independently substituted or unsubstituted alkyl having 1 to 20 carbon atoms, η -33- 201140240 is 2, and plural R4 and R5 are each independently a hydrogen atom or substituted. Or an unsubstituted alkyl group having 1 to 20 carbon atoms, wherein Ar is a photopolymerization initiator of a substituted or unsubstituted aryl group having a carbon number of 6 to 14; (b) R1, R2 and R 3 is independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, η is 2, and a plurality of R 4 and R 5 are each independently a hydrogen atom or a substituted or unsubstituted carbon number is 1 to 20 alkyl groups,

Ar is a photopolymerization initiator which is substituted or unsubstituted to form a heteroaryl group having a carbon number of 5 to 14; (c) R1 and R2 are each independently substituted or unsubstituted carbon number a alkyl group of 1 to 20, R 3 is a substituted or unsubstituted cycloalkyl group having 3 to 18 carbon atoms, η is 2, and a plurality of R 4 and R 5 are each independently a hydrogen atom or a substituted or unsubstituted a photopolymerization initiator substituted with an alkyl group having 1 to 20 carbon atoms; (d) R1 and R2 are each independently substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R3 is The cyclic ether group having 3 to 6 ring atoms is substituted with an alkyl group having 1 to 20 carbon atoms, η is 2, and a plurality of R 4 and R 5 are each independently a hydrogen atom or a substituted or unsubstituted group. A photopolymerization initiator having an alkyl group having 1 to 20 carbon atoms is also preferred. In addition, in the case of the above (a) and (b), the molecular weight is preferably 515 or less, more preferably 500 or less, from the viewpoint of reducing the content of the photopolymerization initiator in the photocurable composition. In the case of the above (c) and (d), the molecular weight is preferably 550 or less. Further, from the viewpoint of the efficacy of the present invention and the viewpoint of reducing contamination of the polymer or contamination of the device due to decomposition products of the photopolymerization initiator, among the above preferred photopolymerization initiators, R4 is more preferable. To R11 are each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Further, each of the groups -34 to 201140240 is preferably as described above. Hereinafter, specific examples of the photopolymerization initiator (I-a) of the present invention are listed, but are not limited thereto.

201140240

ο

-36- 201140240

-37- 201140240

Further, with respect to the general formula (Ib), (e) R1 and R3 are each a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, θ w 疋 an oxygen atom, Ζ is a single bond or An oxygen atom, Ar is a photopolymerization initiator of a substituted or unsubstituted ρ-bonded aryl group having 6 to 14 carbon atoms; (〇Rl & R3 are each independently substituted or unsubstituted carbon The alkyl group 'R2, which has a number of 1 to 2 Å, has an OCOR13 (R13 is as defined above) or a COOR2<) (R2G represents an alkyl group having a carbon number of 1 to 20 or a carbon number forming a ring The alkyl group having a carbon number of 1 to 2 Å, which is an aryl group of 6 to 14), is an oxygen atom, Z is a single bond or an oxygen atom, and Ar is a substituted or unsubstituted ring. a photopolymerization initiator having an aryl group having 6 to 14 carbon atoms; (g) R1 and R3 are each independently substituted or unsubstituted carbon • 38- 201140240 The number is 1 to 20 'hospital base'... a single bond, 2 is >: 1^3' ({13, is as before ^mmm tts ) ' is a photopolymerization initiator which is substituted or unsubstituted to form a ring having an aryl group having 6 to 14 carbon atoms; (h) R1 and R3 are each The ground is a substituted or unsubstituted alkyl group having a carbon number of 1 to 2 Å, and R2 is having ~~0C0Rl3 (R13 is as defined above) or "C〇〇R2<) (R2<) The alkyl group having a carbon number of 1 to 20 representing an ester group having an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 carbon atoms forming a ring is a single bond '2 is> Nr3 , (r3' is as defined above), Ar is a photopolymerization initiator of a substituted or unsubstituted aryl group having a carbon number of 6 to 14; (i) R1 is substituted or not The substituted carbon number is from 1 to 20, R3 is a hydrogen atom, w is a single bond, z is an oxygen atom, and Ar is a substituted or unsubstituted aryl group having a carbon number of 6 to 14 formed into a ring. A photopolymerization initiator is also preferred. Further, in the photopolymerization initiator of the above (g), it is preferable that R3' in the >NR3' is bonded to R3 to form a ring together with a nitrogen atom, and more preferably a morpholine ring is formed. Further, from the viewpoint of the effect of the present invention and the viewpoint of reducing contamination of the polymer or contamination of the device due to decomposition products of the photopolymerization initiator, among the above preferred photopolymerization initiators, R4 is more preferably R11 is each independently a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. Further, each of the groups is preferably as described above. Hereinafter, specific examples of the photopolymerization initiator (I-b) of the present invention are listed, but are not particularly limited thereto. -39- 201140240

-40- 201140240

Further, in the photopolymerization initiator of the present invention, n = 2 is preferable in the formula (Ia) as described above, and specifically, it is preferably represented by the following formula (I-al). Photopolymerization initiator: -41 - 201140240

It’s not right. R4 and R5' are the same as R and R5, respectively, and the same is preferred. [Manufacturing Method of Photopolymerization Initiator] The method for producing the photopolymerization initiator (1) of the present invention is not particularly limited, and for example, the production method of the photopolymerization initiator (I_a) or the photopolymerization initiator (Ib) The manufacturing method can be easily manufactured. (1. Method for producing photopolymerization initiator (I-a)) The method for producing the photopolymerization initiator (I_a) of the present invention is not particularly limited, and can be easily produced, for example, by the following steps to step 4. (Step 1) As the step 1 ', for example, the aforementioned carbazole derivative (1) and Z(CR R )nco〇R3 (z is a halogen atom representing a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like. R3, r4 and R5 are the steps of the reaction of the halide 'represented by the above definition' in the presence of a base. By this step, a carbonylalkyl group as represented by the following formula (3a) can be obtained: -42 - 201140240 R6 R11

(3a) (wherein R3 to R11 are as defined above, preferably the same). As the base, n-butyllithium, tertiary butyllithium, sodium hydroxide, potassium hydroxide, etc. may be exemplified. . The reaction temperature is usually preferably from 〇 to 200 ° C, and the reaction time is usually preferably from 2 to 100 hours. Further, in the case of producing a photopolymerization initiator of n = 2 in the formula (I-a), it is preferred if the step 1 is the following step, since it can be easily produced. The carbazole derivative represented by the following general formula (1) [hereinafter, referred to as "carbazole derivative (1)"): R6 R11

(wherein R6 to R11 are as defined above, preferably the same), and an acrylate derivative represented by the following formula (2a) [hereinafter hereinafter referred to as "acrylate derivative" 2〇"): (wherein 'R3, R4' and R5' are as defined above, preferably also -43-201140240), and the reaction is carried out in the presence of a base to obtain the following formula ( 3 a ') The carbonylalkyl group-introducing body (hereinafter referred to as "carbonylalkyl group-introducing body (3a')"): R6 R11

(wherein R3, R4' 'R5' and R6 to R1 1 are as defined above, and preferably are the same). Hereinafter, this step 1 which is preferable in the case of producing a photopolymerization initiator of n = 2 will be described in detail below. The amount of the acrylate derivative (2a) used in the step 1 is not particularly limited, and is preferably 0.5 to 2 mol per 1 mol of the carbazole derivative (1), further preferably From 88 to 1.2 mol, it is further preferred to carry out the reaction in substantially equal amounts from the viewpoint of reducing unreacted materials. Step 1 is carried out under the action of a base. The base is used as long as it is a base which can be used in a Michael addition reaction, and any of an organic base and an inorganic base can be used. The organic base includes, for example, ruthenium, diazepane, eleven (D B U ), dioxo-cyclo-ene (DBN), and the like. The inorganic base is an alkali metal carbonate such as sodium carbonate or potassium carbonate; an alkaline earth metal carbonate such as magnesium carbonate 'calcium carbonate; or an alkali metal hydrogencarbonate such as sodium hydrogen carbonate or potassium hydrogencarbonate; An alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; an alkaline earth metal hydroxide such as magnesium hydroxide or calcium hydroxide. Among these, 'it is preferably an alkali metal carbonate or an alkaline earth metal carbonate, more preferably an alkali metal carbonate, and even more preferably potassium carbonate. The amount of the base used is not particularly limited, and the reaction efficiency and manufacture are carried out. The viewpoint of cost is preferably 0.5 to 2 moles, more preferably 0.8 to 1.2 moles, and still more preferably used in substantially equal amounts with respect to 1 mole of the carbazole derivative (1). Step 1 is preferably carried out in the presence of a solvent. The solvent is appropriately selected from solvents which can dissolve the carbazole derivative (1), the acrylate derivative (2a) and the base. Specific examples thereof include dimethylformamide (DMF), dimethyl hydrazine (DMSO), and dichloromethane. The reaction temperature of the step 1 is not particularly limited, and it is usually preferably carried out at 10 to 50 ° C, more preferably 15 to 401 :, still more preferably 15 to 3 ° C. The reaction time varies depending on the type or amount of the carbazole derivative (1), the acrylate derivative (2a) and the base, the reaction temperature, and the like, and is usually about 2 hours to 48 hours. The embodiment of the step 1 is not particularly limited. For example, the carbazole derivative (1), the acrylate derivative (2a), and the base are all added to the solvent. Preferably, the mixture is stirred at the aforementioned temperature. A carbonylalkyl group introducer (3 a '). After completion of the reaction, the carbonylalkyl group-introducing body (3a)-45 - 201140240 or (3 a ') can be obtained from the obtained reaction mixture by a separation method of a general organic compound such as extraction. By purifying by a general method of purifying a general organic compound such as distillation, column chromatography or recrystallization, the purity of the carbonylalkyl group-introducing body (3a) or (3a,) can be improved. The steps 2 to 4 of the carbonylalkyl group-introducing body (3a) or (3a') obtained in the above step 1 are explained, taking into consideration the convenience factor 'about a portion of the carbonylalkyl group-introducing body (3a,) equivalent to n=2. The description is omitted. (Step 2) Step 2 is by using the carbonylalkyl group-introducing body (3a) obtained in the step 1 and the two deuterating agents represented by the following formulas (4) and (5) [hereinafter, They are called "deuterated agent (4)" and "deuterated agent (5)"

(wherein 'X represents a halogen atom or -〇C(=〇)Ar, X' represents a halogen atom or -〇C(=0)R2; Ar and .R2' are as defined above, preferably The same is true), the reaction is carried out in the presence of a Lewis acid to obtain a diketone body represented by the following general formula (6 a ) (hereinafter referred to as "diketone body (6a)"): 46-

201140240 (where R2 is the same). In the above formula, 'X, X, each independently represents a halogen atom: a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, preferably with respect to the step 2, from the point of the diketone body (6a) as a target' The carbonylalkyl group-introducing body (3a) and the oximation agent (4) and (5 are preferably a carbonyl alkyl group-introducing body (3a) and a oximation agent (4, followed by a sulfating agent (5) The reaction is carried out from the viewpoint of introducing each of the carbonylalkyl group-introducing bodies (3a) into the respective ones, and the amount of the deuterating agents (4) and (5) is used for each of the ore-based matrix-introducing bodies (3a). Preferably, 〇8 to 1 is further preferably from 1 to 1.3 mol, and further preferably from the reduction of the unreacted matter, the reaction is carried out in substantially equal amounts, particularly in the transductant (3a) and the oximation agent. (4) In the case where the reaction (5) is carried out after the reaction, the use of the deuteration agent (5) does not have any problem in the above range, but even if the corresponding yield is obtained in a too large amount, the result may be Resulting in vain increase step 2 is carried out in the presence of a Lewis acid. Lewis aluminum chloride, boron trifluoride-diethyl ether complex. Preferably, the body also includes a chlorine atom. The yield of the reaction;) is carried out by the antimony thiol 1 molar. 3 moles, the viewpoint is to make the carbonyl alkane and the amount of deuteration even super Can not produce costs. The acid is preferably from the viewpoint of the yield of -47 to 201140240 of (6a), and the Lewis acid is used in an amount of usually from 0.8 to 2.5 moles per 1 mole of the agent (4) or (5). The best is 1 to 2 moles. Step 2 is preferably carried out in the presence of a solvent. When the solvent is a solvent which can be generally used in the F Crafts acylating reaction, it is not particularly specific, and examples thereof include dichloromethane, nifedipine, acetone, acetonitrile, and the like. The reaction temperature in the step 2 is preferably -50 to preferably -1 Torr to 5 °C at the start of the reaction, and is slowly returned to about 15 to 25 ° C as the reaction proceeds. The reaction time is usually from 1 to 30 hours depending on the kind and amount of the carbonylalkyl group-introducing agent, the halogenating agents (4) and (5), and the reaction. Further, in the deuteration agent (5), both of them are an acyl halide or an acid anhydride, and the carbonyl alkyl group-introducing body (3a) may be reacted with the deuteration agent (4) without isolation. And in this case, preferably, the reaction time of the carbonylalkyl group-introducing body (3a) and the deuteration) is set to about 30 minutes to 5 hours (preferably 3 to 3 hours), on the other hand, the reaction time of the carbonylalkyl group-introducing agent (the deuterating agent (5) is set to be, for example, about 30 minutes to 24, preferably 30 minutes to 18 hours) to be sufficient. Go on the ground! In the following, the two comparative forms of step 2 are explained from the viewpoint of yield. [1] The carbonyl initiator (3 a ) and the oxime (4) are mixed in a suitable solvent while cooling in an ice bath, and the mixed solution is slowly simmered in a step as long as it is limited to r i e d e 1 -. ο 5 1 (room temperature ((3a) temperature and: 4) and the situation, after the reaction, : agent (4 1 〇 minutes 3a) and hours (corresponding. Good solid alkyl ground (more than -48- 201140240 Preferably, the Lewis acid is added for 5 minutes to 1 hour, further preferably 10 minutes to 40 minutes. After the addition is completed, return to room temperature and continue stirring for a certain period of time (about 30 minutes to 5 hours). Temporarily separating the obtained product by a separation method of a general organic compound such as extraction and washing, and dissolving the product obtained above in a suitable solvent, and adding the hydrating agent (5) while cooling in an ice bath, and It is slowly added to the Lewis acid (preferably for 5 minutes to 1 hour, further preferably 10 minutes to 40 minutes), and after the end of the addition, it is returned to room temperature and stirring is continued for a certain period of time (about 30 minutes to 24 hours). Thereby, the diketone body (6a) ° [2] can be obtained by mixing the carbonyl alkyl group-introducing body (3a) with an appropriate solvent while cooling in an ice bath, and then slowly adding it (preferably for 5 minutes to 1 hour). Further preferably 10 minutes to 40 Clock) Lewis acid, adding the sulfonating agent (4) slowly (preferably for 5 minutes to 1 hour, further preferably 10 minutes to 40 minutes) to the obtained mixed solution, returning to room temperature and continuing to stir For a certain period of time (about 30 minutes to 5 hours), the Lewis acid is added slowly (preferably for 5 minutes to 1 hour, further preferably 10 minutes to 40 minutes) while cooling with an ice bath. The mixed solution is slowly (preferably 5 minutes to 1 hour, further preferably 10 minutes to 40 minutes) added to the oximation agent (5) and then returned to room temperature and continued to stir for a certain period of time or more (preferably about 3). 0 minutes to 24 hours), whereby the diketone body (6a) can be obtained. Further, after the end of the reaction, the obtained reaction mixture is obtained by extraction, etc. -49-201140240 general organic compound separation method, two The ketone body (6a) can be purified by a general method of purifying a general organic compound such as distillation, column chromatography or recrystallization to increase the purity of the diketone body (6a) (Step 3) Step 3 By taking the steps The obtained diketone body (6a) is reacted with a hydroxylamine to obtain a steroid represented by the following formula (7a) (hereinafter, referred to as "steroid (7a)"):

HO, R6 R11 (wherein R2 to R11 and Ar are as defined above, and preferably the same). In the step 3, the supply source of the hydroxylamine is not particularly limited, and it is preferably a hydroxylamine hydrochloride. The chlorinated hydroxylamine is, for example, reacted with sodium acetate or the like in water, whereby an aqueous solution of a hydroxylamine can be obtained. The hydroxylamine (hydroxylamine chloride) is preferably used in an amount of from 0.8 to 2 mol, more preferably from 1 to 1.5 mol, more preferably from 1 to 1.5 mol, based on 1 mol of the diketone body (6a). From 1 to 1 · 3 moles, from the viewpoint of reducing unreacted materials, it is further preferred to carry out the reaction in substantially equal amounts. Step 3 is preferably carried out in the presence of a solvent. The solvent is preferably a water-soluble organic solvent, and the water-soluble organic solvent is preferably an alcohol such as methanol, ethanol or the like -50-201140240 alcohol, dimethylformamide (DMF) or the like. The reaction temperature of the step 3 is not particularly limited, and it is usually preferably from 40 to 50 to 140 ° C, more preferably from 70 to 1, the type and amount of the diketone body (6a). Preferably, it is preferably 2 to 20 hours, and further than the embodiment of the step 3, there is no particular limitation of mixing the hydroxylamine hydrochloride with sodium acetate to obtain a hydroxyl group to be added to the diketone body (6 a ) and the solvent, preferably Mixing, whereby the carcass (7a) can be obtained. After the completion of the reaction, the separation method of the obtained mixed organic compound can be obtained by purifying the hydrazine by distillation, column chromatography, recrystallization, etc., thereby improving the steroid (7a (step 4)). 4 is carried out by reacting the esterifying agent represented by the general formula (8) obtained in the step 3 (in the lower (8)) · 〇X (8)

R1^Y (wherein Y represents a halogen atom or -〇c(: as defined by the definition, preferably the same), to obtain a photopolymerization represented by the following formula (Ia) The initiator (1-0, from the steroid (7a) at 160 ° C, further preferably 10 ° C. The reaction time varies depending on the reaction temperature, and the enthalpy is 4 to 12 hours. The aqueous solution of the amine in water is added in advance, and the above temperature range is added to the general body (7a) by extraction, etc., by the purity of the appropriate organic compound. The steroid (7 a ) and the following are obtained. , which is called an esterifying agent: 〇) Ri; Ri is a step as described above: polymerization initiator [below]: -51 - 201140240

R3 (wherein R1 to R11 and Ar are as defined above). The halogen atom represented by 'Y' in the above formula includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or the like, and is preferably a chlorine atom. The amount of the esterifying agent (8) used in the step 4 is not particularly limited, and is preferably 0.5 to 2 mol's and further preferably 0.8 to 1.2 with respect to 1 mol of the carcass (7a). From the viewpoint of reducing unreacted materials, it is more preferable to carry out the reaction in substantially the same amount. Step 4 can also be carried out in the presence of a base to promote the reaction. The base includes: an organic base or an inorganic base. The organic base is, for example, an amine such as triethylamine or tributylamine; a nitrogen-containing heterocyclic aromatic compound such as pyridine. The inorganic base is, for example, an alkali metal carbonate such as sodium carbonate; an alkaline earth metal carbonate such as magnesium carbonate; an alkali metal hydroxide such as sodium hydroxide; and an alkaline earth metal hydroxide such as magnesium hydroxide. Among these, it is preferable that the organic test is more preferably an amine or a nitrogen-containing heterocyclic aromatic compound, and more preferably triethylamine or pyridine from the viewpoints of reaction efficiency and production cost. In the case of using a base, 'from the viewpoint of the yield of the photopolymerization initiator (I_a) and the production cost, it is preferably from 1 to 5 mol per 1 mol of the steroid (7a), further Good for 15 to 3 moles. -52- 201140240 Step 4 is preferably carried out in the presence of a solvent. The solvent is preferably an ether such as tertiary butyl methyl ether, ethyl methyl ether, cyclopentyl methyl ether or tetrahydrofuran (THF). The reaction temperature in the step 4 is preferably from -50 to 5 ° C at the start of the reaction (preferably from 1 Torr to 5 ° C), and slowly returns to room temperature as the reaction proceeds (about 15 to 25 ° C). ). The reaction time varies depending on the kind of the steroid (7a), the type and amount of the esterifying agent (8), and the reaction temperature, and is usually preferably from 0.5 to 10 hours, more preferably from 1 to 5 hours. The embodiment of the step 4 is not particularly limited. For example, the steroid (7 a ) and the esterifying agent (8 ) are mixed in a suitable solvent, and a base is added dropwise thereto, and the temperature of the reaction solution is added after the dropwise addition. The photopolymerization initiator (Ia) of the present invention can be obtained by slowly returning to room temperature and continuing stirring. After completion of the reaction, a photopolymerization initiator (I-a) can be obtained by a separation method of a general organic compound such as extraction from the obtained reaction mixture. By purifying by a general method of purifying a general organic compound such as distillation, column chromatography or recrystallization, the photopolymerization initiator (purity of ruthenium) can be improved. The photopolymerization initiator of the present invention obtained as described above can be obtained. (Ia) is a specific substituent which imparts an ester group to a nitrogen atom in the carbazole skeleton. Therefore, it is a compound having an ethylenically unsaturated bond in the photocurable composition (particularly having (methyl) a compound of a propylene oxime group), a compound having an acid bond and/or an ester bond and being a liquid at 25 ° C, and a solvent (including the aforementioned ether bond and/or ester bond at 25 °) C is a liquid compound) has high solubility, and has high sensitivity to light (especially light having a wavelength of 450 nm or less -53 to 201140240), and is excellent in resolution, developability, and deep hardenability. Further, the adhesion to the substrate is good. Further, the photopolymerization initiator (Ia) does not cause contamination of the polymer or contamination of the device due to decomposition products generated by light during exposure. Further, a photopolymerization initiator ( I- a) The compatibility or solubility of a specific compound or solvent contributes to the improvement of sensitivity, resolution, developability, and further deep hardenability, and therefore, it can be called for use in color filters. It is an important factor. In particular, in the use of a color filter, the photopolymerization initiator is more than 100 parts by mass of a solvent having an ether bond and/or an ester bond (particularly, propylene glycol monoethyl ether acetate, etc.). 5 parts by mass or more, more preferably 1 part by mass or more, and the photopolymerization initiator (Ia) of the present invention satisfies these conditions, and thus is suitable as photocurability for color filters. A photopolymerization initiator in the composition, and a photopolymerization initiator for use in a photocurable composition for a black matrix having high light-shielding properties. (1. Method for Producing Photopolymerization Initiator (Ia)) The method for producing the photopolymerization initiator (bb) is not particularly limited, and can be easily produced, for example, by the following steps to step 4. (Step 1) Step 1 is that the manufacturing method differs depending on w and Z, and the following is for In the case of a single bond, z is >NR3'. The carbazole derivative represented by the following formula (1) [hereinafter, referred to as "carbazole derivative (1)" ”::54- 201140240 R6 R11

Wherein 'R6 to R11 are as defined above, and are preferably the same as the acrylamide derivative represented by the following formula (2b) (hereinafter, referred to as "acrylamide derivative (2b) )]]: 0 (2b) R5 R3 · (wherein R 3 , R 3 ', R 4 and R 5 are as defined above, preferably the same), and the reaction is carried out in the presence of a base to obtain the following The mercapto group-introducing body represented by the formula (3b) (hereinafter, referred to as "melamine-based introducing body (3b)"): R6 R11

(wherein R3, R3', and R4 to R11 are as defined above, and preferably are the same). The amount of the two elixirs: the derivative (2^) used in the step 1 is not particularly limited, and is preferably 0.5 to 2 m with respect to 1 mol of the 哩 derivative (1)'. It is further preferred that 〇·8 to 丨·2 旲 ear 'from the viewpoint of reducing the amount of unreacted materials from -55 to 201140240, it is further preferred to carry out the treatment in substantially the same amount. Step 1 is carried out in the presence of a base. The base is a base which can be used in the Michael addition reaction, and is not particularly limited, and any of the organic bases can be used. The organic base is, for example, pyridine, hexadecene (DBU), dinonicycloundecene (DBN), etc., a less basic base, more preferably DBU' DBN» inorganic base includes: sodium, An alkali metal carbonate such as potassium carbonate; a metal carbonate such as magnesium carbonate or calcium carbonate; an alkali metal salt such as sodium hydrogencarbonate or potassium hydrogencarbonate; an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; An alkaline earth metal hydroxide such as calcium hydroxide. Among these, an alkali metal carbonate or an alkaline earth metal carbonate is more preferably an alkali metal, and still more preferably potassium carbonate. The amount of the base to be used is not particularly limited, and is from 0.5 to 2 mol, more preferably from 0.8 to 1.2 mol, based on the reaction efficiency and the present viewpoint, with respect to the 1 mol of the carbazole derivative (1). Jin Jia is used in roughly the same amount. Step 1 is preferably carried out in the presence of a solvent. The solvent is selected to dissolve the carbazole derivative (1) and the acrylamide derivative (the solvent of the base. Specifically, dimethylformamide (DMSO, DMSO), The reaction temperature of the step 1 is not particularly limited and is usually carried out at 10 to 50 ° C, more preferably at 15 to 4 ° C, more preferably at 3 ° C. The reaction pressure is There is no particular limitation, and it is preferred that the reaction be carried out in an inorganic base, a double ring, a parent such as carbon, or the like, preferably a carbonate, preferably a carbonate, preferably a step, more preferably 2b) and a DMF. In: 15 to atmospheric pressure -56- 201140240 implementation. The reaction time is also different depending on the carbazole derivative (1), the acrylamide derivative (2b), the type or amount of the test, the reaction temperature or the reaction pressure, etc., and it is usually preferably about 2 hours to 48 hours. The embodiment of the step 1 is not particularly limited. For example, the carbazole derivative (1), the acetoin derivative (2b) and the base are all added to the solvent, and it is preferred to carry out the stirring at the aforementioned temperature. This makes it possible to produce a guanamine-based introducer (3b). After the completion of the reaction, the guanamine-based introducer (3b) can be obtained by a separation method of a general organic compound such as extraction from the obtained reaction mixture. Purification by the purification method of an organic compound such as an appropriate distillation, column chromatography or recrystallization can increase the purity of the guanamine-introducing body (3b). - Other methods - The production of the guanamine-based introducer (3b) can also be carried out by the following methods. The above carbazole derivative (1) and a carboxylic acid group introducing agent represented by the following formula (2b') (hereinafter, referred to as "carboxylic acid group introducing agent (2b,)"): R5

(wherein R 4 and R 5 are as defined above; R 24 is an alkyl group having 1 to 5 carbon atoms), and the reaction is carried out in the presence of a base (first reaction), which is represented by the following formula A carbazole derivative containing a carboxylic acid group: -57- 201140240 R6 R11

R10

O^^OH (wherein R4 to R11 are as defined above, preferably the same), and HNRR3 (R3 and R3 are as described above), for example, in the presence of thionyl chloride As the definition, it is preferred that the amine represented by the reaction is carried out (second reaction) to obtain a mercapto group-introducing body (3b). A commercially available product can be used as the amidoxime-based introducer (31). Further, the alkyl group having 1 to 5 carbon atoms represented by R24 includes, for example, methyl 'ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like. Among these, a methyl group and an ethyl group are preferable. The base to be used in the first reaction is not particularly limited, and any of an organic base and an inorganic base can be used. The organic base is, for example, pyridine, diindole bicycloundecene (DBU), dinonicycloundecene (DBN) or the like, preferably a base having a low nucleophilicity, more preferably DBU or DBN. The inorganic base is an alkali metal carbonate such as sodium carbonate or potassium carbonate; an alkaline earth metal carbonate such as magnesium carbonate or calcium carbonate; an alkali metal hydrogencarbonate such as sodium hydrogencarbonate or potassium hydrogencarbonate; An alkali metal hydroxide such as potassium hydroxide; an alkaline earth metal hydroxide such as magnesium hydroxide or calcium hydroxide. Among these, the base is preferably an inorganic base, more preferably an alkali metal hydroxide. -58- 201140240 The amount of the base to be used is not particularly limited, and from the viewpoint of reaction efficiency and production cost, it is preferably 0.5 to 2 mol per 1 mol of the carbazole derivative (1), further Preferably, it is from 0.8 to 1.2 moles, and further preferably used in substantially equal amounts. The first reaction is preferably carried out in the presence of a solvent. The solvent is preferably a solvent which can dissolve the carbazole derivative (1), the carboxylic acid group introducing agent (2b') and the above-mentioned base. Specific examples thereof include dimethylformamide (DMF), dimethylammonium (DMSO), dichloromethane, and the like, and DMF is preferred. The reaction temperature of the first reaction is not particularly limited, and it is usually preferably carried out at 10 to 50 ° C', more preferably 15 to 40 ° C, still more preferably 15 to 30 ° C. The reaction pressure of the first reaction is not particularly limited, and it is preferably applied under normal pressure. The reaction time varies depending on the type (1) of the hydrazine derivative, the type and amount of the test, the amount of the carboxylic acid group-introducing agent (2b'), the reaction temperature, the reaction pressure, etc., and is usually preferably about 2 hours. To 4 8 hours. The embodiment of the first reaction is not particularly limited. For example, the carbazole derivative (1), the carboxylic acid group-introducing agent (2b'), and the base are all added to the solvent, and it is preferred to carry out stirring at the aforementioned temperature. Thereby, a carbazole derivative containing a carboxylic acid group can be produced. After completion of the first reaction, the above-mentioned carboxylic acid group-containing carbazole derivative can be obtained by a separation method of a general organic compound such as extraction. The purity of the carboxylic acid group-containing oxazole derivative can be improved by performing purification by a general method for purifying a general organic compound such as distillation, column chromatography or recrystallization. -59- 201140240 The amount of sulfoxide used in the second reaction is preferably about 1 to 10 moles relative to 1 mole of the carbazole derivative (1) used in the first reaction. The ear may be, and is further preferably about 2 to 5 moles. The amount of the amine represented by Η N R3 R3 ' used in the second reaction is preferably about 1 to 1 mol with respect to 1 mol of the carbazole derivative (1)' used in the first reaction. 10 moles may be used, and further preferably about 2 to 7 moles. The second reaction is preferably a solvent which is soluble in the aforementioned carboxylic acid group-containing carbazole, and is not particularly limited. For example, a nitrile or the like can be mentioned, and acetonitrile is preferred. The reaction temperature of the second reaction is from 10 to 50 ° C, and more preferably at 30 ° C. The reaction of the second reaction is carried out under normal pressure. The reaction time is different depending on the type of the derivative, the amine and the base, or the pressure, and it is usually preferred that the second reaction embodiment is a carbazole derivative having a carboxylic acid group and the aforementioned dropwise addition of sulfoxide. The addition of a knot is carried out by stirring, whereby the separation of the obtained anti-organic compound can be carried out in the presence of a suitable distillation or column chromatography after the completion of the reaction of the mercapto group. The solvent is not particularly limited as long as it is a derivative or a solvent of the aforementioned amine, and methylene chloride, n-benzene 'acetone, and B are not particularly limited, and are usually preferably at 15 to 40 ° C, more preferably at 15 to pressure. Preferably, the amount of the carbazole containing the carboxylic acid group is used, and the reaction temperature is reversed from about 1 hour to 1 hour. There is no particular limitation, for example, the addition of the aforementioned amine to the solvent, and after the bundling, it is preferred to introduce the body (3b) at the aforementioned temperature. The hydrazide-based introducer (3b) is obtained by a general extraction of the mixed solution or the like. General organicization such as method and recrystallization. 60-201140240 Purification method of the compound can improve the purity of the guanamine-based product (3b). <W is an oxygen atom, and Z is a single bond> It is preferred to carry out the reaction of the above-mentioned carbazole derivative (1) with ethyl formate in the presence of _ (first reaction), and the following a hydroxy-containing carbazole derivative of the formula α: R6 R11

(wherein R6 to R11 are as defined above, preferably the same), in the presence of a base, and R3COY (R3 is as defined above, preferably the same; in addition, Y The sulfhydryl halide represented by the halogen atom is represented by a halogen atom. The second ester reaction is carried out to obtain an ester group introducer represented by the following formula (3b') (hereinafter, referred to as "ester group introducer" Method of (3b')"]: R6 R11

(wherein R3 to R11 are as defined above, preferably the same. • 61 - 201140240 The amount of ethyl carbonate used in the first reaction described above, relative to 1 mole of carbazole derivative (1) is preferably 0.7 to 15 moles, more preferably 1 to 10 moles. The test used in the first reaction is preferably an organic base such as triethylamine or tributylamine. Amines: nitrogen-containing heterocyclic aromatic compounds such as pyridine, etc. Among them, preferred are amines, more preferably triethylamine. The amount of the base used is not particularly limited, and the reaction efficiency and The viewpoint of the production cost is preferably 0.5 to 2 mols, more preferably 0.8 to 1.2 mol%, with respect to 1 mol of the carbazole derivative (1). Further preferably, it is substantially equal. The first reaction is preferably carried out in the presence of a solvent, and the solvent is appropriately selected from a solvent which can dissolve the carbazole derivative (1) or ethyl carbonate, and the above-mentioned base. Specifically, two Methylformamide (DMF), dimethyl hydrazine (DMSO), dichloromethane, etc., preferably DMF. The temperature is not particularly limited and is usually preferably from 60 to 130 ° C, more preferably from 80 to 120 ° C, still more preferably from 90 to 110 ° C. The reaction pressure of the first reaction There is no special restriction series IJ, which is preferably carried out under normal pressure. The reaction time is dependent on the type or amount of the carbazole derivative (1) and the base, the amount of ethyl carbonate, and the reaction temperature and reaction pressure. It is usually preferably from about 1 hour to 10 hours. The embodiment of the first reaction is not particularly limited. For example, the carbazole derivative (1), ethyl acetate and the base are all added to the solvent. Further, it is preferred to carry out stirring at the above temperature, whereby the above-mentioned hydroxy-containing oxime-62-201140240 azole derivative can be produced. After the first reaction, the separation of the obtained reaction mixture by general organic compounds such as extraction is carried out. According to the method, the hydrazine-containing hydrazine derivative can be obtained, and the hydroxy-containing carbazole can be improved by performing purification by a general organic compound purification method such as distillation, column chromatography or recrystallization. Derivative purity In the case of the mercapto halide represented by r3coy used in the second reaction, 'anthracene chloride, mercapto iodide or the like can be exemplified, preferably mercapto chloride. The amount of the mercapto halide is used. The oxazole derivative (1) used in the first reaction with respect to 1 mole is preferably about 0.7 to 3 moles, more preferably 1 to 2 moles, still more preferably substantially The base used in the second reaction is preferably an amine such as triethylamine, tributylamine or monoisopropylethylamine. The amount used is relative to 1 mol of the foregoing. The mercapto halide is preferably from about 0.7 to 3 moles, more preferably from 1 to 2 moles, still more preferably used in substantially equal amounts. The second reaction is preferably carried out in the presence of a solvent. The solvent is a solvent which can be used in a general deuteration reaction, and is not particularly limited as long as it does not inhibit the reaction. Specifically, it may, for example, be methylene chloride, nifedipine, propylene carbonate or acetonitrile, and acetonitrile is preferred. The reaction temperature of the second reaction is not particularly limited and is usually preferably from 10 to 50 ° C, more preferably from 15 to 40 ° C, still more preferably from 15 to 3 ° C. The reaction pressure of the second reaction is not particularly limited, and it is preferred that -63 to 201140240 be carried out under normal pressure. The reaction time varies depending on the type of the oxazole derivative containing the hydroxyl group, the type or amount of the above-mentioned mercapto halide and the base, the reaction temperature and the reaction pressure, and the like, and is usually preferably about 1 hour to 1 hour. The embodiment of the reaction is not particularly limited, and for example, the hydroxy group-containing carbazole derivative, the sulfonium halide, and the base are all added to a solvent, and it is preferred to carry out stirring at the above temperature, whereby an ester can be produced. Base introducer (3b'). After completion of the reaction, the ester-introducing body (3b') can be obtained by a separation method of a general organic compound such as extraction from the obtained reaction mixture. Purification by a general organic compound purification method such as appropriate distillation, column chromatography or recrystallization can improve the purity of the ester group-introducing body (3b'). (Step 2) Step 2 is to refer to the indole group-introducing body (3b) or the ester group-introducing body (3b') obtained in the step 1 (hereinafter, considering and convenience factors, the summary is referred to as " The functional group introducer (3b)"] and the two deuteration agents represented by the following general formulae (4), (5) (hereinafter, referred to as deuteration agent (4) and deuteration agent, respectively (5 )):

(wherein X represents a halogen atom or - 0C(=0)Ar, X' represents a halogen-64 - 201140240 atom or a 〇C(= 0)R2; Ar and R2 are as defined above, Preferably, the reaction is carried out in the presence of a Lewis acid to obtain a diketone represented by the following formula (6b) (hereinafter referred to as "diketone (6b)"]: ·

(wherein R to RM, Ar, W and Z are as defined above, and the same is preferred). In the above formula, the halogen atom represented by X and X, which are independently represented by each, may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom. Regarding the step 2' from the viewpoint of the yield of the target diketone body (6b), the reaction of the B-energy-introducing body (3b) with the deuterating agents (4) and (5) is preferably a functional group. The base introduction product (3b) is reacted with the deuteration agent (4), and then reacted with the deuteration agent (5). The amount of the brewing agents (4) and (5) from the point of introduction of each of the respective thiol groups to the pseudo-base-introducing body (3b), relative to the 1-mole-based matrix-based introducer ( 3b) ' Each is preferably from 8 to 13 moles, more preferably from 1 to 1.3 moles, from the viewpoint of reducing unreacted materials, then 3i - step is more preferably: the reaction is carried out in substantially equal amounts. In particular, after the reaction of the carbonyl alkane-65-201140240-based introduction product (3b) with the oximation agent (4) and the reaction with the oximation agent (5), the use of the oximation agent (5) Even if the amount exceeds the above range, there is no problem, but even if it is too large, the corresponding yield cannot be obtained, and as a result, it is possible to increase the production cost in vain. Step 2 is preferably carried out in the presence of a Lewis acid. The Lewis acid is preferably aluminum chloride or boron trifluoride-diethyl ether complex. From the viewpoint of the yield of the diketone body (6b), the Lewis acid is used in an amount of usually from 0.8 to 2.5 mole per 1 mol of the deuteration agent (4) or (5). Further preferably, it is 1 to 2 moles. Step 2 is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as it is a solvent which can be generally used in the Friedel-Zraft blending reaction. Specific examples thereof include dichloromethane, nifedipine, acetone, and acetonitrile. The reaction temperature in the step 2 is preferably from -5 to 5 ° C (preferably from -10 to 5 ° C) at the beginning of the reaction, and slowly returns to room temperature as the reaction proceeds (about 15 to 25). °C) The reaction time varies depending on the type and amount of the functional group-introducing body (3b), the deuterating agents (4) and (5), and the reaction temperature, and is usually preferably from 1 to 30 hours. Further, in the case where both of the halogenating agents (4) and (5) are a mercapto halide or an acid anhydride, after the functional group-introducing body (3b) is reacted with the deuterating agent (4), the isolated product may not be isolated. This is followed by reaction with the oxime (5). In this case, it is preferred that the reaction time of the functional group-introducing body (3b) and the deuterating agent (4) is set to be about 3 to 5 hours (preferably 30 to 3 hours), in another In the aspect, the reaction time of the functional group-introducing body (3b) and the deuterating agent (5) is set to -66 to 201140240 as long as about 30 minutes to 24) to sufficiently carry out the step from the viewpoint of yield. The solvent was mixed while cooling in an ice bath, and the mixture was mixed and dissolved for 1 hour to further neutralize the acid. After the end of the addition, the mixture was slowly further preferably 10 minutes until it was returned to room temperature and stirred at a certain time. The diketone body (6b) can be obtained by slowly adding it to the room temperature and preferably stirring for a certain period of time while cooling in an ice bath (preferably for 1 minute to 40 minutes). After the completion of the reaction, the separation method of the obtained organic compound, and the purification by the distillation and column chromatography purification method may be carried out (Step 3). Step 3 is carried out by reacting the base amine to obtain Hereinafter, it is referred to as "the body of the carcass (preferably, 30 minutes to 18 hours of reaction. One of the preferred embodiments of the step 2). The functional group introducing body (3b) is slowly added with an appropriate liquid. Incorporation (preferably 5 minutes to 10 minutes to 40 minutes) Luis (preferably 5 minutes to 1 hour, 4 minutes) is added to the oxime (4), between (about 30 minutes to 5 hours) Continue to add the deuteration agent (5), and for 5 minutes to 1 hour, further preferably into the Lewis acid, after the end of the addition, return (about 30 minutes to 24 hours), thereby obtaining the reaction mixture The diketone body (6b) can be obtained by general extraction, etc. The purity of the diketone body (6b) is improved by general organic compounds such as appropriate recrystallization. Step 2 The diketone body (6b) and hydroxyl group are obtained. Steps of the steroid [(7b)" represented by the following general formula (7b): -67- 20114024 0 to the same as 2 1 R phase, is the Chinese version (good

For example, 2R10 is determined by the above. Regarding step 3, the supply source of the hydroxylamine is not particularly limited, and it is preferably a hydroxylamine hydrochloride. The chlorinated hydroxylamine is, for example, reacted with sodium acetate or the like in water, whereby an aqueous solution of a hydroxylamine can be obtained. The amount of the hydroxylamine (hydroxylamine chloride) used is preferably 0.8 to 2 moles, more preferably 1 to 1.5 moles, still more preferably 1 to 1 mole of the diketone body (6b). 1.3 Mohr, further from the viewpoint of reducing unreacted materials, it is further preferred to carry out the reaction in substantially equal amounts. Step 3 is preferably carried out in the presence of a solvent. The solvent is preferably a water-soluble organic solvent, and the water-soluble organic solvent is preferably an alcohol such as methanol or ethanol, dimethylformamide (DMF) or the like. The reaction temperature of the step 3 is not particularly limited, and is usually preferably from 40 to 1601, more preferably from 50 to 140 ° C, more preferably from 70 to 10 10 ° from the viewpoint of the yield of the steroid (7b). C. The reaction time varies depending on the kind and amount of the diketone body (6b) and the reaction temperature, and is usually preferably from 0.5 to 20 hours, more preferably from 1 to 12 hours. The embodiment of the step 3 is not particularly limited. For example, an aqueous solution of hydroxylamine and sodium acetate is added in advance to obtain a hydroxylamine aqueous solution, and the diketone (6b) and the solvent are preferably added to -68-201140240, preferably Stirring is carried out in the aforementioned temperature range, whereby the steroid (7b) can be obtained. After the completion of the reaction, the oxime (7b) can be obtained by a separation method of a general organic compound such as extraction from the obtained reaction mixture. The purity of the steroid (7b) can be improved by performing purification by a conventional method of purification of a general organic compound such as distillation, column chromatography or recrystallization. (Step 4) Step 4 is by using the steroid (7b) obtained in the step 3 and the esterifying agent represented by the following formula (8) [hereinafter, referred to as "esterification agent (8)" The reaction is carried out: human (8) (wherein Y represents a halogen atom or an OCC^C^R1; R1 is as defined above, preferably the same), to obtain a formula represented by the following formula (Ib) The photopolymerization initiator (hereinafter referred to as "photopolymerization initiator (Ib)"):

Zv (wherein 'R1 to RM, Ar, W and Z are as defined above). In the above formula, the halogen atom represented by Y represents: a fluorine atom, an atom-69-201140240, a bromine atom, An iodine atom or the like is preferably a chlorine atom. The amount of the esterifying agent (8) to be used in the step 4 is not particularly limited, and is preferably from 0.5 to 2 mols with respect to 1 mol of the steroid (7b). Further preferably 0.8. It is further preferable to carry out the reaction in substantially equal amounts from the viewpoint of reducing unreacted materials to 1.2 mol. Step 4 can also be carried out in the presence of a base to promote the reaction. In the case of a base, an organic base or an inorganic base can be exemplified. The organic base may, for example, be an amine such as triethylamine or tributylamine; a nitrogen-containing heterocyclic aromatic compound such as pyridine or the like. The inorganic base may, for example, be an alkali metal carbonate such as sodium carbonate: an alkaline earth metal carbonate such as magnesium carbonate; an alkali metal hydroxide such as sodium hydroxide; an alkaline earth metal hydroxide such as magnesium oxide or the like; . In the above, the organic base is preferably an amine or a nitrogen-containing heterocyclic aromatic compound, and more preferably triethylamine or pyridine from the viewpoint of reaction efficiency and production cost. In the case where the base is used in the step 4, the amount thereof to be used is preferably from 1 to 5 mols per 1 mol of the steroid (7b) from the viewpoint of the yield of the photopolymerization initiator (Ib) and the production cost. Further preferably, the step 5 is preferably carried out in the presence of a solvent. The solvent is preferably an ether such as tertiary butyl methyl ether, ethylene methyl ether, cyclopentyl methyl ether or tetrahydrofuran (THF). The reaction temperature in the step 4 is preferably from _5 Torr to 5 at the start of the reaction. (: (preferably -1 0 to 5 °c), slowly returning to room temperature (about 15 to 25 ° C) as the reaction proceeds. The reaction time is in response to the steroid (7b), the esterifying agent - 70- 201140240 (8) The type and amount of use, and the reaction temperature are different, and it is usually preferably from 0.5 to 10 hours, and further preferably from 1 to 5 hours. The embodiment of step 4 is not particularly limited, for example, The jiang body (7b) and the esterifying agent (8) are mixed in a suitable solvent, and a base is added dropwise thereto, and after the dropwise addition is completed, the temperature of the reaction liquid is slowly returned to room temperature and stirring is continued. The photopolymerization initiator (Lb) of the present invention, after completion of the reaction, a photopolymerization initiator (bb) can be obtained by a separation method of a general organic compound such as extraction from the obtained reaction mixture. Purification of a general organic compound purification method such as column chromatography or recrystallization can increase the purity of the photopolymerization initiator (^b). The photopolymerization initiator (hb) of the present invention obtained as described above. Is a nitrogen atom in the carbazole skeleton attached with an ester group or a guanamine bond ( Or a special substituent which forms a guanamine bond of the ring. Therefore, it has a compound having an ethylenically unsaturated bond (particularly a compound having a (meth)acryloxy group) in the photocurable composition or has The solubility of a compound having an ether bond and/or an ester bond and being a liquid at 25 ° C is high, and solubility to a solvent (comprising a compound having an ether bond and/or an ester bond as described above and being a liquid at 25 ° C) In addition, it is high in sensitivity to light (especially light having a short wavelength of 450 nm or less), and is excellent in resolution, developability, and deep hardenability, and is further excellent in adhesion to a substrate. The photopolymerization initiator (Ib) does not cause contamination of the polymer or contamination of the device due to decomposition products generated by light upon exposure. In addition, the photopolymerization initiator (Ib) is specific to a compound or solvent -71 - 201140240 The compatibility or solubility is a factor that contributes to the improvement of sensitivity, resolution, developability, and deep hardenability. Therefore, it is an important component in the use of color filters. In color In the use of the filter, the photopolymerization initiator is preferably soluble in 5 parts by mass or more with respect to 100 parts by mass of a solvent having an ether bond and/or an ester bond (particularly, propylene glycol monoethyl ether acetate or the like). More preferably, it is 10 parts by mass or more, and the photopolymerization initiator (Ib) of the present invention is suitable as a photopolymerization initiator contained in the photocurable composition for a color filter, and includes A photopolymerization initiator in a photocurable composition for a black matrix having a high light-shielding property. Next, a photocurable composition containing the photopolymerization initiator (I) of the present invention, and a color using the photocurable composition The filter, the pattern forming method, and the liquid crystal display device will be described in order. [Photocurable composition] The photocurable composition of the present invention is a compound containing a compound having an ethylenically unsaturated bond and/or a binder resin, and one or more of the above photopolymerization initiators (I). In the photocurable composition of the present invention, a coloring material may be further contained, and a photopolymerization initiator, a dispersing agent, a polyfunctional monomer, a monofunctional monomer other than the photopolymerization initiator (I) may be optionally contained. A photocurable composition obtained by using a body, a sensitizer, a solvent, or the like is useful for use in a color filter. Further, when the functional group has an ethylenically unsaturated bond, the polyfunctional monomer and the monofunctional monomer can be a compound having an ethylenically unsaturated bond. With respect to the photocurable composition of the present invention, the content of the photopolymerization initiator (?) is higher than that of the photocurable composition, from the viewpoints of sensitivity, resolution, and the apparent property of -72 to 201140240. Preferably, it is 2 to 5 % by mass, and further preferably 2 to 30% by mass, more preferably 4 to 15 % by mass. /〇. In addition, when the photocurable composition of the present invention contains a photopolymerization initiator other than the photopolymerization initiator (I), it is not the photopolymerization initiator (I) as long as it does not significantly impair the effect of the present invention. The content of the photopolymerization initiator is preferably 1 part by mass or less, more preferably 50 parts by mass or less, even more preferably 20 parts by mass or less, per 100 parts by mass of the photopolymerization initiator (I). Further, it is more preferably 1 part by mass or less, and particularly preferably 5 parts by mass or less. (Compound having an ethylenically unsaturated bond) A compound having an ethylenically unsaturated bond is polymerized by light irradiation in the presence of a photopolymerization initiator (I), and can be used as a binder in a photocurable composition. The compound functions as a binder in the formed pixels. In the photocurable composition of the present invention, the compound having an ethylenically unsaturated bond preferably contains 5 to 60% by mass', more preferably 10 to 4% by mass. If it is in this range, the adhesion between the formed pixel and the substrate tends to be good. Further, the compound having an ethylenically unsaturated bond can be used in combination with a binder resin to be described later. When it is used, it is preferable that the total content is within the above range. In the specific example of the compound having an ethylenically unsaturated bond, 'unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloropropanoic acid, and the like; maleic acid, antibutene Unsaturated dicarboxylic acid such as diacid or itaconic acid or its sulphate; trivalent or higher of trimellitic acid, pyrophoric acid, etc. -73- 201140240 Unsaturated polycarboxylic acid or its anhydride; styrene , α-methylstyrene ethylene, methoxystyrene, divinylbenzene 'vinyl toluene and other vinyl compounds; methyl (meth)acrylate, (meth)ethyl ester '(meth)acrylic acid Propyl ester, n-butyl (meth)acrylate, n-butyl (meth)acrylate), butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, cyclohexyl (meth)acrylate, (hydroxyethyl methacrylate, phenoxyethyl (meth) acrylate, methoxyethyl methacrylate, poly(methyl) acrylate (propoxy) ) propyl methyl) vinyl acrylate, ethylene glycol di(meth) acrylate (meth) acrylate Glycol ester, propylene dimercapto di(meth) acrylate, diol di(meth) acrylate, trimethylolpropane tris(meth)acrylate, (methylene methacrylate) a compound obtained by esterifying a polyvalent α,β-unsaturated carboxylic acid such as propyl ester or benzyl (meth)acrylate; (meth) 2-aminoethyl ester; (meth)acrylic acid 2-di Aminoalkyl esters of methylaminoethyl ester, 2-aminopropyl acrylate, 2-dimethyl methacrylate, etc.; or alkyl (meth) acrylate, etc. Saturated carboxylic acid glycidyl esters; vinyl acetate, alkenyl methyl ether, vinyl ethyl ether, allyl glycidyl ether group, such as vinyl acetate, enester, vinyl butyrate, vinyl benzoate An unsaturated ether such as vinyl ether: an aromatic vinyl compound such as (meth)acrylonitrile, α-nitrile or divinylidene; (meth)amine, α-chloropropenylamine, Ν-2- Hydroxyethyl (meth) propylene hydride, propyl propyl propyl acrylate, (methyl, (meth) propyl) propyl ester (, poly 2 Alcohol ester, 1,6-hexyl)propanol with acrylic acid (methylaminopropyl glycidic acid B; B, isobutyl chloride propylene decylamine, etc. -74- 201140240 unsaturated decylamine; Unsaturated quinone imines such as enediamine, N-phenyl-butenylene, N-cyclohexylmethyleneimine, etc., isoprene, chloroprene, etc. In the case of the aliphatic conjugated diene, from the viewpoint of the photopolymerization initiator (I) of the present invention, it is preferred that the compound having a (meth) propylene oxime group has an ethylenically unsaturated bond. The compound may be used singly or in combination of two or more kinds thereof. Further, the compound having an ethylenically unsaturated bond is an ethylenically unsaturated compound having an ester bond (preferably an ether bond and an ester bond). In the case of the photopolymerization initiator of the present invention (I is more excellent in solubility), the amount of the solvent to be used in the photocurable composition of the present invention or the solvent is not used, and such a compound is preferably used. When at least one compound having an ethylenic bond having an ether bond and/or an ester bond is used as the compound having an ethylenically unsaturated bond, the amount of the solvent is only a few % or less with respect to the total amount of the photocurable composition. In addition, it may be further 5% by mass or less, and it may become solvent-free (Binder resin). The binder resin is provided as a binder in the formed pixel as long as it has good adhesion to the substrate. When, then, and limit. The binder resin is preferably contained in the photocurable group solid component of the present invention in an amount of from 5 to 60% by mass, further from 10 to 40% by mass. If it is in this range, the adhesion of the formed tablet tends to be good. In addition, the binder resin is imidium, 1,3-class, and the like. The soluble phase, or the ether bond and the bond phase can be reduced or the bond is not the same. 10 The mass step can also be used as a special product without a special product. The weight of the base and the base is -75- 201140240 The average molecular weight is preferably from 3,000 to 100,000, more preferably from 5,000 to 3,000, from the viewpoint of the adhesion between the formed pixel and the substrate. Further, in the present specification, the weight average molecular weight is measured by a gel method (GPC) and converted in terms of polystyrene. Further, as described above, the binder resin is used in combination with the aforementioned compound having an unsaturated bond. The above binder resin can be used in the same manner as the binder resin generally used for the color filter curable composition. Specifically, an ethylene-vinyl acetate copolymer, an ethylene-vinyl chloride copolymer, an alkene, an acrylonitrile-styrene copolymer, an ABS resin, a polymethyl propyl acrylate, an ethylene-methacrylic resin, a polyvinyl chloride resin, Chlorinated, polyvinyl alcohol, polyethylene terephthalate, polyparaphenylene glycol ester, polycarbonate, polyvinyl acetal, polyether ether ketone, polyether benzene sulfur, polyarylate, polyethylene Alcohol butyral, epoxy resin, phenoxy, polyimide resin, polyamidolimine resin, polyamidoamine, polyetherimide resin, phenol resin, urea resin, and the like. Further, as a polymerizable monomer, methyl (meth)acrylate, (meth)ethyl ester, n-propyl (meth)acrylate, and n-butyl (meth)acrylate (meth)acrylate, ( Isobutyl methacrylate) butyl acrylate, n-pentyl (meth) acrylate, (n-hexyl acrylate, 2-ethylhexyl (meth) acrylate, (n-octyl methacrylate) N-decyl methacrylate, styrene, <styrene, N-vinyl-2-pyrrolidone, oil (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Point, 50,000 transparent chromatographic olefinic light sheet, can be listed as polystyrene acid chloroethylene butyl hydride, poly phenolic acid resin can also be propyl acrylate, (methyl) propyl t- Base Shrinkage Cyclosporin-76- 201140240 Ester, bicyclophenyl (meth) acrylate, phenyl acrylate (meth) acrylate, Acagosei Co., Ikonic acid, crotonic acid And one or a copolymer of acetic acid, such an acid anhydride, etc. Further, The ethylenically unsaturated compound is particularly excellent as an alkali-soluble resin. For example, the alkali-soluble resin is preferably a polymerizable ethylenically unsaturated monomer having both an epoxy group and an ethylenic group. Polyglycidyl acrylate and the like. The above-mentioned carboxyl group-containing unsaturated) acrylic acid crotonic acid, cis-[2-(methyl) propylene phthalate 2-(methyl) propylene oxy ethoxyethyl carboxy caprolactone, etc., particularly preferably (unsaturated) The monomer may be one or more of the above ethylenically unsaturated mono-(n-butyl (meth)acrylate) isobornyl acrylate, (pentaloxyethyl ester, methyl (meth) acrylate, and acrylic acid). And a product obtained by reacting a product (for example, East Asian Synthetic Chemical Industry Co., Ltd.) under the trade name "M-5600", butyric acid, fumaric acid, or vinyl species, will have a glycidyl group. Or a polymer obtained by using a hydroxyl group in the copolymer, etc., including a soluble acrylate-based resin having an acidic functional group such as a carboxyl group, and a copolymer having a carboxyl group-containing unsaturated group and other copolymers, more preferably The compound which is added to the molecularly unsaturated group, for example, (A, the ethylenically unsaturated group is introduced into the side chain and the monomer is included, for example, preferably (methane acid, maleic anhydride, amber) Oxyethyl ester, o-phthalate a mono(meth)ester or a poly(meth)acrylic acid ω-methyl)acrylic acid. Further, the carboxyl group is used alone or in combination of two or more kinds thereof. The body includes: methyl (meth)acrylate, (methyl) Cyclohexyl acrylate, dicyclopentanyl (meth)acrylate, allyl acrylate (methyl-77-201140240), styrene, α-methylstyrene, benzyl (meth)acrylate, Hydroxyethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ( Methyl)dicyclopentenyl acrylate, and the like, and such macromonomers; Ν-methyl maleimide, Ν_cyclohexyl maleimide, Ν benzyl cis Butylene diimide, hydrazine phenyl cis butyl quinone imine, hydrazine - methyl phenyl maleimide, etc., substituted cis-butyl amide, etc. The unsaturated monomer may be used singly or in combination of two or more kinds thereof (color material). The photocurable composition of the present invention may further contain a color. The coloring material is a coloring photocurable composition, and examples of the coloring material include a pigment, a dye, a natural coloring matter, etc. The coloring material may be used singly or in combination of two or more kinds thereof, from color reproducibility, hardenability, and developability. In view of the solid content of the photocurable composition of the present invention, it is preferably a color material containing 5 to 6 % by mass, and more preferably 5 to 50% by mass. The pigment is an organic pigment or an inorganic pigment. From the viewpoints of color developability and heat resistance, organic pigments are preferred. Organic pigments include, for example, compounds classified as pigments in color index (CI; The Sobiety of Dyers and Colourists) (cI pigments) Blue, C_I. Pigment Violet, CI Pigment Green, CI Pigment Red, c". Pigment Yellow, c·〗, Pigment Orange, etc.). Further, the color material is preferably dispersed to be uniform by the following dispersant. -78- · 201140240 (Dispersant) The dispersant is a conventional dispersant as long as it can disperse the above-mentioned color materials to be uniform. Specific examples thereof include a modified polyurethane, a modified polyacrylate, a modified polyester, a modified polymer of a polyamine, a phosphorus dispersant, and the like. A surfactant or pigment derivative such as an alkylamine or a polyoxyethylene alkylphenyl ether. Among these, a polymer dispersant is preferable, and a specific commercial product name includes EFKA-4046, EFKA-4047, EFKA polymer 10, EFKA polymer 400, EFKA polymer 401, and EFKA high. Molecule 4300, EFKA polymer 4 3 3 0 (above is manufactured by Ciba Specialty Chemicals Co., Ltd.); Disperbyk 111, D i sp erb yk 16 1 , Disperbyk 16 5 , Disperbyk 167 ,

Disperbyk 182, Disperbyk 2000, Disperbyk 200 1 (above is BYK Chemie Japan Corp.); SOLSPERSE 24000, SOLSPERSE 27000, SOLSPERSE 28000 (above is manufactured by The Lubrizol Corporation); AJISPER (registered trademark) PB821, PB822 (manufactured by Ajinomoto Fine-Techno Co., Inc.). When the dispersant is to be included in the photocurable composition of the present invention, the content thereof is not particularly limited as long as it is such that the color material can be uniformly dispersed. The dispersibility and photocurability of the color material are not particularly limited. The viewpoint of the developability of the composition and the reduction of the development residue at the unexposed portion is preferably from 0.5 to 30% by mass, and from -79 to 201140240, with respect to the total solid content of the photocurable composition. The step is preferably from 1 to 20 mass. /. . Further, from the viewpoint of the amount of dispersion of the color material and the dispersibility, the color material (particularly pigment) and the dispersing agent are preferably used after being mixed in a solvent to be described later to form a dispersion. (Polyfunctional monomer) The polyfunctional monomer which can be suitably contained in the photocurable composition of the present invention is a monomer including a (meth) acryloxy group having compatibility with the above binder resin, specifically In other words, a difunctional (meth) acrylate and a trifunctional or higher (meth) acrylate are preferable. The polyfunctional monomer may be used singly or in combination of two or more kinds thereof. The difunctional (meth) acrylate is exemplified by, for example, 1,4-butylene glycol (meth)acrylate, neopentyl glycol di(meth)acrylate, and di(methyl)propionic acid 1,6- Hexanediol ester, poly(di)(meth)acrylic acid propylene glycol diethylene glycol di(meth)acrylate, polyethylene di(meth)acrylate, bisphenol A di(meth)acrylate, and the like. Further, examples of the trifunctional or higher (meth) acrylate include trimethylolpropane tris(meth)acrylate, trimethylolethane tris(meth)acrylate, and tris(meth)acrylic acid. Pentaerythritol ester, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate (DPHA), penta(methyl a carboxyl group-containing polyfunctional (meth) acrylate such as dipentaerythritol acrylate or a carboxylic acid-modified pentaerythritol penta(meth)acrylate* to be included in a polyfunctional monomer In the photocurable composition of the present invention, from -80 to 201140240, the content of the photocurable composition is preferably from 3 to 50% by mass based on the total solid content of the photocurable composition. When it is in this range, since the photocuring can be sufficiently performed, there is no concern that the exposed portion is eluted at the time of alkali development, and the alkali developability is good. (monofunctional monomer) The monofunctional monomer which can be suitably contained in the photocurable composition of the present invention is preferably a (meth) acrylate such as allyl (meth) acrylate. Benzyl (meth)acrylate 'butoxyethyl (meth)propionate, butoxyethylene (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid Cyclopentane ester, 2-ethylhexyl (meth)acrylate, glycerol (meth)acrylate, glycidyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (methyl) 2 - hydroxypropyl acrylate, isobornyl (meth) acrylate, isodecyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylate 2 - Methoxyethyl ester, methoxyethylene glycol (meth)acrylate, phenoxyethyl (meth)acrylate, stearyl (meth)acrylate, and the like. (Sensitizer) Further, the photocurable composition of the present invention may contain a sensitizer as needed. The sensitizer is used for absorbing the irradiated energy when the photocurable composition of the present invention is applied onto a substrate and then exposing it, and is responsible for the initiation reaction of the photopolymerization initiator of the present invention. The substance of the role. Specifically, the "sensitizer" is exemplified by 4,4'-bis(diethylamine-81-201140240-based) benzophenone and 4,4'-bis(dimethylamino)diphenyl. Methyl ketone, 4-methyl-4'-diethylamine benzophenone, 4-methoxy-4'-diethylaminobenzophenone, 4,4'-bis(dipropyl Amino)benzophenone, 4,4'-bis(diisopropylamino)benzophenone, and the like. These may be used alone or in combination of two or more. When the sensitizer is to be contained in the photocurable composition of the present invention, the content thereof is preferably from 1 to 10% by mass based on the total amount of the solid content of the photocurable composition. (Solvent) In the photocurable composition of the present invention, a solvent may be contained in the dispersion color material. The solvent is not particularly limited as long as it is used for a photocurable composition for a general color filter. Specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol. Diethyl acid, monopropanol monomethyl acid, etc. (mono- or poly)-extension-based diol (mono- or poly) alkyl ethers, and the acetates thereof; propylene glycol diacetate, diacetic acid Diacetate such as 1,3 -butylene glycol ester; ether such as tetrahydrofuran; ketone such as methyl ethyl ketone, cyclohexanone or 2-heptanone; methyl 2-hydroxypropionate, 3- Ethyl hydroxypropionate, ethyl acetate, n-butyl acetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid An ester, an ester of 3-methoxybutyl acetate, ethyl lactate or cyclohexyl acetate; an aromatic hydrocarbon such as toluene or xylene; and the like. The solvent may be used alone or in combination of two or more. Among these, a compound having an ether bond and/or an ester bond and being a liquid at 25 ° C from the viewpoints of compatibility, solubility, pigment dispersibility, and coatability-82-201140240 is specifically preferable. It is propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monomethyl ether, diethylene glycol diethyl ether, more preferably has an ether bond and an ester bond and is liquid at 25 ° C Compound. When the solvent is contained in the photocurable composition of the present invention, the content thereof is preferably from 50 to 90% by mass based on the total amount of the photohardenable composition. In general, when it is in this range, the pigment dispersibility is good, and the photoresist coating property (in-plane uniformity) can be improved. Further, the photopolymerization initiator of the present invention is excellent in compatibility with a compound having an ether bond and/or an ester bond and being liquid at 25 ° C, and if the above solvent has an ether bond and/or an ester bond at 25 ° When C is a liquid compound, the content of the solvent in the photocurable composition can be drastically reduced. In this case, in the photocurable composition of the present invention, the content of the compound having an ether bond and/or an ester bond and being a liquid at 25 ° C is possible in comparison with 1 part by mass of the photopolymerization initiator (Π The range of preferably 5 to 100 parts by mass is arbitrarily selected, and may be about 5 to 20 parts by mass, more preferably about 5 to 10 parts by mass, per part by mass of the photopolymerization initiator (I), as needed. (Other components) In the photocurable composition of the present invention, an inorganic chelating agent, an adhesion promoter, an anti-aggregating agent, a polymerization stopper, a chain transfer agent, and a leveling agent may be further contained as needed. , plasticizer, defoamer, decane coupling agent, ultraviolet absorber, etc. [Color filter] The color filter is preferably produced by using a color-containing material: -83- 201140240 A method of forming a coloring layer (pattern) having a hole portion by photolithography, and for example, in the case of performing the above-described exposure, even in the case where diffraction of energy or the like occurs, it can be made into Not easily affected by it. So 'can be made in The colored layer forms a high-definition color filter having a fine pattern-like hole portion. (Pattern forming method) A method of patterning by photolithography using the photocurable composition of the present invention will be described below. The method of forming the hole portion in the colored layer is not particularly limited. For example, the photocurable composition of the present invention is applied to a substrate, dried, and then passed through a mask provided with an opening and a shielding portion. The light is irradiated with light, and then developed to form a pattern. Further, this is repeated several times to form respective patterns of, for example, red, green, and blue on the substrate, and secondly, indium tin oxide (ITO) or the like is formed. The transparent electrode film can be used to obtain a color filter. The coating method of the photocurable composition is not particularly limited, and for example, spin coating or spray coating, dip coating, roll coating, and round edge can be used. A conventional coating method such as coating, bar coating, etc. Drying after application is usually carried out at 50 to 150 ° C for 15 seconds to 10 minutes. The light source used may be the same as the light source generally used in forming the color layer, and is preferably a lamp having a high-intensity line in the ultraviolet portion, such as an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, etc. Further, the characteristics of the photocurable composition are effectively exhibited. Further, the method of developing the photocurable composition may be a method of removing an unnecessary photohardenable composition from -84 to 201140240, and The method which is generally used in the production of a color filter is the same as that which is generally used in the production of a color filter. In this case, for example, the type of the developer, the concentration of the developer, the pressure of the developer or the washing water, etc. By optimizing, the hole portion can be formed into a finer pattern. Further, the substrate used in this step can be used in the same manner as the substrate (transparent substrate) generally used for the color filter. Specifically, a non-flexible transparent rigid material such as quartz glass, an alkali-free glass, or a synthetic quartz plate; or a flexible transparent material such as a transparent resin film or an optical resin plate can be used. The thickness of the substrate is not particularly limited, and may be, for example, about 100/zm to 1 mm in accordance with the use of the color filter of the present invention. In the production of the color filter, other steps such as a step of forming a light-shielding portion for forming a light-shielding portion and a step of forming an outer film layer on the colored layer may be appropriately performed as needed. [Liquid Crystal Display Device] The liquid crystal display device of the present invention has the above-described color filter and counter substrate of the present invention, and a liquid crystal layer formed between the color filter and the counter substrate. The limitation can be the same as that of a liquid crystal display device using a conventional color filter. For example, as shown in Fig. 1, the liquid crystal display device 40 of the present invention faces the surface of the obtained color filter 10 (display side substrate) and the counter substrate 20 having the TFT array substrate (liquid crystal driving side substrate). When the inner peripheral side edge portion of the two substrates is joined by a sealant, the two substrates -85 to 201140240 can be bonded together while maintaining a liquid crystal cell gap of a predetermined distance. Then, the liquid crystal is filled in the gap between the substrates and sealed to form the liquid crystal layer 30, whereby an active matrix type color liquid crystal display device belonging to the liquid crystal panel can be obtained. Further, at this time, the color light-emitting sheet 1 of the present invention has the transparent substrate 1, the light-shielding portion 2, and the coloring layer 3. The driving method of the liquid crystal display device is not particularly limited, and in general, a driving method for a liquid crystal display device can be employed. For example, TN (Twisted Nematic), IPS (Intraplane Switching: 111· Plane Switching), OCB (Optically Compensatory Bend), and MVA (Multi-domain Vertical Orientation: Multi-domain Vertical) Alignment) and so on. Further, the liquid crystal constituting the liquid crystal layer is a liquid crystal which is different in dielectric anisotropy depending on the driving method of the liquid crystal display device, and the like. <<Embodiment>> Next, the present invention will be described in more detail by way of examples, but the invention is not limited by the examples. &lt;Example 1 &gt; (Step 1)

-86- 201140240 6.8 g (40 mmol) of carbazole and 4.0 g (40 mmol) of ethyl acrylate and 5.5 g (40 mmol) of potassium carbonate were suspended in dimethylformamide ( DMF) and stirred at room temperature for 24 hours. After the completion of the reaction, water was added thereto, and the mixture was further stirred for 30 minutes, and then extracted with ethyl acetate, washed with water and dried over magnesium sulfate. The solvent was distilled off and dried to obtain 9.6 g of pale yellow liquid. The above compound (i) (yield 93%). The results of 1 Η-NMR measurement of the compound (i) are as follows; 'H-NMR (400 MHz, CDC13, TMS, ppm) δ · 1.15 (t, 3H), 2.8 3 5 (t, 2H), 4.08 ( q, 2H), 4.64 (t, 3H), 7.2 1 5-7.254 (m, 2H), 7.45-7.47 (m, 4H), 8.08 (d, 2H). (Step 2)

2.7 g (l〇 mmol) of compound (i) was dissolved in dichloromethane (i), while 2.7 g (20 mmol) of aluminum chloride was added while cooling in an ice bath for 20 minutes. . To the obtained mixed solution, 1.4 g (11 halo) of benzoyl chloride was added dropwise over 20 minutes. Thereafter, it was slowly returned to room temperature and stirred for 1 hour. Once again, add 2.7 g (20 mmol) of chlorinated inscriptions for 2 〇 minutes while cooling in an ice bath. Add 1.2 g (15 mmol) of bismuth chloride-87- 201140240 (acetyl chloride) dropwise. ) lasted 20 minutes. Thereafter, it was slowly returned to room temperature and stirred overnight. After the completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over magnesium sulfate. The product was separated by a gel column chromatography; methylene chloride-n-hexane: ethyl acetate = 2:1), and the product was isolated to obtain 2.8 g of pale yellow solid compound (ii) (yield 7 〇%). The W-NMR measurement results of the compound (ii) are as follows: 1H-NMR (400 MHz, CDC13, TMS, ppm) δ: 1.16 (t, 3Η), 2.725 (s, 3H), 2.91 (t, 2H) , 4.08 ( q, 2H ), 4.73 ( t, 2H ) , 7.5 2 5 - 7.8 6 ( m, 5H ) , 8. 10 ( dd, 2H ), 8.18 ( dd, 1 H ) , 8.20 ( dd , 1H ) , 8.62 5 ( d, 1H ) ' 8.7 2 5 ( d, 1 H ) 〇 (Step 3)

Ch3 ΝΗ2ΟΗ· HCI CH3COONa

0.12 g (1.7 mmol) of chlorinated hydroxylamine and 0.17 g (2.0 mmol) of sodium acetate were dissolved in 1.4 ml of water and added to 0.60 g (1.58 mmol) of compound (ii) And 11 ml of ethanol and reflux for 7 hours. After the completion of the reaction, the solvent of the reaction solution was distilled off, and the solid obtained was washed with water-88-201140240, and then dissolved in THF, dried over magnesium sulfate, and the solvent was distilled off to obtain a pale yellow color. Liquid compound (iii) (yield 89%). The results of 1 Η-NMR measurement of the compound (iii) are as follows: ^-NMR (400 MHz, CDC13, TMS, ppm) &lt;5: 1.16 (t, 3H), 2.41 (s, 3H), 2.89 (t , 2H) , 4.09 ( q, 2H), 4.69 ( t, 2H ) ' 7.475-7.63 ( m, 5H ), 7.85 (dd, 1H), 8.045 ( dd, 2H) , 8.07 ( dd, 1H) , 8.3 25 (d, 1H), 8.60 (d, 1 H ). (Step 4)

0.60 g (1.4 mmol) of compound (iii) was dissolved in 7 ml of secondary butyl methyl ether 'added to 〇.il g (14 mmol) of acetonitrile chloride while cooling on an ice bath 0.28 mL (2.0 mmol) of triethylamine was added. Stir for 3 hours while slowly returning to room temperature. After the completion of the reaction, the reaction mixture was poured into ice water and extracted with ethyl acetate. After washing with water, a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over magnesium sulfate, the solvent was evaporated. The product was isolated by hydrazine gel column chromatography (eluent; dichloromethane - n-hexane: ethyl acetate = 2:; [) to obtain y. 30 g of pale yellow solid compound (iv) ( Yield -89- 201140240 7 0 % ). The physical properties of the compound (iv) are as follows: 'H-NMR (400 MHz, CDCI3, TMS, ppm) δ ' 1.16 (t, 3H), 2.23 (s, 3H), 2.51 (s, 3H), 2.90 ( t, 2H ), 4.09 ( q, 2H ), 4.71 ( t, 2H) , 7 · 5 1 - 7 · 6 2 ( m, 5 H ), 7.75 ( dd, 2H) , 7.99 ( dd, 1 H ) , 8.09 ( dd, 1 H ) , 8.46 (d,1 H) , 8.59 ( d,1 H ); UV spectrum (mobile layer; acetonitrile): Amax = 260, 292, 333 nm; thermal decomposition temperature (in a nitrogen atmosphere) Next, a sample of 1.5 mg was heated at a temperature increase rate of 10 ° C /min to reduce the temperature at a mass of 5%): 2 2 4.5 ° C; molecular weight: 4 70.5 2 . &lt;Real. Example 2 &gt; In the first step of Example 1, except that the ethyl acrylate (40 mM) was used instead of ethyl acrylate (40 mM), in step 2, in addition to the substitution The benzamidine chloride (11 mmol) was used in the same manner as in Example 1 except that 2-methylbenzoyl chloride (11 mmol) was used to obtain the lower portion. The pale yellow solid compound (v). The physical properties of the compound (v) are as follows: -90- 201140240

1H-NMR (400 MHz, CDC13, TMS, ppm) δ 0.81 (d

, 6H) '1.8 0 5 ( m ' 1 H ) , 2.29 (s, 3H), 2.35 (s'3H ), 2.50 (s, 3H), 2.90 (t, 2H), 3.81 (d, 2H), 4.70 (t ' 2H ), 7.28-7.53 (m, 6H), 7.97 ( dd, 1H) ' 8.10 (dd' 1H) , 8.42 (d, lH), 8.51 (d, lH); UV spectrum (moving layer; acetonitrile) ): Ama?c=260, 295.5, 3 3 4 nm ; Thermal decomposition temperature (in a nitrogen atmosphere, a sample of 1.5 mg is heated at a heating rate of TC / min to reduce the temperature by 5% by mass) : 2 3 6 . . ; molecular weight: 512.6. &lt;Example 3 &gt; In the step 1 of Example 1, 2-methoxyethyl acrylate was used in place of the ethyl acrylate (40 mmol). Milligram), in step 2, except that 2-methylbenzhydryl chloride (1 1 mmol) was used instead of benzamidine chloride (11 mmol), the rest was the same as in Example 1. The procedure was carried out to obtain the following pale yellow solid compound (vi-91 - 201140240). The physical properties of the compound (Vi) are as follows:

Ο / (Vi) ^-NMR ( 400 MHz, CDC13, TMS, ppm) δ , 3H) ' 2.3 5 ( S' 3H ) , 2.50 (s, 3H) ' 2.95 ), 3.32 (s, 3H), 3.50 ( t, 2H), 4.19 (t, 4.70 ( t ' 2H ) , 7.30-7.54 ( m, 6H ), 7.97 ( dd

' 8.10 (dd' 1H) , 8.42 (d, lH), 8.51 (d, lH UV spectrum (moving layer; acetonitrile): λ max = 2 5 8.5 3 3 4.5 nm ; thermal decomposition temperature (under nitrogen atmosphere) , heating at a heating rate of 1.5 mg/min to reduce the temperature by 5% by mass. 2: 3; molecular weight: 514.57. &lt;Example 4 &gt; (Step 1) 2.29 ( s (t, 2H 2H ) , , 1 Η ) ): , 296, sample in degrees): -92- 201140240

Dissolve 5.0 g (3 Torr) of carbazole in 6 ml of one of the methyl carbamide (DMF) 'added to 13.2 g (15 〇 mmol) of ethylene carbonate and 5.5 ml (〇37) The second molar double ring eleven (DBU) was heated under reflux at 1 °C for 3 hours. After cooling, water was added and the mixture was washed with ethyl acetate. After washing with water, the solvent was distilled off. Secondly, the concentrate will be obtained! 5 ml of acetonitrile was diluted, and 2 g (23 mmol) of acetonitrile and 4 ml (29 mmol) of triethylamine were added thereto, and stirred at room temperature for 3 hours. After the completion of the reaction, water was added thereto, and the mixture was extracted with ethyl acetate. The mixture was washed with water and dried over magnesium sulfate. The solvent was distilled off to obtain 6.0 g of the compound (ν?) (yield 80%) of pale yellow liquid. (Step 2)

2.5 g (9.9 mmol) of the compound (vii) was dissolved in 1 mL of dichloromethane. While cooling with an ice bath, 1.5 g of aluminum chloride was added for 20 minutes. Thereafter, 1.4 g (1 〇. 〇 mmol) -93- 201140240 of benzamidine chloride was added dropwise, and the mixture was slowly returned to room temperature and stirred for 1 hour. Further, 1.5 g of aluminum chloride was added thereto while cooling in an ice bath for 20 minutes, and 0.93 g (1·8 mmol) of ethyl hydrazine chloride was added thereto, and the mixture was slowly returned to room temperature and stirred for 1 hour. After the completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over magnesium sulfate. The product was isolated by hydrazine gel column chromatography (eluent; dichloromethane-hexane: ethyl acetate = 2:1) to yield 2.8 g of pale yellow solid compound (viii) (yield 70) %). (Step 3)

Ηη2οη· hci CH3COONa

°K 0.38 g (5.4 mmol) of chlorinated hydroxylamine, 0.54 g (6.4 m mmol) of sodium acetate was dissolved in 4.5 ml of water and added to 2.0 g (5.0 mmol). The above compound (viii) and 35 ml of ethanol were refluxed for 2 hours. After completion of the reaction, the solvent of the reaction solution was distilled off, and the obtained solid was washed with water, dissolved in THF, and dried over magnesium sulfate. The solvent was distilled off to obtain 1.8 g of pale yellow liquid compound (ix) ( Yield 89%) -94- 201140240 (Step 4)

毫 〇 〇 以 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 59 0.4 ml (2.9 mil) of triethylamine was added dropwise while cooling in an ice bath. The mixture was stirred for 3 hours while slowly returning to room temperature. After the reaction was completed, the reaction solution was poured into ice water, and the mixture was washed with ethyl acetate, washed with water, a saturated aqueous solution of sodium hydrogencarbonate and saturated brine. Solvent distillation. The product was isolated by hydrazine gel column chromatography (eluent; dichloromethane-n-hexane: ethyl acetate = 2:1) to obtain 0.6 g of the pale yellow solid compound (X). The rate is 7〇%). (The physical properties of the compound (X)) 'H-NMR (400 MHz, CDC13, TMS, ppm) &lt;5: 193 (3H), 2.50 (s, 3H), 2.85 (s, 3H), 4.31 (t , 2H) 4.40 ( t, 2H ) ' 7.50-7.62 ( m,5H ) , 7.75 ( dd,2H ) 7.99 ( dd, 1 H ) , 8.09 ( dd, 1H ) , 8.46 ( d, 1H ) , 8 (d , 1 H ); UV spectrum (moving layer; acetonitrile): Amax = 260, 296,: • 95- 201140240 Thermal decomposition temperature (under a nitrogen atmosphere, 1.5 mg of the sample is taken as 1 0. (: / min The temperature at which the heating rate is increased to reduce the mass by 5%): 2 2 5 ° C; molecular weight: 456.49. &lt;Example 5 &gt;

After dissolving 0.96 g (40 mmol) of 9-oxazole-9-propionic acid in 10 ml of acetonitrile, 18 g (210 mmol) of morpholine was added. To the obtained mixture, 14 g (1 20 mmol) of sulfinium chloride was added dropwise, and stirred at room temperature for 3 hours. After completion of the reaction, water was added and stirred for 30 minutes. Then, it was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and then evaporated to give 10 g of pale yellow liquid compound (xi) (yield: 81%). (Steps 2 to 4) -96- 201140240 ο ο

The same operation was carried out except that the compound (xi) was used instead of the compound (vii) in the step 2 to the fourth step of Example 4 to obtain the pale yellow solid compound (xii) of the following property. (Compound of compound (xii)) 1H-NMR (400 MHz, CDC13, TMS, ppm) &lt;5: 2.50 ( s, 3H ) , 2.80 ( t, 2H ) 2.85 ( s, 3H ) , 2.90 ( br, 2H ), 3.00 ( br, 2H ) , 3.35 ( br, 2H ) , 3.46 ( br, 2H ) 4.72 ( t, 2H ) , 7.5 1-7.62 ( m, 5H ) , 7.75 ( dd, 2H ) , 7.99 ( dd , 1 H ) ' 8.09 ( dd, 1 H ) , 8_46 (d, lH), 8.59 (d, lH); UV spectrum (moving layer; acetonitrile): Amax = 260, 292, 335 m thermal decomposition temperature (in nitrogen) Under the atmosphere, 1.5 mg of the sample is heated at a temperature increase rate of 1 〇 ° C / min to reduce the temperature by 5% by mass): 2 3 4 ° C ; -97- 201140240 Molecular weight: 5 1 1 . 5 7 . &lt;Test Examples 1 to 5, Comparative Test Examples 1 and 2 &gt; Compatibility and Sensitivity Tests 100 parts by mass of a trifunctional propyl acrylate "M-305" (trade name, manufactured by Toago Chemical Co., Ltd.) 5 parts by mass of the photopolymerization initiators obtained in Examples 1 to 5 (compounds (iv) to (vi), (X) and (X ii ); for Test Examples 1 to 5), and the following "IRGACURE" were added. OXE02" (manufactured by Ciba Specialty Chemicals Co., Ltd., comparative test example 1. In the following, sometimes referred to as "OXE02"), or the following "N-1919" (ADEKA Corporation) Manufacture and comparison test example 2). Here, the presence or absence of a solid in the obtained mixture was visually confirmed as an index of compatibility with a compound having an ethylenically unsaturated bond (particularly a compound having a (meth)acryloxy group). The results are shown in Table 1. Next, the mixture was dissolved in chloroform to prepare a photocurable composition. The obtained photocurable composition was applied onto a chromium-plated glass substrate by a spin coating method. When the coating film obtained by the above-mentioned coating film was exposed to UV light, the amount of decrease in the peak was recorded by the infrared ray splitting device 8 10 cm_1, and it was confirmed how much the disappearance of the double bond was carried out (reaction rate). The indicator of sensitivity. The results are shown in Table 1. -98- 201140240

"IRGACURE OXE02J

UV spectrum (moving layer; acetonitrile): Amax = 2'70, 296, 335 nm Molecular weight: 5 4 2.6 2 UV spectrum (moving layer: acetonitrile): again max = 265, 29 8, 3 3 9 nm trait: 4 1 2.4 8 Table 1 Compatibility of photopolymerization initiator with "M-305" (Reaction rate) Exposure: 0.5 mJ Exposure: 3.0 mJ S test example 1 Compound (iv) 〇56% 70% Test Example 2 Compound (V) 〇 54% 71% Test Example 3 Compound (VI) 〇 52% 72% Test Example 4 Compound U) 〇 50% 65% Test Example 5 Compound (Xii) 〇 50% 70% Comparative Test Example 1 OXE02 X 45% 60% Comparative test example 2 N-1919 X 48% 60% _ 〇: Solids were not confirmed, and compatibility with Μ - 3 0 5 j was high; X : solids were confirmed, and Μ · 3 0 5" lack of compatibility. It can be understood from Table 1 that the photopolymerization initiator of the present invention has high compatibility with a compound having a home bond unsaturated double bond, particularly a polyfunctional (methyl) acid ester, and can also be prepared without a solvent. The photopolymerization initiator and the photocurable composition containing the photopolymerization initiator of the present invention have higher sensitivity than the photocurable composition containing the conventional photopolymerization initiator. &lt;Test Example 6 to 1 〇, Comparative Test Examples 3 and 4> Solubility to Solvent for Methanol, Vinegar Investigation for Propylene Glycol Monoethyl Ether Ether (PGMEA) -99- 201140240 Acid 3-Methoxy-3- The amount of dissolution of each of methyl-1-butane vinegar (MMBA), methyl isobutyl ketone (MIBK), and chloroform to 1 part by mass of the photopolymerization initiator was evaluated for solubility according to the following evaluation criteria. The results are shown in Table 2. A: 1 part by mass or more of dissolved; B: 5 parts by mass or more and less than 1 part by mass; C: 2 parts by mass or less and less than 5 parts by mass; D: only less soluble In 2 parts by mass. The term "dissolved" as used herein means that the solid form m is not visually observed. Table 2

Photopolymerization initiator solvent PGMEA Methanol MMBA MIBK Chloroform test Example 6 Compound (iv) A c BBA Test Example 7 Compound (V) A c BAA Test Example 8 Compound (vi) A c BAA Test Example 9 Compound (X) A c BBA Test Example 10 Compound (xii) A c BBA Comparative Test Example 3 OXE02 BDD c A Comparative Test Example 4 N-1919 AD cc A It can be seen from Table 2 that the light of the present invention is compared with the previous photopolymerization initiator. The polymerization initiator is excellent in solubility in various solvents, particularly compounds having an ether bond and/or an ester bond and being liquid at 25 °C. In addition, the photopolymerization initiator "N-1 9 1 9" used in Comparative Test Example 4 had a higher solubility than the photopolymerization initiator "OXE02" used in Comparative Test Example 3. This is because "N-1919" imparts a substituent to the structure of "OXE02" to improve solubility. The compounds (iv) to (vi), (X) and (xii) used in Test Examples 6 to 10 are not only soluble in the solvent -100-201140240, but also have a molecular weight of more than "N-1 9 1 9". The smaller, the content in the photocurable composition can be reduced, and thus it is a more excellent photopolymerization initiator. &lt;Production Example 1&gt; Production of Binder Resin 30 parts by mass of benzyl methacrylate' 38 parts by mass of styrene, 18 parts by mass of methacrylic acid, and 1 part by mass of peroxy-2_B A mixture of butyl hexanoate ("PERBUTYL 0" manufactured by NOF Corporation) was added dropwise to 150 parts by mass at 100 ° C for 3 hours under a nitrogen stream. The polymerization tank of propylene glycol monoethyl ether acetate. After the dropwise addition was completed, it was further heated at 100 ° C for 3 hours to obtain a polymer solution. To the obtained polymer solution, 14 parts by mass of glycidyl methacrylate, 0.2 part by mass of triethylamine, and 0.05 part by mass of p-methoxyphenol' were heated at 110 ° C for 10 hours. The binder resin obtained by modulating the binder resin 之 had a solid content concentration of 38% by mass, an acid value of 75 m gKOH/g, and a weight average molecular weight of 10,000. &lt;Production Example 2&gt; Preparation of blue pigment dispersion liquid Table 3 Component mixing amount (parts by mass) Production Example 2 LIONOL BLUE ES (manufactured by Toyo Ink Manufacturing Co., Ltd.) 13 LIONOGEN VIOLET RL (manufactured by Toyo Ink Manufacturing Co., Ltd.) 2 Pigment dispersant (Disperbyk 2001: manufactured by BYK Chemie Japan Co., Ltd., solid concentration: 46 mass/〇) 13 Propylene glycol propylene glycol monoethyl ether ester 72 - 101 - 201140240 The ingredients shown in Table 3 were mixed The amount was mixed and dispersed by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) using a 0.3 mm diameter oxidized pin bead for 3 hours to prepare a blue pigment dispersion ( Solid component concentration: 21% by mass). &lt;Production Example 3 &gt; Modulation of Red Pigment Dispersion Table 4 Component Mixing Amount (Parts by Mass) Production Example 3 Irgahor red BT-CF (manufactured by Ciba Specialty Chemicals Co., Ltd.) 12 Irgahor Yellow 2R-CF (Ciba Specialty) 3, a pigment dispersant (Dkperbyk 161: manufactured by BYK Chemie Japan Co., Ltd., solid content concentration: 30% by mass) 20 propylene glycol monoethyl ether acetate 65 Each component shown in Table 4 was mixed The amount was mixed, and the oxidized chrome beads having a diameter of 0.3 mm were dispersed by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 3 hours to prepare a red pigment dispersion (solid content concentration: 21% by mass). &lt;Production Example 4: Preparation of Green Pigment Dispersion Table 5 Component Mixing Amount (Parts by Mass) Production Example 4 LIONOL GREEN 2YS (manufactured by Toyo Ink Manufacturing Co., Ltd.) 9 Yellow Pigment E4GN (manufactured by Lanxess Corporation) 6 Pigment dispersant (AJISPER PB821: Ajinomoto Fine-Techno Co., Ltd.) 6 Propylene glycol propylene glycol monoethyl ether ester 79 -102- 201140240 The components shown in Table 5 were mixed in each mixing amount, and the diameter was The 0.3 mm zirconia beads were dispersed by a paint shaker (manufactured by Asada Iron Works Co., Ltd.) for 3 hours to prepare a green pigment dispersion (solid content concentration: 21% by mass). In the following examples, the evaluation of sensitivity, resolution, developability, and adhesion was carried out as follows. (sensitivity) In the exposure step, the exposure amount is set to 100 mJ/cm 2 or 200 mJ/cm 2 , and the film thickness after development and post-baking of the light-irradiated area is 95% with respect to the film thickness before exposure. In the above case, it is regarded as "the film thickness is sufficient" and is evaluated according to the following evaluation criteria: A : sufficient film thickness is obtained if the exposure amount is 100 mJ/cm2; B: when the exposure amount is 100 mJ/cm2 Not enough, if the exposure amount is 200 mJ/cm2, a sufficient film thickness can be obtained. In addition, the film thickness was measured using a stylus type film thickness measuring device "SURFCORDER ET4000A" (manufactured by Kosaka Laboratory Ltd.). (Resolution) The resolution is evaluated according to the following evaluation criteria: a : Good exposure can be obtained even if the line width is less than 1 〇 in the exposure development; b : If the line width is 1 5 to 2 0 // m A good pattern can be obtained. (developability) The residue of the unexposed portion (the portion not irradiated with light) at the time of exposure was observed, and the developability was evaluated according to the following evaluation criteria: 〇: the residue was not confirmed at all; X : Confirm the residue. (Adhesion) The line width of the independent pattern which was not washed and adhered after development was examined, and the adhesion was evaluated according to the following evaluation criteria: ◎: Good results were obtained even if the line width was 5 // m or less. Isolated pattern; 〇: When the line width is 6 to 10 / / m, a good isolated pattern can be obtained &lt;Example 6 &gt; Modulation and pattern formation of the blue photocurable resin composition Table 6 Composition amount (long copy) Example 6 The blue pigment dispersion liquid obtained in Production Example 2 24.1 The adhesive resin 9.5 "ARONKTO-1382" obtained in Production Example 1 (manufactured by East Asia Synthetic Chemical Industry Co., Ltd., composition: polyfunctional acrylate having a carboxyl group) 9.0 Compound (iv) (photopolymerization initiator) obtained in Example 1 2.0 "KBM-503" (Shin-Etsu Chemical Co., Ltd.), composition: 3: methacryl醯oxypropyltrimethoxydecane) 0.3 Propylene glycol monoethyl ether acetate 55.4 The components shown in Table 6 were mixed in each mixing amount, and stirred in a dissolving disperser for 1 hour to prepare blue light. Sclerosing tree Fat composition. The blue photocurable resin composition obtained by spin coating on a glass substrate was heated at 80 ° C for 3 minutes to form a coating film of a blue photocurable resin composition. The obtained coating film was passed through a mask having a specified line width, and exposed to a high-pressure mercury lamp as a light source from the side of the coating film -104-201140240, and then spray-developed using D'espairs 6Η (manufactured by Henkel) diluted to 100 times. After the development was completed, post-baking was performed at 230 ° C for 30 minutes to form a pattern. The evaluation results of sensitivity, resolution, developability, and adhesion are shown in Table 9. &lt;Comparative Example 1, 2 &gt; Preparation and Patterning of Blue Photocurable Resin Composition In Example 6, the above-mentioned "IRGACURE OXE02" (Cibafin) was used instead of the compound (iv) obtained in Example 1. Other than the above-mentioned "N-1 9 1 9" (manufactured by Asahi Kasei Kogyo Co., Ltd.), the blue photocurable resin composition was prepared in the same manner and patterned. The evaluation results of sensitivity, resolution, developability, and adhesion are shown in Table 9. &lt;Example 7&gt; Preparation and pattern formation of red photocurable resin composition Table 7 Component blending amount (parts by mass) Example 7 Red pigment dispersion liquid obtained in Production Example 3 35.2 Adhesive obtained in Production Example 1树月 7.2 "ARONKTO-1382" (manufactured by East Asia Synthetic Chemical Industry Co., Ltd., composition: polyfunctional propionate containing carboxyl group) 6.8 Compound (iv) obtained in Example 1 (photopolymerization initiator) 2.0 " KBM-503" (Shin-Etsu Chemical Co., Ltd. manufactures 'Ingredients · 3-Methylpropoxypropyltrimethoxydecane) 0.3 Propylene glycol monoethyl ether acetate 48.8 -105- 201140240 Will be as shown in Table 7 Each component was mixed in each mixing amount, and stirred by a dissolving disperser for 1 hour to prepare a red photocurable resin composition. The red light-curable resin composition obtained was subjected to the same operation as in Example 6 to form a pattern. The evaluation results of sensitivity, resolution, developability, and adhesion are shown in Table 9. &lt;Comparative Example 3, 4 &gt; Preparation and Patterning of Red Photocurable Resin Composition In Example 7, except that the compound (iv) obtained in Example 1 was used instead of the above "IRGACURE OXE02" (Cibafin) Other than the above-mentioned "N-1919" (manufactured by Asahi Kasei Kogyo Co., Ltd.), the red photocurable resin composition was prepared in the same manner and patterned. The evaluation results of sensitivity, resolution, developability, and adhesion are shown in Table 9. &lt;Example 8&gt; Preparation and pattern formation of green photocurable resin composition Table 8 Component blending amount (parts by mass) Example 8 Green pigment dispersion liquid obtained in Production Example 4 41.6 The adhesive obtained in Production Example 1 Resin 6.2 "ARONDCTO-1382" (manufactured by East Asia Synthetic Chemical Co., Ltd., component: polyfunctional acrylate containing carboxyl group) 5.9 Compound (iv) obtained in Example 1 (photopolymerization initiator) 2.0 "KBM-503" (Manufactured by Shin-Etsu Chemical Co., Ltd., composition: 3-methylpropenyloxypropyltrimethoxydecane) 0.3 Propylene glycol monoethyl ether acetate 44.3 -106- 201140240 Each component is mixed as shown in Table 8. The amounts were mixed and stirred in a dissolving disperser for 1 hour to prepare a green photocurable resin composition. The green photocurable resin composition obtained was subjected to the same operation as in Example 6 to form a pattern. The results of evaluation of sensitivity, resolution, developability and adhesion are shown in Table 9.

Tps ° &lt;Comparative Example 5,6 &gt; Preparation and Patterning of Green Photocurable Resin Composition In Example 8, the above-mentioned "IRGACURE OXE02" (Vapor) was used instead of the compound (iv) obtained in Example 1. Other than the above-mentioned "N-1919" (manufactured by Asahi Kasei Kogyo Co., Ltd.), the green photocurable resin composition was prepared in the same manner and patterned. The evaluation results of sensitivity, resolution, developability, and adhesion are shown in Table 9. &lt;Examples 9 to 1 1 &gt; Each of Examples 6 to 8 was used in the same manner except that the compound (v) obtained in Example 2 was used instead of the compound (v) obtained in Example 1. A blue photocurable resin composition, a red photocurable resin composition, and a green photocurable resin composition are prepared and patterned. The evaluation results of sensitivity, resolution, developability, and adhesion are shown in Table 9. <Example 1 to 2 4 &gt; -107- 201140240 Each of Examples 6 to 8 was used except for the compound (vi) obtained in Example 3 except for the compound (iv) obtained in Example 1, and the others were The blue photocurable resin composition, the red photocurable resin composition, and the green photocurable resin composition were prepared in the same manner to form a pattern. The evaluation results of sensitivity, resolution, developability, and adhesion are shown in Table 9. <Examples 1 to 5 7 &gt; Each of Examples 6 to 8 was prepared in the same manner except that the compound (X) obtained in Example 4 was used instead of the compound (iv) obtained in Example 1. A blue photocurable resin composition, a red photocurable resin composition, and a green photocurable resin composition are patterned. The results of evaluation of sensitivity, resolution, developability, and adhesion are shown in Table 9. 0 &lt;Examples 18 to 20 &gt; Each of Examples 6 to 8 was replaced by the compound obtained in Example 1 (iv) The blue photocurable resin composition, the red photocurable resin composition, and the green photocurable resin composition were prepared in the same manner except that the compound (xii) obtained in Example 5 was used, and a pattern was formed. The evaluation results of sensitivity, resolution, developability, and adhesion are shown in Table 9. -108- 201140240 Table 9 Photopolymerization Initiator Sensitivity Resolution Developability Adhesion Example 6 Compound (iv) A a 〇 ◎ Example 9 Compound (V) A a 〇 ◎ Example 12 Compound (v〇A a 〇 ◎ Example 15 Compound (X) A a 〇〇 Example 18 Compound (xii) A a 〇 ◎ Comparative Example 1 OXE02 B b 〇〇 Comparative Example 2 N-1919 B b 〇〇 Example 7 Compound (iv) A a 〇 ◎ Example 10 Compound (V) A a 〇 ◎ Example 13 Compound 〇i) A a 〇 ◎ Example 16 Compound (X) A a 〇〇 Example 19 Compound (xii) A a 〇 ◎ Comparative Example 3 OXE02 B b 〇〇Comparative Example 4 N-1919 B b 〇〇 Example 8 Compound (iv) A a 〇 ◎ Example 11 Compound (V) A a 〇 ◎ Example 14 Compound (vi) A a 〇 ◎ Example Π Compound (X) A a 〇〇 Example 20 Compound (xii) A a 〇 ◎ Comparative Example 5 OXE02 B b 〇〇 Comparative Example 6 N-1919 B b 〇〇 From Table 9, it can be known that 'the light containing the present invention The photocurable composition of the polymerization initiator has and contains a photopolymerization initiator of the prior art. Curable composition is equivalent to the developer, in addition, about the sensitivity, resolution and adhesion aspects, the specific previous photopolymerization initiator agent to the curable composition containing excellent. Therefore, the photocurable composition containing the photopolymerization initiator of the present invention can be said to have excellent deep hardenability. [Industrial Applicability] The photopolymerization initiator of the present invention has a high sensitivity to light (especially a short-wavelength light having a wavelength of 45 nm or less), can be thinned, and can be formed at a low cost. The pattern of quality 'and compatibility with a compound having an ethylenically unsaturated bond (particularly a compound having a (meth) acryloxy group) or a solubility in a solvent can be used as contained in -109-201140240 A photopolymerization initiator in a photocurable composition for a color filter and a photopolymerization initiator for a photocurable composition for a black matrix having high light-shielding properties. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a liquid crystal display device of the present invention. [Description of main component symbols] 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Colored furnace light sheet 20 Counter substrate 30 Liquid crystal layer 40 Liquid crystal display device -110-

Claims (1)

201140240 VII. Patent application scope: 1 · A photopolymerization initiator represented by the following general formula (I) Π d1 (wherein R1 to R11 are independently substituted for a hydrogen atom, a halogen atom, a substituted or unsubstituted carbon number of 1 to 20, and a substituted or unsubstituted carbon number of 2 to 20 a substituted, unsubstituted or substituted ring-forming alkyl group having 3 to 1 ring atomic number, substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, hydroxy group, substituted or unsubstituted Alkoxy groups having 1 to 20 carbon atoms, substituted or unsubstituted alkenyloxy groups having 2 to 20 carbon atoms, substituted or unsubstituted alkyl alkano groups having 1 to 20 carbon atoms, a substituted or unsubstituted olefin group having 2 to 20 carbon atoms, a substituted or unsubstituted ring-forming aryl group having 6 to 14 carbon atoms or a substituted or unsubstituted ring forming atomic number 3 to 14 of the heterocyclic group 'R3 may form a ring together with R4 or R5, and R4 may form a ring together with R5; further, ΑΓ is a substituted or unsubstituted ring forming carbon number (to 14 aryl or substituted or unsubstituted ring forming atomic number, to 14 heteroaryl; -111 - 201140240 w is a single bond or oxygen atom; Z is Form bond, oxygen atom or &gt; NR3' (R3' is a substituted or unsubstituted alkyl group having a carbon number of 20 to 20, or R3' is bonded to R3 to form a ring together with a nitrogen atom); In the case of an integer from 1 to 10, where η is an integer from 2 to 1 ,, the plurality of R 4 and R 5 may each be the same or different). 2 · The photopolymerization initiator of claim 1 of the patent application may be Representative of the following general formula (Ia): /R1 (wherein 'R to R are each independently represent a hydrogen atom, a _ atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted; or an unsubstituted carbon number of 2 to 20 alkenyl, substituted or unsubstituted cycloalkyl group having 3 to 1 ring atomic number, substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, hydroxy group, substituted or Unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkane having 1 to 20 carbon atoms a substituted, unsubstituted or unsubstituted olefin group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having a carbon number of 6 to 14 or a substituted or unsubstituted ring. a heterocyclic group having 3 to 14 atoms, R3 may form a ring together with R4 or R5, and R4 may be -112-201140240 together with R5 to form a ring; further, Ar represents a generation or an The substituted aryl group having 6 to 14 carbon atoms or the unsubstituted substituted heteroaryl group having 5 to 14 atomic groups; η疋 represents an integer of 1 to 1 ' 'n is 2 To 1〇 In the case of an integer, a plurality of "and R5 may each be the same or different." 3. As in the scope of claim 2, a polymerization initiator, wherein in the formula (I - a), R1, R2 and r 3 曰々丄 &amp; K 疋 are each independently a substituted or unsubstituted carbon number of 1 to 20, (pit basis, η is 2, plural scales 4 and R5 are each independently hydrogen Atom or 卞4 substituted or unsubstituted alkyl group having 1 to 2 Å carbon atoms, and Ar is a substituted or unsubstituted aryl group having a carbon number of 6 to 14. 4. a photopolymerization initiator according to item 2, wherein in the formula (Ia), the towels 'R, R &amp; R3帛 are each independently substituted or unsubstituted, and the number of carbon atoms is 1S2〇, which is 2, plural R4 and rS are each independently a gas atom or a substituted or unsubstituted carbon number of from ! to 20, and Ar is a substituted or unsubstituted heterocyclic ring having a ring number of 5 to 14. 5. The photopolymerization initiator according to the patent application No. 3 $ 4 has a molecular weight of 5 15 or less. 6. The photopolymerization is initiated according to the second item of the patent application. n initiator, wherein in the formula (Ia), Ri and R2 are each independently substituted or unsubstituted alkyl having a carbon number of 1 to 20, and R3 is substituted or not by the rib member 4 The substituted ring having a carbon number of 3 to 18 is 2, a plurality of ... and R5 is each -113 - 201140240 independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. 7. The photopolymerization initiator according to claim 2, wherein in the formula (I - a ), R1 and R2 are each independently substituted or unsubstituted carbon having a carbon number of 1 to 20 The base 'R3 is an alkyl group having 1 to 20 carbon atoms substituted by a cyclic ether group having 3 to 6 atomic groups forming a ring, and η is 2, and the plurality of R4 and R5 are each independently a hydrogen atom or a The substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. 8. The photopolymerization initiator according to claim 6 or 7, which has a molecular weight of 550 or less. 9. The photopolymerization initiator according to item 1 of the patent application, which can be represented by the following formula (I-b): 〇, , /R1 (wherein R1 to R11 are each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted carbon number of 2 to 20 Alkenyl, substituted or unsubstituted cycloalkyl group having 3 to 10 ring atoms, substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, hydroxy group, substituted or not-114 - 201140240 Substituted alkoxy group having a carbon number of 1 to 20, substituted or unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted carbon number of 1 to 20 Mercapto group, substituted or unsubstituted thiol group having 2 to 20 carbon atoms, substituted or unsubstituted ring-forming carbon group having 6 to 14 carbon atoms or substituted or unsubstituted a heterocyclic group having 3 to 14 atomic number of the ring; Ar is an atomic group representing a substituted or unsubstituted ring-forming carbon group of 6 to j 4 or a substituted or unsubstituted ring-forming atom a heterocyclic group of 5 to 14; W represents a single bond or an oxygen atom; ζ represents a single bond, an oxygen atom or &gt; NR3 (R3 represents a substituted or unsubstituted carbon number of 1 to 2 〇 The alkyl group, or R3', is bonded to R3 to form a ring together with the nitrogen atom.) 10. The photopolymerization initiator of claim 9, wherein in the formula (Ib), 'R1 and R3 are each Independently substituted or unsubstituted alkyl having 1 to 20 carbon atoms, w is an oxygen atom, 2 is a single bond or an oxygen atom, and Ar is a substituted or unsubstituted ring forming carbon number of 6 to 14 aryl. 1 1 · The photopolymerization initiator as claimed in claim 10, wherein further R 2 has a carbon number of -〇C〇R13 (R丨3 is an alkyl group having a carbon number of 1 to 20 or a ring is formed) The number of carbon atoms of the ester group represented by an aryl group of 6 to 14 or a COOR 20 (R2Q is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 carbon atoms forming a ring) is 1 to 20 Alkyl group. The photopolymerization initiator of claim 9, wherein in the formula (Ib), 'R1 and R3 are each independently substituted or unsubstituted -115- 201140240, and the carbon number is 1 An alkyl group of 20, W is a single bond, Z is &gt;NR3' (R3' is as defined above), and Ar is a substituted or unsubstituted aryl group having a carbon number of 6 to 14 formed into a ring. . 13. The photopolymerization initiator according to claim 12, wherein further R2 has a ruthenium group of -OCOR13 (R13 represents a carbon number of 1 to 2 Å or a ring forms a carbon number of 6 to 14) The aryl group or ~c〇OR20 (R2() is an alkyl group having a carbon number of 1 to 20 or an aryl group having a carbon number of 6 to 14 forming a ring) has a carbon number of 1 to 20 Alkyl group. A photocurable composition comprising a binder resin and/or a compound having an ethylenically unsaturated bond, and a photopolymerization initiator according to any one of claims 1 to 13. The photocurable composition of claim 14, wherein the content of the photopolymerization initiator is from 2 to 50% by mass based on the solid content of the photocurable composition. A photocurable composition according to claim 14 or 15 of the patent application, further comprising a color material. The photocurable composition according to any one of claims 1 to 4, further comprising 5 to 100 parts by mass of an ether bond with respect to 1 part by mass of the photopolymerization initiator / or ester bond and a compound that is liquid at 25 ° C. The photocurable composition according to any one of claims 14 to 16, wherein the compound having an ethylenically unsaturated bond is at least one having an ether bond and/or an ester bond. The compound of the bond unsaturated bond, and the solvent contained therein is only 10% by mass of the total amount of the photocurable composition - 116 to 201140240 or less. The photocurable composition according to any one of claims 16 to 18, which is used for a color filter. A color filter using the photocurable composition according to any one of claims 16 to 18. A liquid crystal display device comprising the color filter and the counter substrate of claim 20, and a liquid crystal layer formed between the color filter and the counter substrate. 22. A method of forming a pattern by coating a photocurable composition according to any one of claims 16 to 18 on a substrate, drying it, using a photomask, and then performing development. . A method for producing a photopolymerization initiator which is obtained by the following steps to obtain a photopolymerization initiator represented by the following formula (I - a 1 ): (wherein 'R1 to R3, R4', R5', R6 to R11 and Ar are as defined below), the step comprising: a carbazole derivative represented by the following formula (1): -117 - 201140240 R6 R11 (wherein R6 to R11 are each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted or unsubstituted carbon number of 2 to 20; Alkenyl, substituted or unsubstituted cycloalkyl group having 3 to 10 ring atoms, substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, hydroxy group, substituted or unsubstituted An alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyloxy group having 2 to 20 carbon atoms, a substituted or unsubstituted alkyl alkene group having 1 to 20 carbon atoms, A substituted or unsubstituted olefin group having 2 to 20 carbon atoms, a substituted or unsubstituted ring-forming aryl group having 6 to 14 carbon atoms or a substituted or unsubstituted ring-forming atom The number of 3 to 14 heterocyclic groups, and the acrylate derivative represented by the following formula (2a): 0 r4.^A〇/R3 (2 a) R5, (wherein, R3, R4' And R5' are each independently represent a hydrogen atom, a _ atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, Substituted or not Instead, a cycloalkyl group having a ring number of 3 to 10, a substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, and a hydroxyl group substituted or unsubstituted have a carbon number of 1 to 20 alkoxy, substituted or unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkyl alkano group having 1 to 20 carbon atoms, substituted or unsubstituted Carbon number -118- 201140240 is an alkenyl group of 2 to 20, a substituted or unsubstituted aryl group of 6 to 14 or a substituted or unsubstituted heterocyclic group having 3 to 14 subunits, R3 is It can be reacted with R5, in the presence of a base to obtain a ring of the following formula (the carbonylalkyl group of the formula:: ^ ring-forming carbon oxime to form a ring) 3a') by R6 R11 ( Where, R3 The carbonyl group-introducing body obtained as described above and the two deuterating agents represented by the following formula (4): Ο AX (4) R2 χ χ (5) (wherein X represents a halogen atom or _〇 C(=〇)Ar, a halogen atom or —〇C(=0)r2; Ar is a radical representing a substituted or unsubstituted carbon number forming a ring or a substituted or unsubstituted atom forming a ring 14 Heteroaryl; L definition is shown, (5) where X' is represented by 6 to 14 and 5 to -119- 201140240 R2 is a hydrogen atom, a halogen atom, a substituted or unsubstituted carbon number of 1 An alkyl group of 20, a substituted or unsubstituted alkenyl group having 2 to 2 Å, a substituted or unsubstituted cycloalkyl group having 3 to 1 ring atomic number, substituted or unsubstituted a substituted cycloalkenyl group having 4 to 20 carbon atoms, a hydroxyl group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number of 2 to 20 a substituted, unsubstituted or substituted alkanofluorenyl group having 1 to 20 carbon atoms, a substituted or unsubstituted olefin group having 2 to 20 carbon atoms, a substituted or unsubstituted ring-forming carbon number An aryl group of 6 to 14 or a substituted or substituted group of a heterocyclic group having 3 to 14 ring atoms, which is represented by the following formula (6a, ) is carried out in the presence of a Lewis acid. Diketone body: (wherein R2, R3, R4', R5', R6 to R&quot; and Ar are as defined above); reacting the obtained diketone body with a hydroxylamine to obtain the following formula (7a' ) represented by the carcass: -120- (7201140240 R2 10 R' R: (defined in the formula and will be used as a counter-reagent: (in addition, carbon is 2 to 3 to 20 to 20, diloxy, substituted or unsubstituted or not R2' R3 is shown; the obtained steroids are obtained by the following formulas R6 to R1 and A: are photopolymerizations represented by the above-mentioned formula (1 gal represented by the amine) (8) 'Y is a halogen atom or -〇C(:= 〇)Rl; R1 is a hydrogen atom 'dentate atom, substituted or unsubstituted alkyl group of 1 to 20, substituted or not Substituted carbon number 20 alkenyl, substituted or unsubstituted ring-forming atom to 1 fluorene ring, substituted or unsubstituted carbon ring of 4, hydroxy, substituted or not Substituted carbon number of 1: anoxyl group, substituted or unsubstituted carbon number of 2 to 20, substituted or unsubstituted carbon number of dec. An olefin group having 2 to 20 carbon atoms, an aryl group having 6 to 14 carbon atoms formed by substitution, or a heterocyclic group having 3 to 14 atoms formed by substitution of a substituted ring) -12 1 -