WO2011105518A1

WO2011105518A1 - Photopolymerization initiator, photocurable composition, pattern formation method, colour filter, lcd device, and manufacturing method for photopolymerization initiator

Info

Publication number: WO2011105518A1
Application number: PCT/JP2011/054193
Authority: WO
Inventors: 寛子天野; 寛酒井
Original assignee: 大日本印刷株式会社
Priority date: 2010-02-25
Filing date: 2011-02-24
Publication date: 2011-09-01
Also published as: TW201140240A; TWI501035B; JP5626332B2; JP2012251128A; JPWO2011105518A1; JP5477367B2

Abstract

Disclosed is a photopolymerization initiator which exhibits: high compatibility with compounds which have an ethylenically unsaturated bond in a photocurable composition, and compounds which are liquid at 25℃ and which have an ether bond and/or an ester bond; high solubility in solvents; high sensitivity to light (especially short wavelength light having a wavelength of 450nm or below); and no contamination of polymers or devices by decomposition products generated by light exposure. The photopolymerization initiator, which has the structure outlined below, provides a photocurable composition which exhibits excellent definition, development properties, deep curing properties, and adhesion to substrates. Also disclosed are a photocurable composition containing said photopolymerization initiator, a pattern formation method using said photocurable composition, a colour filter using said photocurable composition, and an LCD device having said colour filter. Further disclosed is a low cost and simple manufacturing method for the photopolymerization initiator. (In the formula, R¹-R¹¹ represent hydrogen atoms, alkyl groups, or the like. R³ can form a ring together with R⁴ or R⁵. R⁴ can form a ring together with R⁵. Ar represents an aryl group or a heteroaryl group. W represents a single bond or an oxygen atom. Z represents a single bond, an oxygen atom, or >NR³' (R³' represents an alkyl group, or R³' joins with R³ and forms a ring with a nitrogen atom). n represents an integer from 1-10. When n is an integer from 2-10, R⁴ and R⁵ can each be the same or different.)

Description

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

The present invention relates to a photopolymerization initiator, a photocurable composition, a pattern formation method using the composition, a color filter using the composition, a liquid crystal display device having the color filter, and production of a photopolymerization initiator. Regarding the method. More specifically, a compound having an ethylenically unsaturated bond, an ether bond and / or an ester bond and a liquid compound at 25 ° C. which is liquid at 25 ° C., and a solvent (the aforementioned ether bond and / or A compound having an ester bond and a liquid compound at 25 ° C.), a high sensitivity to light (especially light having a short wavelength of 450 nm or less), and a polymer produced by a decomposition product generated by light during exposure. A photopolymerization initiator that is free from contamination or equipment contamination, and that provides a photocurable composition that provides good resolution, developability, deep curability, and adhesion to a substrate, and the photopolymerization initiation Curable composition containing an agent, a pattern formation method using the photocurable composition, a color filter using the photocurable composition, a liquid crystal display device having the color filter, and the light Process for the preparation of initiator.

The photocurable resin composition contains, for example, a binder resin, a polymerizable monomer, and a photopolymerization initiator, and can be polymerized and cured by irradiation with light (electromagnetic waves including radiation such as particle beams). , Photocurable inks, photosensitive printing plates, color filters, various photoresists, and the like. As light for curing the photocurable resin composition, light (ultraviolet light) having a wavelength of 450 nm or less is often used from the viewpoint of easy handling and sensitivity, and the light source has wavelengths of 365 nm, 405 nm, High pressure mercury lamps having strong emission at a wavelength of 436 nm and excimer lasers such as KrF and ArF are used. In addition, when used for forming a finer pattern, the application of electromagnetic waves or radiation having a short wavelength such as an electron beam or EUV (Extreme Ultra Violet) has been studied.
Curing with light is more energy-saving than heat-curing and can be cured in a desired pattern by irradiating it through a photomask. In addition, there is an increasing demand for highly sensitive photopolymerizable initiators that can reduce the amount of photopolymerization initiator added.
Color filters using the pigment dispersion method are usually exposed to light using a photomask after the photocurable composition is coated on a glass substrate in a pigment dispersion obtained by dispersing the pigment with a dispersant or the like, dried. A colored pattern is formed by developing, and the pattern is fixed by heating to form a pixel. These steps are repeated for each color to form a color filter. The photocurable composition used for image formation of such a color filter is required to have characteristics such as sufficient resolution, adhesion to a substrate and low development residue.
Furthermore, in recent years, pixels with high color density and black matrix resists with high optical density, which themselves function as light-shielding layers, have been used, and the inclusion of black pigments such as colored pigments and carbon black in photocurable compositions. The amount increases and the light transmittance of the photocurable composition tends to decrease. As a result, the light from the exposure light source does not reach the deep part of the photo-curable resin coating film, and there is a problem that the resolution, adhesion to the substrate, developability, etc. are deteriorated. The accuracy and further reliability required for the above are reduced.
In addition, the glass substrate on which the color filter is formed is getting larger year by year, and since the large area exposure is performed, the exposure illuminance tends to decrease and the exposure time is shortened for further productivity improvement. Therefore, a more sensitive photopolymerization initiator is required.
Therefore, as a method for obtaining a photocurable composition that can achieve high sensitivity and high resolution, it has been proposed to use an oxime ester compound as a photopolymerization initiator (see Patent Documents 1 to 5).

Japanese Patent No. 3860170 JP 2006-036750 A Japanese Patent No. 3993725 JP 2010-037542 A Korean Public Patent No. 2009-0046108

In the photopolymerization initiators described in Patent Documents 1 to 5, compounds having an ethylenically unsaturated bond (especially (meth) acryloyl) in photocurable compositions, such as sensitivity, resolution, developability, and compatibility and solubility. There is room for further improvement since the compatibility with a compound having an oxy group) and the solubility in a solvent are insufficient, and the use conditions are limited. In addition, in the photopolymerization initiators described in Patent Documents 1 to 5, decomposition products generated by light at the time of exposure adhere to the mask, resulting in pattern formation failure during printing and a decrease in yield. was there. Therefore, a photopolymerization initiator is desired in which the generated decomposition product does not contaminate the polymer or apparatus.

Therefore, an object of the present invention is to provide a compound having an ethylenically unsaturated bond (particularly a compound having a (meth) acryloyloxy group), an ether bond and / or an ester bond in a photocurable composition at 25 ° C. High compatibility with compounds and high solubility in solvents (including compounds that are ether-bonded and / or ester-bonded and liquid at 25 ° C.) and sensitivity to light (especially light having a short wavelength of 450 nm or less) Is a photopolymerization initiator that is high and has no contamination of polymer or equipment due to decomposition products generated by light at the time of exposure, and has good resolution, developability, deep curability and adhesion to the substrate. It is providing the photoinitiator which can provide a curable composition. 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 liquid crystal display device having the color filter Is to provide. Furthermore, it is providing the method of manufacturing the said photoinitiator simply at low cost.

As a result of intensive studies to achieve the above-mentioned problems, the present inventor can solve the above-mentioned problems as long as it is a photopolymerization initiator having a specific structure represented by the general formula (Ia) described later. I found.
That is, the present invention relates to the following [1] to [23].
[1] A photopolymerization initiator represented by the following general formula (I).

(Wherein R ¹ to R ¹¹ are each independently a hydrogen atom, a halogen 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 an 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, substituted or Unsubstituted alkenyloxy group having 2-20 carbon atoms, substituted or unsubstituted alkanoyl group having 1-20 carbon atoms, substituted or unsubstituted alkenoyl group having 2-20 carbon atoms, substituted or unsubstituted ring carbon atoms 6 .R ³ that an aryl group or a substituted or unsubstituted heterocyclic group ring atoms 3 to 14 of to 14, to form a ring together with R ⁴ or R ⁵ Good .R ⁴ may form a ring together with R ^5.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
W represents a single bond or an oxygen atom. Z represents a single bond, an oxygen atom, or> NR ³ ′ (R ³ ′ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R ³ ′ is connected to R ³ together with a nitrogen atom. Forming a ring).
n represents an integer of 1 to 10. When n is an integer of 2 to 10, the plurality of R ⁴ and R ⁵ may be the same or different. )
[2] The photopolymerization initiator according to the above [1], represented by the following general formula (Ia):

(Wherein R ¹ to R ¹¹ are each independently a hydrogen atom, a halogen 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 an 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, substituted or Unsubstituted alkenyloxy group having 2-20 carbon atoms, substituted or unsubstituted alkanoyl group having 1-20 carbon atoms, substituted or unsubstituted alkenoyl group having 2-20 carbon atoms, substituted or unsubstituted ring carbon atoms 6 .R ³ that an aryl group or a substituted or unsubstituted heterocyclic group ring atoms 3 to 14 of to 14, to form a ring together with R ⁴ or R ⁵ Good .R ⁴ may form a ring together with R ^5.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
n represents an integer of 1 to 10. When n is an integer of 2 to 10, the plurality of R ⁴ and R ⁵ may be the same or different. )
[3] In the general formula (Ia), R ¹ , R ² and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, n is 2, 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 aryl group having 6 to 14 ring carbon atoms. The photopolymerization initiator according to [2] above.
[4] In the general formula (Ia), R ¹ , R ² and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, n is 2, Each of R ⁴ and R ⁵ independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and Ar represents a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms. The photopolymerization initiator according to [2] above.
[5] The photopolymerization initiator according to the above [3] or [4], which has a molecular weight of 515 or less.

[6] In the general formula (Ia), R ¹ and R ² are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ³ is a substituted or unsubstituted carbon number. A cycloalkyl group having 3 to 18; n is 2; and the 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. ] The photoinitiator as described in.
[7] In the general formula (Ia), R ¹ and R ² are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ³ is 3 to 6 ring atoms. An alkyl group having 1 to 20 carbon atoms substituted with a cyclic ether group, n is 2, and a plurality of R ⁴ and R ⁵ are each independently a hydrogen atom or a substituted or unsubstituted carbon atom having 1 to 20 carbon atoms. The photopolymerization initiator according to [2], which is an alkyl group of
[8] The photopolymerization initiator according to the above [6] or [7], which has a molecular weight of 550 or less.
[9] The photopolymerization initiator according to [1], which is represented by the following general formula (Ib).

(Wherein R ¹ to R ¹¹ are each independently a hydrogen atom, a halogen 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 an 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, substituted or Unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted ring forming carbon number A 6 to 14 aryl group or a substituted or unsubstituted heterocyclic group having 3 to 14 ring atoms is shown.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
W represents a single bond or an oxygen atom. Z represents a single bond, an oxygen atom, or> NR ³ ′ (R ³ ′ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R ³ ′ is connected to R ³ together with a nitrogen atom. Forming a ring). )

[10] In the general formula (Ib), R ¹ and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, W is an oxygen atom, and Z is a single atom. The photopolymerization initiator according to [9] above, which is a bond or an oxygen atom, and Ar is a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms.
[11] Further, R ² represents —OCOR ¹³ (R ¹³ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 ring carbon atoms) or —COOR ²⁰ (R ²⁰ represents carbon The alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 14 ring carbon atoms). The photopolymerization according to the above [10], which is an alkyl group having 1 to 20 carbon atoms having an ester group represented by: Initiator.
[12] In the general formula (Ib), R ¹ and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, W is a single bond, and Z is> The photopolymerization according to the above [9], wherein NR ³ ′ (R ³ ′ is as defined above), and Ar is a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms. Initiator.
[13] Furthermore, R ² represents —OCOR ¹³ (R ¹³ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 ring carbon atoms) or —COOR ²⁰ (R ²⁰ represents carbon The photopolymerization according to the above [12], which is an alkyl group having 1 to 20 carbon atoms or an ester group having an ester group represented by: Initiator.
[14] A photocurable composition comprising a binder resin and / or a compound having an ethylenically unsaturated bond, and the photopolymerization initiator according to any one of [1] to [13].
[15] The photocurable composition as described in [14] above, wherein the content of the photopolymerization initiator is 2 to 50% by mass with respect to the solid content of the photocurable composition.
[16] The photocurable composition according to the above [14] or [15], further containing a coloring material.
[17] Any of [14] to [16] above, further containing 5 to 100 parts by mass of a compound having an ether bond and / or an ester bond at 25 ° C. with respect to 1 part by mass of the photopolymerization initiator The photocurable composition as described in 2. above.
[18] As the compound having an ethylenically unsaturated bond, at least one compound having an ethylenically unsaturated bond having an ether bond and / or an ester bond is used, and the solvent is only 10% by mass or less of the total amount of the photocurable composition. The photocurable composition according to any one of the above [14] to [16], which is contained.
[19] The photocurable composition according to any one of [16] to [18], which is used for a color filter.
[20] A color filter using the photocurable composition according to any one of [16] to [18].
[21] A liquid crystal display device comprising the color filter according to [20], a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate.
[22] A pattern forming method comprising applying the photocurable composition according to any one of [16] to [18] to a substrate, drying the substrate, exposing the substrate using a photomask, and then developing the pattern. .
[23] The following general formula (1)

(Wherein R ⁶ to R ¹¹ are each independently a hydrogen atom, a halogen 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 an 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, substituted or Unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted ring forming carbon number Represents a 6 to 14 aryl group or a substituted or unsubstituted heterocyclic group having 3 to 14 ring atoms.)
A carbazole derivative represented by the following general formula (2a)

Wherein R ³ , R ⁴ ′ and R ⁵ ′ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number 2 to 20 Alkenyl group, substituted or unsubstituted cycloalkyl group having 3 to 10 ring atoms, substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, hydroxyl group, substituted or unsubstituted 1 to 20 carbon atoms Alkoxy group, substituted or unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted .R ³ showing a heterocyclic group having ring carbon atoms of 6 to 14 aryl group or a substituted or unsubstituted ring atoms from 3 to 14, to form a ring together with R ⁵ ' And it may be.)
Is reacted with an acrylate derivative represented by the following general formula (3a ′):

(Wherein R ³ , R ⁴ ′, R ⁵ ′ and R ⁶ to R ¹¹ are as defined above.)
A carbonylalkyl group-introduced product represented by the following general formula (4), (5)

(Wherein X represents a halogen atom or —OC (═O) Ar, and X ′ represents a halogen atom or —OC (═O) R ² .
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
R ² represents a hydrogen atom, a halogen 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, a substituted or unsubstituted ring atom having 3 to 10 ring atoms. A cycloalkyl group, 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 having 2 to 20 carbon atoms Group, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, or substituted or unsubstituted And a heterocyclic group having 3 to 14 ring atoms. )
Is reacted in the presence of a Lewis acid to give the following general formula (6a ′):

(Wherein R ² , R ³ , R ⁴ ′, R ⁵ ′, R ⁶ to R ¹¹ and Ar are as defined above.)
A diketone product represented by the following general formula (7a ′) is obtained by reacting the resulting diketone product with hydroxylamine.

(Wherein R ² , R ³ , R ⁴ ′, R ⁵ ′, R ⁶ to R ¹¹ and Ar are as defined above.)
The oxime body represented by the following formula (8)

Wherein Y represents a halogen atom or —OC (═O) R ¹ .
R ¹ represents a hydrogen atom, a halogen 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, a substituted or unsubstituted ring-forming atom number of 3 -10 cycloalkyl group, substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, hydroxyl group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted 2 to 20 carbon atoms An alkenyloxy group, a substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, An unsubstituted heterocyclic group having 3 to 14 ring atoms is shown. )
By reacting with an esterifying agent represented by the following general formula (I-a1)

(Wherein R ¹ to R ³ , R ⁴ ′, R ⁵ ′, R ⁶ to R ¹¹ and Ar are as defined above.)
The manufacturing method of the photoinitiator represented by these.

The photopolymerization initiator of the present invention has a very high sensitivity to light (especially light having a short wavelength of 450 nm or less, for example, light having a wavelength of 365 nm or 405 nm), and thus can be thinned. A high-quality pattern can be formed at low cost. Furthermore, a compound having an ethylenically unsaturated double bond, a compatibility with a liquid compound at 25 ° C. having an ether bond and / or an ester bond, and a solvent (at 25 ° C. having an ether bond and / or an ester bond as described above) It is possible to prepare a solvent-free photocurable composition because of its high solubility in liquid compounds.) In the photocurable composition for color filters, the amount of photopolymerization initiator added As a result, sensitivity, resolution, developability and deep part curability are improved.
Conventionally, the solubility in a solvent has been enhanced while increasing the molecular weight by adding various substituents to the photopolymerization initiator. However, the photopolymerization initiator of the present invention has a relatively small molecular weight and is photocurable. The amount added to the composition can be reduced, and the compatibility with a compound having an ethylenically unsaturated double bond, an ether bond and / or an ester bond at 25 ° C., which is higher than that of a conventional photopolymerization initiator, And a solvent (including a compound that is liquid at 25 ° C. having the ether bond and / or ester bond described above), and is excellent in sensitivity, resolution, developability, and adhesion to a substrate.

It is a schematic diagram which shows the liquid crystal display device of this invention.

[Photopolymerization initiator]
The photopolymerization initiator of the present invention is represented by the following general formula (I).

(Wherein R ¹ to R ¹¹ are each independently a hydrogen atom, a halogen 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 an 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, substituted or Unsubstituted alkenyloxy group having 2-20 carbon atoms, substituted or unsubstituted alkanoyl group having 1-20 carbon atoms, substituted or unsubstituted alkenoyl group having 2-20 carbon atoms, substituted or unsubstituted ring carbon atoms 6 .R ³ that an aryl group or a substituted or unsubstituted heterocyclic group ring atoms 3 to 14 of to 14, to form a ring together with R ⁴ or R ⁵ Good .R ⁴ may form a ring together with R ^5.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
W represents a single bond or an oxygen atom. Z represents a single bond, an oxygen atom, or> NR ³ ′ (R ³ ′ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R ³ ′ is connected to R ³ together with a nitrogen atom. Forming a ring).
n represents an integer of 1 to 10. When n is an integer of 2 to 10, the plurality of R ⁴ and R ⁵ may be the same or different. )

Among the photopolymerization initiators of the present invention represented by the general formula (I), from the viewpoint of the effect of the present invention, a photopolymerization initiator represented by the following general formula (Ia) (W: single bond) , Z: corresponding to an oxygen atom) and a photopolymerization initiator represented by the following general formula (Ib) (corresponding to the case where n is 1) are preferred.

In the above formula, R ¹ to R ¹¹ are each independently a hydrogen atom, a halogen 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, a substituted group Or an 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, substituted or Unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted aryl having 6 to 14 ring carbon atoms And a substituted or unsubstituted heterocyclic group having 3 to 14 ring atoms. In the general formula (I-a), R ³ together with R ⁴ or R ⁵ may form a ring, also, R ⁴ is a ring together with R ⁵ It may be formed.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
W in the general formula (Ib) represents a single bond or an oxygen atom. In general formula (Ib), Z represents a single bond, an oxygen atom, or> NR ³ ′ (R ³ ′ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R ³ 'Is connected to R ³ to form a ring with the nitrogen atom.
N in the general formula (Ia) represents an integer of 1 to 10. When n is an integer of 2 to 10, the plurality of R ⁴ and R ⁵ may be the same or different.

(Regarding each group in general formulas (I), (Ia) and (Ib))
n represents a low molecular weight, is compatible with a compound having an ethylenically unsaturated double bond (hereinafter simply referred to as “compatible”), and is soluble in a solvent (hereinafter simply referred to as “soluble”). In view of the above and the ease of production, an integer of 2 to 8 is preferable, an integer of 2 to 4 is more preferable, and 2 is more preferable.
Examples of the halogen atom independently represented by R ¹ to R ¹¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The alkyl group having 1 to 20 carbon atoms independently represented by R ¹ to R ¹¹ may be linear or branched, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl Group, isobutyl group, t-butyl group, n-pentyl group, isopentyl group, n-hexyl group, n-octyl group, 2-ethyl-n-octyl group, n-decyl group, n-dodecyl group and the like. . Among these, an alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable from the viewpoint of low molecular weight, compatibility and solubility, and ease of production.
The alkenyl group having 2 to 20 carbon atoms independently represented by R ¹ to R ¹¹ may be linear or branched, and examples thereof include a vinyl group, an allyl group, and a 7-octenyl group. Among these, an alkenyl group having 2 to 10 carbon atoms is preferred, and an alkenyl group having 2 to 6 carbon atoms is more preferred from the viewpoint of low molecular weight, compatibility and solubility, and ease of production.
Examples of the cycloalkyl group having 3 to 10 ring atoms independently represented by R ¹ to R ¹¹ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Among these, a cycloalkyl group having 3 to 6 ring atoms is preferable from the viewpoint of low molecular weight, compatibility and solubility, and ease of production.
Examples of the C 4-20 cycloalkenyl group independently represented by R ¹ to R ¹¹ include a cyclopentenyl group, a cyclohexenyl group, a cyclohexadienyl group, a cyclooctenyl group, and the like. Among these, a cycloalkenyl group having 4 to 10 carbon atoms is preferable, and a cycloalkenyl group having 4 to 6 carbon atoms is more preferable from the viewpoint of low molecular weight, compatibility and solubility, and ease of production.

Examples of the alkoxy group having 1 to 20 carbon atoms independently represented by R ¹ to R ¹¹ include those in which the alkyl group moiety is the aforementioned alkyl group having 1 to 20 carbon atoms. Among these, an alkoxy group having 1 to 10 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms is more preferable from the viewpoint of low molecular weight, compatibility and solubility, and ease of production.
Examples of the alkenyloxy group having 2 to 20 carbon atoms independently represented by R ¹ to R ¹¹ include those in which the alkenyl group moiety is the aforementioned alkenyl group having 2 to 20 carbon atoms. Among these, an alkenyloxy group having 2 to 10 carbon atoms is preferred, and an alkenyloxy group having 2 to 6 carbon atoms is more preferred from the viewpoint of low molecular weight, compatibility and solubility, and ease of production.
The alkanoyl group having 1 to 20 carbon atoms independently represented by R ¹ to R ¹¹ may be linear or branched. For example, methanoyl group, ethanoyl group, n-propanoyl group, isopropanoyl group, n -Butanoyl group, t-butanoyl group, n-hexanoyl group, n-octanoyl group, n-decanoyl group, n-dodecanoyl group and the like. Among these, an alkanoyl group having 1 to 10 carbon atoms is preferable, and an alkanoyl group having 1 to 5 carbon atoms is more preferable from the viewpoint of low molecular weight, compatibility and solubility, and ease of production.
The alkenoyl group having 2 to 20 carbon atoms independently represented by R ¹ to R ¹¹ may be linear or branched. For example, ethenoyl group, n-propenoyl group, isopropenoyl group, n-butenoyl group, t -Butenoyl group, n-hexenoyl group, n-octenoyl group, n-decenoyl group, n-dodecenoyl group and the like. Among these, an alkenoyl group having 2 to 10 carbon atoms is preferred, and an alkenoyl group having 2 to 6 carbon atoms is more preferred from the viewpoint of low molecular weight, compatibility and solubility, and ease of production.

Examples of the aryl group having 6 to 14 ring carbon atoms independently represented by R ¹ to R ¹¹ include a phenyl group, a naphthyl group, and an anthryl group.
Examples of the heterocyclic group having 3 to 14 ring atoms independently represented by R ¹ to R ¹¹ include a 2-furanyl group, a 2-thiophenyl group, a 2-pyridinyl group, and the following formula (A): Group (hereinafter referred to as substituent (A))

An unsaturated heterocyclic group having 5 to 14 ring atoms such as 2-tetrahydrofuryl group, 3-tetrahydrofuryl group, pyrrolidinyl group, piperidinyl group, 2,2,6,6-trimethylpiperidin-4-yl group, etc. And a saturated heterocyclic group having 3 to 10 ring atoms. Among these, from the viewpoints of low molecular weight, compatibility and solubility, and ease of production, unsaturated heterocyclic groups having 5 to 6 ring atoms and saturated heterocyclic rings having 3 to 6 ring atoms are preferable. Groups are preferred.

The above-mentioned “R ³ and R ⁴ or R ⁵ together form a ring” means that n = 2, W is a single bond and Z is an oxygen atom. The ring illustrated in the right side and exemplified on the right side is given as a specific example.

Examples of the ring formed by combining R ⁴ and R ⁵ include rings having 3 to 10 (preferably 3 to 6) ring-forming carbon atoms such as a cyclopentyl ring and a cyclooctyl ring.

The alkyl group, alkenyl group, cycloalkyl group, cycloalkenyl group, alkoxy group, alkenyloxy group, alkanoyl group, alkenoyl group, aryl group and heterocyclic group, each independently represented by R ¹ to R ¹¹ , It may have a substituent.
Examples of the substituent for the alkyl group and alkenyl group independently represented by R ¹ to R ¹¹ include a hydroxyl group; a carboxyl group; a straight-chain or branched-chain carbon atom such as a methoxy group, an ethoxy group, and a propoxy group. 18 (preferably 1-10, more preferably 1-5) alkoxy group; linear or branched alkenyloxy group having 2-18 (preferably 2-10, more preferably 2-6) carbon atoms Linear or branched alkenylthio group having 2 to 18 carbon atoms (preferably 2 to 10 and more preferably 2 to 6); linear or branched carbon atom number 1 to 18 (preferably 1) -10, more preferably 1-5) alkylthio group; C5-C18 cycloalkenyl group (preferably 5-10); C3-C18 (preferably cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.) Or a cycloalkyl group having 3 to 10, more preferably 3 to 6) an aryloxy group having 6 to 10 ring carbon atoms such as a phenoxy group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom; Oxygen atom (= O); sulfur atom (= S); cyano group; nitro group; trialkylsilyl group such as trimethylsilyl group; trialkoxysilyl group such as trimethoxysilyl group; phenyl group, naphthyl group, anthryl group, etc. -COR ¹² ; -OCOR ¹³ ; -NR ¹⁴ R ¹⁵ ; -NHCOR ¹⁶ ; -NHCOOR ¹⁷ ; -CONR ¹⁸ R ¹⁹ ; -COOR ²⁰ ; _{^{^{-SO 3 NR 21 R 22; -SO}}} 3 R 23; epoxy group and tetrahydronaphthyl ring atoms 3-6 cyclic ether groups such as furanyl group, 2-thienyl, 2-pyridyl Group, a furyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, a saturated or unsaturated heterocyclic group having 3 to 10 (preferably 3 to 6) ring atoms such as the substituent (A), and the like. .
In the above general formula, R ¹² to R ²³ each independently represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 ring carbon atoms. Examples of the alkyl group and aryl group are the same as those for R ¹ to R ¹¹ .

Examples of the substituent of the alkoxy group, alkenyloxy group, alkanoyl group, and alkenoyl group independently represented by R ¹ to R ¹¹ include a hydroxyl group; a carboxyl group; a linear or branched group such as a methoxy group, an ethoxy group, and a propoxy group A linear alkoxy group having 1 to 18 carbon atoms (preferably 1 to 10, more preferably 1 to 5); a linear or branched carbon group having 2 to 18 carbon atoms (preferably 2 to 10 carbon atoms, more preferably 2 carbon atoms) To 6) alkenyloxy group; linear or branched alkenylthio group having 2 to 18 carbon atoms (preferably 2 to 10, more preferably 2 to 6); linear or branched carbon number An alkylthio group having 1 to 18 (preferably 1 to 10, more preferably 1 to 5); a cycloalkenyl group having 5 to 18 carbon atoms (preferably 5 to 10); a cyclopropyl group, a cyclopentyl group A cycloalkyl group having 3 to 18 carbon atoms (preferably 3 to 10, more preferably 3 to 6) such as a cyclohexyl group; an aryloxy group having 6 to 10 ring carbon atoms such as a phenoxy group; a fluorine atom, a chlorine atom, Halogen atoms such as bromine atom and iodine atom; oxygen atom (= O); sulfur atom (= S); cyano group; nitro group; trialkylsilyl group such as trimethylsilyl group; trialkoxysilyl group such as trimethoxysilyl group; An aryl group having 6 to 14 (preferably 6 to 10) ring carbon atoms such as a phenyl group, a naphthyl group and an anthryl group; —COR ¹² ; —OCOR ¹³ ; —NR ¹⁴ R ¹⁵ ; —NHCOR ¹⁶ ; —NHCOOR ¹⁷ ; -CONR ¹⁸ R ^19; -COOR ^20; ring-forming atoms of 3 to 6 such as an epoxy group or a tetrahydrofuranyl _{^{^{group; -SO 3 NR 21 R 22;}}} -SO 3 R 23 Number of saturated or unsaturated ring-forming atoms such as an ether group, 2-thienyl group, 2-pyridyl group, furyl group, thiazolyl group, benzothiazolyl group, morpholino group, and the substituent (A) (preferably 3 To 6) and the like (wherein R ¹² to R ²³ are as defined above).

Examples of the substituent for the cycloalkyl group or cycloalkenyl group independently represented by R ¹ to R ¹¹ include a hydroxyl group; a carboxyl group; a linear or branched carbon number of 1 to 18 such as a methyl group or an ethyl group (preferably Is an alkyl group of 1 to 10, more preferably 1 to 5; linear or branched carbon number of 1 to 18 (preferably 1 to 10, more preferably 1) such as methoxy group, ethoxy group, propoxy group, etc. To 5) alkoxy group; linear or branched alkenyloxy group having 2 to 18 carbon atoms (preferably 2 to 10 and more preferably 2 to 6); linear or branched carbon number 2 -18 (preferably 2 to 10, more preferably 2 to 6) alkenylthio group; straight chain having 2 to 18 carbon atoms (preferably 2 to 10, more preferably 2 to 6) such as vinyl group and allyl group Or branched alkeni A linear or branched alkylthio group having 1 to 18 (preferably 1 to 10, more preferably 1 to 5) carbon atoms; a cycloalkenyl group having 5 to 18 (preferably 5 to 10) carbon atoms; Aryloxy group having 6 to 10 ring carbon atoms such as phenoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; oxygen atom (= O); sulfur atom (= S); cyano group; A trialkylsilyl group such as a trimethylsilyl group; a trialkoxysilyl group such as a trimethoxysilyl group; an aryl group having 6 to 14 (preferably 6 to 10) ring-forming carbon atoms such as a phenyl group, a naphthyl group, and an anthryl group; ^{^{^{-COR 12; -OCOR 13; -NR 14}}} R 15; -NHCOR 16; -NHCOOR 17; -CONR 18 R 19; -COOR 20; -SO 3 NR 21 R 22; -SO 3 R 23 A cyclic ether group having 3 to 6 ring atoms such as an epoxy group and a tetrahydrofuranyl group, a 2-thienyl group, a 2-pyridyl group, a furyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, the substituent (A), etc. Examples thereof include a saturated or unsaturated heterocyclic group having 3 to 10 (preferably 3 to 6) ring-forming atoms (wherein R ¹² to R ²³ are as defined above).

The substituents of the aryl group and heterocyclic group which R ¹ to R ¹¹ each independently represent include a hydroxyl group, a carboxyl group, a straight chain or branched chain having 1 to 18 carbon atoms (preferably a methyl group, an ethyl group, etc.) (preferably An alkyl group having 1 to 10, more preferably 1 to 5; a linear or branched carbon number of 1 to 18 (preferably 1 to 10, more preferably 1 to 1) such as a methoxy group, an ethoxy group, or a propoxy group 5) an alkoxy group; a linear or branched alkenyloxy group having 2 to 18 carbon atoms (preferably 2 to 10, more preferably 2 to 6); a linear or branched carbon number 2 to 18 (preferably 2 to 10, more preferably 2 to 6) alkenylthio group; linear or branched alkylthio group having 1 to 18 carbon atoms (preferably 1 to 10, more preferably 1 to 5) ; Straight of vinyl group, allyl group, etc. Or a branched alkenyl group having 2 to 18 (preferably 2 to 10, more preferably 2 to 6) carbon atoms; a cycloalkenyl group having 5 to 18 (preferably 5 to 10) carbon atoms; a cyclopropyl group, A cycloalkyl group having 3 to 18 carbon atoms (preferably 3 to 10, more preferably 3 to 6) such as a cyclopentyl group and a cyclohexyl group; an aryloxy group having 6 to 10 ring carbon atoms such as a phenoxy group; a fluorine atom; trialkoxysilyl group such as trimethoxysilyl group; a trialkylsilyl group such as trimethylsilyl group; a cyano group; a nitro group chlorine atom, a bromine atom, a halogen atom such as iodine atom -COR ^12; -OCOR ^13; -NR ¹⁴ ^{^{^{R 15; -NHCOR 16; -NHCOOR 17}}} ; -CONR 18 R 19; -COOR 20; -SO 3 NR 21 R 22; -SO 3 R 23; epoxy A saturated ether such as a cyclic ether group having 3 to 6 ring-forming atoms such as a group or a tetrahydrofuranyl group, a 2-thienyl group, a 2-pyridyl group, a furyl group, a thiazolyl group, a benzothiazolyl group, a morpholino group, or the substituent (A). Alternatively, an unsaturated heterocyclic group having 3 to 10 (preferably 3 to 6) ring-forming atoms can be used (wherein R ¹² to R ²³ are as defined above).

Examples of the aryl group having 6 to 14 ring carbon atoms represented by Ar include a phenyl group, a naphthyl group, an anthryl group, a chrycenyl group, a phenanthrenyl group, an azulenyl group, and an acenaphthylenyl group. Among these, an aryl group having 6 to 10 ring carbon atoms is preferred, and a phenyl group is more preferred from the viewpoint of low molecular weight, compatibility and solubility, and ease of production. Examples of the heteroaryl group having 5 to 14 ring atoms represented by Ar include a 2-furanyl group, a 2-thiophenyl group, and a 2-pyridinyl group. Among these, from the viewpoint of low molecular weight, compatibility and solubility, and ease of production, a heteroaryl group having 5 to 6 ring atoms is preferable, and a 2-furanyl group and a 2-thiophenyl group are more preferable. preferable.
These aryl groups and heteroaryl groups may have a substituent. Examples of the substituent include the same substituents as the aryl group independently represented by R ¹ to R ¹¹ described above, and among them, the number of carbon atoms is 1 to 18 (preferably 1 to 10, more preferably The alkyl group of 1 to 5) is preferable, and a methyl group is more preferable.
In addition, when this substituent is an alkyl group or an alkenyl group, it may form a condensed ring with Ar, for example, a fluorene ring, an indene ring, or the like.

Z represents>'R ³ in' NR ^3, as described above, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R ³ 'is connected to the R ^3, ring together with the nitrogen atom Is forming.
Examples of the alkyl group having 1 to 20 carbon atoms include the same as those in the case of R ¹ to R ¹¹ , and preferable examples thereof are the same, and a methyl group is particularly preferable.
Specific examples of the ring formed by R ³ ′ connecting to R ³ together with the nitrogen atom include a morpholine ring, a pyrrolidine ring, a piperidine ring, a pipecoline ring, and a piperazine ring. Among these, a morpholine ring is preferable.
As a combination of W and Z, when W is a single bond, Z is preferably an oxygen atom or> Nr ³ ′, and when W is an oxygen atom, Z is preferably a single bond or an oxygen atom.

Further, in the general formula (Ia), (a) R ¹ , R ² and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, n is 2, 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 aryl group having 6 to 14 ring carbon atoms. (B) R ¹ , R ² and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, n 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 heteroaryl group having 5 to 14 ring carbon atoms. polymerization initiator, is (c) R ¹ and R ^2, each independently, location Or an alkyl group unsubstituted carbon atoms 1 ~ 20, R ³ is a substituted or unsubstituted cycloalkyl group having a carbon 3 ~ 18, n is 2, a plurality of R ⁴ and R ^5, Each independently a photopolymerization initiator which is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, (d) R ¹ and R ² are each independently substituted or unsubstituted carbon atoms having 1 to 20 alkyl groups, R ³ is an alkyl group having 1 to 20 carbon atoms substituted with a cyclic ether group having 3 to 6 ring atoms, n is 2, and a plurality of R ⁴ and R ⁵ are Independently, a photopolymerization initiator which is a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms is also preferable. Furthermore, from the viewpoint of reducing the content of the photopolymerization initiator in the photocurable composition to be described later, in the case of (a) and (b), the molecular weight is preferably 515 or less, and 500 or less. More preferably, in the case of the above (c) and (d), the molecular weight is preferably 550 or less.
Further, from the viewpoint of the effect of the present invention and from the viewpoint of reducing contamination of the polymer due to the decomposition product of the photopolymerization initiator and contamination of the apparatus, in the above preferable photopolymerization initiator, R ⁴ to R ¹¹ are each independently More preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. In addition, the preferable thing of each group is as having mentioned above.
Specific examples of the photopolymerization initiator (Ia) of the present invention are shown below, but are not particularly limited thereto.

Further, in the general formula (Ib), (e) R ¹ and R ³ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, W is an oxygen atom, and Z is A single bond or an oxygen atom, and Ar is a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms; (f) R ¹ and R ³ are each independently substituted or unsubstituted. A substituted alkyl group having 1 to 20 carbon atoms, and R ² is —OCOR ¹³ (R ¹³ is as defined above) or —COOR ²⁰ (R ²⁰ is an alkyl group having 1 to 20 carbon atoms). Or an aryl group having 6 to 14 ring carbon atoms.) And an ester group having 1 to 20 carbon atoms, W is an oxygen atom, and Z is a single bond or an oxygen atom. , Ar is a substituted or unsubstituted aryl having 6 to 14 ring carbon atoms Photoinitiator is a group, (g) R ¹ and R ³ are each independently a substituted or unsubstituted alkyl group having a carbon number of 1 ~ 20, W is a single bond, Z is> NR ³ (R ³ 'is as defined above), and Ar is a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, (h) R ¹ and R ³ is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ² is —OCOR ¹³ (R ¹³ is as defined above) or —COOR ²⁰ (R ²⁰ Represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 ring carbon atoms.), And W is a single bond. , Z is> NR ^³ '(R ^3', the are as defined.) and, Ar is a substituted if Photoinitiator is unsubstituted ring aryl group having 6 ~ 14, (i) R 1 is a substituted or unsubstituted alkyl group having a carbon number of 1 ~ 20, R ³ is a hydrogen atom Also preferred are photopolymerization initiators in which W is a single bond, Z is an oxygen atom, and Ar is a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms.
In the above photopolymerization initiator (g), R ³ ′ in> NR ³ ′ is preferably connected to R ³ to form a ring with a nitrogen atom, and forms a morpholine ring. Is more preferable.
Further, from the viewpoint of the effect of the present invention and from the viewpoint of reducing contamination of the polymer due to the decomposition product of the photopolymerization initiator and contamination of the apparatus, in the above preferable photopolymerization initiator, R ⁴ to R ¹¹ are each independently More preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. In addition, the preferable thing of each group is as having mentioned above.
Specific examples of the photopolymerization initiator (Ib) of the present invention are shown below, but are not particularly limited thereto.

The photopolymerization initiator of the present invention is preferably n = 2 in the general formula (Ia) as described above, and specifically, photopolymerization represented by the following general formula (Ia1) Initiators are preferred.

In the above formula (I-a1), R ¹ to R ³ , R ⁶ to R ¹¹ and Ar are as defined above. R ⁴ ′ and R ⁵ ′ have the same definitions as R ⁴ and R ⁵ , respectively, and preferred ones are also the same.

[Method for producing photopolymerization initiator]
The method for producing the photopolymerization initiator (I) of the present invention is not particularly limited. It can be manufactured easily.
(1. Method for producing photopolymerization initiator (Ia))
The method for producing the photopolymerization initiator (Ia) of the present invention is not particularly limited, but can be easily produced by, for example, the following steps 1 to 4.

(Process 1)
Step 1 includes, for example, the carbazole derivative (1) and Z (CR ⁴ R ⁵ ) _n COOR ³ (Z represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. R ³ , R ⁴ and R ⁵ are as defined above), and a step of reacting with a halide represented by By this step, a carbonylalkyl group-introduced product represented by the following general formula (3a) is obtained.

(Wherein R ³ to R ¹¹ are as defined above, and preferred ones are also the same).
Examples of the base include n-butyl lithium, t-butyl lithium, sodium hydroxide, potassium hydroxide and the like. The reaction temperature is usually preferably 0 to 200 ° C., and the reaction time is usually preferably 2 to 100 hours.

In the case of producing a photopolymerization initiator with n = 2 in the general formula (Ia), it is preferable that Step 1 is the following step because production is easy.
The following general formula (1)

(Wherein R ⁶ to R ¹¹ are as defined above, and preferred ones are also the same.)
[Hereinafter referred to as a carbazole derivative (1). And the following general formula (2a)

(In the formula, R ³ , R ⁴ ′ and R ⁵ ′ are as defined above, and preferred ones are also the same.)
An acrylate derivative represented by the formula [hereinafter referred to as an acrylate derivative (2a). And in the presence of a base, the following general formula (3a ′)

(In the formula, R ³ , R ⁴ ′, R ⁵ ′ and R ⁶ to R ¹¹ are as defined above, and preferred ones are also the same.)
Embedded image [hereinafter referred to as a carbonylalkyl group-introduced product (3a ′)]. The process of obtaining.
Hereinafter, this step 1 which is preferable when producing a photopolymerization initiator of n = 2 will be described in detail.

The amount of the acrylate derivative (2a) used in Step 1 is not particularly limited, but is preferably 0.5 to 2 mol, more preferably 0.8 to 1.2, relative to 1 mol of the carbazole derivative (1). From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially equal amounts.
Step 1 is performed in the presence of a base. The base may be any base that can be used for the Michael addition reaction, and any of organic bases and inorganic bases can be used. Examples of the organic base include pyridine, diazabicycloundecene (DBU), diazabicyclononene (DBN), and the like. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; sodium hydroxide And alkali metal hydroxides such as potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide. Among these, alkali metal carbonates and alkaline earth metal carbonates are preferable, alkali metal carbonates are more preferable, and potassium carbonate is more preferable.
The amount of the base to be used is not particularly limited, but from the viewpoint of reaction efficiency and production cost, it is preferably 0.5 to 2 mol, more preferably 0.8 to 1. mol per mol of the carbazole derivative (1). More preferably, it is 2 moles and is used in an approximately equal amount.
Step 1 is preferably performed in the presence of a solvent. What is necessary is just to select suitably the solvent which can melt | dissolve a carbazole derivative (1), an acrylate derivative (2a), and a base as this solvent. Specific examples include dimethylformamide (DMF), dimethylsulfoxide (DMSO), methylene chloride and the like.

The reaction temperature in step 1 is not particularly limited, but is usually preferably 10 to 50 ° C, more preferably 15 to 40 ° C, and further preferably 15 to 30 ° C. The reaction time varies depending on the type and amount of the carbazole derivative (1), acrylate derivative (2a) and base, the reaction temperature, etc., but is usually about 2 to 48 hours.
The embodiment of Step 1 is not particularly limited, and for example, the carbazole derivative (1), the acrylate derivative (2a), and the base are all added to the solvent, and preferably stirred at the above temperature to thereby introduce the carbonylalkyl group-introduced compound (3a ') Can get.

After completion of the reaction, the carbonylalkyl group-introduced product (3a) or (3a ′) can be obtained from the obtained reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the carbonylalkyl group-introduced product (3a) or (3a ′) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

Hereinafter, Steps 2 to 4 using the carbonylalkyl group-introduced body (3a) or (3a ′) obtained in Step 1 will be described. For convenience, the carbonylalkyl group-introduced body (3a ′) corresponding to n = 2 Will be omitted.
(Process 2)
In step 2, the carbonylalkyl group-introduced product (3a) obtained in step 1 and the following general formulas (4) and (5)

(Wherein X represents a halogen atom or —OC (═O) Ar, and X ′ represents a halogen atom or —OC (═O) R ^2. Ar and R ² are as defined above. The preferred ones are also the same.)
These are referred to as acylating agent (4) and acylating agent (5), respectively. In the presence of a Lewis acid, the following general formula (6a)

(Wherein R ² to R ¹¹ and Ar are as defined above, and preferred ones are also the same).
[Hereinafter referred to as diketone body (6a). ] Is a step of obtaining.

In the above formula, examples of the halogen atom independently represented by X and X ′ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferred.
In Step 2, the reaction between the carbonylalkyl group-introduced product (3a) and the acylating agents (4) and (5) is carried out from the viewpoint of the yield of the desired diketone product (6a). It is preferable to react the acylating agent (5) after reacting 3a) with the acylating agent (4).
The amount of the acylating agents (4) and (5) used is from the viewpoint of introducing one acyl group into the carbonylalkyl group-introduced product (3a), and 1 mol of the carbonylalkyl group-introduced product (3a). Each of these is preferably 0.8 to 1.3 mol, more preferably 1 to 1.3 mol, and from the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially equal amounts. In particular, when the carbonylalkyl group-introduced product (3a) and the acylating agent (4) are reacted and then the acylating agent (5) is reacted, the amount of the acylating agent (5) used is as described above. If it exceeds the range, there is no problem, but if it is too much, the yield corresponding to it is not obtained, and the production cost can be unnecessarily high.
Step 2 is performed in the presence of a Lewis acid. As the Lewis acid, aluminum chloride and boron trifluoride diethyl ether complex are preferable. The amount of Lewis acid used is usually preferably from 0.8 to 2.5 mol, more preferably from 1 mol of the acylating agent (4) or (5) from the viewpoint of the yield of the diketone body (6a). Is 1 to 2 moles.

Step 2 is preferably performed in the presence of a solvent. The solvent is not particularly limited as long as it is a solvent that can be used in a normal Friedel-Crafts acylation reaction. Specific examples include dichloromethane, nitrobenzene, acetone, acetonitrile and the like.
The reaction temperature in step 2 is preferably −50 to 5 ° C. (preferably −10 to 5 ° C.) at the start of the reaction, and gradually returned to room temperature (about 15 to 25 ° C.) as the reaction proceeds. The reaction time varies depending on the type and amount of the carbonylalkyl group-introduced product (3a), acylating agents (4) and (5), and the reaction temperature, but is usually preferably 1 to 30 hours. When both of the acylating agents (4) and (5) are acyl halides or acid anhydrides, the product is obtained after reacting the carbonylalkyl group-introduced product (3a) with the acylating agent (4). Can be subsequently reacted with the acylating agent (5) without isolation. In this case, the reaction time of the carbonylalkyl group-introduced product (3a) and the acylating agent (4) is about 30 minutes to 5 hours (preferably 30 minutes to 3 hours), while the carbonylalkyl group-introduced product (3a ) And the acylating agent (5) are preferably provided with a long reaction time of about 30 minutes to 24 hours (preferably 30 minutes to 18 hours) for sufficient reaction.

From the viewpoint of yield, two preferred embodiments of Step 2 are described below.
[1] The carbonyl alkyl group-introduced product (3a) and the acylating agent (4) are appropriately mixed in a solvent while cooling in an ice bath, and the Lewis acid is slowly added to the mixed solution (preferably 5 minutes to 1 hour, more (Preferably over 10 minutes to 40 minutes) After the addition, the mixture is returned to room temperature and stirring is continued for a certain time (about 30 minutes to 5 hours). Preferably, the product is once separated and obtained by performing usual organic compound separation means such as extraction and washing.
The product thus obtained is appropriately dissolved in a solvent, acylating agent (5) is added while cooling in an ice bath, and Lewis acid is slowly added thereto (preferably 5 minutes to 1 hour, more preferably 10 minutes to (Over 40 minutes), and after completion of the addition, the mixture is returned to room temperature and stirred for a certain time (about 30 minutes to 24 hours) to obtain the diketone body (6a).
[2] The carbonyl alkyl group-introduced product (3a) is appropriately mixed with a solvent while cooling in an ice bath, and then the Lewis acid is slowly added (preferably 5 minutes to 1 hour, more preferably 10 minutes to 40 minutes). The acylating agent (4) is added slowly (preferably over 5 minutes to 1 hour, more preferably over 10 minutes to 40 minutes) to the resulting mixed solution, and then returned to room temperature for a certain time (30 minutes). Continue stirring for about 5 hours. The Lewis acid is added slowly (preferably over 5 minutes to 1 hour, more preferably over 10 minutes to 40 minutes) while cooling again in an ice bath, and the acylating agent (5) is added slowly (preferably over 10 minutes to 40 minutes). Is added for 5 minutes to 1 hour, more preferably over 10 minutes to 40 minutes, and after returning to room temperature, stirring is continued for a certain period of time (preferably about 30 minutes to 24 hours), whereby the diketone body (6a) Can be obtained.
In addition, after completion | finish of reaction, diketone body (6a) can be obtained from the obtained reaction liquid mixture by the isolation | separation means of normal organic compounds, such as extraction. The purity of the diketone body (6a) can also be increased by appropriately purifying by a usual means for purifying organic compounds such as distillation, column chromatography, recrystallization and the like.

(Process 3)
Step 3 is a reaction of the diketone body (6a) obtained in Step 2 with hydroxylamine to give the following general formula (7a).

(Wherein R ² to R ¹¹ and Ar are as defined above, and preferred ones are also the same).
[Hereinafter referred to as the oxime body (7a). ] Is a step of obtaining.

In step 3, the hydroxylamine source is not particularly limited, but hydroxylamine chloride is preferred. The hydroxylamine chloride can be reacted with, for example, sodium acetate in water to obtain an aqueous solution of hydroxylamine.
The amount of hydroxylamine (hydroxylamine chloride) to be used is preferably 0.8 to 2 mol, more preferably 1 to 1.5 mol, still more preferably 1 to 1.3 mol, relative to 1 mol of the diketone body (6a). From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially the same amount.
Step 3 is preferably performed in the presence of a solvent. As the solvent, a water-soluble organic solvent is preferable, and as the water-soluble organic solvent, for example, alcohols such as methanol and ethanol, dimethylformamide (DMF) and the like are preferable.

The reaction temperature in step 3 is not particularly limited, but is usually preferably 40 to 160 ° C., more preferably 50 to 140 ° C., and still more preferably 70 to 110 ° C. from the viewpoint of the yield of the oxime (7a). is there. The reaction time varies depending on the type and amount of diketone (6a) and the reaction temperature, but is usually preferably 2 to 20 hours, more preferably 4 to 12 hours.
There is no particular limitation on the embodiment of Step 3, for example, hydroxylamine chloride and sodium acetate are mixed in water to obtain an aqueous solution of hydroxylamine, and a diketone (6a) and a solvent are added thereto. An oxime body (7a) can be obtained by stirring in the said temperature range.
After completion of the reaction, the oxime body (7a) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the oxime body (7a) can also be increased by appropriately purifying by a usual means for purifying organic compounds such as distillation, column chromatography, recrystallization and the like.

(Process 4)
Step 4 includes the oxime body (7a) obtained in Step 3 and the following general formula (8):

(In the formula, Y represents a halogen atom or —OC (═O) R ^1. R ¹ is as defined above, and preferred ones are also the same.)
The esterifying agent represented by the formula [hereinafter referred to as the esterifying agent (8). And the following general formula (Ia):

(Wherein R ¹ to R ¹¹ and Ar are as defined above.)
[Hereinafter referred to as photopolymerization initiator (Ia)]. ] Is a step of obtaining.

In the above formula, examples of the halogen atom represented by Y include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
Although there is no restriction | limiting in particular in the usage-amount of the esterifying agent (8) used at the process 4, Preferably it is 0.5-2 mol with respect to 1 mol of oxime bodies (7a), More preferably, it is 0.8-1. From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially the same amount.
Step 4 may be performed in the presence of a base to promote the reaction. Examples of the base include organic bases and inorganic bases. Examples of the organic base include amines such as triethylamine and tributylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate; alkaline earth metal carbonates such as magnesium carbonate; alkali metal hydroxides such as sodium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide Is mentioned. Among these, organic bases are preferable, amines and nitrogen-containing heterocyclic aromatic compounds are more preferable, and triethylamine and pyridine are more preferable from the viewpoint of reaction efficiency and production cost.
When a base is used, the amount used is preferably 1 to 5 moles, more preferably 1 mole relative to 1 mole of the oxime (7a), from the viewpoint of the yield of the photopolymerization initiator (Ia) and the production cost. Is 1.5 to 3 moles.

Step 4 is preferably performed in the presence of a solvent. Preferred examples of the solvent include ethers such as t-butyl methyl ether, ethyl methyl ether, cyclopentyl methyl ether, and tetrahydrofuran (THF).
The reaction temperature in step 4 is preferably −50 to 5 ° C. (preferably −10 to 5 ° C.) at the start of the reaction, and gradually returned to room temperature (about 15 to 25 ° C.) as the reaction proceeds. The reaction time varies depending on the type and amount of the oxime (7a) and esterifying agent (8), and the reaction temperature, but is usually preferably 0.5 to 10 hours, more preferably 1 to 5 hours. .
There is no restriction | limiting in particular in embodiment of process 4, For example, an oxime body (7a) and an esterifying agent (8) are mixed in a solvent suitably, a base is dripped there, and the temperature of a reaction liquid is made gradually after completion | finish of dripping. By returning to room temperature and continuing stirring, the photopolymerization initiator (Ia) of the present invention can be obtained.
After completion of the reaction, the photopolymerization initiator (Ia) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the photopolymerization initiator (Ia) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography or recrystallization.

The photopolymerization initiator (Ia) of the present invention thus obtained has a special substituent containing an ester group attached to the nitrogen atom in the carbazole skeleton. Therefore, compatibility with a compound having an ethylenically unsaturated bond in the photocurable composition (particularly a compound having a (meth) acryloyloxy group), a compound having an ether bond and / or an ester bond and liquid at 25 ° C., And a solvent (including a compound having an ether bond and / or ester bond and a liquid at 25 ° C.), high sensitivity to light (especially light having a short wavelength of 450 nm or less), resolution and development It is considered that the properties and the deep part curability are excellent, and the adhesion to the substrate is further improved. In addition, the photopolymerization initiator (Ia) is free from contamination of the polymer or apparatus due to decomposition products generated by light during exposure.
Note that the high compatibility and solubility of the photopolymerization initiator (Ia) with respect to the specific compound or solvent is considered to contribute to the improvement of sensitivity, resolution and developability, and thus deep curability. It can be said that this is an important factor in color filter applications. Particularly in color filter applications, the photopolymerization initiator is preferably dissolved in an amount of 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). More preferably, 10 parts by mass or more is dissolved, and the photopolymerization initiator (Ia) of the present invention satisfies such conditions, and is included in the photocurable composition for color filters, It is suitable as a photopolymerization initiator to be contained in a highly light-shielding photocurable composition for black matrix.

(1. Method for producing photopolymerization initiator (Ia))
The method for producing the photopolymerization initiator (Ib) of the present invention is not particularly limited, but can be easily produced by, for example, the following steps 1 to 4.

(Process 1)
Since the manufacturing method of Step 1 is different depending on W and Z, each case will be described below.
<When W is a single bond and Z is> NR ³ '>
The following general formula (1)

(Wherein R ⁶ to R ¹¹ are as defined above, and preferred ones are also the same.)
[Hereinafter referred to as a carbazole derivative (1). And the following general formula (2b)

(In the formula, R ³ , R ³ ′, R ⁴ and R ⁵ are as defined above, and preferred ones are also the same.)
[Hereinafter referred to as acrylamide derivative (2b). And in the presence of a base, the following general formula (3b)

(In the formula, R ³ , R ³ ′ and R ⁴ to R ¹¹ are as defined above, and preferred ones are also the same.)
[In the following, it is referred to as an amide group introduced product (3b). ] Is a step of obtaining.

The amount of the acrylamide derivative (2b) used in Step 1 is not particularly limited, but is preferably 0.5 to 2 mol, more preferably 0.8 to 1.2, relative to 1 mol of the carbazole derivative (1). From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially equal amounts.
Step 1 is performed in the presence of a base. As the base, a base that can be used in the Michael addition reaction can be used, and there is no particular limitation, and either an organic base or an inorganic base can be used. Examples of the organic base include pyridine, diazabicycloundecene (DBU), diazabicyclononene (DBN) and the like, and bases having low nucleophilicity are preferable, and DBU and DBN are more preferable. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; Examples include alkali metal hydroxides such as sodium and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide. Among these, alkali metal carbonates and alkaline earth metal carbonates are preferable, alkali metal carbonates are more preferable, and potassium carbonate is more preferable.
The amount of the base to be used is not particularly limited, but from the viewpoint of reaction efficiency and production cost, it is preferably 0.5 to 2 mol, more preferably 0.8 to 1. mol per mol of the carbazole derivative (1). More preferably, it is 2 moles and is used in an approximately equal amount.
Step 1 is preferably performed in the presence of a solvent. What is necessary is just to select suitably the solvent which can melt | dissolve a carbazole derivative (1), an acrylamide derivative (2b), and a base as this solvent. Specific examples include dimethylformamide (DMF), dimethylsulfoxide (DMSO), methylene chloride and the like.

The reaction temperature in step 1 is not particularly limited, but is usually preferably 10 to 50 ° C, more preferably 15 to 40 ° C, and further preferably 15 to 30 ° C. Although there is no restriction | limiting in particular in reaction pressure, Implementing under a normal pressure is preferable. The reaction time varies depending on the kind and amount of the carbazole derivative (1), acrylamide derivative (2b) and base, reaction temperature, reaction pressure, etc., but is usually preferably about 2 to 48 hours.
There is no restriction | limiting in particular in embodiment of process 1, For example, carbazole derivative (1), acrylamide derivative (2b), and a base are all added to a solvent, Preferably it is stirred at the said temperature, Amide group introduction body (3b) Can be manufactured.
After the completion of the reaction, the amide group-introduced product (3b) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the amide group-introduced product (3b) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

-Alternative method-
The following method can also be adopted for the production of the amide group-introduced product (3b).
The carbazole derivative (1) and the following general formula (2b ′)

(In the formula, R ⁴ and R ⁵ are as defined above. R ²⁴ represents an alkyl group having 1 to 5 carbon atoms.)
[Hereinafter referred to as a carboxylic acid group introducing agent (2b ′). ] In the presence of a base (first reaction)

(Wherein R ⁴ to R ¹¹ are as defined above, and preferred ones are also the same).
In the presence of thionyl chloride, for example, HNR ³ R ³ ′ (R ³ and R ³ ′ are as defined above, and preferred ones are also the same). This is a method for obtaining an amide group-introduced product (3b) by reacting with the amine to be reacted (second reaction). A commercial item can also be used as this amide group introduction | transduction body (3b).
Examples of the alkyl group having 1 to 5 carbon atoms represented by R ²⁴ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Among these, a methyl group and an ethyl group are preferable.

There is no restriction | limiting in particular as a base used by said 1st reaction, Both an organic base and an inorganic base can be used. Examples of the organic base include pyridine, diazabicycloundecene (DBU), diazabicyclononene (DBN) and the like, and bases having low nucleophilicity are preferable, and DBU and DBN are more preferable. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; Examples include alkali metal hydroxides such as sodium and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide. Among these, as the base, an inorganic base is preferable, and an alkali metal hydroxide is more preferable.
The amount of the base to be used is not particularly limited, but from the viewpoint of reaction efficiency and production cost, it is preferably 0.5 to 2 mol, more preferably 0.8 to 1. mol per mol of the carbazole derivative (1). More preferably, it is 2 moles and is used in an approximately equal amount.
The first reaction is preferably carried out in the presence of a solvent. As the solvent, a solvent capable of dissolving the carbazole derivative (1), the carboxylic acid group introducing agent (2b ′) and the base may be appropriately selected. Specific examples include dimethylformamide (DMF), dimethylsulfoxide (DMSO), methylene chloride and the like, with DMF being preferred.

The reaction temperature of the first reaction is not particularly limited, but is usually preferably 10 to 50 ° C, more preferably 15 to 40 ° C, and further preferably 15 to 30 ° C. Although there is no restriction | limiting in particular in the reaction pressure of 1st reaction, Implementing under a normal pressure is preferable. The reaction time varies depending on the type and amount of the carbazole derivative (1) and the base, the amount of the carboxylic acid group introducing agent (2b ′), the reaction temperature, the reaction pressure, etc., but it is usually preferably 2 hours to 48 hours. It is about time.
There is no particular limitation on the embodiment of the first reaction. For example, the carbazole derivative (1), the carboxylic acid group introducing agent (2b ′) and the base are all added to the solvent, and preferably stirred at the above temperature to obtain the carboxylic acid. A group-containing carbazole derivative can be produced.
After completion of the first reaction, the carboxylic acid group-containing carbazole derivative can be obtained by an ordinary organic compound separation means such as extraction. The purity of the carboxylic acid group-containing carbazole derivative can be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

The amount of thionyl chloride used in the second reaction is preferably about 1 to 10 mol, more preferably about 2 to 5 mol, per 1 mol of the carbazole derivative (1) used in the first reaction. It is.
The amount of the amine represented by HNR ³ R ³ ′ used in the second reaction is preferably about 1 to 10 mol per 1 mol of the carbazole derivative (1) used in the first reaction. More preferably, it is about 2 to 7 mol.
The second reaction is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as it is a solvent capable of dissolving the carboxylic acid group-containing carbazole derivative and the amine. For example, dichloromethane, nitrobenzene, acetone, acetonitrile and the like can be mentioned, and acetonitrile is preferable.

The reaction temperature of the second reaction is not particularly limited, but is usually preferably 10 to 50 ° C, more preferably 15 to 40 ° C, and further preferably 15 to 30 ° C. Although there is no restriction | limiting in particular in the reaction pressure of 2nd reaction, Implementing under a normal pressure is preferable. The reaction time varies depending on the kinds and amounts of the carboxylic acid group-containing carbazole derivative, the amine and the base, the reaction temperature, the reaction pressure, and the like, but is usually preferably about 1 to 10 hours.
The embodiment of the second reaction is not particularly limited. For example, the carboxylic acid group-containing carbazole derivative and the amine are added to a solvent, and thionyl chloride is added dropwise thereto. After completion of the addition, stirring is preferably performed at the temperature. By doing so, an amide group-introduced product (3b) can be produced.
After the completion of the reaction, the amide group-introduced product (3b) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the amide group-introduced product (3b) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

<When W is an oxygen atom and Z is a single bond>
The following general formula obtained by reacting the carbazole derivative (1) with ethylene carbonate in the presence of a base (first reaction).

(Wherein R ⁶ to R ¹¹ are as defined above, and preferred ones are also the same.)

In the presence of a base, the hydroxyl group-containing carbazole derivative is R ³ COY (where R ³ is as defined above, and the preferred one is also the same. Y represents a halogen atom). By reacting with the acyl halide represented (second reaction), the following general formula (3b ′)

(Wherein R ³ to R ¹¹ are as defined above, and preferred ones are also the same).
An ester group-introduced body represented by the formula [hereinafter referred to as an ester group-introduced body (3b ′). ] Is preferable.

The amount of ethylene carbonate used in the first reaction is preferably 0.7 to 15 mol, more preferably 1 to 10 mol, relative to 1 mol of the carbazole derivative (1).
The base used in the first reaction is preferably an organic base, and examples thereof include amines such as triethylamine and tributylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine. Among these, amines are preferable, and triethylamine is more preferable. The amount of the base to be used is not particularly limited, but from the viewpoint of reaction efficiency and production cost, it is preferably 0.5 to 2 mol, more preferably 0.8 to 1. mol per mol of the carbazole derivative (1). More preferably, it is 2 moles and is used in an approximately equal amount.
The first reaction is preferably carried out in the presence of a solvent. What is necessary is just to select suitably the solvent which can melt | dissolve a carbazole derivative (1), ethylene carbonate, and the said base as a solvent. Specific examples include dimethylformamide (DMF), dimethylsulfoxide (DMSO), methylene chloride and the like, with DMF being preferred.

The reaction temperature of the first reaction is not particularly limited, but is usually preferably 60 to 130 ° C, more preferably 80 to 120 ° C, and further preferably 90 to 110 ° C. Although there is no restriction | limiting in particular in the reaction pressure of 1st reaction, Implementing under a normal pressure is preferable. The reaction time varies depending on the type and amount of the carbazole derivative (1) and base, the amount of ethylene carbonate used, the reaction temperature, the reaction pressure, etc., but it is usually preferably about 1 to 10 hours.
The embodiment of the first reaction is not particularly limited, and for example, the carbazole derivative (1), ethylene carbonate, and base are all added to a solvent, and preferably stirred at the temperature to produce the hydroxyl group-containing carbazole derivative. be able to.
After the completion of the first reaction, the hydroxyl group-containing carbazole derivative can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the hydroxyl group-containing carbazole derivative can also be increased by appropriately purifying by an ordinary organic compound purification means such as distillation, column chromatography, recrystallization and the like.

Examples of the acyl halide represented by R ³ COY used in the second reaction include acyl chloride and acyl iodide, and acyl chloride is preferred.
The amount of the acyl halide used is preferably about 0.7 to 3 mol, more preferably 1 to 2 mol, based on 1 mol of the carbazole derivative (1) used in the first reaction. More preferably.
As the base used in the second reaction, for example, amines such as triethylamine, tributylamine and diisopropylethylamine are preferable. The amount of the base used is preferably about 0.7 to 3 mol, more preferably 1 to 2 mol, more preferably about 1 to 2 mol, relative to 1 mol of the acyl halide.
The second reaction is preferably carried out in the presence of a solvent. As the solvent, a solvent that can be used in a usual acylation reaction can be used, and there is no particular limitation as long as the reaction is not inhibited. Specific examples include dichloromethane, nitrobenzene, acetone, acetonitrile and the like, and acetonitrile is preferred.

The reaction temperature of the second reaction is not particularly limited, but is usually preferably 10 to 50 ° C, more preferably 15 to 40 ° C, and further preferably 15 to 30 ° C. Although there is no restriction | limiting in particular in the reaction pressure of 2nd reaction, Implementing under a normal pressure is preferable. The reaction time varies depending on the kinds and amounts of the hydroxyl group-containing carbazole derivative, the acyl halide and the base, the reaction temperature, the reaction pressure, and the like, but is usually preferably about 1 to 10 hours.
Although there is no restriction | limiting in particular in embodiment of 2nd reaction, For example, by adding all the said hydroxyl group containing carbazole derivatives, the said acyl halide, and a base in a solvent and preferably stirring at the said temperature, ester group introduction body ( 3b ′) can be produced.
After completion of the reaction, an ester group-introduced product (3b ′) can be obtained from the resulting reaction mixture by a usual organic compound separation means such as extraction. The purity of the ester group-introduced product (3b ′) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

(Process 2)
In step 2, the amide group introduced body (3b) or ester group introduced body (3b ′) obtained in step 1 [hereinafter, these are collectively referred to as a functional group introduced body (3b) for convenience. ] And the following general formulas (4) and (5)

(Wherein X represents a halogen atom or —OC (═O) Ar, and X ′ represents a halogen atom or —OC (═O) R ^2. Ar and R ² are as defined above. The preferred ones are also the same.)
These are referred to as acylating agent (4) and acylating agent (5), respectively. In the presence of a Lewis acid, the following general formula (6b)

(Wherein R ² to R ¹¹ , Ar, W and Z are as defined above, and preferred ones are also the same).
[Hereinafter referred to as a diketone body (6b). ] Is a step of obtaining.

In the above formula, examples of the halogen atom independently represented by X and X ′ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferred.
In step 2, the reaction between the functional group-introduced product (3b) and the acylating agents (4) and (5) is performed in terms of the yield of the desired diketone product (6b). It is preferable to react the acylating agent (5) with the acylating agent (4).
The amount of the acylating agent (4) and (5) used is from the viewpoint of introducing each acyl group into the functional group-introduced body (3b) one by one with respect to 1 mol of the functional group-introduced body (3b). The amount is preferably 0.8 to 1.3 mol, more preferably 1 to 1.3 mol, and it is more preferable to carry out the reaction in substantially the same amount from the viewpoint of reducing unreacted substances. In particular, when the functional group-introduced product (3b) and the acylating agent (4) are reacted, and then the acylating agent (5) is reacted, the amount of the acylating agent (5) used is within the above range. There is no problem if the amount exceeds the limit, but even if the amount is excessively large, the yield corresponding to that is not obtained, and the production cost may be unnecessarily high.
Step 2 is performed in the presence of a Lewis acid. As the Lewis acid, aluminum chloride and boron trifluoride diethyl ether complex are preferable. The amount of Lewis acid used is usually preferably 0.8 to 2.5 mol, more preferably 1 mol per mol of the acylating agent (4) or (5) from the viewpoint of the yield of the diketone body (6b). Is 1 to 2 moles.

Step 2 is preferably performed in the presence of a solvent. The solvent is not particularly limited as long as it is a solvent that can be used in a normal Friedel-Crafts acylation reaction. Specific examples include dichloromethane, nitrobenzene, acetone, acetonitrile and the like.
The reaction temperature in step 2 is preferably −50 to 5 ° C. (preferably −10 to 5 ° C.) at the start of the reaction, and gradually returned to room temperature (about 15 to 25 ° C.) as the reaction proceeds. The reaction time varies depending on the type and amount of the functional group-introduced product (3b), the acylating agents (4) and (5), and the reaction temperature, but is usually preferably 1 to 30 hours. When both of the acylating agents (4) and (5) are acyl halides or acid anhydrides, after reacting the functional group-introducing body (3b) with the acylating agent (4), the product is It can also be reacted with the acylating agent (5) without isolation. In that case, the reaction time of the functional group-introduced product (3b) and the acylating agent (4) is about 30 minutes to 5 hours (preferably 30 minutes to 3 hours), while the functional group-introduced product (3b) It is preferable that the reaction time with the acylating agent (5) is set to be as long as about 30 minutes to 24 hours (preferably 30 minutes to 18 hours) for sufficient reaction.

From the viewpoint of yield, one preferred embodiment of step 2 will be described. For example, the functional group-introducing body (3b) is appropriately mixed with a solvent while cooling in an ice bath, and Lewis acid is slowly added to the mixed solution (preferably 5 minutes to 1 hour, more preferably 10 minutes to 40 minutes). After the addition, the acylating agent (4) is slowly added (preferably 5 minutes to 1 hour, more preferably over 10 minutes to 40 minutes), and the temperature is returned to room temperature for a certain time (30 minutes to 5 hours). Degree) Continue stirring. Again, the acylating agent (5) is added while cooling in an ice bath, and the Lewis acid is added slowly (preferably over 5 minutes to 1 hour, more preferably over 10 minutes to 40 minutes). The diketone body (6b) can be obtained by returning to room temperature and continuing stirring for a certain period of time (about 30 minutes to 24 hours).
After completion of the reaction, the diketone body (6b) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the diketone body (6b) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

(Process 3)
Step 3 is a reaction of the diketone body (6b) obtained in Step 2 with hydroxylamine to give the following general formula (7b):

(Wherein R ² to R ¹¹ , Ar, W and Z are as defined above, and preferred ones are also the same).
[Hereinafter referred to as oxime body (7b). ] Is a step of obtaining.

In step 3, the hydroxylamine source is not particularly limited, but hydroxylamine chloride is preferred. The hydroxylamine chloride can be reacted with, for example, sodium acetate in water to obtain an aqueous solution of hydroxylamine.
The amount of hydroxylamine (hydroxylamine chloride) to be used is preferably 0.8 to 2 mol, more preferably 1 to 1.5 mol, and still more preferably 1 to 1.3 mol, relative to 1 mol of the diketone body (6b). From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially equal amounts.
Step 3 is preferably performed in the presence of a solvent. As the solvent, a water-soluble organic solvent is preferable, and as the water-soluble organic solvent, for example, alcohols such as methanol and ethanol, dimethylformamide (DMF) and the like are preferable.

The reaction temperature in step 3 is not particularly limited, but is usually preferably 40 to 160 ° C., more preferably 50 to 140 ° C., and still more preferably 70 to 110 ° C. from the viewpoint of the yield of the oxime (7b). is there. While the reaction time varies depending on the type and amount of diketone (6b) and the reaction temperature, it is usually preferably 0.5 to 20 hours, more preferably 1 to 12 hours.
There is no particular limitation on the embodiment of Step 3. For example, hydroxylamine chloride and sodium acetate are mixed in water to obtain an aqueous solution of hydroxylamine, and a diketone (6b) and a solvent are added thereto. An oxime body (7b) can be obtained by stirring in the said temperature range.
After completion of the reaction, the oxime body (7b) can be obtained from the resulting reaction mixture by an ordinary organic compound separation means such as extraction. The purity of the oxime body (7b) can also be increased by appropriately purifying it by a usual means for purifying organic compounds such as distillation, column chromatography, recrystallization and the like.

(Process 4)
Step 4 includes the oxime body (7b) obtained in Step 3 and the following general formula (8):

(In the formula, Y represents a halogen atom or —OC (═O) R ^1. R ¹ is as defined above, and preferred ones are also the same.)
The esterifying agent represented by the formula [hereinafter referred to as the esterifying agent (8). And the following general formula (Ib):

(Wherein R ¹ to R ¹¹ , Ar, W and Z are as defined above.)
[Hereinafter referred to as photopolymerization initiator (Ib)]. ] Is a step of obtaining.

In the above formula, examples of the halogen atom represented by Y include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
The amount of the esterifying agent (8) used in Step 4 is not particularly limited, but is preferably 0.5 to 2 mol, more preferably 0.8 to 1. mol based on 1 mol of the oxime (7b). From the viewpoint of reducing unreacted substances, it is more preferable to carry out the reaction in substantially the same amount.
Step 4 may be performed in the presence of a base to promote the reaction. Examples of the base include organic bases and inorganic bases. Examples of the organic base include amines such as triethylamine and tributylamine; nitrogen-containing heterocyclic aromatic compounds such as pyridine. Examples of the inorganic base include alkali metal carbonates such as sodium carbonate; alkaline earth metal carbonates such as magnesium carbonate; alkali metal hydroxides such as sodium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide Is mentioned. Among these, organic bases are preferable, amines and nitrogen-containing heterocyclic aromatic compounds are more preferable, and triethylamine and pyridine are more preferable from the viewpoint of reaction efficiency and production cost.
When a base is used in Step 4, the amount used is preferably 1 to 5 with respect to 1 mol of the oxime (7b) from the viewpoint of the yield of the photopolymerization initiator (Ib) and the production cost. Mol, more preferably 1.5 to 3 mol.

Step 4 is preferably performed in the presence of a solvent. Preferred examples of the solvent include ethers such as t-butyl methyl ether, ethyl methyl ether, cyclopentyl methyl ether, and tetrahydrofuran (THF).
The reaction temperature in step 4 is preferably −50 to 5 ° C. (preferably −10 to 5 ° C.) at the start of the reaction, and gradually returned to room temperature (about 15 to 25 ° C.) as the reaction proceeds. The reaction time varies depending on the kind and amount of the oxime (7b) and esterifying agent (8), and the reaction temperature, but is usually preferably 0.5 to 10 hours, more preferably 1 to 5 hours. .
There is no restriction | limiting in particular in embodiment of process 4, For example, an oxime body (7b) and an esterifying agent (8) are mixed in a solvent suitably, a base is dripped there, and the temperature of a reaction liquid is gradually made to drop after completion | finish of dripping. By returning to room temperature and continuing stirring, the photopolymerization initiator (Ib) of the present invention can be obtained.
After completion of the reaction, the photopolymerization initiator (Ib) can be obtained from the resulting reaction mixture by a usual organic compound separation means such as extraction. The purity of the photopolymerization initiator (Ib) can also be increased by appropriately purifying by a usual organic compound purification means such as distillation, column chromatography, recrystallization and the like.

The photopolymerization initiator (Ib) of the present invention thus obtained has a special substituent containing an ester group or an amide bond (or an amide bond forming a ring) on the nitrogen atom in the carbazole skeleton. . Therefore, compatibility with a compound having an ethylenically unsaturated bond (particularly a compound having a (meth) acryloyloxy group) and a compound having an ether bond and / or an ester bond in a photocurable composition at 25 ° C. High solubility in solvents (including the above-mentioned liquid compounds at 25 ° C. having an ether bond and / or ester bond), high sensitivity to light (especially light having a short wavelength of 450 nm or less), resolution In addition, it is considered that the developability, and hence the deep part curability, is excellent, and the adhesion to the substrate is improved. In addition, the photopolymerization initiator (Ib) is free from contamination of the polymer or apparatus due to decomposition products generated by light during exposure.
Note that the high compatibility and solubility of the photopolymerization initiator (Ib) with respect to a specific compound or solvent is considered to contribute to the improvement of sensitivity, resolution and developability, and thus deep curability. It can be said that this is an important factor in color filter applications. Particularly in color filter applications, the photopolymerization initiator is preferably dissolved in an amount of 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). More preferably, 10 parts by mass or more is dissolved, and the photopolymerization initiator (Ib) of the present invention satisfies such conditions, and is included in the photocurable composition for color filters, It is suitable as a photopolymerization initiator to be contained in a highly light-shielding photocurable composition for black matrix.

Next, a photocurable composition containing the photopolymerization initiator (I) of the present invention, a color filter using the photocurable composition, a pattern forming method, and a liquid crystal display device will be described in order.
[Photocurable composition]
The photocurable composition of the present invention contains at least one compound having an ethylenically unsaturated bond and / or binder resin and the photopolymerization initiator (I). The photocurable composition of the present invention further includes a colorant and, if necessary, a photopolymerization initiator other than the photopolymerization initiator (I), a dispersant, a polyfunctional monomer, a monofunctional monomer, and sensitization. An agent and a solvent may be contained, and the photocurable composition thus obtained is useful for color filter applications. In addition, if a functional group has an ethylenically unsaturated bond, a polyfunctional monomer and a monofunctional monomer can also become a compound which has an ethylenically unsaturated bond.
In the photocurable composition of the present invention, the content of the photopolymerization initiator (I) is preferably 2 to 50 mass based on the solid content of the photocurable composition from the viewpoints of sensitivity, resolution and developability. %, More preferably 2 to 30% by mass, still more preferably 4 to 15% by mass.
Moreover, when the photocurable composition of the present invention contains a photopolymerization initiator other than the photopolymerization initiator (I), the content of the photopolymerization initiator other than the photopolymerization initiator (I) is: Although there is no restriction | limiting in particular unless the effect of this invention is inhibited remarkably, Preferably it is 100 mass parts or less with respect to 100 mass parts of photoinitiators (I), More preferably, it is 50 mass parts or less, More preferably, it is 20 mass parts. Hereinafter, it is more preferably 10 parts by mass or less, particularly preferably 5 parts by mass or less.

(Compound having an ethylenically unsaturated bond)
A compound having an ethylenically unsaturated bond is a compound that is capable of becoming a binder in a photocurable composition by causing a polymerization reaction when irradiated with light in the presence of the photopolymerization initiator (I). It can serve as a binder in the pixel. The compound having an ethylenically unsaturated bond is preferably contained in the photocurable composition of the present invention in an amount of 5 to 60% by mass, more preferably 10 to 40% by mass. Within this range, the adhesion between the formed pixel and the substrate tends to be good. In addition, you may use together the compound which has an ethylenically unsaturated bond with the binder resin mentioned later. When using together, it is preferable in the total content being in the said range.
Specific examples of the compound having an ethylenically unsaturated bond include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid and α-chloroacrylic acid; unsaturated dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid Or anhydrides thereof; trivalent or higher unsaturated polycarboxylic acids such as trimellitic acid and pyromellitic acid or anhydrides thereof; styrene, α-methylstyrene, chlorostyrene, methoxystyrene, divinylbenzene, vinyltoluene, etc. Aromatic vinyl compounds of: methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Uril (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, poly (propyloxy) propyl (meth) acrylate, vinyl (meth) acrylate, Ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) ) Compound obtained by esterifying (poly) alcohol with α, β-unsaturated carboxylic acid, such as acrylate, allyl (meth) acrylate, benzyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl esters such as minoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate; glycidyl (meth) acrylate Unsaturated carboxylic acid glycidyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc .; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, allyl glycidyl ether, isobutyl vinyl ether Class: vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide; (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) And unsaturated amides such as acrylamide; unsaturated imides such as maleimide, N-phenylmaleimide and N-cyclohexylmaleimide; and aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene. Among these, a compound having a (meth) acryloyloxy group is preferable from the viewpoint of compatibility with the photopolymerization initiator (I) of the present invention.
As the compound having an ethylenically unsaturated bond, one type may be used alone, or two or more types may be used in combination.

When the compound having an ethylenically unsaturated bond is a compound having an ethylenically unsaturated bond having an ether bond and / or an ester bond (preferably an ether bond and an ester bond), the photopolymerization initiator ( Since the compatibility with I) is further improved, the amount of the solvent described later in the photocurable composition of the present invention can be reduced or no solvent can be used. Therefore, it is also preferable to use such a compound. When at least one compound having an ethylenically unsaturated 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 10 mass relative to the total amount of the photocurable composition. % Or less, further 5% by mass or less, and solvent-free.

(Binder resin)
The binder resin plays a role as a binder in the formed pixel and is not particularly limited as long as it has good adhesion to the substrate. Such a binder resin is preferably contained in the solid content of the photocurable composition of the present invention in an amount of 5 to 60% by mass, more preferably 10 to 40% by mass. Within this range, the adhesion between the formed pixel and the substrate tends to be good. The weight average molecular weight of the binder resin is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, from the viewpoint of adhesion between the formed pixel and the substrate. In the present specification, the weight average molecular weight is a value in terms of polystyrene measured by gel permeation chromatography (GPC).
As described above, the binder resin may be used in combination with the compound having an ethylenically unsaturated bond.

As the binder resin, the same binder resin as that used in a general photocurable composition for a color filter can be used. Specifically, ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin, polymethacrylic acid resin, ethylene methacrylic acid resin, polyvinyl chloride resin, chlorination Vinyl chloride, polyvinyl alcohol, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl acetal, polyether ether ketone, polyether sulfone, polyphenylene sulfide, polyarylate, polyvinyl butyral, epoxy resin, phenoxy resin, polyimide resin, polyamideimide resin, Examples thereof include polyamic acid resins, polyetherimide resins, phenol resins, urea resins and the like. Further, polymerizable monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, s-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, n-decyl (meth) acrylate, styrene, α- Methyl styrene, N-vinyl-2-pyrrolidone, glycidyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, phenyl (meth) acrylic And dimers of acrylic acid, methacrylic acid and acrylic acid (for example, trade name “M-5600” manufactured by Toa Synthetic Chemical Co., Ltd.), itaconic acid, croton Examples thereof include polymers or copolymers obtained by reacting at least one of acid, maleic acid, fumaric acid, vinyl acetic acid, and acid anhydrides thereof. Moreover, the polymer etc. which added the ethylenically unsaturated compound which has a glycidyl group or a hydroxyl group to this copolymer are mentioned.

Particularly preferable binder resins include alkali-soluble resins having an acidic functional group such as a carboxyl group, such as alkali-soluble acrylic resins. As the alkali-soluble resin having a carboxyl group, a copolymer of a carboxyl group-containing unsaturated monomer and another copolymerizable ethylenically unsaturated monomer is preferable, and an epoxy group and an ethylenically unsaturated group are further included in the molecule. A compound having a group and a group such as glycidyl (meth) acrylate added thereto and an ethylenically unsaturated group introduced into the side chain is preferred.
Examples of the carboxyl group-containing unsaturated monomer include (meth) acrylic acid, crotonic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and phthalic acid mono [2]. -(Meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate and the like are preferable, and (meth) acrylic acid is particularly preferable. In addition, a carboxyl group-containing unsaturated monomer may be used individually by 1 type, and may use 2 or more types together.
Examples of the ethylenically unsaturated monomer include methyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and allyl (meth). Acrylate, styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyl (meth) ethyl acrylate, di Cyclopentenyl (meth) acrylate and the like, and macromonomers thereof; N-methylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-methylphenylmaleimide, etc. Substituted maleimide, and the like can be mentioned. In addition, an ethylenically unsaturated monomer may be used individually by 1 type, and may use 2 or more types together.

(Coloring material)
The photocurable composition of the present invention may further contain a coloring material to form a colored photocurable composition. Examples of the coloring material include pigments, dyes, and natural pigments. A color material may be used individually by 1 type, and may use 2 or more types together. From the viewpoint of color reproducibility, curability and developability, the color material is preferably contained in the solid content of the photocurable composition of the present invention in an amount of 5 to 60% by mass, more preferably 5 to 50% by mass.
Examples of the pigment include organic pigments and inorganic pigments, and organic pigments are preferable from the viewpoint of color developability and heat resistance. Examples of the organic pigment include compounds classified as Pigment (CI Pigment Blue, CI Pigment Violet, C.I .; issued by The Society of Dyers and Colorists). CI pigment green, CI pigment red, CI pigment yellow, CI pigment orange, and the like.
The color material is preferably more uniformly dispersed by the following dispersant.

(Dispersant)
Any dispersant can be used as long as it can uniformly disperse the colorant, and a known dispersant can be used. Specific examples include polymer dispersants such as modified polyurethane, modified polyacrylate, modified polyester, and modified polyamide, and surfactants and pigment derivatives such as phosphate esters, alkylamines, and polyoxyethylene alkylphenyl ethers. . Among these, polymer dispersants are preferable, and specific commercial product names include EFKA-4046, EFKA-4047, EFKA polymer 10, EFKA polymer 400, EFKA polymer 401, EFKA polymer 4300, and EFKA polymer 4330 ( As described above, manufactured by Ciba Specialty Chemicals Co., Ltd., Disperbyk111, Disperbyk161, Disperbyk165, Disperbyk167, Disperbyk182, Disperbyk2000, Disperbyk2001, ER made by ER ), Addisper (registered trademark) PB821, PB 22 (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and the like.

When the dispersing agent is contained in the photocurable composition of the present invention, the content is not particularly limited as long as the above-described coloring material can be uniformly dispersed. From the viewpoint of dispersibility, developability of the photocurable composition, and reduction of development residue at unexposed locations, preferably 0.5 to 30% by mass relative to the total solid content of the photocurable composition. The content is preferably 1 to 20% by mass.
In addition, it is preferable to use a coloring material (especially pigment) and a dispersing agent by mixing in a below-mentioned solvent from a viewpoint of the dispersion amount and dispersibility of a coloring material, and using it as a dispersion liquid.

(Polyfunctional monomer)
As the polyfunctional monomer that may be appropriately contained in the photocurable composition of the present invention, a monomer having a (meth) acryloyloxy group compatible with the binder resin, specifically, a bifunctional (meth) acrylate and Trifunctional or higher functional (meth) acrylates are preferred. A polyfunctional monomer may be used individually by 1 type, and may use 2 or more types together.
Examples of the bifunctional (meth) acrylate include 1,4-butanediol (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and polypropylene glycol di (meth) Examples include acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and bisphenol A di (meth) acrylate.
Examples of the trifunctional or higher functional (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Carboxyl group-containing polyfunctional (meta ) Acrylates.

When the polyfunctional monomer is contained in the photocurable composition of the present invention, the content thereof is preferably 3 to 50% by mass with respect to the total solid content of the photocurable composition. If it is in this range, photocuring sufficiently proceeds, so that there is no possibility that the exposed portion is eluted during alkali development, and the alkali developability is good.

(Monofunctional monomer)
Monofunctional monomers that may be appropriately contained in the photocurable composition of the present invention are preferably (meth) acrylates, such as allyl (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, butoxy Ethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycerol (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate 2-hydroxypropyl (meth) acrylate, isobornyl (meth) acrylate, isodexyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, 2-methoxyethyl Meth) acrylate, methoxy ethylene glycol (meth) acrylate, phenoxyethyl (meth) acrylate, stearyl (meth) acrylate.

(Sensitizer)
Furthermore, you may make the photocurable composition of this invention contain a sensitizer as needed. The sensitizer absorbs the irradiated energy when it is exposed after the photocurable composition of the present invention is applied on the substrate, and the absorbed energy is used to initiate the reaction of the photopolymerization initiator of the present invention. It is a substance that plays a role of contributing to
Specific examples of the sensitizer include 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dimethylamino) benzophenone, 4-methyl-4′-diethylaminobenzophenone, 4-methoxy-4 ′. -Diethylaminobenzophenone, 4,4'-bis (dipropylamino) benzophenone, 4,4'-bis (diisopropylamino) benzophenone and the like. These may be used individually by 1 type and may use 2 or more types together.
When the photocurable composition of the present invention contains a sensitizer, the content thereof is preferably 1 to 10% by mass with respect to the total solid content of the photocurable composition.

(solvent)
The photocurable composition of the present invention may contain a solvent in order to disperse the coloring material. The solvent is not particularly limited as long as it is used for a general photocurable composition for a color filter. Specifically, (mono or poly) alkylene glycol (mono or poly) such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and dipropylene glycol dimethyl ether. ) Alkyl ethers and their acetates; diacetates such as propylene glycol diacetate and 1,3-butylene glycol diacetate; ethers such as tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone and 2-heptanone; Methyl hydroxypropionate, ethyl 3-hydroxypropionate, ethyl acetate, n-butyl Esters such as cetate, isobutyl acetate, isobutyl butyrate, n-butyl butyrate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, ethyl lactate, cyclohexanol acetate; aromatics such as toluene and xylene Group hydrocarbons and the like. A solvent may be used individually by 1 type and may use 2 or more types together.

Among these, from the viewpoint of compatibility, solubility, pigment dispersibility, and coatability, a compound that has an ether bond and / or an ester bond and is liquid at 25 ° C., specifically, propylene glycol monomethyl ether acetate, 3-methoxy Butyl acetate, ethylene glycol monomethyl ether, and diethylene glycol diethyl ether are preferable, and a liquid compound having an ether bond and an ester bond at 25 ° C. is more preferable.
When the photocurable composition of the present invention contains a solvent, the content thereof is preferably 50 to 90% by mass in the total amount of the photocurable composition. Usually, within this range, the pigment dispersibility is good and the resist coating characteristics (in-plane uniformity) can be made good. In addition, since the photopolymerization initiator of the present invention is excellent in compatibility with a liquid compound at 25 ° C. having an ether bond and / or an ester bond, the solvent has an ether bond and / or an ester bond at 25 ° C. If it is a liquid compound, the content of the solvent in the photocurable composition can be greatly reduced. In that case, the content of the compound having an ether bond and / or an ester bond and having a liquid at 25 ° C. in the photocurable composition of the present invention is preferably 5 to 1 part by weight with respect to 1 part by weight of the photopolymerization initiator (I). Since it can be arbitrarily selected in the range of 100 parts by mass, if necessary, the amount is as small as about 5 to 20 parts by mass, more preferably about 5 to 10 parts by mass with respect to 1 part by mass of the photopolymerization initiator (I). It is also possible to do.

(Other ingredients)
The photocurable composition of the present invention further contains an inorganic filler, an adhesion promoter, an aggregation inhibitor, a polymerization terminator, a chain transfer agent, a leveling agent, a plasticizer, an antifoaming agent, and a silane coupling, if necessary. Agent: You may contain a ultraviolet absorber etc.

[Color filter]
As a method for producing a color filter, it is preferable to use a method of forming a colored layer (pattern) having pores by photolithography using the photocurable composition of the present invention containing a colorant. With this method, for example, even when energy diffraction or the like occurs during the exposure, it is difficult to be affected by the influence. Therefore, it is possible to obtain a high-definition color filter in which holes are formed in a fine pattern in the colored layer.

(Pattern formation method)
As a pattern forming method, a method performed by a photolithography method using the photocurable composition of the present invention will be described. About the method, if it is a method which can form a hole in a colored layer, it will not specifically limit. For example, after applying the photocurable composition of the present invention to a substrate and drying it, exposure is performed by irradiating energy using a photomask or the like provided with an opening and a shielding part, and then development is performed. Thus, a pattern is formed. By repeating this a plurality of times, for example, red, green, and blue patterns are formed on the substrate, and then a transparent electrode film such as indium tin oxide (ITO) is formed to manufacture a color filter. be able to.
There is no restriction | limiting in particular in the coating method of the said photocurable composition, For example, it can utilize for well-known coating methods, such as a spin coat method, spray coat, dip coat, roll coat, bead coat, bar coat. Drying after coating is usually preferably performed at 50 to 150 ° C. for 15 seconds to 10 minutes.
The light source used for the exposure can be the same as the light source generally used for the formation of the colored layer, but in the ultraviolet region such as an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, Lamps with high emission lines are preferred. Thereby, it becomes possible to exhibit the characteristic of the said photocurable composition more effectively.
Further, the method for developing the photocurable composition is not particularly limited as long as the unnecessary portion of the photocurable composition can be removed. It can be made to be the same as the developing method performed at the time of manufacture. Here, for example, by optimizing the type of the developing solution, the concentration of the developing solution, the pressure of the developing solution or the washing water, and the like, the hole can be formed in a finer pattern.

In addition, as a board | substrate used for this process, the thing similar to the board | substrate (transparent substrate) used for a general color filter can be used. Specific examples include inflexible transparent rigid materials such as quartz glass, alkali-free glass, and synthetic quartz plates, or transparent flexible materials having flexibility such as transparent resin films and optical resin plates. It is done.
The thickness of the substrate is not particularly limited, but a substrate having a thickness of, for example, about 100 μm to 1 mm can be used depending on the use of the color filter of the present invention.
In the production of the color filter, for example, other steps may be appropriately included as necessary, such as a light shielding portion forming step for forming a light shielding portion and a step for forming an overcoat layer on the colored layer.

[Liquid Crystal Display]
The liquid crystal display device of the present invention includes the above-described color filter of the present invention, a counter substrate, and a liquid crystal layer formed between the color filter and the counter substrate, and the configuration thereof is particularly limited. Instead, it can have the same configuration as a liquid crystal display device using a known color filter.
For example, as shown in FIG. 1, the liquid crystal display device 40 of the present invention has the obtained color filter 10 (display side substrate) and a counter substrate 20 having a TFT array substrate (liquid crystal drive side substrate) facing each other. When the inner peripheral edge of the substrate is joined with a sealant, the two substrates are bonded together while maintaining a cell gap of a predetermined distance. An active matrix color liquid crystal display device belonging to the liquid crystal panel can be obtained by filling the liquid crystal layer 30 with the liquid crystal in the gap between the substrates and sealing it. Here, the color filter 10 of the present invention has a transparent substrate 1, a light shielding part 2, and a colored layer 3.
There is no particular limitation on the driving method of the liquid crystal display device, and a driving method generally used for a liquid crystal display device can be adopted. For example, a TN method, an IPS method, an OCB method, an MVA method, and the like can be given. As the liquid crystal constituting the liquid crystal layer, various liquid crystals having different dielectric anisotropies and mixtures thereof can be used depending on the driving method of the liquid crystal display device.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Example 1>
(Process 1)

Carbazole (6.8 g, 40 mmol), ethyl acrylate (4.0 g, 40 mmol) and potassium carbonate (5.5 g, 40 mmol) were suspended in dimethylformamide (DMF) and stirred at room temperature for 24 hours. After completion of the reaction, water was added and the mixture was further stirred for 30 minutes, and then extracted with ethyl acetate, washed with water, dried over magnesium sulfate, the solvent was distilled off and dried, whereby the above compound as a pale yellow liquid was obtained. (I) 9.6 g (93% yield) was obtained. The ¹ H-NMR measurement results of the compound (i) are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 1.15 (t, 3H), 2.835 (t, 2H), 4.08 (q, 2H), 4.64 (t, 3H) ), 7.215-7.254 (m, 2H), 7.45-7.47 (m, 4H), 8.08 (d, 2H)

(Process 2)

2.7 g (10 mmol) of compound (i) was dissolved in 10 ml of dichloromethane, and 2.7 g (20 mmol) of aluminum chloride was added over 20 minutes while cooling with an ice bath. To the obtained mixed solution, 1.4 g (11 mmol) of benzoyl chloride was added dropwise over 20 minutes. Thereafter, the mixture was gradually returned to room temperature and stirred for 1 hour. While cooling in an ice bath again, 2.7 g (20 mmol) of aluminum chloride was added over 20 minutes, and 1.2 g (15 mmol) of acetyl chloride was added dropwise thereto over 20 minutes. Thereafter, the mixture was gradually returned to room temperature and stirred overnight. After completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off.
The product was isolated by silica gel column chromatography (eluent: dichloromethane → normal hexane: ethyl acetate = 2: 1) to obtain 2.8 g of light yellow solid compound (ii) (yield 70%). The results of ¹ H-NMR measurement of the compound (ii) are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 1.16 (t, 3H), 2.725 (s, 3H), 2.91 (t, 2H), 4.08 (q, 2H) ), 4.73 (t, 2H), 7.525-7.86 (m, 5H), 8.10 (dd, 2H), 8.18 (dd, 1H), 8.20 (dd, 1H) 8.625 (d, 1H), 8.725 (d, 1H)

(Process 3)

0.12 g (1.7 mmol) of hydroxylamine chloride and 0.17 g (2.0 mmol) of sodium acetate were dissolved in 1.4 ml of water, and 0.60 g (1.58 mmol) of compound (ii) and 11 ml of ethanol were added thereto. And refluxed for 7 hours.
After completion of the reaction, the solvent of the reaction solution was distilled off, and the resulting solid was washed with water, dissolved in THF, dried over magnesium sulfate, and the solvent was distilled off to give a pale yellow liquid compound (iii ) 0.60 g (89% yield) was obtained. The ¹ H-NMR measurement results of the compound (iii) are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 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) 8.325 (d, 1H), 8.60 (d, 1H)

(Process 4)

0.60 g (1.4 mmol) of compound (iii) is dissolved in 7 ml of t-butyl methyl ether, 0.11 g (1.4 mmol) of acetyl chloride is added, and 0.28 ml (2.0 mmol) of triethylamine is added while cooling in an ice bath. ) Was added dropwise. The mixture was stirred for 3 hours while gradually returning to room temperature. After completion of the reaction, the reaction mixture was poured into ice water, extracted with ethyl acetate, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off. The product was isolated by silica gel column chromatography (eluent: dichloromethane → normal hexane: ethyl acetate = 2: 1) to obtain 0.30 g (yield 70%) of a light yellow solid compound (iv). The physical properties of the compound (iv) are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , 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), 7.51-7.62 (m, 5H), 7.75 (dd, 2H), 7.99 (dd, 1H) 8.09 (dd, 1H), 8.46 (d, 1H), 8.59 (d, 1H)
UV spectrum (moving layer; acetonitrile): λmax = 260, 292, 333 nm
Thermal decomposition temperature (temperature at which a 1.5 mg sample is heated at a heating rate of 10 ° C./min under a nitrogen gas atmosphere and the mass is reduced by 5%): 224.5 ° C.
Molecular weight: 470.52

<Example 2>
Example 1 except that isobutyl acrylate (40 mmol) was used instead of ethyl acrylate (40 mmol) in Step 1 of Example 1, and 2-methylbenzoyl chloride (11 mmol) was used instead of benzoyl chloride (11 mmol) in Step 2. The same operation as in Example 1 was performed to obtain the following pale yellow solid compound (v). The physical properties of the compound (v) are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 0.81 (d, 6H), 1.805 (m, 1H), 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, 1H), 8.51 (d, 1H)
UV spectrum (moving layer; acetonitrile): λmax = 260, 295.5, 334 nm
Thermal decomposition temperature (temperature at which a 1.5 mg sample was heated at a heating rate of 10 ° C./min under a nitrogen gas atmosphere and the mass decreased by 5%): 236 ° C.
Molecular weight: 512.6

<Example 3>
In Step 1 of Example 1, 2-methoxyethyl acrylate (40 mmol) was used instead of ethyl acrylate (40 mmol), and in Step 2, 2-methylbenzoyl chloride (11 mmol) was used instead of benzoyl chloride (11 mmol). Except for this, the same operation as in Example 1 was carried out to obtain the following pale yellow solid compound (vi). The physical properties of the compound (vi) are shown below.

¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 2.29 (s, 3H), 2.35 (s, 3H), 2.50 (s, 3H), 2.95 (t, 2H ), 3.32 (s, 3H), 3.50 (t, 2H), 4.19 (t, 2H), 4.70 (t, 2H), 7.30-7.54 (m, 6H) 7.97 (dd, 1H), 8.10 (dd, 1H), 8.42 (d, 1H), 8.51 (d, 1H)
UV spectrum (moving layer; acetonitrile): λmax = 258.5, 296, 334.5 nm
Thermal decomposition temperature (temperature at which a 1.5 mg sample was heated at a heating rate of 10 ° C./min under a nitrogen gas atmosphere and the mass decreased by 5%): 243 ° C.
Molecular weight: 514.57

<Example 4>
(Process 1)

Dissolve 5.0 g (30 mmol) of carbazole in 6 ml of dimethylformamide (DMF), add 13.2 g (150 mmol) of ethylene carbonate and 5.5 ml (037 mmol) of diazabicycloundecene (DBU) and add at 100 ° C. for 3 hours. Heated to reflux. After cooling, water was added, extracted with ethyl acetate, washed with water, and then the solvent was distilled off.
Next, the obtained concentrate was diluted with 15 ml of acetonitrile, 2 g (23 mmol) of acetyl chloride and 4 ml (29 mmol) of triethylamine were added thereto, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, water was added, extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and the solvent was distilled off to obtain 6.0 g (yield) of the above compound (vii) as a pale yellow liquid. 80%).

(Process 2)

Compound (vii) (2.5 g, 9.9 mmol) was dissolved in dichloromethane (10 ml), and aluminum chloride (1.5 g) was added over 20 minutes while cooling in an ice bath. Thereafter, 1.4 g (10.0 mmol) of benzoyl chloride was added dropwise, and after gradually returning to room temperature, the mixture was stirred for 1 hour.
While cooling in an ice bath again, 1.5 g of aluminum chloride was added over 20 minutes, 0.93 g (11.8 mmol) of acetyl chloride was added thereto, and the mixture was gradually returned to room temperature and stirred for 1 hour.
After completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off.
The compound was isolated by silica gel column chromatography (eluent: dichloromethane → normal hexane: ethyl acetate = 2: 1) to obtain 2.8 g (yield 70%) of a light yellow solid compound (viii).

(Process 3)

Hydroxylamine chloride (0.38 g, 5.4 mmol) and sodium acetate (0.54 g, 6.4 mmol) were dissolved in water (4.5 ml), and the compound (viii) (2.0 g, 5.0 mmol) and ethanol (35 ml) were added thereto. Added and refluxed for 2 hours.
After completion of the reaction, the solvent of the reaction solution was distilled off, and the resulting solid was washed with water, dissolved in THF, dried over magnesium sulfate, and the solvent was distilled off to obtain a compound (ix ) 1.8 g (yield 89%) was obtained.

(Process 4)

Compound (ix) 0.8 g (2.0 mmol) was dissolved in t-butyl methyl ether 10 ml, acetyl chloride 0.16 g (2.0 mmol) was added, and triethylamine 0.4 ml (2. 9 mmol) was added dropwise. The mixture was stirred for 3 hours while gradually returning to room temperature.
After completion of the reaction, the reaction solution was poured into ice water, extracted with ethyl acetate, washed with water, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried over magnesium sulfate, and then the solvent was distilled off.
The compound was isolated by silica gel column chromatography (eluent: dichloromethane → normal hexane: ethyl acetate = 2: 1) to obtain 0.6 g (yield 70%) of a light yellow solid compound (x) having the following physical properties.

(Physical properties of compound (x))
¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 1.93 (s, 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, 1H), 8.09 (dd, 1H) 8.46 (d, 1H), 8.59 (d, 1H)
UV spectrum (moving layer; acetonitrile): λmax = 260, 296, 334 nm
Thermal decomposition temperature (temperature at which a 1.5 mg sample is heated at a heating rate of 10 ° C./min under a nitrogen gas atmosphere and the mass is reduced by 5%): 225 ° C.
Molecular weight: 456.49

<Example 5>
(Process 1)

After 0.96 g (40 mmol) of 9-carbazole-9-propionic acid was dissolved in 10 ml of acetonitrile, 18 g (210 mmol) of morpholine was added. To the obtained mixture, 14 g (120 mmol) of thionyl 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. Thereafter, the mixture was extracted with ethyl acetate, washed with water, dried over magnesium sulfate, and then the solvent was distilled off to obtain 10 g (yield 81%) of a light yellow liquid compound (xi).

(Process 2-4)

As shown in the above chemical reaction formula, the same operations were performed in steps 2 to 4 of Example 5 except that compound (xi) was used instead of compound (vii) in step 2 in steps 2 to 4 of Example 4. Was employed to obtain a light yellow solid compound (xii) having the following physical properties.

(Physical properties of compound (xii))
¹ H-NMR (400 MHz, CDCl ₃ , TMS, ppm) δ: 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), 7.51-7.62 (m, 5H), 7 .75 (dd, 2H), 7.99 (dd, 1H), 8.09 (dd, 1H), 8.46 (d, 1H), 8.59 (d, 1H)
UV spectrum (moving layer; acetonitrile): λmax = 260,292,335 nm
Thermal decomposition temperature (temperature when a 1.5 mg sample is heated at a rate of temperature increase of 10 ° C./min under a nitrogen gas atmosphere and the mass is reduced by 5%): 234 ° C.
Molecular weight: 511.57

<Test Examples 1 to 5 and Comparative Test Examples 1 and 2> Compatibility and Sensitivity Test Obtained in Examples 1 to 5 to 100 parts by mass of the trifunctional acrylate “M-305” (trade name, manufactured by Toagosei Co., Ltd.) Photopolymerization initiator (compounds (iv) to (vi), (x) and (xii); for Test Examples 1 to 5), the following “IRGACURE OXE02” (manufactured by Ciba Specialty Chemicals Co., Ltd., comparative test example) 1) (hereinafter may be abbreviated as “OXE02”) or 5 parts by mass of the following “N-1919” (manufactured by ADEKA Corporation, for Comparative Test Example 2). Here, the presence or absence of a solid in the obtained mixture was confirmed by visual observation, and used as an index of compatibility with a compound having an ethylenically unsaturated bond (particularly a compound having a (meth) acryloyloxy group). The results are shown in Table 1. Next, a photocurable composition was prepared by dissolving the mixture in chloroform.
Each of the obtained photocurable compositions was spin-coated on a chromium-sputtered glass substrate and applied.
While the coating film thus obtained was exposed to UV, the amount of decrease in the peak at 810 cm ⁻¹ was recorded over time with an infrared spectrometer, and the extent of disappearance of the double bond (reaction rate) was recorded. Confirmed and used as an index of sensitivity. The results are shown in Table 1.

From Table 1, the photopolymerization initiator of the present invention is highly compatible with a compound having an ethylenically unsaturated double bond, particularly a polyfunctional (meth) acrylate, and can also be used to prepare a solvent-free photopolymerization initiator. Is possible. At the same time, it can be seen that the photocurable composition containing the photopolymerization initiator of the present invention is more sensitive than the conventional photocurable composition containing the photopolymerization initiator.

<Test Examples 6 to 10, Comparative Test Examples 3 and 4> Solvent solubility test Propylene glycol monoethyl ether acetate (PGMEA), methanol, 3-methoxy-3-methyl-1-butyl acetate (MMBA), methyl isobutyl ketone The amount of photopolymerization initiator dissolved in 100 parts by mass of (MIBK) and chloroform was investigated, and the solubility was evaluated according to the following evaluation criteria. The results are shown in Table 2.
A: 10 parts by mass or more dissolved.
B: Dissolved in the range of 5 parts by mass or more and less than 10 parts by mass.
C: Dissolved in the range of 2 parts by mass or more and less than 5 parts by mass.
D: Only less than 2 parts by mass dissolved.
Here, “dissolved” refers to a state in which no solid is visible by visual inspection.

From Table 2, it can be seen that the photopolymerization initiator of the present invention is superior in solubility with respect to various solvents, in particular, a liquid compound at 25 ° C. having an ether bond and / or an ester bond, as compared with the conventional photopolymerization initiator. Recognize.
In addition, the photopolymerization initiator “N-1919” used in Comparative Test Example 4 has higher solubility than the photopolymerization initiator “OXE02” used in Comparative Test Example 3. This is because “N-1919” has improved solubility by adding a substituent to the structure of “OXE02”. The compounds (iv) to (vi), (x) and (xii) used in Test Examples 6 to 10 not only have higher solubility in the solvent than “N-1919”, but also have a smaller molecular weight. Thus, the content in the photocurable composition can be reduced, and the photopolymerization initiator is more excellent.

<Production Example 1> 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 t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation) ) 10 parts by mass of the mixed solution was dropped into a polymerization tank containing 150 parts by mass of propylene glycol monoethyl ether acetate at 100 ° C. for 3 hours under a nitrogen stream. After completion of dropping, the mixture 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 added and heated at 110 ° C. for 10 hours to prepare a binder resin.
The obtained binder resin had a solid content concentration of 38% by mass, an acid value of 75 mgKOH / g, and a weight average molecular weight of 10,000.

<Production Example 2> Preparation of blue pigment dispersion

Each component shown in Table 3 was mixed in each blending amount, and dispersed with a paint shaker (manufactured by Asada Tekko Co., Ltd.) for 3 hours using zirconia beads having a diameter of 0.3 mm, and a blue pigment dispersion (solid content concentration: 21 mass) %) Was prepared.

<Production Example 3> Preparation of red pigment dispersion

Each component shown in Table 4 was mixed in each compounding amount, and dispersed for 3 hours with a paint shaker (manufactured by Asada Tekko Co., Ltd.) using zirconia beads having a diameter of 0.3 mm, and a red pigment dispersion (solid content concentration: 21 mass). %) Was prepared.

<Production Example 4> Preparation of green pigment dispersion

Each component shown in Table 5 was mixed in each compounding amount and dispersed for 3 hours with a paint shaker (manufactured by Asada Tekko Co., Ltd.) using zirconia beads having a diameter of 0.3 mm, and a green pigment dispersion (solid content concentration: 21 mass) %) Was prepared.

In the following examples, evaluation of sensitivity, resolution, developability, and adhesion was performed 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 in the region irradiated with light is 95% or more with respect to 100% of the film thickness before exposure. In such a case, “the film thickness was sufficient” was evaluated according to the following evaluation criteria.
A: A sufficient film thickness was obtained when the exposure amount was 100 mJ / cm ² .
B: An exposure amount of 100 mJ / cm ² was insufficient, but an exposure amount of 200 mJ / cm ² provided a sufficient film thickness.
The film thickness was measured using a stylus-type film thickness measuring device “SURFCORDER ET4000A” (manufactured by Kosaka Laboratory Ltd.).
(resolution)
The resolution was evaluated according to the following evaluation criteria.
a: A favorable pattern was obtained even when the line width was less than 10 μm during exposure and development.
b: A good pattern was obtained when the line width was 15 to 20 μm.
(Developability)
At the time of exposure, the residue of an unexposed part (part which was not irradiated with light) was observed, and developability was evaluated according to the following evaluation criteria.
○: No residue was confirmed.
X: A residue was confirmed.
(Adhesion)
The line width of the independent pattern that was in close contact without being washed after development was investigated, and the adhesion was evaluated according to the following evaluation criteria.
A: A good isolated pattern was obtained even when the line width was 5 μm or less.
○: When the line width is 6 to 10 μm, a good isolated pattern was obtained.

<Example 6> Preparation and pattern formation of blue light curable resin composition

Each component described in Table 6 was mixed in each compounding amount and stirred for 1 hour with a dissolver to prepare a blue light curable resin composition.
The obtained blue light curable resin composition was spin coated on a glass substrate and heated at 80 ° C. for 3 minutes to form a coating film of the blue light curable resin composition. The obtained coating film is exposed with a high-pressure mercury lamp as a light source from the coating film side through a mask having a predetermined line width, and then spray development is performed using Disperse H (manufactured by Henkel) diluted 100 times. After the completion, post baking was performed at 230 ° C. for 30 minutes to form a pattern.
Table 9 shows the evaluation results of sensitivity, resolution, developability and adhesion.

<Comparative Examples 1 and 2> Preparation and pattern formation of blue light curable resin composition In Example 6, instead of the compound (iv) obtained in Example 1, the “IRGACURE OXE02” (Ciba Specialty Chemicals ( Co., Ltd.) or “N-1919” (manufactured by ADEKA Co., Ltd.) was used in the same manner to prepare a blue light curable resin composition to form a pattern.
Table 9 shows the evaluation results of sensitivity, resolution, developability and adhesion.

<Example 7> Preparation of red light curable resin composition and pattern formation

Each component described in Table 7 was mixed at each blending amount and stirred for 1 hour with a dissolver to prepare a red photocurable resin composition.
About the obtained red photocurable resin composition, the pattern was formed by performing operation similar to Example 6. FIG.
Table 9 shows the evaluation results of sensitivity, resolution, developability and adhesion.

<Comparative Examples 3 and 4> Preparation and pattern formation of red photocurable resin composition In Example 7, instead of the compound (iv) obtained in Example 1, the “IRGACURE OXE02” (Ciba Specialty Chemicals ( Co., Ltd.) or “N-1919” (manufactured by ADEKA Co., Ltd.) was used in the same manner to prepare a red photocurable resin composition to form a pattern.
Table 9 shows the evaluation results of sensitivity, resolution, developability and adhesion.

<Example 8> Preparation and pattern formation of green light curable resin composition

Each component shown in Table 8 was mixed in each compounding amount and stirred for 1 hour with a dissolver to prepare a green light curable resin composition.
About the obtained green light curable resin composition, the pattern was formed by performing operation similar to Example 6. FIG.
Table 9 shows the evaluation results of sensitivity, resolution, developability and adhesion.

<Comparative Examples 5 and 6> Preparation and pattern formation of green light curable resin composition In Example 8, instead of the compound (iv) obtained in Example 1, the “IRGACURE OXE02” (Ciba Specialty Chemicals ( Co., Ltd.) or “N-1919” (manufactured by ADEKA Co., Ltd.) was used in the same manner to prepare a green light curable resin composition to form a pattern.
Table 9 shows the evaluation results of sensitivity, resolution, developability and adhesion.

<Examples 9 to 11>
In each of Examples 6 to 8, a blue light curable resin composition was prepared in the same manner except that the compound (v) obtained in Example 2 was used instead of the compound (iv) obtained in Example 1. A red light curable resin composition and a green light curable resin composition were prepared, and a pattern was formed.
Table 9 shows the evaluation results of sensitivity, resolution, developability and adhesion.

<Examples 12 to 14>
In each of Examples 6 to 8, a blue light curable resin composition was prepared in the same manner except that the compound (vi) obtained in Example 3 was used instead of the compound (iv) obtained in Example 1. A red light curable resin composition and a green light curable resin composition were prepared, and a pattern was formed.
Table 9 shows the evaluation results of sensitivity, resolution, developability and adhesion.

<Examples 15 to 17>
In each of Examples 6 to 8, a blue light curable resin composition 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 red light curable resin composition and a green light curable resin composition were prepared, and a pattern was formed.
Table 9 shows the evaluation results of sensitivity, resolution, developability and adhesion.

<Examples 18 to 20>
In each of Examples 6 to 8, a blue light curable resin composition was prepared in the same manner except that the compound (xii) obtained in Example 5 was used instead of the compound (iv) obtained in Example 1. A red light curable resin composition and a green light curable resin composition were prepared, and a pattern was formed.
Table 9 shows the evaluation results of sensitivity, resolution, developability and adhesion.

From Table 9, the photocurable composition containing the photopolymerization initiator of the present invention has developability equivalent to that of the conventional photocurable composition containing the photopolymerization initiator, and also has sensitivity, resolution and About adhesiveness, it turns out that it is superior to the photocurable composition containing the conventional photoinitiator. From this, it can be said that the photocurable composition containing the photoinitiator of this invention is excellent in deep part sclerosis | hardenability.

Since the photopolymerization initiator of the present invention has high sensitivity to light (especially light having a short wavelength of 450 nm or less), it can be thinned and can form a high-quality pattern at low cost. Furthermore, photopolymerization starts to be incorporated into the photocurable composition for color filters due to its high compatibility with compounds having ethylenically unsaturated bonds (especially compounds having (meth) acryloyloxy groups) and high solubility in solvents. It is useful as a photopolymerization initiator to be contained in a photo-curable composition for a black matrix having a high light-shielding property.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 2 Light-shielding part 3 Colored layer 10 Color filter 20 Opposite substrate 30 Liquid crystal layer 40 Liquid crystal display device

Claims

The photoinitiator represented by the following general formula (I).

(Wherein R 1 to R 11 are each independently a hydrogen atom, a halogen 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 an 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, substituted or Unsubstituted alkenyloxy group having 2-20 carbon atoms, substituted or unsubstituted alkanoyl group having 1-20 carbon atoms, substituted or unsubstituted alkenoyl group having 2-20 carbon atoms, substituted or unsubstituted ring carbon atoms 6 .R 3 that an aryl group or a substituted or unsubstituted heterocyclic group ring atoms 3 to 14 of to 14, to form a ring together with R 4 or R 5 Good .R 4 may form a ring together with R 5.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
W represents a single bond or an oxygen atom. Z represents a single bond, an oxygen atom, or> NR 3 ′ (R 3 ′ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R 3 ′ is connected to R 3 together with a nitrogen atom. Forming a ring).
n represents an integer of 1 to 10. When n is an integer of 2 to 10, the plurality of R 4 and R 5 may be the same or different. )
The photopolymerization initiator according to claim 1, which is represented by the following general formula (Ia):

(Wherein R 1 to R 11 are each independently a hydrogen atom, a halogen 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 an 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, substituted or Unsubstituted alkenyloxy group having 2-20 carbon atoms, substituted or unsubstituted alkanoyl group having 1-20 carbon atoms, substituted or unsubstituted alkenoyl group having 2-20 carbon atoms, substituted or unsubstituted ring carbon atoms 6 .R 3 that an aryl group or a substituted or unsubstituted heterocyclic group ring atoms 3 to 14 of to 14, to form a ring together with R 4 or R 5 Good .R 4 may form a ring together with R 5.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
n represents an integer of 1 to 10. When n is an integer of 2 to 10, the plurality of R 4 and R 5 may be the same or different. )
In the general formula (Ia), R 1 , R 2 and R 3 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, n is 2, and a plurality of R 4 And R 5 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and Ar is a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms. Item 3. The photopolymerization initiator according to Item 2.
In the general formula (Ia), R 1 , R 2 and R 3 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, n is 2, and a plurality of R 4 And R 5 is 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 heteroaryl group having 5 to 14 ring atoms. The photopolymerization initiator according to claim 2.
The photopolymerization initiator according to claim 3 or 4, having a molecular weight of 515 or less.
In the general formula (Ia), R 1 and R 2 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R 3 is a substituted or unsubstituted carbon number 3 to 18 The cycloalkyl group according to claim 2, wherein n is 2, and the 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. Photopolymerization initiator.
In the general formula (Ia), R 1 and R 2 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R 3 is a cyclic ether having 3 to 6 ring atoms. An alkyl group having 1 to 20 carbon atoms substituted with a group, n 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. The photopolymerization initiator according to claim 2, wherein
The photopolymerization initiator according to claim 6 or 7, wherein the molecular weight is 550 or less.
The photopolymerization initiator according to claim 1, which is represented by the following general formula (Ib).

(Wherein R 1 to R 11 are each independently a hydrogen atom, a halogen 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 an 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, substituted or Unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted ring forming carbon number A 6 to 14 aryl group or a substituted or unsubstituted heterocyclic group having 3 to 14 ring atoms is shown.
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
W represents a single bond or an oxygen atom. Z represents a single bond, an oxygen atom, or> NR 3 ′ (R 3 ′ represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or R 3 ′ is connected to R 3 together with a nitrogen atom. Forming a ring). )
In the general formula (Ib), R 1 and R 3 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, W is an oxygen atom, and Z is a single bond or oxygen The photopolymerization initiator according to claim 9, wherein the photopolymerization initiator is an atom, and Ar is a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms.
Further, R 2 represents —OCOR 13 (R 13 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 ring carbon atoms) or —COOR 20 (R 20 represents 1 to 20 carbon atoms). The photopolymerization initiator according to claim 10, which is an alkyl group having 1 to 20 carbon atoms having an ester group represented by: 20 alkyl group or aryl group having 6 to 14 ring carbon atoms.
In the general formula (Ib), R 1 and R 3 are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, W is a single bond, and Z is> NR 3 ′. The photopolymerization initiator according to claim 9, wherein R 3 'is as defined above, and Ar is a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms.
Further, R 2 represents —OCOR 13 (R 13 represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 14 ring carbon atoms) or —COOR 20 (R 20 represents 1 to 20 carbon atoms). The photopolymerization initiator according to claim 12, which is an alkyl group having 1 to 20 carbon atoms having an ester group represented by: 20 alkyl group or aryl group having 6 to 14 ring carbon atoms.
A photocurable composition comprising a binder resin and / or a compound having an ethylenically unsaturated bond and the photopolymerization initiator according to any one of claims 1 to 13.
The photocurable composition according to claim 14, wherein the content of the photopolymerization initiator is 2 to 50% by mass with respect to the solid content of the photocurable composition.
The photocurable composition according to claim 14 or 15, further comprising a coloring material.
The photocurable composition according to any one of claims 14 to 16, further comprising 5 to 100 parts by mass of a compound having an ether bond and / or an ester bond at 25 ° C and 1 part by mass of the photopolymerization initiator. Composition.
As the compound having an ethylenically unsaturated bond, at least one compound having an ethylenically unsaturated bond having an ether bond and / or an ester bond is used, and the solvent contains only 10% by mass or less of the total amount of the photocurable composition. The photocurable composition according to any one of claims 14 to 16.
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.
21. A liquid crystal display device comprising: the color filter according to claim 20; a counter substrate; and a liquid crystal layer formed between the color filter and the counter substrate.
A pattern forming method comprising applying the photocurable composition according to any one of claims 16 to 18 to a substrate, drying the substrate, exposing the substrate to light using a photomask, and then performing development.
The following general formula (1)

(Wherein R 6 to R 11 are each independently a hydrogen atom, a halogen 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 an 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, substituted or Unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted ring forming carbon number Represents a 6 to 14 aryl group or a substituted or unsubstituted heterocyclic group having 3 to 14 ring atoms.)
A carbazole derivative represented by the following general formula (2a)

Wherein R 3 , R 4 ′ and R 5 ′ are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted carbon number 2 to 20 Alkenyl group, substituted or unsubstituted cycloalkyl group having 3 to 10 ring atoms, substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, hydroxyl group, substituted or unsubstituted 1 to 20 carbon atoms Alkoxy group, substituted or unsubstituted alkenyloxy group having 2 to 20 carbon atoms, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted Or a substituted or unsubstituted heterocyclic group having 3 to 14 ring atoms, and R 3 together with R 5 ′ forms a ring. May be.)
Is reacted with an acrylate derivative represented by the following general formula (3a ′):

(Wherein R 3 , R 4 ′, R 5 ′ and R 6 to R 11 are as defined above.)
A carbonylalkyl group-introduced product represented by the following general formula (4), (5)

(Wherein X represents a halogen atom or —OC (═O) Ar, and X ′ represents a halogen atom or —OC (═O) R 2 .
Ar represents a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 5 to 14 ring atoms.
R 2 represents a hydrogen atom, a halogen 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, a substituted or unsubstituted ring atom having 3 to 10 ring atoms. A cycloalkyl group, 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 having 2 to 20 carbon atoms Group, substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, or substituted or unsubstituted And a heterocyclic group having 3 to 14 ring atoms. )
Is reacted in the presence of a Lewis acid to give the following general formula (6a ′):

(Wherein R 2 , R 3 , R 4 ′, R 5 ′, R 6 to R 11 and Ar are as defined above.)
A diketone product represented by the following general formula (7a ′) is obtained by reacting the resulting diketone product with hydroxylamine.

(Wherein R 2 , R 3 , R 4 ′, R 5 ′, R 6 to R 11 and Ar are as defined above.)
The oxime body represented by the following formula (8)

Wherein Y represents a halogen atom or —OC (═O) R 1 .
R 1 represents a hydrogen atom, a halogen 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, a substituted or unsubstituted ring-forming atom number of 3 -10 cycloalkyl group, substituted or unsubstituted cycloalkenyl group having 4 to 20 carbon atoms, hydroxyl group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, substituted or unsubstituted 2 to 20 carbon atoms An alkenyloxy group, a substituted or unsubstituted alkanoyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenoyl group having 2 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 14 ring carbon atoms, An unsubstituted heterocyclic group having 3 to 14 ring atoms is shown. )
By reacting with an esterifying agent represented by the following general formula (I-a1)

(Wherein R 1 to R 3 , R 4 ′, R 5 ′, R 6 to R 11 and Ar are as defined above.)
The manufacturing method of the photoinitiator represented by these.