Diaroyl carbazole compound and use thereof as sensitising agent

Abstract

Provided in the present invention is a novel diaroyl carbazole compound, used together with a carbazolyl oxime ester photoinitiator to show a significant synergistic initiation effect in a photoresist composition; the best sensitising effect is shown when the molar ratio of the diaroyl carbazole compound and the carbazolyl oxime ester photoinitiator is 0.1-1.4.

Claims

1. A diaroyl carbazole compound, wherein said diaroyl carbazole compound is selected from the group consisting of following compounds and any combination thereof: ##STR00020## ##STR00021##

2. A method for preparing the diaroyl carbazole compound of claim 1, comprising preparing a symmetric or asymmetric diaroyl compound via one-step or two-step Friedel-Crafts acylation reaction using a compound of formula III-A or formula III-B as a raw material reacting with corresponding substituted aroyl chloride or acid anhydride; and carrying out an esterification reaction or etherification reaction with an R.sub.20OH alcohol compound when any aryl group contains a carboxyl group or a halogen atom, obtaining a diaroyl carbazole compound of formula I-1 to I-7 or formula II-1 to II-4: ##STR00022## wherein R.sub.1, R.sub.8, R.sub.11 and R.sub.18 are H, R.sub.9 is CH.sub.2CH.sub.3, R.sub.19 is CH.sub.2CH.sub.3 or CH.sub.2CH(CH.sub.2CH.sub.3)(CH.sub.2).sub.3CH.sub.3, or R.sub.9 and R.sub.1 optionally form a C6 heterocyclic structure as shown in formula I-7; or R.sub.19 and R.sub.11 optionally form a C6 heterocyclic structure as shown in formula II-4.

3. A photoinitiator composition, comprising at least one diaroyl carbazole compound of claim 1 and at least one carbazolyl oxime ester photoinitiator, wherein the carbazolyl oxime ester photoinitiator comprises at least one oxime ester group ##STR00023## which is connected to a N-substituted carbazole parent structure directly or via a carbonyl group; wherein, R.sub.22 is a C1-C12 alkyl unsubstituted or substituted by one or more groups selected from the group consisting of halogen, OR.sub.24, SR.sub.24, C3-C8 cycloalkyl, phenyl, C4-C20 heteroaryl, and COOR.sub.24; or R.sub.22 is C6-C20 aryl or C4-C20 heteroaryl, each unsubstituted or substituted by one or more groups selected from the group consisting of halogen, C1-C20 alkyl, one or more F-substituted C1-C8 alkyl, CN, OR.sub.24, SR.sub.24, and NR.sub.25R.sub.26; or R.sub.22 is C6-C20 aroyl or C4-C20 heteroaroyl; R.sub.23 is selected from the group consisting of C1-C12 alkyl, C6-C20 aryl and C1-C4 alkoxy; R.sub.24 is selected from the group consisting of H, C1-C8 alkyl, phenyl, and C1-C20 alkyl phenyl, wherein the C1-C8 alkyl is optionally substituted by one or more of C3-C8 heterocyclic group, F and acetoxy; R.sub.25 and R.sub.26 are each independently C1-C4 alkyl, or OR.sub.24 substituted C2-C4 alkyl, or NR.sub.25R.sub.26 is a cyclic structure selected from ##STR00024## the carbazole parent structure is selected from the group consisting of carbazole, benzocarbazole and dibenzocarbazole, wherein hydrogen atoms on the parent structure are optionally substituted by one or more groups selected from C1-C20 alkyl, halogen, NO.sub.2, CN, OR.sub.27, C6-C20 aroyl, C4-C20 heteroaroyl and 4,5-diphenylimidazole-2-yl in addition to the above oxime ester group or carbonyl group connected with the oxime ester group, and adjacent substituents on the parent structure optionally form a new five-membered to seven-membered ring structure; wherein the C1-C20 alkyl is unsubstituted or substituted by one or more groups selected from halogen, C3-C8 cycloalkyl, C3-C8 heterocyclic group, phenyl, COOR.sub.27, OR.sub.27, PO(OC.sub.nH.sub.2n+1).sub.2, and Si(C.sub.nH.sub.2n+1).sub.3, wherein n is an integer from 1 to 4, or the C1-C20 alkyl is interrupted by one or more oxygen atoms when the number of carbon atoms is greater than 3; R.sub.27 is C1-C8 alkyl, or C3-C8 heterocyclic alkyl substituted C1-C8 alkyl; wherein aryl or heteroaryl in the C6-C20 aroyl and the C4-C20 heteroaroyl is unsubstituted or substituted by one or more groups selected from halogen, CN, ##STR00025## R.sub.24, OR.sub.24, SR.sub.24, NR.sub.25R.sub.26, COOR.sub.24 and R.sub.24SO.sub.2; and wherein R.sub.22, R.sub.23, R.sub.24 and NR.sub.25R.sub.26 have the same definition as corresponding R.sub.22, R.sub.23, R.sub.24 and NR.sub.25R.sub.26.

4. The photoinitiator composition of claim 3, wherein, the carbazolyl oxime ester photoinitiator is selected from the group consisting of the following compounds and any combination thereof: ##STR00026## ##STR00027## ##STR00028## ##STR00029## ##STR00030## ##STR00031## ##STR00032## ##STR00033## ##STR00034## ##STR00035##

5. The photoinitiator composition of claim 3, wherein, a molar ratio of the diaroyl carbazole compound to the carbazolyl oxime ester photoinitiator is 0.1:1 to 1.4:1.

6. The photoinitiator composition of claim 5, wherein, a molar ratio of the diaroyl carbazole compound to the carbazolyl oxime ester photoinitiator is 0.22:1 to 1.16:1.

7. A photocurable composition, comprising: a. at least one photoinitiator composition of claim 3, and b. at least one radically polymerizable compound.

8. The photocurable composition of claim 7, wherein, the radically polymerizable compound is selected from the group consisting of an acrylate compound, a methacrylate compound, a resin containing acrylate or methacrylate groups, and any combination thereof.

9. The photocurable composition of claim 7, wherein, component a accounts for 1-10% by weight of a total weight of all solids.

10. An ink comprising the photocurable composition of claim 7.

11. A coating comprising the photocurable composition of claim 7.

12. An adhesive comprising the photocurable composition of claim 7.

13. A photoresist, comprising: a. at least one photoinitiator composition of claim 3, b. a multifunctional acrylate monomer, c. an alkali soluble resin, d. a pigment, and e. a solvent.

14. A black photoresist, the photoresist of claim 13, wherein the pigment is well-dispersed carbon black or titanium black.

15. A black matrix prepared from the black photoresist of claim 14.

16. An optical spacer prepared from the black photoresist of claim 14.

17. A color filter device prepared by a filter processing process using the photoresist of claim 13 as a raw material.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) The following embodiments and comparative examples are provided for illustrating the present invention in details.

(2) Light Source Apparatus:

(3) 365 nm LED surface light source, Lantian Special Light Development Co., Ltd.
Test Equipment: Stereo microscope, COVS-50G, Guangzhou Mingmei Optoelectronic Technology Co., Ltd., wherein the unit of line width is m.
Experimental Materials: A compound of formula I-1, from compound preparation example 1; A compound of formula II-2, from compound preparation example 2; Omnirad DETX, a photoinitiator product of IGM Resin Company; Esacure 364, a photoinitiator product of IGM Resin Company; Omnirad EMK, a photoinitiator product of IGM Resin Company; OXE 02: a compound of formula IV-1, a photoinitiator product of BASF Company; OXE 03: a compound of formula IV-22, a photoinitiator product of BASF Company; NCI 831: a compound of formula IV-9, a product of ADEKA Company, Japan; PBG 304: a compound of formula IV-2, a product of Changzhou Qiangli Electronic New Material Co., Ltd.; Photomer 6010: aliphatic urethane triacrylate, a product of IGM Resin Company; DPHA: dipentaerythritol penta/hexaacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.; HPMA: polymaleic acid, a product of Aladdin Industries, USA.

COMPOUND PREPARATION EXAMPLES

Preparation of Diaroyl Carbazole Compounds

Preparation Example 1: Preparation of 9-ethyl-3,6-bis[4-(2,2,3,3-tetrafluoroproxy)benzoyl]carbazole (a compound of formula I-1)

1a. Preparation of 9-ethyl-3,6-bis(4-fluorobenzoyl)carbazole

(4) 19.5 g of N-ethyl carbazole is dissolved in 250 ml of dichloroethane, and 34 g of aluminum trichloride is added to obtain a solution. The temperature is kept at 05 C., and 40 g of p-fluorobenzoyl chloride is added drop wise into the solution, then the temperature is kept at 05 C. to react for 15 h. The reaction solution is added into 100 ml of 10% HCl solution of 0 C. in batches, followed by stirring for 30 min. After standing for 30 min, a dichloroethane phase is separated and washed with 50 ml of 2% sodium hydroxide solution for 30 min. The dichloroethane solution is vacuum distilled to recover dichloroethane. The residue is crystallized by adding 80 ml of ethyl acetate to obtain 30.5 g of a product as a white powder having a content of 98.5% and a yield of 69.5%.

1b. Preparation of 9-ethyl-3,6-bis [4-(2,2,3,3-tetrafluoropropoxy)benzoyl] carbazole

(5) 30 g of 9-ethyl-3,6-bis(4-fluorobenzoyl) carbazole prepared in step 1a, 25 g of 2,2,3,3-tetrafluoropropanol and 8 g of sodiam hydroxide are dissolved in 200 ml of pyridine and reacted at 70 C. for 18 h. Vacuum distillation is carried out to evaporate pyridine and redundant 2,2,3,3-tetrafluoropropanol. 100 ml of water and 250 ml of dichloroethane are added to the residue and stirred for 1 h. Then an aqueous phase is separated. The dichloroethane solution is washed twice with 100 ml of water, and vacuum distilled to recover dichloroethane. 150 ml of ethyl acetate and 2 g of activated carbon are added to the residue, followed by refluxing under heating for 1 h and filtering to remove activated carbon to obtain a filtrate. The filtrate is vacuum distilled to remove about 100 ml of ethyl acetate, then cooled to crystallize, and filtered. The filter cake is dried to obtain 27.8 g of a product as a light yellow powder having a content of 98.5% and a yield of 61.4%.

(6) The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3), [ppm]: 1.512 (t, 3H), 4.425-4.483 (m, 6H), 5.949-6.277 (m, 2H), 7.016-7.045 (m, 4H), 7.496-7.517 (d, 2H), 7.844-7.868 (d, 4H), 7.990-8.011 (d, 2H), 8.534 (s, 2H).

Preparation Example 2: Preparation of 11-(2-ethylhexyl)-5,8bis[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]-11H-benzo[z]carbazole (a compound of formula II-2)

2a. Preparation of 11-(2-ethylhexyl)-5,8-bis(4-fluorobenzoyl)-11H-benzo[a]carbazole

(7) 2.0 g of B03D is added into to a 50 ml single-necked flask, and 20 ml of dichioroethane is added to dissolve it, then 0.2 g of zinc chloride and 2.3 g of o-fluorobenzoyl chloride are added, and stirred and reacted at 80 C. for 10 h. After cooling, the reaction solution is washed twice with 20 ml of water, and then concentrated under reduced pressure to dryness to obtain 4.0 g of a brown viscous substance, which is used in the reaction of 2b without purification.

2b. Preparation of 11-(2-ethylhexyl)-5,8bis[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]-11H-benzo[a]carbazole

(8) 4.0 g of 11-(2-ethylhexyl)-5,8-bis(4-fluorobenzoyl)-11H-benzo[a]carbazole obtained in step 2a is dissolved with 20 ml pyridine in a 50 ml single-necked flask, then 2.2 g of tetrafluoropropanol and 1.2 g of sodium hydroxide are added, heated to 80 C. and stirred for 5 h. The reaction solution is added dropwise to 100 ml of water, then stirred with 100 ml of dichloroethane for 1 h, and allowed to stand for separation. The separated dichloroethane solution is concentrated under reduced pressure to dryness to obtain 4.7 g of brown solid. The brown solid is dissolved under heating in a mixed solvent of 20 ml ethyl acetate and 20 ml ethanol, then 0.25 g activated carbon is added, followed by refluxing for 1 h. The resulted solution is hot filtered, and the filtrate is cooled down to precipitate a yellow crystal, which is dried to obtain 2.5 g product. The total yield of the two-step reaction is 51.3%, and the content of 11-(2-ethylhexyl)-5,8bis[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]-11H-benzo[a]carbazole is 98.51%.

(9) The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3), [ppm]: 0.754-0.789 (m, 6H), 1.126-1.328 (m, 8H), 2.113 (s, 1H), 4.369-4.452 (t, 2H), 4.513-4.599 (t, 2H), 4.928 (m, 2H), 4.994-5.342 (m, 1H), 5.537-5.885 (m, 1H), 7.251-7.272 (m, 4H), 7.430-7.455 (d, 1H)), 7.566-7.811 (m, 6H), 7.950-7.979 (d, 1H), 8.430 (s, 1H), 8.571 (s, 1H), 8.668-8.695 (d, 1H). 8.736-8.764 (d, 1H)).

Preparation of Photoinitiator Compositions

Composition Preparation Example 1

(10) 12 g of the compound of formula II-2 and 28 g of OXE-02 are mixed and ground in a mortar to obtain 40 g of a composition. A molar ratio of the diaroyl carbazole compound to the carbazolyl oxime ester photoinitiator is 0.22.

Composition Preparation Example 2

(11) 12 g of the compound of formula I-1 and 28 g of OXE-02 are mixed and ground in a mortar to obtain 40 g of a composition. A molar ratio of the diaroyl carbazole compound to the carbazolyl oxime ester photoinitiator is 0.27.

Composition Preparation Example 3

(12) 12 g of the compound of formula I-1 and 12 g of OXE-03 are mixed and ground in a mortar to obtain 24 g of a composition. A molar ratio of the diaroyl carbazole compound to the carbazolyl oxime ester photoinitiator is 1.16.

Composition Preparation Example 4

(13) 12 g of the compound of formula II-2 and 28 g of OXE-03 28 g are mixed and ground in a mortar to obtain 40 g of a composition. A molar ratio of the diaroyl carbazole compound to the carbazolyl oxime ester photoinitiator is 0.41.

(14) Preparation of Alkali-Soluble Resin

(15) 18 g of benzyl methacrylate, 6 g of methacrylic acid, 6 g of hydroxyethyl methacrylate, 1.5 g of azobisisobutyronitrile, 0.6 g of dodecanethiol, and 200 ml of toluene are added into a 1 L constant pressure dropping funnel, 100 ml of toluene is added into a 500 ml four-necked flask, air in the four-necked flask is replaced with nitrogen, and the temperature is increased to 80 C., then the solution in the funnel is added therein dropwise. After reacting for 6 h, the reaction solution is cooled down and filtered to obtain 24 g of a white alkali-soluble resin.

Photoresist Composition Examples and Comparative Examples

(16) The examples and comparative examples are prepared according to the components described in tables 1 to 4.

(17) The compositions prepared in the composition preparation examples can be used as the initiator and sensitizing agent, or can be mixed according to the proportion in the table and dissolved in the PMA, and then the composition solution is mixed with the black color paste in proportion. After the components are mixed well, the resulted is coated onto a glass slide using a 10 m wire rod, and put into an oven for drying at 90 C. for 5 min. A 365 nm light source is used to perform curing with a 120 m mask, and then development is carried out using a 1% NaOH solution at 25 C., followed by soaking and cleaning for 10 s with pure water. After diving in an oven at 90 C. for 30 minutes, the line width of the developed image is measured. The unit of line width is m.

(18) TABLE-US-00001 TABLE 1 Examples Comarative examples 1 2 3 4 1 2 3 4 5 Compound of 0.024 0.04 0.024 0.04 0 0.08 0.056 0.056 0 formula I-1 OXE 02 0.056 0.04 0 0 0.08 0 0.024 0 0 OXE 03 0 0 0.056 0.04 0 0 0 0.024 0.08 PMA 2 2 2 2 2 2 2 2 2 black color 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 paste sensitizing 0.32 0.75 0.49 1.16 0 0 1.74 2.69 0 agent/initiator molar ratio

(19) TABLE-US-00002 TABLE 2 Comparative Comparative Example 5 Example 6 example 6 example 7 Compound of 0.024 0.024 0 0 formula I-1 NCI 831 0.056 0 0.08 0 PBG 304 0 0.056 0 0.08 PMA 2 2 2 2 black color 4.5 4.5 4.5 4.5 paste sensitizing 0.27 0.23 0 0 agent/initiator molar ratio

(20) TABLE-US-00003 TABLE 3 Example Example Example Comparative examples 7 8 9 1 2 8 9 Compound of 0.024 0.04 0.024 0 0 0.056 0.08 formula II-2 OXE 02 0 0 0.056 0.08 0 0 0 OXE 03 0.056 0.04 0 0 0.08 0.024 0 PMA 2 2 2 2 2 2 2 black color 4.5 4.5 4.5 4.5 4.5 4.5 4.5 paste sensitizing 0.41 0.96 0.27 0 0 2.24 0 agent/initiator molar ratio

(21) TABLE-US-00004 TABLE 4 Comparative 10 Comparative 11 Comparative 12 Omnirad 0.024 0 0 DETX ESacure 0 0.024 0 3644 Omnirad 0 0 0.024 EMK OXE 02 0.056 0.056 0.056 PMA 2 2 2 black color 4.5 4.5 4.5 paste sensitizing 0.79 0.25 0.65 agent/initiator molar ratio

(22) The examples and comparative examples in tables 1, 2 and 4 are used to perform coating, curing, developing, and measuring. The data are shown in tables 5, 6, 7 and 8. The results show that: examples where the compound of formula I-1 is used as a sensitizing agent in combination with various carbazolyl oxime esters at a ratio within the range of the present invention exhibit significantly better development effect than comparative examples in which a sensitizing agent is not used, or a sensitizing agent is used alone or the amount of sensitizing agent is outside the range of the present invention. In particular, the results of comparative example 2 show that the compound of formula I-1 alone cannot form a developed pattern, and has almost no effect of initiating polymerization. Comparing the formulations in table 4 and the data in table 8, it is found that the compound of formula I-1 as a sensitizing agent has significantly better sensitising effect than thioxanthone, coumarin and tetraethyl Michler's ketone, and the developing line width of the latter three is even smaller than that of comparative example 1 in which oxime ester is used alone.

(23) The examples and comparative examples in table 3 are used to perform coating, curing, developing, and measuring. The data are shown in table 7. The results show that: examples where the compound of formula II-2 is used as a sensitizing agent in combination with various carbazolyl oxime esters at a ratio within the range of the present invention exhibit significantly better development effect than comparative examples in which a sensitizing agent is not used, or a sensitizing agent is used alone or the amount of sensitizing agent is outside the range of the present invention. In particular, the results of comparative example 9 show that the compound of formula II-2 alone cannot form a developed pattern, and has almost no effect of initiating polymerization. Comparing the formulations in table 4 and the data in table 8, it is found that the compound of formula II-2 as a sensitizing agent has significantly better sensitising effect than of thioxanthone, coumarin, and tetraethyl Michler's ketone.

(24) TABLE-US-00005 TABLE 5 Examples Comparative examples 1 2 3 4 1 2 3 4 5 Break 20 20 34 34 20 20 20 20 35 point/s Line width 135.8 127.0 141.8 160.4 119.6 0 104.2 113.3 131.5

(25) TABLE-US-00006 TABLE 6 Comparative Comparative Example 5 Example 6 example 6 example 7 Break point/s 32 25 30 22 Line width 163.0 130.0 138.0 115.0

(26) TABLE-US-00007 TABLE 7 Example Example Example Comparative examples 7 8 9 1 5 8 9 Break 34 30 21 20 35 22 20 point/s Line width 143.2 133.6 126.0 119.6 131.5 110.2 0

(27) TABLE-US-00008 TABLE 8 Comparative Comparative Comparative example 10 example 11 example 12 Break point/s 22 25 24 Line width 112.0 118.0 109.0

Adhesive Examples

(28) The examples and comparative examples are prepared according to the components described in table 9. After the components are mixed well, they are coated onto a glass slide using a 50 m wire rod to form a film, which is then cured under a 365 nm light source with a mask. After curing, the film weight is measured. After immersing in acetone at room temperature for 36 h, the film weight is measured again, and the gel conversion rate is calculated.

(29) TABLE-US-00009 TABLE 9 Example 10 Example 11 Example 13 Photomer 6010 5 5 5 HPMA 4.5 4.5 4.5 OXE 02 0 0 0.5 Composition preparation 0.5 0 0 example 1 Composition preparation 0 0.5 0 example 2

(30) Test data of the comparative examples and examples in table 9 are shown in Table 10. The data show that the adhesives in embodiments 10 and 11 in which the photocurable composition of the present inventions are used have significantly higher double bond gel conversion rate under lights than that in comparative example 13 in which oxime ester photoinitiator is used alone.

(31) TABLE-US-00010 TABLE 10 Example 10 Example 11 Comparative example 13 Gel conversion 92.5% 92.7% 85.2% rate

(32) In summary, there is a significant sensitizing effect when the novel diaroyl carbazole compounds provided by the present invention are used together with carbazolyl oxime ester photoinitiators in photoresist compositions or adhesives. The best sensitising effect is shown when the molar ratio of the diaroyl carbazole compound to the carbazolyl oxime ester photoinitiator is 0.1 to 1.4.