PHOTOINITIATOR COMPOSITION CONTAINING ACYLCARBAZOLE DERIVATIVE AND CARBAZOLYL OXIME ESTER, AND USE THEREOF IN PHOTOCURABLE COMPOSITION

Abstract

Provided is a photoinitiator composition containing an acylcarbazole derivative and a carbazolyl oxime ester. The photoinitiator composition is used in a photocurable composition, especially a photoresist formulation, and exhibits the best sensibilization effect when the molar ratio of the acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is between 0.1 and 1.4.

Claims

1. A photoinitiator composition comprising a sensitizing agent and a carbazolyl oxime ester, wherein the sensitizing agent is selected from the group consisting of acylcarbazole derivatives of formula I, acyl benzocarbazole derivatives of formula II-A, II-B or II-C, acyl dibenzocarbazole derivatives of formula II-D or II-E, and biyclic carbazole derivatives of formula II-F, II-G or II-H, and wherein the carbazolyl oxime ester is selected from the group consisting of compounds of formulas III and IV-A to IV-E: ##STR00027## ##STR00028## ##STR00029## wherein, R.sub.1, R.sub.2, R.sub.4, R.sub.5, R.sub.7, R.sub.8, R.sub.24, R.sub.25, R.sub.27, R.sub.28, R.sub.34, R.sub.35, R.sub.37, R.sub.38, R.sub.41, R.sub.42, R.sub.44, R.sub.45, R.sub.47, R.sub.48, R.sub.54, R.sub.55, R.sub.61, R.sub.62, R.sub.67, R.sub.68, R.sub.102-R.sub.108, R.sub.112, R.sub.114, R.sub.115, R.sub.117, R.sub.118, R.sub.121, R.sub.122 and R.sub.124-R.sub.127 are each independently selected from the group consisting of H, halogen, C1-C8 alkyl, C1-C8 alkoxy and CN; R.sub.11, R.sub.12, R.sub.14, R.sub.15, R.sub.17, R.sub.18, R.sub.71, R.sub.72, R.sub.74, R.sub.75, R.sub.84, R.sub.85, R.sub.87, R.sub.88, R.sub.91, R.sub.92, R.sub.94, R.sub.97 and R.sub.98 are each independently selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkoxy, halogen, CN and NO.sub.2; R.sub.6, R.sub.26, R.sub.36, R.sub.46, R.sub.56, R.sub.66, R.sub.106 and R.sub.116 are each independently selected from the group consisting of H, halogen, CN, C1-C8 alkyl, C1-C12 alkyl acyl, C5-C6 substituted C1-C3 alkyl acyl, C6-C20 aroyl, C4-C20 heteroaryl acyl, ##STR00030## or wherein the above groups can optionally be connected with other adjacent substituents together with the parent structure to form a five-membered to seven-membered ring; wherein the C6-C20 aroyl and the C4-C20 heteroaryl acyl are independently substituted by substituents selected from the group consisting of H, halogen, R.sub.40, OR.sub.50, SR.sub.50, NR.sub.51R.sub.52, COOR.sub.50 and CONR.sub.51R.sub.52; R.sub.9, R.sub.29, R.sub.39, R.sub.49, R.sub.59, R.sub.69, R.sub.19, R.sub.79, R.sub.89 and R.sub.99 are each independently selected from the group consisting of C1-C12 straight or branched alkyl, C2-C12 alkenyl, C3-C12 alkenyl alkyl, with hydrogen atoms on the carbon atoms being unsubstituted or substituted by one or more groups selected from the group consisting of: phenyl, C5-C6 cycloalkyl, C3-C6 heterocyclic group, halogen, COOR.sub.20, OR.sub.20, SR.sub.20, PO(OC.sub.nH.sub.2n+1).sub.2, and Si(C.sub.nH.sub.2n+1).sub.3, and wherein n is an integer from 1 to 4; or R.sub.9, R.sub.29, R.sub.39, R.sub.49, R.sub.59, R.sub.69, R.sub.19, R.sub.79, R.sub.89 and R.sub.99 are each independently selected from the group consisting of C3-C12 alkyl and C3-C12 alkenyl alkyl, with its alkyl chain being interrupted by one or more groups selected from the group consisting of O, S, SO, SO.sub.2, CO and COO; or R.sub.9, R.sub.29, R.sub.39, R.sub.49, R.sub.59, R.sub.69, R.sub.19, R.sub.79, R.sub.89 and R.sub.99 are each independently selected from the group consisting of C2-C12 alkylene and double bond-containing C4-C12 alkylene, wherein groups connected with the terminal of the C2-C12 alkylene and the double bond-containing C4-C12 alkylene have the same definition as the groups originally connected with R.sub.9, R.sub.29, R.sub.39, R.sub.49, R.sub.59, R.sub.69, R.sub.19, R.sub.79, R.sub.89 and R.sub.99; or R.sub.9, R.sub.29, R.sub.39, R.sub.49, R.sub.59, R.sub.69, R.sub.19, R.sub.79, R.sub.89 and R.sub.99 are each independently phenyl unsubstituted or substituted by one or more groups selected from the group consisting of: C1-C8 alkyl, halogen, OR.sub.20, SR.sub.20, COR.sub.30, CN, COOH and ##STR00031## R.sub.16, R.sub.76, R.sub.86, R.sub.96 and R.sub.116 are each independently selected from the group consisting of C6-C20 aroyl, C4-C20 heteroaryl acyl, NO.sub.2, 4,5-diphenylimidazol-2yl; and when R.sub.16, R.sub.76, R.sub.86, R.sub.96 and R.sub.116 are each independently selected from the group consisting of C6-C20 aroyl or C4-C20 heteroaryl acyl, substituents at ortho-position of the acyl on the aromatic ring or heteroaromatic ring can be optionally connected with the carbazole ring; R.sub.13, R.sub.73, R.sub.83, R.sub.93 and R.sub.113 are each independently selected from the group consisting of C1-C8 alkyl, and C1-C3 alkyl substituted by C5-C6 cycloalkyl or phenyl at terminal thereof, or the above-mentioned alkyl can optionally form a ring together with carbon or substituents on the carbon on an adjacent parent ring; provided that R.sub.16, R.sub.76, R.sub.86 and R.sub.96 on the same molecule are each independently selected from C6-C20 aroyl or C4-C10 heteroaroyl group; or R.sub.13, R.sub.73, R.sub.83 and R.sub.93 are each independently selected from the group consisting of C6-C20 aryl, C6-C20 aroyl and C4-C20 heteroaroyl, provided that R.sub.16, R.sub.76, R.sub.86 and R.sub.96 on the same molecule are each independently selected from the group consisting of C6-C20 aroyl, C4-C20 heteroaryl acyl, NO.sub.2 and 4,5-diphenylimidazol-2-yl ##STR00032## R.sub.10, R.sub.70, R.sub.50, R.sub.90, R.sub.110, R.sub.120 and R.sub.130 are each independently selected from C1-C12 alkyl and C6-C20 aryl; Ar.sub.1, Ar.sub.2, Ar.sub.3, Ar.sub.4, Ar.sub.5, Ar.sub.6, Ar.sub.7 and Ar.sub.8 are each independently selected from C6-C20 aroyl and C4-C20 heteroaroyl, wherein ortho-position of acyl on Ar.sub.1, Ar.sub.2 and Ar.sub.5 can be optionally connected to a carbazole ring via O atom or S atom; Y is straight or branched C1-C3 alkylene; m=0 or 1; substituents on all the above C6-C20 aryl and C4-C20 heteroaryl comprise H, halogen, CN, R.sub.40, OR.sub.50, SR.sub.50, NR.sub.51R.sub.52, COOR.sub.50 and CONR.sub.51R.sub.52; R.sub.20 and R.sub.30 are each independently selected from the group consisting of H, C1-C8 alkyl, C1-C8 alkyl substituted by one or more groups selected from halogen and C5-C6 cycloalkyl, phenyl, phenyl substituted by one or more halogen, and C1-C4 alkyl acyl; R.sub.40 and R.sub.50 are each independently selected from the group consisting of C1-C8 alkyl, C1-C8 alkyl substituted by one or more groups selected from F, C1 and hydroxyl, C3-C8 alkyl interrupted by one or more oxygen atoms and substituted by hydroxyl and acetoxy, a five-membered or six-membered ring containing one or two of heteroatoms selected from O, S and N, phenyl, and C1-C4 alkylphenyl; R.sub.51 and R.sub.52 are each independently selected from the group consisting of C1-C4 alkyl, and hydroxyl substituted C1-C4 alkyl; or NR.sub.51R.sub.52 is a ring structure selected from the group consisting of ##STR00033##

2. The photoinitiator composition of claim 1, wherein the sensitizing agent of formula I is selected from compounds of formulas I-1 to I-36 and any combination thereof: ##STR00034## ##STR00035## ##STR00036## ##STR00037## ##STR00038## ##STR00039##

3. The photoinitiator composition of claim 1, wherein the sensitizing agent of formulas II-A to II-H is selected from compounds of formulas II-1 to II-16 and any combination thereof: ##STR00040## ##STR00041## ##STR00042## ##STR00043## ##STR00044##

4. The photoinitiator composition of claim 1, wherein the carbazolyl oxime ester of formula III is selected from compounds of formulas III-1 to III-17 and any combination thereof: ##STR00045## ##STR00046## ##STR00047## ##STR00048## ##STR00049##

5. The photoinitiator composition of claim 1, wherein the carbazolyl oxime ester of formulas IV-A to IV-E is selected from compounds of formulas IV-1 to IV-21 and any combination thereof: ##STR00050## ##STR00051## ##STR00052## ##STR00053## ##STR00054## ##STR00055##

6. The photoinitiator composition of claim 1, wherein a molar ratio of the sensitizing agent to the carbazolyl oxime ester is 0.1:1 to 1.4:1, preferably 0.22:1 to 1.3:1.

7. A photocurable composition, comprising: a. at least one photoinitiator composition of claim 1, 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 a acrylate compound, a methacrylate compound, a resin containing acrylate or methacrylate groups, and any mixtures thereof.

9. The photocurable composition of claim 7, wherein component a accounts for 0.2-10%, preferably 1-8% by weight of a total weight of all solid components.

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 the following components: a. at least one photoinitiator composition of claim 1, 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.

18. (canceled)

Description

DETAILED DESCRIPTION OF EMBODIMENTS

[0058] The following non-limiting embodiments and comparative examples are provided for illustrating the present invention in details.

[0059] Light Source Apparatus:

[0060] 365 nm LED surface light source, Lantian Special Light Development Co., Ltd.

[0061] Testing Equipment:

[0062] Stereo microscope, COVS-50G, Guangzhou Mingmei Optoelectronic Technology Co., Ltd.

[0063] Experimental Materials:

[0064] A compound of formula of I-1: from compound preparation example 3;

[0065] A compound of formula of I-27: from compound preparation example 4;

[0066] A compound of formula of I-34: from compound preparation example 1;

[0067] A compound of formula of II-1: from compound preparation example 5;

[0068] A compound of formula of II-3: from compound preparation example 6;

[0069] A compound of formula of II-5: from compound preparation example 2;

[0070] Omnirad DETX: a photoinitiator product of IGM Resin Company;

[0071] Esacure 3644: a photoinitiator product of IGM Resin Company;

[0072] Omnirad EMK: a photoinitiator product of IGM Resin Company;

[0073] OXE 02: a compound of formula of III-1: a photoinitiator product of BASF Company;

[0074] OXE 03: a compound of formula of IV-6: a photoinitiator product of BASF Company;

[0075] NCI 831: a compound of formula of III-9: a product of ADEKA Company, Japan;

[0076] PBG 304: a compound of formula of III-2: a product of Changzhou Qiangli Electronic New Material Co., Ltd.;

[0077] Photomer 6010: aliphatic urethane triacrylate, a product of IGM Resin Company, Netherlands;

[0078] DPHA: dipentaerythritol penta/hexaacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.;

[0079] HPMA: polymaleic acid, a product of Aladdin Industries, USA.

PREPARATION EXAMPLES

[0080] Preparation of Acylcarbazole Derivatives

Compound Preparation Example 1 Preparation of 9-ethyl-3,6-bis[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]carbazole (a Compound of Formula I-34)

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

[0081] 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 0˜-5° C., and 40 g of p-fluorobenzoyl chloride is added dropwise into the solution, then the temperature is kept at 0-5° 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. 9-ethyl-3,6-bis [4-(2,2,3,3-tetrafluoropropoxy) benzoyl]carbazole

[0082] 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 sodium 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%.

[0083] The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3), δ[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).

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

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

[0084] 2.0 g of B03D is added into to a 50 mL single-necked flask, and 20 mL of dichloroethane 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. 11-(2-ethylhexyl)-5,8bis[4-(2,2,3,3-tetrafluoropropoxy)benzoyl]-11H-benzo[a]carbazole

[0085] 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%. The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3), δ[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, 11H), 8.668-8.695 (d, 1H), 8.736-8.764 (d, 1H)).

Compound Preparation Example 3: Preparation of 3-(2-methylbenzoyl)-9-ethylcarbazole (a Compound of Formula I-1)

[0086] The operation as described in step 1.a in example 1 on page 81 of the specification of CN100528838C is incorporated by reference. Wherein, o-methylbenzoyl chloride is used instead of benzoyl chloride. 5.88 g (44.1 mmol) of AClC.sub.3 is added to 7.83 g (40.1 mmol) of N-ethylcarbazole in 40 mL of CH.sub.2Cl.sub.2 to obtain a solution. The temperature is kept at below 10° C., and 6.5 g (42 mmol) o-methylbenzoyl chloride is added dropwise into the solution, followed by stirring for 4 h at room temperature to obtain a reaction mixture. Then, the reaction mixture is added dropwise into hydrochloric acid-containing ice-water. An organic phase is separated, washed with water until the pH is 7, dried over anhydrous MgSO4, purified by silica gel column chromatography with dichloromethane-hexane (1:1) as eluent, obtaining 9.45 g of a white solid having a yield of 75.1% and a content of 98.51%.

[0087] The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3), δ[ppm]: 1.431/1.455/1.479 (t, 3H); 2.349 (s, 3H); 4.352/4.376/4.400/4.424 (quartet, 2H); 7.246-7.530 (m, 8H); 7.989/7.994/8.018/8.023 (dd, 1H); 8.065/8.090 (d, 1H); 8.561/8.564 (d, 1H).

Compound Preparation Example 4: Preparation of 3,6-bis(2-methylbenzoyl)-9-(3-methylbutyl)carbazole (a Compound of Formula I-27)

[0088] 4.5 g (19 mmol) of N-(3-methylbutyl) carbazole is dissolved in 20 mL of 1,2-dichloroethane, and the temperature is cooled to −5° C. in a low temperature bath, followed by adding 5.3 g (40 mmol) of anhydrous AlCl.sub.3. Then, a solution comprising 6.0 g (38.8 mmol) of o-methylbenzoyl chloride and 10 g of dichloroethane is added dropwise therein. The temperature is kept at 5° C. to react for 3 h. The reaction solution is added dropwise to 20 ml of concentrated hydrochloric acid and 40 ml of water having a temperature not exceeding 10° C., followed by stirring for 30 min. After standing, an organic phase is separated, washed with 80 mL of water until the pH is 7, and concentrated under a reduced pressure to remove dichloroethane, obtaining 10.0 g of light yellow vitreous substance. 150 ml of absolute ethanol is added to completely dissolve the vitreous substance under refluxing and heating. The resulted solution is cooled to precipitate a crystal, followed by filtration to give a filter cake which is then dried to obtain 8.0 g of white powder. HPLC analysis shows the content is 98.53%, and the yield is 96.4%.

[0089] The structure is confirmed by .sup.1H-NMR spectrum (CDCl.sub.3), δ [ppm]: 1.031/1.052 (d, 6H); 1.681-1.815 (m, 3H); 2.344 (s, 6H); 4.347/4.374/4.397 (t, 2H)); 7.289-7.467 (m, 10H); 8.018/8.023/8.047/8.052 (dd, 2H); 8.535/8.540 (s, 2H).

Compound Preparation Example 5: Preparation of 5-(2,4,6-trimethylbenzoyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazole (Compound of Formula II-1)

[0090] The operation as described in step (a) in example 18 on page 63 of the specification of CN103153952A is incorporated by reference. In a 1 L reaction flask, 47.16 g (143.0 mmol) of 11-(2-ethylhexyl)-11H-benzo[a]carbazole is dissolved in 400 ml CH.sub.2Cl.sub.2 to obtain a solution. 20.0 g (150 mmol) of AlCl.sub.3 is added thereto. The temperature is kept at 0° C., and 27.45 g (150 mmol) of 2,4,6-trimethylbenzoyl chloride is added dropwise to the solution, followed by stirring for 2 h at room temperature to obtain a reaction mixture. Then, the reaction mixture is poured into ice-water, and a CH.sub.2Cl.sub.2 solution phase is separated. The aqueous phase is extracted twice with CH.sub.2Cl.sub.2. The organic phases are combined and washed with water until the pH is 7, and dried over MgSO4. After most CH.sub.2Cl.sub.2 is removed by concentration, 230 ml of n-hexane is added therein to precipitate a beige solid. The solid is dried under a reduced pressure to obtain 65.0 g of a product having a content of 99.1% and a yield of 95.6%. .sup.1H-NMR spectrum confirms that the product is 5-(2,4,6-trimethylbenzoyl)-11-(2-ethylhexyl)-11H-benzo[a]carbazole, δ[ppm, CDCl.sub.3]: 0.805/0.823/0.841 (t, 3H); 0.872/0.891/0.909 (t, 3H); 1.184-1.408 (m, 9H); 2.198 (s, 6H); 2.390 (s, 3H); 4.670-4.785 (m, 2H); 6.946 (s, 2H); 7.271/7.288 (d, 1H); 7.450/7.453//7.471/7.474//7.489/7.491 (dt, 1H); 7.550/7.571 (d, 1H); 7.667/7.670//7.684/7.687/7.691//7.705/7.709 (dt, 1H); 7.720/7.724//7.738/7.742/7.746//7.759/7.762 (dt, 1H); 7.939/7.958 (d, 1H); 8.361 (s, 11H); 8.643/8.662 (d, 2H); 9.629/9.632//9.650/9.653 (dd, 1H).

Compound Preparation Example 6: Preparation of 5-(2,4,6-trimethylbenzoyl)-8-[2-(2,2,3,3-tetrafluoropropoxy)benzoyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazole (a Compound of Formula II-3)

[0091] Part operations as described in steps 18.a and 18.b in example 18 on pages 63-64 of the specification of CN103153952A are incorporated by reference. Wherein, 2,2,3,3-tetrafluoro-1-propanol is used instead of 2-methoxyethanol to carry out the etherification reaction, and a etherification product is extracted to obtain a beige solid. .sup.1H-NMR spectrum confirms that the solid is 5-(2,4,6-trimethylbenzoyl)-8-[2-(2,2,3,3-tetrafluoropropoxy)benzoyl]-11-(2-ethylhexyl)-11H-benzo[a]carbazole, δ[ppm, CDCl.sub.3]: 0.795/0.819/0.843/0.870/0.894 (dt, 6H); 1.170-1.465 (m, 9H); 2.189 (s, 6H); 2.398 (s, 3H); 4.243/4.281/4.318 (t, 2H); 4.660-4.817 (m, 2H); 5.072/5.091/5.110//5.249/5.267/5.286//5.425/5.444/5.463 (tt, 1H); 6.958 (s, 2H); 6.958/6.989 (d, 1H);

[0092] 7.158/7.183/7.207 (t, 1H); 7.456-7.549 (m, 3H); 6.682-7.795 (m, 3H); 8.362 (s, 1H); 8.607/8.611 (d, 1H); 8.621/8.649 (d. 1H); 9.540/9.544//9.568/9.572 (dd, 1H).

Composition Preparation Example 1

[0093] 12 g of the compound of formula II-5 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 acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 0.22:1.

Composition Preparation Example 2

[0094] 12 g of the compound of formula I-34 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 acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 0.27:1.

Composition Preparation Example 3

[0095] 12 g of the compound of formula II-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 acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 0.37:1.

Composition Preparation Example 4

[0096] 12 g of the compound of formula I-27 and 28 g of OXE-03 are mixed and ground in a mortar to obtain 40 g of a composition. A molar ratio of the acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 0.75:1.

Composition Preparation Example 5

[0097] 12 g of the compound of formula I-34 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 acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 1.16:1.

Composition Preparation Example 6

[0098] 12 g of the compound of formula II-5 and 28 g of OXE-03 are mixed and ground in a mortar to obtain 40 g of a composition. A molar ratio of the acylcarbazole derivative to the carbazolyl oxime ester photoinitiator is 0.41:1.

[0099] Preparation of Alkali-Soluble Resin

[0100] 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.

Preparation of Black Color Paste

[0101] 50 g of the alkali-soluble resin, 50 g of P25 carbon black, 100 g of DPHA, and 250 g of propylene glycol methyl ether acetate are added into a 500 mL beaker, and mixed using a high-speed shear mixer at a speed of 3000 r/min for 15 min to obtain a black color paste.

Photoresist Examples 1-14 and Comparative Examples 1-14

[0102] The examples and comparative examples are prepared according to the components described in tables 1 to 4.

[0103] 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 μm 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 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 drying in an oven at 90° C. for 30 minutes, the line width of the developed image is measured.

TABLE-US-00001 TABLE 1 Examples Comparative examples 1 2 3 1 2 3 4 OXE 02 0.056 0.04 0.032 0.08 0.056 0 0.024 Compound of 0.024 0.04 0.048 0 0 0.08 0.056 formula II-1 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 0.37 0.87 1.3 0 0 0 2.02 agent/initiator molar ratio

TABLE-US-00002 TABLE 2 Examples Comparative examples 4 5 1 5 6 OXE 02 0.056 0.04 0.08 0 0.024 Compound of formula 0.024 0.04 0 0.08 0.056 I-34 PMA 2 2 2 2 2 black color paste 4.5 4.5 4.5 4.5 4.5 sensitizing 0.27 0.62 0 0 1.45 agent/initiator molar ratio

TABLE-US-00003 TABLE 3 Examples Comparative examples 6 7 8 9 7 8 9 OXE 03 0.056 0.04 0.056 0.04 0.08 0.024 0.024 Compound of 0.024 0.04 0 0 0 0.056 0 formula I-34 Compound of 0 0 0.024 0.04 0 0 0.056 formula II-5 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 0.49 1.16 0.41 0.96 0 2.69 2.24 agent/initiator molar ratio

TABLE-US-00004 TABLE 4 Examples Comparative examples 10 11 12 13 1 10 11 12 OXE 02 0.056 0.056 0.056 0.056 0.08 0.056 0.056 0.056 Compound of 0.024 0 0 0 0 0 0 0 formula I-27 Compound of 0 0.024 0 0 0 0 0 0 formula II-5 Compound of 0 0 0.024 0 0 0 0 0 formula II-3 Compound of 0 0 0 0.024 formula I-1 Omnirad DETX 0 0 0 0 0 0.024 0 0 Esacure3644 0 0 0 0 0 0 0.024 0 Omnirad EMK 0 0 0 0 0 0 0 0.024 PMA 2 2 2 2 2 2 2 2 black color paste 4.5 4.5 4.5 4.5 4.5 4.5 4.5 4.5 sensitizing 0.37 0.22 0.25 0.56 0 0.66 0.21 0.54 agent/initiator molar ratio

TABLE-US-00005 TABLE 5 Example Example Comparative Comparative 14 15 example 13 example 14 NCI 831 0.056 0 0.08 0 PBG 304 0 0.056 0 0.08 Compound of formula 0.024 0.024 0 0 I-34 PMA 2 2 2 2 black color paste 4.5 4.5 4.5 4.5 sensitizing 0.27 0.23 0 0 agent/initiator molar ratio

[0104] The examples and comparative examples in table 1 are used to perform coating, curing, developing, and measuring. The data are shown in table 6. The results show that: examples where OXE 02 is used as an initiator, and the compound of formula II-1 is used as a sensitizing agent at a ratio within the range of the present invention exhibit significantly greater developing line width values than the corresponding comparative examples, and exhibit significantly better sensibilization 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 3 show that the compound of formula II-1 alone has almost no effect of initiating polymerization.

TABLE-US-00006 TABLE 6 Examples Comparative examples 1 2 3 1 2 3 4 Break point/s 20 19 19 20 20 15 19 120 μm Line 135 129 122 119.58 103.78 0 115.12 width/μm

[0105] The examples and comparative examples in table 2 are used to perform coating, curing, developing, and measuring. The data are shown in table 7. The results show that: examples where

[0106] OXE 02 is used as an initiator, and the compound of formula I-34 is used as a sensitizing agent at a ratio within the range of the present invention exhibit significantly greater developing line width values than the corresponding comparative examples, and exhibit significantly better sensibilization 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.

TABLE-US-00007 TABLE 7 Examples Comparative examples 4 5 1 5 6 Break point/s 20 20 20 20 20 120 μm Line 135.81 127 119.58 0 104.17 width/μm

[0107] The examples and comparative examples in table 3 are used to perform coating, curing, developing, and measuring. The data are shown in table 8. The results show that: examples where

[0108] OXE 03 is used as an initiator, and the compound of formula II-5 or I-34 is used as a sensitizing agent at a ratio within the range of the present invention exhibit significantly greater developing line width values than the corresponding comparative examples, and exhibit significantly better sensibilization than comparative examples in which a sensitizing agent is not used, or the amount of sensitizing agent is outside the range of the present invention.

TABLE-US-00008 TABLE 8 Examples Comparative examples 6 7 8 9 7 8 9 Break point/s 34 34 34 30 35 20 22 120 μm Line 141.8 160.4 143.2 133.6 131.5 113.3 110.2 width/μm

[0109] The examples and comparative examples in table 4 are used to perform coating, curing, developing, and measuring. The data are shown in table 9. The results show that: examples where

[0110] OXE 02 is used as an initiator, and the compound of formula I-27, II-5 or II-3 is used as a sensitizing agent exhibit significantly greater curing and developing line width values than the corresponding comparative examples, and exhibit significantly better sensibilization than comparative examples in which a sensitizing agent is not used or Esacure 3644, Omnirad DETX or EMK is used as a sensitizing agent.

TABLE-US-00009 TABLE 9 Examples Comparative examples 10 11 12 13 1 10 11 12 Break point/s 32 21 32 30 20 22 25 24 120 μm Line 131 126 123 132 119 112 118 109 width/μm

[0111] The examples and comparative examples in table 5 are used to perform coating, curing, developing, and measuring. The data are shown in table 10. The results show that: examples where NC1831 or PBG304 is used as an initiator, and the compound of formula I-35 is used as a sensitizing agent exhibit significantly greater curing and developing line width values than the corresponding comparative examples, and exhibit significantly better sensibilization than comparative examples in which a sensitizing agent is not used.

TABLE-US-00010 TABLE 10 Comparative Examples examples 14 15 13 14 Break point/s 32 25 30 22 120 μm Line 163 130 138 115 width/μm

Adhesive Examples 16, 17 and Comparative Example 15

[0112] The examples and comparative examples are prepared according to the components described in table 11. After the components are mixed well, they are coated onto a glass slide using a 50 μm 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.

TABLE-US-00011 TABLE 11 Example Example Comparative example 16 17 15 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

[0113] Test data of the comparative examples and examples in table 11 are shown in Table 12. The data show that the adhesives in embodiments 16 and 17 in which the photocurable composition of the present inventions are used have significantly higher gel conversion rate under lights than that in comparative example 15 in which oxime ester photoinitiator is used alone.

TABLE-US-00012 TABLE 12 Example Example Comparative example 16 17 15 Gel conversion rate 92.5% 92.7% 85.2%

[0114] In summary, in the present invention, the photoinitiator composition comprising an acylcarbazole derivative and a carbazolyl oxime ester shows a significant higher curing activity than the corresponding photoinitiator composition in which the same kind of carbazolyl oxime ester is used alone. The best sensitising effect is shown when the molar ratio of the acylcarbazole derivatives to the carbazolyl oxime ester is 0.1 to 1.4.