WO2012068879A1

WO2012068879A1 - High photosensibility carbazole oxime ester photoinitiator,preparation and use thereof

Info

Publication number: WO2012068879A1
Application number: PCT/CN2011/076658
Authority: WO
Inventors: 钱晓春; 胡春青; 王兵
Original assignee: 常州强力先端电子材料有限公司
Priority date: 2010-11-23
Filing date: 2011-06-30
Publication date: 2012-05-31
Also published as: KR101700476B1; CN102020727A; KR20140032938A; CN102020727B; JP5647738B2; JP2013543875A

Abstract

A carbazole oxime ester-type photoinitiator represented by the following structural formula (I) is disclosed. The photoinitiator has excellent properties in application, especially high photosensibility. The photoinitiator can greatly improve the photocuring properties of photopolymers when applying on them, thus can significantly increase the productivity of photosensitive compositions in application fields such as preparing color filter. The preparation method of the carbazole oxime ester-type photoinitiator and its use in photosensitive composition are also disclosed.

Description

High-sensitivity carbazolyl ester photoinitiator, preparation method and application thereof

Technical field

The invention relates to the technical field of photoinitiators, in particular to an oxazole ester photoinitiator and a preparation method and application thereof.

Background technique

Photocuring refers to the curing process of monomers, oligomers or polymer matrices under light induction. This technology has a wide range of applications in modern microelectronics, such as photocurable inks, liquid crystal panel packaging, photosensitive printing plates, Filters, photoresists, etc. At the heart of the photocuring technology is a photocurable polymerizable monomer and a suitable photoinitiator. At a certain wavelength of ultraviolet/visible, X-ray or laser irradiation, the photoinitiator generates reactive groups that excite unsaturated groups in the polymerizable monomer to cause polymerization to cause curing of the material.

The photoinitiator is the most important factor affecting the photosensitivity of the photocurable composition (photosensitive composition). At present, there have been many reports on photoinitiators, such as benzoin derivatives, benzil ketals, α, α-dimethoxy acetophenones, benzophenones/amines, Michler's ketone. , thiazolone/amines, aromatic diazonium salts, triazazines, oxime esters, etc., representative examples are commercially available Irga _C ure369, Darocurel l73, OXE-1 and 0XE_2. However, these photoinitiators have more or less low sensitivity (high polymerization rate and high exposure dose), poor solubility (high transparency and lithography residue), low storage stability, short-wavelength sensitivity, etc. in practical applications. Defects, which affect the performance of photosensitive materials as a whole, cannot meet the application needs of high-end color filters and next-generation LED displays. In addition, the use of low-sensitivity photoinitiators creates additional requirements for equipment configuration in actual production, with adverse effects on product productivity.

At this stage, research on high-sensitivity photoinitiators has received a lot of attention, and a small amount Report. For example, Publication No. CN101508744A discloses an oxazolidinyl ester photoinitiator having a photosensitive property superior to 0XE-2, which can initially satisfy the current production requirements of color filters. However, with the rapid development of electronic technology, it is bound to put forward higher requirements for photoinitiators, which leads to the existing photoinitiators gradually failing to meet the needs of high-end color filters and LED applications. It is of great practical and economic significance to research and develop photoinitiators with higher performance, especially higher sensibility.

Summary of the invention

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel photoinitiator which has excellent application properties, particularly high sensitivity, which can meet the production requirements of high-end color filters and 0 LED displays.

In order to achieve the above technical effects, the technical solution of the present invention is: an oxazolidinyl ester photoinitiator having the structure represented by the formula (I):

n= l __ 5, m= l __ 6;

R ₂ is a linear or branched fluorenyl group of (TC ₂ );

Ar is an S or 0 heterocyclic group having an optional substituent (ie, a substituent may or may not be), or a substituted aryl group having a 0, S, N atom in the substituent group.

In the oxazolium ester compound represented by the formula (I), the substituent is preferably n = 2 and m = 3 or 4. Preferably (^ a (straight chain or branched chain alkyl group having _5, and more preferably methyl, ethyl, n-propyl, n-butyl group, an ethyl group is particularly preferred.

In Ar, the S or O-containing heterocyclic group having an optional substituent preferably has 0 to 2 substituents, particularly 0 to 2 methyl or ethyl; the S or 0-containing heterocyclic group A furyl group or a thienyl group is preferred; the substituent group having a 0, S, and N atom in the substituted aryl group is preferably an anthracenyl group, a decyloxy group, a decylamino group, a piperazinyl group, a morpholinyl group or the like.

Specifically, the Ar group in the oxazolidin ester compound represented by the formula (I) is preferably selected from the following structures:

The invention also provides a preparation method of an oxazolidinyl ester photoinitiator having the structure represented by the above formula (I), which comprises carbazole as a starting material, comprising the following steps:

(1) Substitution reaction: The carbazole is dissolved in an organic solvent and subjected to a substitution reaction with a brominated hydrazine hydrocarbon R ₂ —Br to obtain an intermediate a, that is, a 9-yl oxazole, and the reaction process is as follows:

(2) acylation: intermediate a (9-R ₂ -based carbazole) is dissolved in an organic solvent and subjected to acylation under the catalysis of aluminum trichloride to obtain intermediate b, ie, acyl-6-Aracyl -9- carbazole, the reaction process is as follows:

(3) Deuteration reaction: Intermediate c is obtained from the obtained intermediate b (3-acyl-6-Aryl-9-R ₂ -ylcarbazole) by deuteration reaction, that is, 1-(6-Aracyl- 9- oxazolone oxime, the reaction process is as follows:

(4) Esterification reaction: esterification reaction of the obtained intermediate c ( l-(6-Ar acyl-9-R ₂ oxazolone oxime) with acetic anhydride to obtain the target product, ie, formula (I) The oxazolium ester photoinitiator shown has the following reaction:

All of the starting materials used in the preparation process of the present invention are known compounds in the prior art and are commercially available or can be prepared by known synthetic methods.

The oxazolium ester compound of the structure represented by the formula (I) can be used in a photosensitive (photocurable) composition Used as a photoinitiator, it has excellent photographic properties. The other components in the photosensitive composition are not particularly limited herein, and may be components well known and commonly used in the art (for example, see

The disclosure of CN101059655A, which is incorporated herein by reference, for example, photopolymerizable acrylic acid. Advantageous technical effects of the present invention: In the present invention, the carbazolyl ester photoinitiator of the formula (I) has excellent application properties, The particularly high sensitizing property is superior to the photoinitiators _such as Irg _acUre 369 and 0XE-2 which are commercially available at present, and is superior to the oxazolidinyl ester photoinitiators disclosed in CN101508744A. The application to the photosensitive composition can greatly improve the photocuring performance and significantly improve the production efficiency of the photosensitive composition application field such as the preparation of the color filter. At the same time, the production method of the invention is simple, no pollution waste is produced in the production process, and the product has high purity and is suitable for industrial production.

Specific implementation method

Preparation example

Example 1

Preparation of 1_[6-(2-thiophenecarbonyl)-9-ethylcarbazol-3-yl]-(3-cyclopentylacetone)-1-indole acetate as shown below

To a 250 mL four-necked flask, 20 g of carbazole, 0.8 g of tetraethylammonium bromide, and 100 mL of toluene were added, and 70 g of a 50% aqueous NaOH solution was added thereto, and 15.6 g of bromoacetamidine was added dropwise, and the mixture was dropped for about 30 minutes. Then, the reaction was heated to reflux for 6 h. Cooled to room temperature, layer of water, feed liquid layer was washed 3 times, dried over anhydrous MgS0 _4, suction filtered, concentrated under reduced pressure to remove the solvent, the residue was recrystallized from ethanol to give white needles 33. 5g, close 0%。 The relative purity was 99.0%.

Into a 500 ml four-necked flask, 30 g of 9-ethylcarbazole, 21. 6 g of A1C1 ₃ (fine), 150 ml of dichloromethane, stirred, argon-protected, and cooled in an ice bath, when the temperature dropped to 0 ° The mixture of 23. 2g of 2-thiophenecarbonyl chloride and 21g of dichloromethane is started to be added dropwise, the temperature is controlled below 10 ° C, about 1.5 h is added, stirring is continued for 2 h, and then added to the flask. 6g AlCl ₃ (finely) was added dropwise propionyl chloride 27. 2g cyclopentyl, and a mixture of 20g of dichloromethane, at temperature below 10 ° C, about 1. 5h dropwise, the temperature was raised to 15 ° C, Continue to stir for 2h, discharging.

Post processing:

With stirring, the material was slowly poured into dilute hydrochloric acid of 400 g of ice and 65 ml of concentrated hydrochloric acid. The lower layer was separated by a separating funnel, and the upper layer was extracted with 50 ml of dichloromethane, and the extract was combined with the solution, washed with 10 g of NaHC0 ₃ and 200 g of water in NaHC0 ₃ solution, and then washed 3 times with 200 ml of water to The pH value is neutral, and the water is removed by drying with 30 g of anhydrous MgS0 ₄ , and the dichloromethane is distilled off. After the steaming, the crude product in the rotary flask is in the form of a solid powder, and poured into 200 ml of petroleum ether under normal pressure. After suction filtration, a pale yellow powdery solid was obtained, which was baked in an oven at 70 ° C for 2 h to obtain a product of 46.2 g, a yield of 70%, and a purity of more than 94%. Step 3: Preparation of 1-[6-(2-thiophenecarbonyl)-9-ethyloxazol-3-yl]-(3-cyclopentylacetone)-1-pyrene

Into a 500 ml four-necked flask, 46.2 g of the second step product, 11.2 g of hydroxylamine hydrochloride, 16.4 g of sodium acetate, 150 g of ethanol, and 50 g of water were added, and the mixture was stirred under reflux with heating for 5 hours.

Post processing:

The material was poured into a large beaker, stirred with 1000 ml of water, and allowed to stand overnight. After suction filtration, a white powdery solid was obtained, poured into 200 ml of THF, dried over 50 g of anhydrous MgSO ₄ , filtered, filtered, and evaporated. The oily viscous material is obtained, and the viscous material is poured into 150 ml of anhydrous methanol, and the mixture is stirred and filtered to obtain a white powdery solid, which is baked at 70 ° C for 5 hours to obtain a product of 38.6 g, a yield of 81%, a purity of more than 95. %.

Step 4: 1-[6-(2-Thienyl)-9-ethyloxazol-3-yl]-(3-cyclopentylacetone)-1- Preparation of hydrazine acetate

Into a 500 ml four-necked flask, 32 g of the third step product, 150 ml of dichloromethane, and 1 lg of acetic anhydride were added, and the mixture was stirred at room temperature for 2 hours, then the pH was adjusted to neutral with a 5% NaHC0 solution, and the separating funnel was layered. The product is washed with 200 ml of water, and dried over 50 g of anhydrous MgSO ₄ , and the solvent is evaporated to give a viscous liquid. The product is obtained as a white solid product, which is filtered and dried to give the product 30. 5 g, yield 87%, purity greater than 95%.

The structure of the product was confirmed by nuclear magnetic resonance spectroscopy. The specific characterization results are as follows:

'H-NMRCCDCl 3 , 500MHz ) : δ 1. 131-1. 170 (2H, m, _CH ₂ _), 1. 468 1. 497 (3H, t , - C3⁄4), 1. 537—1. 893 ( 9H, m, cyclopentamidine), 2. 281 (3H, s, - C3⁄4), 2. 955-2. 987 (2H, q, -CH ₂ -), 4. 401-4. 444 (2H, q , _CH2_), 7. 285-8. 542 (9H, m, benzene ring).

Example 2-12:

The compounds of Examples 2-12 were prepared from the corresponding acylating reagents, corresponding aldehydes or ketones by the procedure shown in Example 1. The target compound and its 3⁄4-NMR data are listed in Table 1.

Table 1

Ή-NMR

1.132—1.170 (2H, m) 1.468 (3H, t)

1.543—1.901 (11H, m)

2.290 (3H, s) 2.973(2H, q) 4.450 (2H, q) 6.915—8.832 (9H, m) 1.133—1.175 (2H, m) 1.466 (3H, t)

1. 535—1.883 (9H, m)

3.907(3H, s)

4.428 (2H, q)

7.091—8.798 (10H, m) 1.126—1.168 (2H, m) 1.454 (3H, t) (9H, m)

m=3

2.878 (2H, q) 4.428 (2H, q)

7.125—8.808 (15H, m) 1.130—1.169 (2H, m) 1.514 (3H, t)

m=3 1. 532—1.785 (9H, m)

2.285 (3H, s) 2.878 (2H, q)

4.453 (2H, q)

7.230—8.911 (15H, m)

1.123—1.165 (2H, m)

1. 511—1.796 (23H, m)

4.483 (2H, q)

7.497—8.801 (10H, m) 1.131—1.172 (2H, m) 1.463 (3H, t)

1. 534—1.875 (9H, m)

3.067—3.419 (6H, m)

4.422 (2H, q)

6.803—8.910 (10H, m) 1.133—1.175 (2H, m) 1.458 (3H, t)

1. 541—1.815 (9H, m)

2.288 (3H, s) 2 775 (2H, q)

3 187—3. 659 (8H, m) 4 424 (2H, q)

6 865—8. 532 (10H, m) 1 123—1. 153 (2H, m) 1 456 (3H, t)

1 538— 1. 805 (9H, m) 236 (3H, s)

336 (3H, s)

2 775 (2H, q)

3 367—3. 658 (8H, m) 4 432 (2H, q)

6 861—8. 656 (10H, m) 1 133—1. 168 (2H, m) 1 408 (3H, t)

(9H, m)

4 453 (2H, q)

7 563-8. 926 (13H, m)

The sensitivity test method is to use the Step Tablet (refer to Chinese translation, standard plate for concentration meter). It is a plastic plate, or mask, with a plastic ruler on it, printed with equal-spaced rectangular frames on it, and how many rectangular frames are called Step Tablets for the number of grayscales. The increasing optical density is printed from colorless transparent to light gray to black to adjust the amount of illumination. The lighter part can pass more light than the darker part. The number in front of the gray scale corresponds to the color. The smaller the number, the smaller the gray scale, the lighter the color, the more light that can pass, and the lower the sensitivity of the corresponding photoinitiator. The larger the number, the higher the gray scale. Larger, the darker the color, the less light that can pass, and the higher the sensitivity of the corresponding photoinitiator.

Specifically, the photosensitivity of the photoinitiator represented by the formula (I) was tested in accordance with the following procedure.

(1) A photosensitive composition containing a photoinitiator is prepared by taking the following composition as an example:

Acrylate copolymer 200 parts by mass

(Benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate (molar ratio 70/10/20) copolymer (Mw: 10,000))

Dipentaerythritol hexaacrylate 100 parts by mass

Photoinitiator 5 parts by mass

Butanone (solvent) 900 parts by mass.

The photoinitiator in the above composition is selected from the oxazolium ester compound of the formula (I) of the present invention or a photoinitiator known in the art (as a comparison).

(2) Photographic performance test

The above complex is stirred under a yellow light, and a certain amount of the material is applied to the PET template, and the film is formed by roll coating, and dried at 90 ° C for 2 minutes to obtain a coating film having a dry film thickness of 2 μm; The coating process can be carried out in one step or in multiple steps. Then, it was cooled to room temperature, and a mask of 12 gray scales was attached, and the coating film was exposed to ultraviolet light at 365 nm, 405 nm, and 436 nm with a high pressure mercury lamp. The total radiation dose on the backsheet of the test meter measurement is 1000mJ / _C m ^2. After exposure, the mask was removed and the exposed backsheet was developed using a 1% aqueous solution of sodium carbonate at 30 ° C. The sensitivity of the initiator system was characterized by the highest gray scale retained (i.e., polymerized) after development. The higher the gray level, the higher the sensitivity of the test system. Result

Photoinitiator sensitivity (gray scale)

Example 1 Compound 4 9. 5

Example 2 Compound 4 9

Example 4 Compound 4 9

Example 5 Compound 4 8. 5

Example 7 Compound 4 9. 5

Example 10 Compound 9. 5

PBG-304 7. 5

0XE-02 7

Irgacure369 1 In Table 2, PBG-304 represents the photoinitiator 1_(6-o-methylbenzoyl-9-ethylcarbazol-3-yl)-(3-cyclopentylacetone)-1 disclosed in CN101508744A - hydrazine acetate, 0XE-02 represents 1_(6-o-methylbenzoyl-9-ethyloxazol-3-yl)-(3-ethanone)-1-indenyl acetate, Irgacure369 represents 2- Phenyl-2-dimethylamino-1-(-4-morpholinylphenyl)-butanone-1. It is apparent from the experimental results in Table 2 that the photoinitiator of the formula (I) disclosed in the present invention has higher gray scale numbers than the commercially available Irga _C ure369 and 0XE-2 photoinitiators, and is higher than CN101508744A. The oxazolium ester photoinitiator disclosed in the above. That is, the carbazolyl ester compound of the present invention is more excellent in photosensitive (photocuring) performance as a photoinitiator.

In summary, the carbazolyl ester photoinitiator of the formula (I) disclosed in the present invention has excellent application performance and particularly high sensitizing property, and is superior to the commercially available Irg _acUre 369, 0XE-2. It is a photoinitiator and is superior to the oxazolidinyl ester photoinitiator disclosed in CN101508744A. The application to the photosensitive composition can greatly improve the photocuring performance and significantly improve the production efficiency of the photosensitive composition application field such as the preparation of the color filter. On the other hand, higher photographic properties indicate that the composition system can be crosslinked and cured well at lower photoinitiator concentrations and/or exposure doses, for example in the production of color filters, including the use of the present invention. The photosensitive composition of the photoinitiator can be used to produce BM at a very low exposure dose.

Claims

Claim

An oxazole oxime-based photoinitiator having the structure represented by the formula (I):

R ₂ is a linear or branched alkyl group of CC _2Q ;

Ar is a substituted aryl group having an S or 0 heterocyclic group having an optional substituent or a substituent having a 0, S, N atom.

2, carbazole oxime ester according to claim 1 photoinitiator, wherein, in R & lt ₁ n = 2, m = 3 or

4.

The carbazolyl ester photoinitiator according to any one of claims 1 to 2, wherein ^ is a linear or branched alkyl group of CrC ₅ , preferably methyl, ethyl or n-propyl A base or an n-butyl group is particularly preferably an ethyl group.

The oxazolidinyl ester photoinitiator according to any one of claims 1 to 3, wherein the S or O-containing heterocyclic group having an optional substituent has 0 to 2 A S or a heterocyclic group containing a substituent.

The carbazolyl ester photoinitiator according to claim 4, wherein the 0 to 2 substituents are 0 to 2 methyl groups or ethyl groups.

The carbazolyl ester photoinitiator according to any one of claims 1 to 5, wherein the S or 0-containing heterocyclic group is a furyl group or a thienyl group. Claim

The carbazolyl ester photoinitiator according to any one of claims 1 to 6, wherein the substituent group containing a 0, S, and N atom in the substituted aryl group is an alkylthio group. Alkoxy, alkylamino, piperazinyl, morpholinyl.

The carbazolyl ester type photoinitiator according to any one of claims 1 to 7, wherein the Ar group is selected from one of the following structures:

Claim

9. The method for preparing an oxazolyl ester photoinitiator according to claim 1, comprising the steps of:

(1) Substitution reaction: The carbazole is dissolved in an organic solvent and subjected to a substitution reaction with a bromo alkane R ₂ -Br to obtain an intermediate a, that is, a carbazole, and the reaction process is as follows:

(2) acylation reaction: The intermediate a is dissolved in an organic solvent, and subjected to acylation under the catalytic action of aluminum trichloride to obtain an intermediate b, that is, an acyl-6-Aracyl-9-ylcarbazole. The reaction process is as follows:

(3) Deuteration reaction: Intermediate c is obtained from the obtained intermediate b by deuteration reaction, that is, 1-(6-Aryl-9-R ₂ -oxazolone oxime, the reaction process is as follows: Claim

The use of the carbazolyl ester photoinitiator of claim 1 in a photosensitive composition.