CN102020727A - Pyrazole oxime ester photoinitiator with high photosensibility, preparation method and application thereof - Google Patents

Pyrazole oxime ester photoinitiator with high photosensibility, preparation method and application thereof Download PDF

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CN102020727A
CN102020727A CN 201010557275 CN201010557275A CN102020727A CN 102020727 A CN102020727 A CN 102020727A CN 201010557275 CN201010557275 CN 201010557275 CN 201010557275 A CN201010557275 A CN 201010557275A CN 102020727 A CN102020727 A CN 102020727A
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oxime ester
carbazole
group
ester photoinitiator
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CN102020727B (en
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钱晓春
胡春青
王兵
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Changzhou Tronly Advanced Electronic Materials Co Ltd
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Priority to KR1020137011138A priority patent/KR101700476B1/en
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029

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Abstract

The invention relates to a pyrazole oxime ester photoinitiator with a chemical formula (I). The photoinitiator has excellent application performance and extremely high photographic performance, can greatly improve the photocuring performance when being applied to photosensitive compositions and remarkably improve the production efficiency of the photosensitive compositions in the application fields, such as the preparation of color filters, and the like. The invention also relates to a preparation method of the pyrazole oxime ester photoinitiator and the application of the pyrazole oxime ester photoinitiator to the photosensitive compositions.

Description

High-sensitivity carbazole oxime ester photoinitiator, and preparation method and application thereof
Technical Field
The invention relates to the technical field of photoinitiators, and particularly relates to a carbazole oxime ester photoinitiator and a preparation method and application thereof.
Background
Photocuring refers to the photo-induced curing of a monomer, oligomer or polymer substrate, and has wide application in modern microelectronics, such as photocuring inks, packaging of liquid crystal panels, photosensitive printing plates, optical filters, photoresists, and the like. The core of the photocuring technology is the photocurable polymeric monomers and suitable photoinitiators. Under the irradiation of ultraviolet/visible light, X-ray or laser with certain wavelength, the photoinitiator generates active groups to excite unsaturated groups in the polymerizable monomers to generate polymerization reaction, thereby causing the curing of the material.
The photoinitiator is the most important factor affecting the photosensitive property of the photocurable composition (photosensitive composition). Currently, there are very many reports on photoinitiators, such as benzoin derivatives, benzil ketals, α -dialkoxyphenones, benzophenones/amines, mikrolones, thiazolones/amines, aromatic diazonium salts, triazines, oxime esters, etc., as representative examples of which are commercially available as Irgacure369, Darocure1173, OXE-1 and OXE-2. However, these photoinitiators have disadvantages of low sensitivity (high polymerization rate and exposure dose), poor solubility (high transparency and high photo-etching residue), low storage stability, and insufficient sensitivity at short wavelengths, which affect the performance of the photosensitive material as a whole, and thus cannot meet the application requirements of high-end color filters and new-generation LED displays. In addition, the use of low-sensitive photoinitiators also places additional demands on the equipment configuration in actual production, adversely affecting product production efficiency.
At the present stage, much attention has been paid to the research of the high-sensitivity photoinitiator, and a small number of reports have been made. For example, publication No. CN101508744A discloses a carbazole oxime ester photoinitiator, which has a photosensitivity superior to OXE-2, and can preliminarily meet the manufacturing requirements of the current color filter. However, with the development of electronic technology, higher requirements are inevitably put forward on the photoinitiator, so that the existing photoinitiator cannot gradually adapt to the application requirements of high-end color filters and LEDs. The research and development of photoinitiators with higher performance, in particular higher photosensitivity, is of great practical and economic importance.
Disclosure of Invention
The invention aims to provide a novel photoinitiator which has excellent application performance, particularly very high sensitivity and can meet the manufacturing requirements of high-end color filters and OLED displays.
In order to achieve the technical effects, the technical scheme of the invention is as follows: a carbazole oxime ester photoinitiator has a structure shown in a formula (I):
Figure BDA0000033756950000021
wherein
R1Is that
Figure BDA0000033756950000022
n＝1--5，m＝1--6；
R2Is C1～C20Linear or branched alkyl of (a);
ar is an S or O-containing heterocyclic group having an optional substituent (i.e., the substituent may be present or absent), or a substituted aryl group having O, S, N atoms in the substituent group.
In the carbazole oxime ester compound shown as the formula (I), R1The substituents are preferably n ═ 2 and m ═ 3 or 4.
R2Preferably C1--C5More preferably methyl, ethyl, n-propyl, n-butyl, and especially preferably ethyl.
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 groups; the S or O containing heterocyclic group is preferably furyl or thienyl; the substituent containing O, S, N atoms in the substituted aryl group is preferably alkylthio, alkoxy, alkylamino, piperazinyl, morpholinyl, or the like.
Specifically, the Ar group in the carbazole oxime ester compound represented by formula (I) is preferably selected from the following structures:
Figure BDA0000033756950000031
Figure BDA0000033756950000041
the invention also provides a preparation method of the carbazole oxime ester photoinitiator with the structure shown in the formula (I), which takes carbazole as a starting raw material and comprises the following steps:
(1) and (3) substitution reaction: dissolving carbazole in organic solvent, reacting with bromoalkane R2The substitution reaction of-Br is carried out to obtain an intermediate a, namely 9-R2Carbazole, the reaction process of which is as follows:
Figure BDA0000033756950000042
(2) acylation reaction: intermediate a (9-R)2Carbazole) in an organic solvent, and carrying out an acylation reaction under the catalysis of aluminum trichloride to obtain an intermediate b, namely 3-R1acyl-6-Ar acyl-9-R2Carbazole, the reaction process of which is as follows:
Figure BDA0000033756950000051
(3) oximation reaction: from the intermediate b (3-R) thus obtained1acyl-6-Ar acyl-9-R2Carbazole) to prepare an intermediate c, namely 1- (6-Ar acyl-9-R2Carbazole) -1-R1Ketoxime, the reaction process is as follows:
Figure BDA0000033756950000052
(4) esterification reaction: from the intermediate c (1- (6-Ar acyl-9-R) thus obtained2Carbazole) -1-R1Ketoxime) and acetic anhydride to prepare a target product, namely a carbazole oxime ester photoinitiator shown in a formula (I), wherein the reaction process is as follows:
Figure BDA0000033756950000053
all starting materials used in the preparation process of the present invention are known compounds in the art, and are commercially available or prepared by known synthetic methods.
The carbazole oxime ester compound with the structure shown in the formula (I) can be used as a photoinitiator in a photosensitive (photocuring) composition, and has very excellent photosensitive performance. The other components in the photosensitive composition are not particularly limited and may be those known and commonly used in the art (see, for example, the disclosure of CN101059655A, incorporated herein by reference), such as photopolymerizable acrylic resins.
The invention has the beneficial technical effects that: in the invention, the carbazole oxime ester photoinitiator shown in the formula (I) has excellent application performance and particularly high photosensitivity, is superior to the prior commercially available photoinitiators such as Irgacure369 and OXE-2, and is superior to the carbazole oxime ester photoinitiator disclosed in CN 101508744A. The application of the photosensitive composition can greatly improve the photocuring performance and remarkably improve the production efficiency of the application field of the photosensitive composition such as the preparation of color filters. Meanwhile, the production method is simple, no polluting waste is generated in the production process, the product purity is high, and the method is suitable for industrial production.
Detailed description of the invention
Preparation examples
Example 1:
preparation of 1- [6- (2-thenoyl) -9-ethylcarbazol-3-yl ] - (3-cyclopentylacetone) -1-oxime acetate of the formula
Figure BDA0000033756950000061
The method comprises the following steps: preparation of 9-ethylcarbazole
Figure BDA0000033756950000071
20g of carbazole, 0.8g of tetraethylammonium bromide and 100mL of toluene are put into a 250mL four-neck flask, 70g of ready-prepared 50% NaOH aqueous solution is added under stirring, 15.6g of bromoethane is dropwise added, the dropwise addition is finished within about 30min, and then the heating reflux reaction is carried out for 6 h. Cooling to room temperature, removing water layer, washing the feed liquid layer with water for 3 times, and collecting anhydrous MgSO4Drying, vacuum filtering, concentrating under reduced pressure to remove solvent, and recrystallizing the residue with anhydrous ethanol to obtain white needle crystal 33.5g, with yield of 72.0% and relative purity of 99.0%.
Step two: preparation of 3- (3-cyclopentylpropionyl) -6- (2-thenoyl) -9-ethylcarbazole
Figure BDA0000033756950000072
Into a 500ml four-necked flask, 30g of 9-ethylcarbazole and 21.6g of AlCl were charged3Grinding, 150ml of dichloromethane, stirring, introducing argon for protection, cooling in an ice bath, beginning to dropwise add a mixed solution of 23.2g of 2-thiophenecarbonyl chloride and 21g of dichloromethane when the temperature is reduced to 0 ℃, controlling the temperature to be below 10 ℃, completing the addition for about 1.5h, continuing to stir for 2h, and then adding 21.6g of AlCl into the flask3(porphyrizing), dropwise adding a mixed solution of 27.2g of cyclopentyl propionyl chloride and 20g of dichloromethane, controlling the temperature below 10 ℃, completing dropwise adding within about 1.5h, raising the temperature to 15 ℃, continuing stirring for 2h, and discharging.
And (3) post-treatment:
the mixture was slowly poured into dilute hydrochloric acid prepared from 400g of ice and 65ml of concentrated hydrochloric acid with stirringSeparating the lower layer with separating funnel, extracting the upper layer with 50ml dichloromethane, mixing the extractive solution with the feed solution, and adding 10g NaHCO3NaHCO with 200g water3Washing with 200ml water for 3 times until pH is neutral, and washing with 30g anhydrous MgSO4Drying to remove water, evaporating dichloromethane in a rotary manner, after evaporation, pouring the crude product in a rotary evaporation bottle into 200ml of petroleum ether which is evaporated at normal pressure, filtering to obtain light yellow powdery solid, and drying in an oven at 70 ℃ for 2h to obtain 46.2g of the product, wherein the yield is 70%, and the purity is more than 94%.
Step three: preparation of 1- [6- (2-thenoyl) -9-ethylcarbazol-3-yl ] - (3-cyclopentylacetone) -1-oxime
Figure BDA0000033756950000081
A500 ml four-necked flask was charged with 46.2g of the second step product, 11.2g of hydroxylamine hydrochloride, 16.4g of sodium acetate, 150g of ethanol and 50g of water, and the mixture was refluxed for 5 hours under heating and stirring.
And (3) post-treatment:
pouring the material into a big beaker, adding 1000ml of water, stirring, standing overnight, filtering to obtain white powdery solid, pouring the white powdery solid into 200ml of THF, adding 50g of anhydrous MgSO4Drying, suction filtering, rotary evaporating the filtrate, rotating in a bottle to obtain oily sticky matter, pouring the sticky matter into 150ml of anhydrous methanol, stirring, separating out, suction filtering to obtain white powdery solid, drying at 70 ℃ for 5h to obtain 38.6g of a product, wherein the yield is 81%, and the purity is more than 95%.
Step four: preparation of 1- [6- (2-thenoyl) -9-ethylcarbazol-3-yl ] - (3-cyclopentylacetone) -1-oxime acetate
Into a 500ml four-necked flask were charged 32g of the third step product, 150ml of dichloromethane, 11g of acetic anhydride, stirred at room temperature for 2 hours, and then charged with 5% NaHCO3Adjusting pH of the aqueous solution to neutral, separating with a separating funnel, washing with 200ml water, and collecting 50g anhydrous MgSO4The mixture is dried and then is dried,and (3) rotatably evaporating the solvent to obtain a viscous liquid, recrystallizing to obtain a white solid product, filtering, and drying to obtain 30.5g of the product, wherein the yield is 87%, and the purity is more than 95%.
The structure of the product is confirmed by a nuclear magnetic resonance hydrogen spectrum, and the specific characterization result is as follows:
1H-NMR(CDCl3，500MHz)：δ1.131--1.170(2H，m，-CH2-)，1.4681.497(3H，t，-CH3) 1.537- -1.893(9H, m, cyclopentane), 2.281(3H, s, - -CH)3)，2.955--2.987(2H，q，-CH2-), 4.401- -4.444(2H, q, - -CH2- -), 7.285- -8.542(9H, m, phenyl ring).
Examples 2 to 12:
the compounds of examples 2-12 were prepared from the corresponding acylating agent, the corresponding aldehyde or ketone by the method described in example 1. Target compound and its use1The H-NMR data are shown in Table 1.
TABLE 1
Figure BDA0000033756950000091
Figure BDA0000033756950000092
Figure BDA0000033756950000101
Figure BDA0000033756950000111
Figure BDA0000033756950000121
Figure BDA0000033756950000131
Test of light sensitivity
The sensitivity was measured by using Step Tablet (refer to chinese translation, standard plate for densitometer). The ruler is a plastic plate or called a mask plate, a plastic ruler is shaped outside, rectangular frames with equal intervals are printed on the plastic ruler, and how many rectangular frames are called Step tablets with more or less gray levels. These rectangular frames are printed with a color ranging from colorless transparent to light gray to black in accordance with a certain optical density increment, and are used to adjust the quantity of irradiation light. The light portions can pass more light than the dark portions. The numbers in front of the gray scale number correspond to the colors, the smaller the number is, the smaller the gray scale number is, the lighter the color is, the more the light quantity can pass through, and the lower the sensitivity of the corresponding photoinitiator is; the larger the number, the larger the number of gradations, the darker the color, the less the amount of 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 according to the following procedure.
(1) A photosensitive composition containing a photoinitiator was prepared by taking the following composition as an example:
200 parts by mass of an acrylic ester copolymer
(benzyl methacrylate/methacrylic acid/hydroxyethyl methacrylate (molar ratio 70/10/20)
Copolymer (Mw: 10,000)
100 parts by mass of dipentaerythritol hexaacrylate
5 parts by mass of photoinitiator
900 parts by mass of butanone (solvent).
The photoinitiator in the composition is selected from carbazole oxime ester compounds shown in formula (I) of the invention or photoinitiators known in the prior art (for comparison).
(2) Test of light sensitivity
Stirring the complex under a yellow light, taking a certain amount of material on a PET template, forming a film by using roll coating, and drying at 90 ℃ for 2min to obtain a coating film with the dry film thickness of 2 mu m; to obtain a coating film of the above thickness, the coating process may be carried out once or in multiple steps.
Then, the resultant was cooled to room temperature, a mask plate of 12 gradations was attached, and the coating film was exposed to ultraviolet radiation having wavelengths of 365nm, 405nm and 436nm using a high-pressure mercury lamp. The total irradiation dose on the test negative is measured by an optical power meter and is 1000mJ/cm2. After exposure, the mask plate was removed and the exposed negative developed using a 1% aqueous solution of sodium carbonate at 30 ℃ and the sensitivity of the initiator system was characterized by the retention of the highest (i.e. polymerized) grey scale number after development. The higher the number of gray levels, the higher the sensitivity of the test system. The results are shown in Table 2.
TABLE 2
EXAMPLES/COMPARATIVE EXAMPLES Photoinitiator Sensitivity (grey scale number)
13 Example 1 Compounds 9.5
14 Example 2 Compounds 9
15 Example 4 Compounds 9
16 Example 5 Compounds 8.5
17 Example 7 Compounds 9.5
18 Example 10 Compounds 9.5
Comparative example 1 PBG-304 7.5
Comparative example 2 OXE-02 7
Comparative example 3 Irgacure369 1
In Table 2, PBG-304 represents the photoinitiator 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) - (3-cyclopentylacetone) -1-oxime acetate disclosed in CN101508744A, OXE-02 represents 1- (6-o-methylbenzoyl-9-ethylcarbazol-3-yl) - (3-ethanone) -1-oxime acetate, and Irgacure369 represents 2-phenyl-2-dimethylamino-1- (-4-morpholinophenyl) -butanone-1.
As is apparent from the experimental results in Table 2, the gray scale number of the photoinitiator shown in formula (I) disclosed by the invention is higher than that of the commercially available Irgacure369 and OXE-2 photoinitiators, and is higher than that of the carbazole oxime ester photoinitiator disclosed in CN 101508744A. That is, the carbazole oxime ester compound provided by the invention is used as a photoinitiator, and the photosensitive (photocuring) performance of the carbazole oxime ester compound is more excellent.
In conclusion, the carbazole oxime ester photoinitiator shown in the formula (I) disclosed by the invention has excellent application performance, particularly high photosensitivity, is superior to the photoinitiators commercially available at present, such as Irgacure369, OXE-2 and the like, and is superior to the carbazole oxime ester photoinitiator disclosed in CN 101508744A. The application of the photosensitive composition can greatly improve the photocuring performance and remarkably improve the production efficiency of the application field of the photosensitive composition such as the preparation of color filters. On the other hand, higher photosensitivity indicates that the composition system can be well cross-linked and cured at lower photoinitiator concentration and/or exposure dose, for example, in the manufacture of color filters, and the BM can be manufactured at very low exposure dose by using the photosensitive composition containing the photoinitiator of the invention.

Claims (10)

1. A carbazole oxime ester photoinitiator has a structure shown in a formula (I):
Figure FDA0000033756940000011
wherein,
R1is thatn＝1～5，m＝1～6；
R2Is C1～C20Linear or branched alkyl of (a);
ar is an S or O containing heterocyclic group having an optional substituent, or a substituted aryl group having O, S, N atoms in the substituent.
2. The carbazole oxime ester photoinitiator according to claim 1, wherein R is R1Wherein n is 2, and m is 3 or 4.
3. The carbazole oxime ester photoinitiator according to any one of claims 1 to 2, wherein R is2Is C1～C5The straight-chain or branched alkyl group of (1) is preferably methyl, ethyl, n-propyl or n-butyl, and particularly preferably ethyl.
4. The carbazole oxime ester photoinitiator according to any one of claims 1 to 3, wherein the S-or O-containing heterocyclic group having an optional substituent is an S-or O-containing heterocyclic group having 0 to 2 substituents.
5. The carbazole oxime ester photoinitiator according to claim 4, wherein the 0 to 2 substituents are 0 to 2 methyl groups or ethyl groups.
6. The carbazole oxime ester photoinitiator according to any one of claims 1 to 5, wherein the S-or O-containing heterocyclic group is a furyl group or a thienyl group.
7. The carbazole oxime ester photoinitiator according to any one of claims 1 to 6, wherein a substituent group containing O, S, N atoms in the substituted aryl group is an alkylthio group, an alkoxy group, an alkylamino group, a piperazinyl group, or a morpholinyl group.
8. The carbazole oxime ester photoinitiator according to any one of claims 1 to 7, wherein Ar group is selected from one of the following structures:
Figure FDA0000033756940000021
9. the method for preparing carbazole oxime ester photoinitiators of claim 1, comprising the steps of:
(1) and (3) substitution reaction: dissolving carbazole in organic solvent, reacting with bromoalkane R2The substitution reaction of-Br is carried out to obtain an intermediate a, namely 9-R2Carbazole, the reaction process of which is as follows:
Figure FDA0000033756940000032
(2) acylation reaction: the intermediate a is dissolved in an organic solvent, and is subjected to acylation reaction under the catalytic action of aluminum trichloride to obtain an intermediate b, namely 3-R1acyl-6-Ar acyl-9-R2Carbazole, the reaction process of which is as follows:
Figure FDA0000033756940000033
(3) oximation reaction: the intermediate b is subjected to oximation reaction to prepare an intermediate c, namely 1- (6-Ar acyl-9-R)2Carbazole) -1-R1Ketoxime, the reaction process is as follows:
Figure FDA0000033756940000041
(4) esterification reaction: the intermediate c and acetic anhydride are subjected to esterification reaction to prepare a target product, namely a carbazole oxime ester photoinitiator shown in a formula (I), and the reaction process is as follows:
Figure FDA0000033756940000042
10. use of the carbazole oxime ester photoinitiator according to claim 1 in a photosensitive composition.
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JP2013540220A JP5647738B2 (en) 2010-11-23 2011-06-30 High-sensitivity carbazole oxime ester photoinitiator, process for its production and use
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