CN109651534B - Polyketoxime ester photoinitiator and preparation method and application thereof - Google Patents

Polyketoxime ester photoinitiator and preparation method and application thereof Download PDF

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CN109651534B
CN109651534B CN201710946223.0A CN201710946223A CN109651534B CN 109651534 B CN109651534 B CN 109651534B CN 201710946223 A CN201710946223 A CN 201710946223A CN 109651534 B CN109651534 B CN 109651534B
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钱晓春
胡春青
于培培
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Changzhou Tronly New Electronic Materials Co Ltd
Changzhou Tronly Advanced Electronic Materials Co Ltd
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Abstract

A novel ketoxime ester photoinitiator has a structure shown as a general formula (I). The product has excellent photosensitivity, is not easy to migrate, has good applicability to single-wavelength UV-LED, has very good performance even in a curing system containing dye, and has photosensitivity obviously superior to that of the existing similar photoinitiator.

Description

Polyketoxime ester photoinitiator and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photoinitiators, and particularly relates to a poly-ketoxime ester photoinitiator as well as a preparation method and application thereof.
Background
Due to good photosensitive performance, oxime ester photoinitiators have become a research and development hotspot in the field of photocuring in recent years. Oxime ester products having carbazole, diphenyl sulfide, fluorene, etc. groups are widely known and used, for example, patent documents CN106132929A, JP2016206488A, CN102492059A, CN106483764A, etc. disclose various photoinitiators based on ketoxime ester structures, and these products have good photosensitivity, storage stability, etc., and provide more choices for photocuring applications in different environments. However, in practice, it is found that the existing ketoxime ester photoinitiators have insufficient performance. On the one hand, they have a low molecular weight and a pronounced tendency to migrate during use, while the large molecular weight of the compounds (to overcome the migration problem) leads to a marked decrease in the triggering activity. On the other hand, in the field of photocuring, UV-LED light sources having advantages of environmental protection, no pollution, no thermal radiation, long service life, stable output light intensity, and the like are being vigorously popularized to replace conventional UV light sources such as mercury lamps, but there are few photoinitiators applicable to UV-LED light sources, and typically, insufficient initiation activity is exhibited. Therefore, a continuous demand exists for a novel oxime ester photoinitiator product which is difficult to migrate, has high photosensitive activity and is suitable for a UV-LED light source.
Disclosure of Invention
Aiming at the defects and technical requirements of the prior art, the invention mainly aims to provide a novel poly-ketoxime ester photoinitiator which has excellent photosensitivity, is not easy to migrate, has good applicability to UV-LED with single wavelength (such as 395nm), has very good performance even in a curing system containing dye, and has photosensitivity obviously superior to that of the conventional similar photoinitiator.
Specifically, the ketoxime ester photoinitiator has a structure shown as a general formula (I):
Figure RE-GDA0001566289060000021
wherein the content of the first and second substances,
R11、R12、R13、R14、R15、R16independently of one another, hydrogen, halogen, nitro, sulfonic acid, amino, cyano, C1-C5Alkyl of, or C1-C5Alkyl of (2)An oxy group;
R2、R3and R4Independently of one another represent C1-C20Linear or branched alkyl of (2), C2-C20Straight-chain or branched alkenyl of (C)3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Optionally, acyclic-CH in the radical2May be substituted by-O-, -S-or-NH-and the hydrogen in the radical may be replaced by halogen or C1-C5Alkyl of (a);
z represents null (i.e., the left and right benzene rings are connected to each other only through A), a single bond or C1-C5An alkylene group of (a);
a represents O, S, NR5、C(R6)(R7) Or C1-C5Wherein R is5、R6And R7Independently of each other, hydrogen and C1-C20Linear or branched alkyl of (2), C2-C20Straight-chain or branched alkenyl of (C)3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20An alkylcycloalkyl group of (a);
m represents a single bond, C1-C10Linear or branched alkylene of (a);
q represents an n-valent linking group;
n represents 2, 3 or 4.
In a preferred embodiment of the present invention, R in the above-mentioned ketoxime ester photoinitiator represented by the general formula (I)11、R12、R13、R14、R15、R16Independently of one another, hydrogen, nitro, or C1-C5Alkyl group of (1). Further preferably, R11、R12、R14And R15Represents hydrogen, R13And R16Independently of one another, hydrogen or nitro.
Preferably, R2、R3And R4Independently of one another represent C1-C10Linear or branched alkyl of (2), C2-C10Straight-chain or branched alkenyl of (C)3-C12Cycloalkyl of, C4-C14Cycloalkylalkyl of (C)4-C14Alkylcycloalkyl of (A), C6-C12Optionally, hydrogen in the radical may be replaced by halogen or C1-C5Is substituted with an alkyl group. Further preferably, R2、R3And R4Independently of one another represent C1-C4Linear or branched alkyl of (2), C2-C6Straight-chain or branched alkenyl of (C)3-C8Cycloalkyl of, C4-C10Cycloalkylalkyl of (C)4-C10Alkyl cycloalkyl, phenyl, C1-C5Alkyl-substituted phenyl.
Preferably, Z represents a void or a single bond.
Preferably, A represents O, S, NR5、C(R6)(R7) Or C1-C3Wherein R is5、R6And R7Independently of each other, hydrogen and C1-C12Linear or branched alkyl groups of (1). Further preferably, a represents O, S, NR5、C(R6)(R7) Or methylene, wherein R5、R6And R7Independently of each other, hydrogen and C1-C10Linear or branched alkyl groups of (1).
Preferably, M represents a single bond, C1-C4Linear or branched alkylene groups of (a).
Preferably, Q represents C1-C10Linear or branched n-valent alkyl of (2), C2-C10A straight-chain or branched n-valent alkenyl group of (C)3-C12N-valent cycloalkyl of (1), C6-C20An n-valent aryl group of (1). Further preferably, Q represents C1-C6Linear or branched n-valent alkyl of (2), C2-C8A straight-chain or branched n-valent alkenyl group of (C)3-C8An n-valent cycloalkyl group, an n-valent phenyl group, or an n-valent biphenyl group.
Without limitation, the ketoxime ester photoinitiators of the present invention may preferably be selected from compounds having the following structure:
Figure RE-GDA0001566289060000041
Figure RE-GDA0001566289060000051
Figure RE-GDA0001566289060000061
Figure RE-GDA0001566289060000071
Figure RE-GDA0001566289060000081
the ketoxime ester photoinitiator shown in the general formula (I) can be prepared through Friedel-crafts acylation reaction, oximation reaction and esterification reaction in sequence, and the preparation method can comprise the following reaction steps:
(1) friedel-crafts acylation reaction
Under the catalytic action of aluminum trichloride or zinc chloride, carrying out Friedel-crafts acylation reaction on the raw material a and the raw material b to obtain an intermediate a;
Figure RE-GDA0001566289060000091
in the starting materials b, X represents halogen, in particular F, Cl, Br or I;
(2) oximation reaction
Under the existence of an organic solvent and concentrated hydrochloric acid, carrying out oximation reaction on the intermediate a and nitrite at normal temperature to generate an intermediate b;
Figure RE-GDA0001566289060000092
Figure RE-GDA0001566289060000101
(3) esterification reaction
Intermediate b with acid anhydride (R)4-CO)2O or acyl chloride compounds R4Carrying out esterification reaction on-CO-Cl to obtain a target product;
Figure RE-GDA0001566289060000102
the reactions involved in steps (1) to (3) in the above-mentioned preparation methods are all conventional reactions in the art for synthesizing analogous compounds. Specific reaction conditions are readily determined by those skilled in the art, given the structure and synthetic considerations of the products disclosed herein.
In the step (1), the starting material a is a monoketoxime ester compound, which is a known compound in the prior art and can be prepared by a synthetic method disclosed in patent documents such as CN101565472A, CN102492059A, and CN 102778814A.
In the oximation reaction in the step (2), the nitrite can be selected from ethyl nitrite, isoamyl nitrite, isooctyl nitrite and the like, and the nitrite can be selected from sodium nitrite, potassium nitrite and the like.
The invention also relates to application of the ketoxime ester photoinitiator shown in the general formula (I) in a photocuring composition (namely a photosensitive composition). Without limitation, the photoinitiator can be applied to color Resists (RGB), black resists (BM), space barriers (Photo-spacers), dry films, semiconductor photoresists, anisotropic conductive films, and inks. In application, the product can bring excellent photosensitive performance, is not easy to migrate, and has good applicability to single-wavelength UV-LEDs.
Detailed Description
The present invention will be further described with reference to the following specific examples, which should not be construed as limiting the scope of the invention.
Preparation examples
Example 1 (preparation of compound 1):
(1) preparation of intermediate 1a
Figure RE-GDA0001566289060000111
Figure RE-GDA0001566289060000121
62.7g of the raw material 1a, 26.7g of aluminum trichloride and 100mL of dichloromethane are added into a 500mL four-neck flask, the temperature of the four-neck flask is reduced to 0 ℃ in an ice water bath, a mixed solution of 21.1g of the raw material 1b and 50mL of dichloromethane is dropwise added under the stirring state, the temperature is controlled to be below 10 ℃, the dropwise addition is completed within about 2 hours, the stirring is continued for 2 hours after the dropwise addition is completed, and the liquid phase tracking reaction is completed. The mixture was then slowly poured into dilute hydrochloric acid prepared from 400g of ice water and 50mL of concentrated hydrochloric acid (37%), stirred while adding, and then poured into a separatory funnel, the lower dichloromethane layer was separated, and the aqueous layer was washed with 50mL of dichloromethane, and the dichloromethane layers were combined. The dichloromethane layer was washed with 5% aqueous sodium bicarbonate (150 mL each for 3 times), then washed with water until the pH was neutral, dried over 80g anhydrous magnesium sulfate, filtered, and the dichloromethane product solution was rotary evaporated, recrystallized from methanol, and oven dried at 80 ℃ for 2h to give 68.8g of intermediate 1a in 90% yield and 98% purity.
The structure of intermediate 1a was confirmed by nmr hydrogen and mass spectral data:
1H-NMR(CDCl3，500MHz)：1.2876-1.3006(4H,m),1.4023-1.4886 (4H,m),1.9079-2.0865(12H,m),2.5063-2.5672(4H，t)，7.2836-7.6118(1 6H,m)。
MS(m/z)：765(M+1)+。
(2) preparation of intermediate 1b
Figure RE-GDA0001566289060000122
Figure RE-GDA0001566289060000131
A250 mL four-necked flask was charged with 61.2g of intermediate 1a, 10.8g of 37% hydrochloric acid, 18.7g of isoamyl nitrite, and 100mL of tetrahydrofuran, and stirred at room temperature for 5 hours to stop the reaction. Pouring the material into a 1000mL big beaker, adding 500mL water, stirring, extracting with 100mL dichloromethane, adding 30g anhydrous MgSO to the extract4Drying, suction filtering, removing solvent from the filtrate by rotary evaporation under reduced pressure, rotating the bottle to obtain oily sticky matter, pouring the sticky matter into 100mL petroleum ether, stirring, separating out, suction filtering to obtain white powdery solid, and drying at 70 ℃ for 5h to obtain intermediate 1b 53.0g, with yield of 75% and purity of 98%.
The structure of intermediate 1b was confirmed by mass spectrometry data:
MS(m/z)：883(M+1)+。
(3) preparation of Compound 1
Figure RE-GDA0001566289060000132
Adding 44.1g of intermediate 1b and 100mL of dichloromethane into a 250mL four-neck flask, stirring at room temperature for 5min, then dropwise adding 10.2g of acetic anhydride, continuing to stir for 2h after about 30min of dropwise addition is finished, and then adding 5% NaHCO3Adjusting pH of the aqueous solution to neutral, separating organic layer with separating funnel, washing with 200mL water for 2 times, 50g anhydrous MgSO4Drying, filtering, rotary evaporating solvent to obtain viscous liquid, recrystallizing with methanol, and drying to obtain white solid powder product 39.9g with yield of 88% and purity of 99%.
The structure of compound 1 was confirmed by nmr hydrogen and mass spectral data:
1H-NMR(CDCl3，500MHz)：1.3657-1.5098(8H,m),1.9049-2.0950 (18H，m)，7.3823-7.6241(16H，m)。
MS(m/z)：907(M+1)+。
example 2 (preparation of compound 2):
(1) preparation of intermediate 2a
Figure RE-GDA0001566289060000141
Adding 75.3g of raw material 2a, 26.7g of aluminum trichloride and 100mL of dichloromethane into a 500mL four-neck flask, cooling to 0 ℃ in an ice water bath, dropwise adding a mixed solution of 22.5g of raw material 2b and 50mL of dichloromethane under the stirring state, controlling the temperature to be below 10 ℃, completing dropwise addition within about 2 hours, continuing stirring for 2 hours after completing dropwise addition, and tracking and reacting a liquid phase to be complete. The mixture was then slowly poured into dilute hydrochloric acid prepared from 400g of ice water and 50mL of concentrated hydrochloric acid (37%), stirred while adding, and then poured into a separatory funnel, the lower dichloromethane layer was separated, and the aqueous layer was washed with 50mL of dichloromethane, and the dichloromethane layers were combined. The dichloromethane layer was washed with 5% aqueous sodium bicarbonate (150 mL each for 3 times), then washed with water until the pH was neutral, dried over 80g anhydrous magnesium sulfate, filtered, and the dichloromethane product solution was rotary evaporated, recrystallized from methanol, and oven dried at 80 ℃ for 2h to give 80.5g of intermediate 2a in 89% yield and 98% purity.
The structure of intermediate 2a was confirmed by nmr hydrogen and mass spectral data:
1H-NMR(CDCl3，500MHz)：1.1293-1.1342(6H，m),1.2205-1.2920 (6H，m)，1.4793-1.6841(22H，m)，1.9022-2.0842(6H，s)，2.4978-2.5492 (4H，t)，3.0056-3.1127(4H，m)，7.2806-7.6936(12H，m)。
MS(m/z)：906(M+1)+。
(2) preparation of intermediate 2b
Figure RE-GDA0001566289060000151
A250 mL four-necked flask was charged with 72.4g of intermediate 2a, 10.8g of 37% hydrochloric acid, 18.7g of isoamyl nitrite, and 10 g of0mL of tetrahydrofuran was stirred at room temperature for 5 hours to stop the reaction. Pouring the material into a 1000mL big beaker, adding 500mL water, stirring, extracting with 100mL dichloromethane, adding 30g anhydrous MgSO to the extract4Drying, suction filtering, decompressing and rotary steaming the filtrate to remove the solvent, rotating the bottle to obtain oily sticky matter, pouring the sticky matter into 100mL petroleum ether, stirring and separating out, suction filtering to obtain white powdery solid, drying for 5h at 70 ℃ to obtain 56.2g of intermediate 2b, wherein the yield is 73%, and the purity is 98%.
The structure of intermediate 2b was confirmed by mass spectrometry data:
MS(m/z)：964(M+1)+。
(3) preparation of Compound 2
Figure RE-GDA0001566289060000161
To a 250mL four-necked flask, 48.2g of intermediate 2b and 100mL of dichloromethane were added, the mixture was stirred at room temperature for 5min, 7.9g of acetyl chloride was added dropwise, the stirring was continued for 2h after about 30min, and 5% NaHCO was added3Adjusting pH of the aqueous solution to neutral, separating organic layer with separating funnel, washing with 200mL water for 2 times, 50g anhydrous MgSO4Drying, filtering, rotary evaporating solvent to obtain viscous liquid, recrystallizing with methanol, and drying to obtain white solid powder product 46.6g, with yield of 89% and purity of 99%.
The structure of compound 2 was confirmed by nmr hydrogen and mass spectral data:
1H-NMR(CDCl3，500MHz)：1.2865-1.3126(6H，m)， 1.5027-1.7095(28H，m)，2.00544-2.1007(6H，s)，3.8001-3.8937
(4H，m)，7.3757-7.7214(16H，m)。
MS(m/z)：1408(M+1)+。
examples 3 to 15:
referring to the procedure of example 1 or 2, compounds 3-15 were prepared from the corresponding starting materials.
The structure of the target product and its MS (m/z) data are listed in Table 1:
TABLE 1
Figure RE-GDA0001566289060000171
Figure RE-GDA0001566289060000181
Figure RE-GDA0001566289060000191
Performance characterization
The photoinitiators of formula (I) of the present invention were evaluated for key application properties, including sensitivity, developability and pattern integrity, migration, etc., by formulating exemplary photocurable compositions.
1. Preparation of Photocurable compositions
Acrylate copolymer 100
(benzyl methacrylate/methacrylic acid/methyl methacrylate (molar ratio 50/15/30), Mw 15000)
Figure RE-GDA0001566289060000192
Figure RE-GDA0001566289060000201
In the composition, the photoinitiator is the ketoxime ester compound shown in the general formula (I) of the invention or the similar photoinitiator known in the prior art as a comparison. The parts shown are parts by mass.
2. Evaluation of Performance
Stirring the light-cured composition in the dark, taking the material on a PET template, coating by using a wire rod, drying at 90 ℃ for 5min to remove the solvent, and forming a coating film with the thickness of about 2 mu m. Cooling the substrate with the coating film to room temperature, attaching a mask plate, irradiating with an LED point light source (Shenzhen blue spectrum Rick science and technology Co., Ltd., model UVEL-ET), exposing the coating film at 395nm wavelength through the gap of the mask plate, immersing in 2.5% sodium carbonate solution at 25 ℃ for 20s for development, washing with ultrapure water, air drying, and hard baking at 220 ℃ for 30min to fix the pattern.
(1) Sensitivity of light
At the time of exposure, the minimum exposure amount at which the residual film ratio after development of the light-irradiated region in the exposure step is 90% or more is evaluated as the exposure demand. The smaller the exposure demand, the higher the sensitivity.
(2) Developability and pattern integrity
The substrate pattern was observed with a Scanning Electron Microscope (SEM) to evaluate developability and pattern integrity.
The developability was evaluated according to the following criteria:
o: no residue was observed in the unexposed parts;
very good: a small amount of residue was observed in the unexposed parts, but the residue was acceptable;
●: a clear residue was observed in the unexposed parts.
Pattern integrity was evaluated according to the following criteria:
o: no pattern defects were observed;
□: a small part of the pattern was observed to have some defects;
solid content: many pattern defects were clearly observed.
(3) Mobility of
Cutting the cured film, weighing 0.5g of the cured film sample, placing the cured film sample in a 50mL beaker, adding 4.5mL of methanol, ultrasonically dispersing for 30min by utilizing ultrasonic waves, carrying out solid-liquid separation, transferring the obtained methanol solution to a 10mL volumetric flask, continuously washing the solid sample twice (2mL multiplied by 2) by using the methanol, and pouring a cleaning solution into the volumetric flask. Transferring 0.1mL of toluene as an internal standard substance by using a pipette, adding a methanol solution for dissolving, shaking uniformly, and standing.
Whether or not the presence of the photoinitiator was detected was observed by Shimadzu LC-20A liquid chromatography (shim pack column, 150X 6.0nm, detector SPD-20A, detection limit 20ppm, detection wavelength 254nm) at 25 ℃ using a mobile phase (methanol/water: 90/10) at a flow rate of 1.0 mL/min. The higher the initiator content in the liquid phase, in terms of percentage of the area of the liquid phase peak to toluene, the greater the mobility.
The results of the performance evaluation are shown in table 2:
TABLE 2
Figure RE-GDA0001566289060000211
Figure RE-GDA0001566289060000221
In Table 2, comparative compound 1 represented bis- { [4- (3-cyclopentyl-1, 2-dione-2-oxime-O-propionate) propyl ] phenylene } -sulfide, a photoinitiator disclosed in CN103833872A, comparative compound 2 represented 1-nitro-3- (1-oxime acetate) propyl-6- (1-oxime acetate-3-cyclohexyl) propyl-9-ethyl-carbazole, a photoinitiator disclosed in CN103819583A, comparative compound 3 represented 1- {4- [4- (2-thenoyl) phenylthio ] phenyl } - (3-cyclopentyl) -propane-1-ketoxime-O-acetate, a photoinitiator disclosed in CN10249206 102492060A, and comparative compound 4 represented 1- [6- (2-thienylmethyl) phenyl ] phenyl } - (3-cyclopentyl) -propane-1-ketoxime-O-acetate, a photoinitiator disclosed in CN103130919A Acyl) -9-ethylcarbazol-3-yl ] -3-cyclopentyl-propane-1, 2-dione-2-oxime-O-acetate, comparative compound 5 represents the photoinitiator 1- (6-O-methylbenzoyl-9-ethylcarbazol-3-yl) - (3-cyclopentylacetone) -1-oxime-acetate disclosed in CN 101508744A. The structures of comparative compounds 1-5 are shown below:
Figure RE-GDA0001566289060000231
Figure RE-GDA0001566289060000241
as can be seen from the results in table 2, when the poly (ketoxime) ester photoinitiator represented by the general formula (I) of the present invention is applied to a photocuring system using a UV-LED as an irradiation light source, the photoinitiator can provide significantly higher sensitivity, is excellent in developability and pattern integrity, and has no migration. In contrast, in comparative compounds 1 to 5, which are similar photoinitiators, comparative compounds 1 and 2 are good in developability and pattern integrity, but low in sensitivity and have mobility; the exposure requirements for comparative compounds 3-5 were nearly 10 times that of the examples, poor developability and pattern integrity, and significant migration.
In conclusion, the poly-ketoxime ester photoinitiator shown in the general formula (I) has excellent application performance, has good adaptability with a UV-LED light source, can greatly improve the performance of a photocuring product, and has a good promotion effect on the popularization and application of the UV-LED light source in the field of photocuring.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and it will be obvious to those skilled in the art that the photoinitiator according to the present invention may be used in combination with other photoinitiators or sensitizers, and that the monomers, resins, and auxiliaries used may be replaced, modified, or changed. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (16)

1. A ketoxime ester photoinitiator has a structure shown as a general formula (I):
Figure FDA0002940666870000011
wherein the content of the first and second substances,
R11、R12、R13、R14、R15、R16independently of one another, hydrogen, halogen, nitro, sulfonic acid, amino, cyano, C1-C5Alkyl of, or C1-C5Alkoxy group of (a);
R2、R3and R4Independently of one another represent C1-C20Linear or branched alkyl of、C2-C20Straight-chain or branched alkenyl of (C)3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20Alkylcycloalkyl of (A), C6-C20Optionally, acyclic-CH in the radical2May be substituted by-O-, -S-or-NH-and the hydrogen in the radical may be replaced by halogen or C1-C5Alkyl of (a);
z represents null, a single bond or C1-C5An alkylene group of (a);
a represents O, S, NR5、C(R6)(R7) Or C1-C5Wherein R is5、R6And R7Independently of each other, hydrogen and C1-C20Linear or branched alkyl of (2), C2-C20Straight-chain or branched alkenyl of (C)3-C20Cycloalkyl of, C4-C20Cycloalkylalkyl of (C)4-C20An alkylcycloalkyl group of (a);
m represents a single bond, C1-C10Linear or branched alkylene of (a);
q represents an n-valent linking group;
n represents 2, 3 or 4.
2. The ketoxime ester photoinitiator according to claim 1, wherein: r11、R12、R13、R14、R15、R16Independently of one another, hydrogen, nitro, or C1-C5Alkyl group of (1).
3. The polyketone oxime ester photoinitiator according to claim 1 or 2, wherein: r11、R12、R14And R15Represents hydrogen, R13And R16Independently of one another, hydrogen or nitro.
4. The ketoxime ester photoinitiator according to claim 1, wherein: r2、R3And R4Independently of one another represent C1-C10Linear or branched alkyl of (2), C2-C10Straight-chain or branched alkenyl of (C)3-C12Cycloalkyl of, C4-C14Cycloalkylalkyl of (C)4-C14Alkylcycloalkyl of (A), C6-C12Optionally, hydrogen in the radical may be replaced by halogen or C1-C5Is substituted with an alkyl group.
5. The polyketone oxime ester photoinitiator according to claim 1 or 4, wherein: r2、R3And R4Independently of one another represent C1-C4Linear or branched alkyl of (2), C2-C6Straight-chain or branched alkenyl of (C)3-C8Cycloalkyl of, C4-C10Cycloalkylalkyl of (C)4-C10Alkyl cycloalkyl, phenyl, C1-C5Alkyl-substituted phenyl.
6. The ketoxime ester photoinitiator according to claim 1, wherein: a represents O, S, NR5、C(R6)(R7) Or C1-C3Wherein R is5、R6And R7Independently of each other, hydrogen and C1-C12Linear or branched alkyl groups of (1).
7. The polyketone oxime ester photoinitiator according to claim 1 or 6, wherein: a represents O, S, NR5、C(R6)(R7) Or methylene, wherein R5、R6And R7Independently of each other, hydrogen and C1-C10Linear or branched alkyl groups of (1).
8. The ketoxime ester photoinitiator according to claim 1, wherein: m represents a single bond, C1-C4Linear or branched alkylene groups of (a).
9. The ketoxime ester photoinitiator according to claim 1, wherein: q represents C1-C10Linear or branched n-valent alkyl of (2), C2-C10A straight-chain or branched n-valent alkenyl group of (C)3-C12N-valent cycloalkyl of (1), C6-C20An n-valent aryl group of (1).
10. The polyketone oxime ester photoinitiator according to claim 1 or 9, wherein: q represents C1-C6Linear or branched n-valent alkyl of (2), C2-C8A straight-chain or branched n-valent alkenyl group of (C)3-C8An n-valent cycloalkyl group, an n-valent phenyl group, or an n-valent biphenyl group.
11. The process for preparing the ketoxime ester photoinitiator according to any one of claims 1 to 10, comprising the following reaction steps:
(1) friedel-crafts acylation reaction
Under the catalytic action of aluminum trichloride or zinc chloride, carrying out Friedel-crafts acylation reaction on the raw material a and the raw material b to obtain an intermediate a;
Figure FDA0002940666870000031
in the raw material b, X represents halogen;
(2) oximation reaction
Under the existence of an organic solvent and concentrated hydrochloric acid, carrying out oximation reaction on the intermediate a and nitrite at normal temperature to generate an intermediate b;
Figure FDA0002940666870000032
(3) esterification reaction
Intermediate b with acid anhydride (R)4-CO)2O or acyl chloride compounds R4Carrying out esterification reaction on-CO-Cl to obtain a target product;
Figure FDA0002940666870000041
12. the method of claim 11, wherein: in the raw material b, X represents F, Cl, Br or I.
13. The method of claim 11, wherein: in the oximation reaction in the step (2), the nitrite is selected from ethyl nitrite, isoamyl nitrite and isooctyl nitrite, and the nitrite is selected from sodium nitrite and potassium nitrite.
14. Use of the polyketone oxime ester photoinitiator according to any one of claims 1 to 10 in a photocurable composition.
15. Use according to claim 14, characterized in that: the photoinitiator is applied to the preparation of color photoresistors, black photoresistors, space barriers, dry films, semiconductor photoresists, anisotropic conductive films and printing ink.
16. Use according to claim 14 or 15, characterized in that: the application uses UV-LED as the irradiation light source.
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