Carbazole compounds, cyclohexyl-containing carbazole compounds, photoinitiators, photosensitive resin compositions, and cured films

Abstract

The application provides a kind of carbazole compound, cyclohexyl carbazole compound, photoinitiator, photosensitive resin composition and cured film, relates to the field of semiconductor materials.The structure general formula of carbazole compound is: the structure general formula of photoinitiator is: the raw materials for preparing photosensitive resin composition include the photoinitiator.The raw materials for preparing cured film include the photosensitive resin composition.The photoinitiator provided by the application has small dosage, fast curing speed, low photosensitive energy, and the film is not easy to yellow after curing.

Description

[0001] This application is a divisional application of the parent patent application, filed on December 8, 2022, with application number CN202211574334.0. Technical Field

[0002] This application relates to the field of semiconductor materials, and more particularly to a carbazole compound, a cyclohexylcarbazole compound, a photoinitiator, a photosensitive resin composition, and a cured film. Background Technology

[0003] Photoinitiators are one of the important raw materials for preparing photoresists, and there are many types of photoinitiators on the market. Oxime esters are widely used as photoinitiators in the field of high-end photoresists.

[0004] Existing oxime ester compounds have problems such as insufficient solubility with the matrix resin, slow curing speed, high photosensitive energy, easy yellowing of the cured film and high migration rate, and the need for large dosage during use.

[0005] Therefore, it is necessary to develop a new photoinitiator to solve the above problems. The development of intermediates for photoinitiators is also a key research focus. Summary of the Invention

[0006] The purpose of this application is to provide a carbazole compound, a cyclohexylcarbazole compound, a photoinitiator, a photosensitive resin composition, and a cured film to solve the above-mentioned problems.

[0007] To achieve the above objectives, this application adopts the following technical solution:

[0008] A carbazole compound with the following general structural formula:

[0009] ;

[0010] R6 is selected from C1-C20 straight-chain alkyl, C4-C20 branched alkyl, and C3-C20 cycloalkyl; X is a halogen element.

[0011] This application also provides a cyclohexylcarbazole compound, the raw materials for which include the above-mentioned carbazole compound, and its general structural formula is:

[0012] ;

[0013] R6 is selected from C1-C20 straight-chain alkyl, C4-C20 branched alkyl, and C3-C20 cycloalkyl.

[0014] This application also provides a cyclohexylcarbazole-containing compound, the raw materials for which include the above-mentioned cyclohexylcarbazole-containing compound, and its general structural formula is:

[0015] ;

[0016] R1-R5 are each independently selected from straight-chain alkyl groups of C1-C20, branched alkyl groups of C4-C20, and cycloalkyl groups of C3-C20; R6 is selected from straight-chain alkyl groups of C1-C20, branched alkyl groups of C4-C20, and cycloalkyl groups of C3-C20.

[0017] This application also provides a cyclohexylcarbazole-containing compound, the raw materials for which include the above-mentioned cyclohexylcarbazole-containing compound, and its general structural formula is:

[0018] .

[0019] The three cyclohexylcarbazole-containing compounds mentioned above can also be represented by the following general formula:

[0020] ;

[0021] Where Y is H or Z represents O or -N-OH.

[0022] This application also provides a photoinitiator with the following general structural formula:

[0023] ;

[0024] Among them, R1-R5 are each independently selected from straight-chain alkyl groups of C1-C20, branched-chain alkyl groups of C4-C20, and cycloalkyl groups of C3-C20;

[0025] R6 is selected from C1-C20 straight-chain alkyl, C4-C20 branched alkyl, and C3-C20 cycloalkyl;

[0026] R7 is selected from C2-C20 straight-chain alkyl, C4-C20 branched alkyl, C3-C20 cycloalkyl, C6-C20 aryl, oxygen-containing five-membered cycloalkyl, oxygen-containing six-membered cycloalkyl, sulfur-containing five-membered cycloalkyl, and sulfur-containing six-membered cycloalkyl.

[0027] It should be noted that oxygen-containing five-membered cycloalkyl refers to a saturated five-membered cycloalkanes composed of four carbon atoms and one oxygen atom, with the following structure:

[0028] ;

[0029] Oxygen-containing six-membered cycloalkyl compounds refer to saturated six-membered cycloalkanes composed of five carbon atoms and one oxygen atom, with the following structure:

[0030] ;

[0031] Sulfur-containing five-membered cycloalkyl groups and sulfur-containing six-membered cycloalkyl groups can be explained in a similar way.

[0032] Preferably, R1-R5 are each independently selected from methyl, ethyl, propyl, and butyl;

[0033] R6 is selected from methyl, ethyl, propyl, and butyl;

[0034] R7 is selected from ethyl, propyl, butyl, pentyl, hexyl, tetrahydrofuranyl, tetrahydrothiophenyl, tetrahydropyranyl, tetrahydrothiophenyl or phenyl, or C1-C20 straight-chain alkyl groups substituted with cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

[0035] More preferably, R7 is selected from cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.

[0036] This application also provides a photoinitiator selected from one or more compounds shown in the following structural formulas:

[0037] , , , , , , , , , .

[0038] This application also provides a photosensitive resin composition, the raw materials of which include the aforementioned photoinitiator.

[0039] Preferably, the photosensitive resin composition further includes an acrylate copolymer.

[0040] This application also provides a cured film, the raw materials of which include the aforementioned photosensitive resin composition.

[0041] Compared with the prior art, the beneficial effects of this application include:

[0042] The carbazole compounds and cyclohexylcarbazole compounds provided in this application serve as intermediates for the photoinitiator provided in this application, providing raw materials for obtaining the final oxime ester photoinitiator containing cyclohexylcarbazole groups.

[0043] The photoinitiator provided in this application is an oxime ester photoinitiator containing a cyclohexyl and carbazole group. Based on the carbazole group, a cyclohexyl group is introduced to ultimately form an oxime ester structure. It exhibits good compatibility with the matrix resin, fast curing speed, low photosensitivity, and the cured film prepared using it is less prone to yellowing and has low migration rate, requiring only a small dosage. The carbazole ring is cyclofused with a cycloalkyl group, and an oxime ester is attached to the cycloalkyl group. Furthermore, R7 is limited to a substituent of C2 or higher, which increases the matching performance between the photoinitiator and the matrix resin, increases the photoinitiation efficiency, and prevents the cured film from yellowing.

[0044] The photosensitive resin composition and cured film provided in this application have the advantages of fast curing speed, non-yellowing of the cured film and low migration rate by using the above-mentioned photoinitiator as the initiator. Attached Figure Description

[0045] To more clearly illustrate the technical solutions of the embodiments of this application, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this application and should not be regarded as a limitation on the scope of this application.

[0046] Figure 1 This is the HPLC spectrum of compound P-1. Detailed Implementation

[0047] As used in this article:

[0048] "Prepared from" is synonymous with "comprising". The terms "comprising", "including", "having", "containing", or any other variations thereof as used herein are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0049] The conjunction "composed of..." excludes any unspecified elements, steps, or components. If used in a claim, this phrase makes the claim closed, excluding materials other than those described, except for associated conventional impurities. When the phrase "composed of..." appears in a clause of the body of a claim rather than immediately following it, it limits only the elements described in that clause; other elements are not excluded from the claim as a whole.

[0050] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1–5” is disclosed, the described range should be interpreted as including ranges “1–4”, “1–3”, “1–2”, “1–2 and 4–5”, “1–3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0051] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0052] "Parts by mass" refers to the basic unit of measurement that expresses the mass ratio of multiple components. One part can represent any unit mass, such as 1g or 2.689g. If we say that component A has "a" parts by mass and component B has "b" parts by mass, it means the ratio of the mass of component A to the mass of component B is a:b. Alternatively, it can mean that the mass of component A is aK and the mass of component B is bK (where K is any number representing a multiplier). It is important to understand that, unlike parts by mass, the sum of the mass parts of all components is not limited to 100 parts.

[0053] "And / or" is used to indicate that one or both of the described situations may occur, for example, A and / or B includes (A and B) and (A or B).

[0054] The implementation schemes of this application will be described in detail below with reference to specific embodiments. However, those skilled in the art will understand that the following embodiments are only for illustrating this application and should not be regarded as limiting the scope of this application. Unless otherwise specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments used without specified manufacturers are all conventional products that can be purchased commercially.

[0055] First, taking X as Cl as an example, the preparation process of the photoinitiator of this application is demonstrated through the following reaction equation:

[0056] .

[0057] Example

[0058] Synthesis of intermediate M1 in Preparation Example 1

[0059] The reaction equation is as follows:

[0060] .

[0061] In a 500 mL three-necked flask, add 2.0 g of N-ethylcarbazole, 50 mL of dichloromethane, and slowly add 4.7 g of anhydrous aluminum trichloride. Cool to 0 °C and control the temperature between 0-5 °C. Slowly add 1.5 g of 4-chlorobutyryl chloride in 20 mL of dichloromethane solution. After the addition is complete, slowly raise the temperature to 5-10 °C and react for 8 hours. Add water to dissolve the mixture. Wash the organic layer until neutral. Dry with magnesium sulfate, filter off the desiccant, concentrate the organic layer to dryness, and crystallize from ethanol to obtain intermediate M1 with a mass of 1.8 g.

[0062] The mass spectra of intermediate M1 were measured, m / z: 299.11.

[0063] Preparation Example 2: Synthesis of Intermediate M2

[0064] The reaction equation is as follows:

[0065] .

[0066] Add 5.0 g of the starting material shown in M1 and 80 mL of nitrobenzene to a 500 mL three-necked flask. Control the temperature at 10-20 °C and slowly add 60 mL of 30% hydrogen chloride ethanol solution. After the addition is complete, react at 10-20 °C for 24 hours. Add water to the mixture, wash the organic layer until neutral, dry with magnesium sulfate, filter off the desiccant, concentrate the organic layer to dryness, and separate by silica gel column chromatography. Elute with petroleum ether:ethyl acetate = 10:0.5 (volume ratio) to obtain intermediate M2 with a mass of 1.6 g.

[0067] The mass spectra of intermediate M2 were measured, m / z: 263.13.

[0068] Measure the NMR of intermediate M2. 1 1H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ8.86 (s, 1H), δ8.33 (m, 1H), δ7.70 (m, 1H), δ7.57~7.52 (m, 2H), δ7.36 (m, 1H), δ4.55 (m, 2H), δ2.99 (m, 2H), δ2.72 (m, 2H), δ2.09 (m, 2H), δ1.39 (m, 3H).

[0069] Synthesis of intermediate A-1 in Preparation Example 3

[0070] The reaction equation is as follows:

[0071] .

[0072] In a 500 mL three-necked flask, add 5.8 g of M2 and 100 mL of dichloromethane. Slowly add 9.6 g of anhydrous aluminum trichloride. Cool to 0 °C and control the temperature between 0-5 °C. Slowly add 3.5 g of benzoyl chloride in 30 mL of dichloromethane solution. After the addition is complete, slowly raise the temperature to 20 °C and react for 1 hour. Add water to dissolve the mixture. Wash the organic layer until neutral. Dry with magnesium sulfate, filter off the desiccant, concentrate the organic layer to dryness, and crystallize with a mixed solvent of ethanol and toluene to obtain intermediate A-1, 6.6 g.

[0073] The mass spectra of intermediate A-1 were measured, m / z: 367.16.

[0074] Preparation Examples 4-6

[0075] Following the synthesis of intermediate A-1, the following intermediates were prepared by reacting M2 with the corresponding acyl chloride, and the mass spectra of the prepared intermediates were measured. Details are shown in Table 1 below:

[0076] Table 1 Preparation Examples 4-6

[0077]

[0078] Preparation Example 7: Synthesis of Intermediate B-1

[0079] The reaction equation is as follows:

[0080] .

[0081] In a 500 mL three-necked flask, add 4 g of intermediate A-1, 60 mL of acetonitrile, 2.8 g of hydroxylamine hydrochloride, and 3.0 g of sodium acetate. Heat under reflux for 48 hours, cool down, pour the reaction solution into 200 mL of water, filter to obtain a solid, crystallize from ethanol to obtain intermediate B-1, 3.3 g.

[0082] The mass spectra of intermediate B-1 were measured at m / z: 382.17.

[0083] Preparation Examples 8-10

[0084] Following the synthesis of intermediate B-1, the following intermediates were prepared by reacting the corresponding starting material 1 with hydroxylamine hydrochloride, and the mass spectra of the prepared intermediates were measured. Details are shown in Table 2 below:

[0085] Table 2 Preparation Examples 8-10

[0086]

[0087] Synthesis of Compound P-1 in Example 1

[0088] The reaction equation is as follows:

[0089] .

[0090] In a 500 mL three-necked flask, add 4.0 g of intermediate B-1, 60 mL of dichloromethane, and 1.6 g of triethylamine. Cool to 10-15 °C, then add dropwise a solution of 1.5 g of cyclopentylformyl chloride in 10 mL of dichloromethane. After the addition is complete, slowly heat to 20-25 °C and react for 2 hours. Cool, add water to dissolve the organic layer, wash with water until neutral, dry with magnesium sulfate, filter off the desiccant, evaporate the solvent under reduced pressure, and crystallize with a mixture of toluene and ethanol to give compound P-1, 3.1 g, HPLC 99.88% (HPLC chromatogram see [link]). Figure 1 ).

[0091] The mass spectra of the compound were measured at p-1, m / z: 478.23.

[0092] Elemental analysis of the obtained compound P-1 yielded the following values: theoretical C, 77.80%, H, 6.32%, N, 5.85%; and measured values: C, 77.76%, H, 6.30%, N, 5.81%.

[0093] Synthesis Examples 2-10

[0094] Following the synthesis of P1, the compound was prepared by reacting reactant 2 with the corresponding acyl chloride, and the mass spectra (m / z) of the compound were measured. Details are shown in Table 3 below:

[0095] Table 3 Synthesis Examples 2-10

[0096]

[0097] Preparation of photosensitive resin composition 1

[0098] In a yellow-light laboratory, a photocurable coating was prepared using 220 parts by weight of an acrylate copolymer (benzyl methacrylate: methacrylic acid: ethyl methacrylate = 70:10:20, Mw: 10000), 90 parts by weight of dipentaerythritol hexaacrylate, 2 parts by weight of a photoinitiator, 160 parts by weight of butanone, and 30 parts by weight of propylene glycol methyl ether acetate. In this embodiment, the photoinitiator is compound P-1 provided in this application.

[0099] The above composition was stirred under a yellow light lamp, and the material was applied to a PET template and coated by roller coating. The coating was dried at 90°C for 5 minutes. The resulting coating was cooled to room temperature and then exposed to a high-pressure mercury lamp (exposure machine model: RW-UV70201, single exposure dose 50mJ / cm2) to cure it.

[0100] The curing speed is evaluated by the number of times the coating passes through the exposure belt to cure into a cured film. The fewer the number of passes, the faster the curing speed.

[0101] The cured film obtained above was subjected to an aging test using an RW-UV .2BP ultraviolet aging test chamber. The light source was a high-pressure mercury lamp (main wavelength 365nm, total power: approximately 2.2KW). The cured film was continuously irradiated for 6 hours, and the yellowing of the cured film was observed.

[0102] 1. Colorless and transparent with a smooth surface;

[0103] 2: Slightly yellow or with a sticky surface;

[0104] 3: The surface turns yellow or the viscosity increases.

[0105] Preparation of photosensitive resin compositions 2-8

[0106] Referring to Example 1, the difference lies in the type of photoinitiator, as detailed in Table 4 below.

[0107] Comparative Examples 1-3

[0108] Preparation of photosensitive resin compositions

[0109] Referring to Example 1, the difference lies in the type and amount of photoinitiator, as detailed in Table 4 below.

[0110] Table 4 Test Results

[0111]

[0112] As shown in Table 4 above, the cured film prepared in the examples is superior to that in the comparative examples.

[0113] As can be seen from the comparison between Example 7 and Examples 1-3, when R7 is selected from cycloalkyl groups, fewer exposure times are required.

[0114] As can be seen from Examples 3 and 12, when one of R1 and R5 is selected from tert-butyl, the cured film exhibits severe yellowing.

[0115] Furthermore, a comparison between Examples 9-11 and Example 12 shows that oxygen-containing five-membered cycloalkyl, oxygen-containing six-membered cycloalkyl, sulfur-containing five-membered cycloalkyl, and sulfur-containing six-membered cycloalkyl are better.

[0116] In Table 4, the structural formulas of D-1 and D-2 are as follows:

[0117] , .

[0118] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit them. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of this application.

[0119] Furthermore, those skilled in the art will understand that although some embodiments herein include certain features included in other embodiments but not others, combinations of features from different embodiments are intended to be within the scope of this application and form different embodiments. For example, in the foregoing claims, any of the claimed embodiments can be used in any combination. The information disclosed in this background section is intended only to enhance the understanding of the general background of this application and should not be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

Claims

1. A compound containing cyclohexylcarbazole, characterized in that, Selected from one or more compounds shown in the following structural formulas: 、 。 2. A photoinitiator, characterized in that, Selected from one or more compounds shown in the following structural formulas: 、 、 、 、 、 、 。 3. A photosensitive resin composition, characterized in that, The raw materials for its preparation include the photoinitiator described in claim 2.

4. The photosensitive resin composition according to claim 3, characterized in that, It also includes acrylate copolymers.

5. A cured film, characterized in that, The raw materials for its preparation include the photosensitive resin composition as described in claim 3 or 4.

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