Compounds containing carbazolylindanone groups and oxime ester photoinitiators, photocurable coatings and cured films

Abstract

The application provides a compound containing a carbazole-indenone group and an oxime ester photoinitiator, a photocuring coating and a cured film, and relates to the technical field of semiconductors. The general structural formula of the photoinitiator is: the raw material of the photocuring coating comprises the oxime ester photoinitiator containing the carbazole-indenone group. The oxime ester photoinitiator containing the carbazole-indenone group provided by the application has good solubility, fast curing speed, high photosensitive energy, and a cured film which is not easy to turn yellow, and the use amount is small.

Description

[0001] This application is a divisional application of the parent patent application, filed on December 8, 2022, with application number CN202211572132.2. Technical Field

[0002] This application relates to the field of semiconductor technology, and in particular to a compound containing a carbazole-indanone group and an oxime ester photoinitiator, a photocurable coating, and a cured film. Background Technology

[0003] Photoinitiators, also known as photosensitizers or photocuring agents, are compounds that can absorb energy of a certain wavelength in the ultraviolet (250–420 nm) or visible (400–800 nm) light regions, generating free radicals, cations, etc., thereby initiating monomer polymerization, cross-linking, and curing.

[0004] Oxime esters are common photoinitiators and are widely used in the field of high-end photoresists.

[0005] Existing oxime ester photoinitiators with carbazole groups as the main group generally suffer from poor compatibility with the matrix resin, slow curing speed, high photosensitive energy, easy yellowing of the cured film, and large dosage.

[0006] Developing new photoinitiators requires first developing the intermediates needed to prepare them. Summary of the Invention

[0007] The purpose of this application is to provide a compound containing a carbazole-indanone group and an oxime ester photoinitiator, a photocurable coating, and a cured film to solve the above-mentioned problems.

[0008] To achieve the above objectives, this application adopts the following technical solution:

[0009] A compound containing a carbazole-indanone group has the following general structural formula:

[0010] ;

[0011] R is selected from C1-C20 straight-chain alkyl, C4-C20 branched alkyl, and C3-C20 cycloalkyl; R1 is selected from C1-C20 straight-chain alkyl, C4-C20 branched alkyl, C3-C20 cycloalkyl, and C6-C20 aryl.

[0012] Preferably, the compound containing the carbazoindanone group comprises one or more of the following structural formulas:

[0013] , , , , , .

[0014] This application also provides a compound containing a carbazole-indanone group, the general structural formula of which is:

[0015] ;

[0016] R is selected from C1-C20 straight-chain alkyl, C4-C20 branched alkyl, and C3-C20 cycloalkyl; R1 is selected from C1-C20 straight-chain alkyl, C4-C20 branched alkyl, C3-C20 cycloalkyl, and C6-C20 aryl.

[0017] Preferably, the compound containing the carbazoindanone group comprises one or more of the following structural formulas:

[0018] , , , , , .

[0019] This application also provides an oxime ester photoinitiator containing a carbazole-indanone group, the general structural formula of which is:

[0020] ;

[0021] R is selected from C1-C20 straight-chain alkyl, C4-C20 branched alkyl, and C3-C20 cycloalkyl; R1 and R2 are each independently selected from C1-C20 straight-chain alkyl, C4-C20 branched alkyl, C3-C20 cycloalkyl, and C6-C20 aryl.

[0022] This application also provides an oxime ester photoinitiator containing a carbazole-indanone group, selected from one or more of the following structural formulas:

[0023] , , , , , , , , , , , .

[0024] The reaction equation for this oxime ester photoinitiator containing a carbazole-indanone group is as follows:

[0025] ;

[0026] ;

[0027] ;

[0028] Where X is a halogen element.

[0029] Preferably, R is selected from methyl, ethyl, propyl, and butyl.

[0030] Preferably, R1 and R2 are each independently selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or phenyl.

[0031] Preferably, R1 and R2 are each independently selected from any one of the substituted C1-C20 straight-chain alkyl groups, namely cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0032] Preferably, the straight-chain alkyl group of C1-C20 is selected from methyl, ethyl, propyl, butyl, pentyl, and hexyl.

[0033] This application also provides a photocurable coating, the raw materials of which include the aforementioned oxime ester photoinitiator containing carbazole and indanone groups.

[0034] Preferably, the oxime ester photoinitiator containing a carbazole-indanone group is... .

[0035] Preferably, the raw materials further include resin, solvent and additives.

[0036] Preferably, the photocurable coating comprises an acrylate copolymer, dipentaerythritol hexaacrylate, Butanone and propylene glycol methyl ether acetate;

[0037] The acrylate copolymer is a copolymer of benzyl methacrylate, methacrylic acid, and ethyl methacrylate.

[0038] This application also provides a cured film, the raw material of which includes the aforementioned photocurable coating.

[0039] Compared with the prior art, the beneficial effects of this application include:

[0040] The compounds containing carbazoindanone groups provided in this application provide necessary raw materials for the preparation of oxime ester photoinitiators containing carbazoindanone groups.

[0041] The oxime ester photoinitiator containing a carbazole-indanone group provided in this application forms a carbazole-indanone structure by introducing an indanone group into the structure. The carbonyl group of the carbazole-indanone group is more likely to generate free radicals through cleavage. Moreover, when free radicals are generated through cleavage, ring A and ring B can still be connected by a single bond. This solves the problems of poor compatibility with the matrix resin, slow curing speed, high photosensitivity, easy yellowing of the cured film, and large dosage of existing oxime ester photoinitiators. It has the advantages of rapid curing under conditions of small dosage and low photosensitivity, good compatibility with the matrix resin, and the curing film is not prone to yellowing.

[0042] Ring A and Ring B are shown below:

[0043] .

[0044] The method for preparing oxime ester photoinitiators containing carbazole-indanone groups provided in this application involves a three-step reaction to obtain the target product, and the process is simple.

[0045] The photocurable coating and cured film provided in this application can be cured quickly under conditions of small amount of photoinitiator and low photosensitive energy, and the cured film is not prone to yellowing.

[0046] The method for preparing the cured film provided in this application is simple to operate. Attached Figure Description

[0047] 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.

[0048] Figure 1 This is the HPLC chromatogram of compound P-1. Detailed Implementation

[0049] As used in this article:

[0050] "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.

[0051] 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.

[0052] 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.

[0053] In these embodiments, unless otherwise specified, the portions and percentages are all by weight.

[0054] "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.

[0055] "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).

[0056] 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.

[0057] Example 1

[0058] This embodiment provides an oxime ester photoinitiator containing a carbazole-indanone group, and its preparation method is as follows:

[0059] Preparation Example 1

[0060] Synthesis of intermediate A-1

[0061] In a 500 mL three-necked flask, add 6 g of A-0 and 120 mL of dichloromethane, then slowly add 10 g of anhydrous aluminum trichloride. Cool to 0 °C and control the temperature between 0-5 °C. Slowly add 1.7 g of acetyl chloride in 10 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, 4.1 g.

[0062] The mass spectra of intermediate A-1 were measured, m / z: 339.13.

[0063] 1 H-NMR (Bruker, Switzerland, Avance II 400MHz NMR spectrometer, CDCl3), δ8.80 (d, 1H), δ8.71 (s, 1H), δ8.40 (m, 1H), δ8.31 (m, 1H), δ8.18 (m, 1H), δ8.00 (s, 1H), δ7.88 (d, 1H), δ7.75 (m, 1H), δ7.66 (m, 1H), δ4.55 (m, 2H), δ2.51 (s, 3H), δ1.39 (m, 3H).

[0064] The reaction equation is as follows:

[0065] .

[0066] Following the synthesis of intermediate A-1, the following intermediates were prepared by reacting A-0 with the corresponding acyl chloride, and the mass spectra of the prepared intermediates were measured.

[0067] The details are shown in Table 1 below:

[0068] Table 1. First intermediate and mass spectrometry information

[0069]

[0070] Preparation Example 7: Synthesis of Intermediate B-1

[0071] The reaction equation is as follows:

[0072] .

[0073] In a 500 mL three-necked flask, add 5 g of intermediate A-1, 70 mL of acetonitrile, 3.2 g of hydroxylamine hydrochloride, and 3.5 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, 3.5 g.

[0074] The mass spectra of intermediate B-1 were measured at m / z: 354.14.

[0075] Preparation Examples 8-12

[0076] 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.

[0077] The details are shown in Table 2 below:

[0078] Table 2. Second intermediate and mass spectrometry information

[0079]

[0080] Synthesis Example 1: Synthesis of Compound P-1

[0081] The reaction equation is shown below:

[0082] .

[0083] In a 500 mL three-necked flask, add 3.5 g of intermediate B-1, 50 mL of dichloromethane, and 1.2 g of triethylamine. Cool to 10-15 °C, and add dropwise 6 mL of a dichloromethane solution containing 0.8 g of acetyl chloride. After the addition is complete, slowly heat to 20-25 °C and react for 2 hours. Cool down, 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 mixed solvent of toluene and ethanol to obtain compound P-1, 2.5 g, with an HPLC purity of 99.95%.

[0084] The mass spectra of the compound were measured at p-1, m / z: 396.15.

[0085] Elemental analysis of the obtained compound P-1 yielded the following values: theoretical C, 75.74%, H, 5.08%, N, 7.07%; and measured C, 75.78%, H, 5.06%, N, 7.05%.

[0086] Synthesis example 2-12

[0087] Following the synthesis of P-1, the compound was prepared by reacting reactant 2 with the corresponding acyl chloride (HPLC chromatogram shown in [reference]). Figure 1 The mass spectra (m / z) of the compounds were measured.

[0088] The details are shown in Table 3 below:

[0089] Table 3. Final Products and Mass Spectrometry Information

[0090]

[0091] Example 2

[0092] This embodiment provides a photocurable coating and a cured film, the preparation method of which is as follows:

[0093] 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, 3 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-2 provided in this application.

[0094] The above composition was stirred under a yellow light lamp, and the material was applied to a PET template to form a film by roller coating. The film was dried at 90°C for 5 minutes. The resulting film 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.

[0095] The curing speed is evaluated by the number of times the coating film passes through the exposure belt to cure into a cured film. The fewer the number of passes, the faster the curing speed.

[0096] The cured film obtained above was subjected to an aging test using an RW-UV2BP 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.

[0097] 1. Colorless and transparent with a smooth surface;

[0098] 2: Slightly yellow or with a sticky surface;

[0099] 3: The surface turns yellow or the viscosity increases.

[0100] Examples 3-9

[0101] Referring to Example 2, the difference lies in the type of photoinitiator, as detailed in Table 4 below.

[0102] Comparative Examples 1-2

[0103] Referring to Example 2, the difference lies in the type and amount of photoinitiator, as detailed in Table 4 below.

[0104] Table 4 Test Results

[0105]

[0106] The structural formula of D-1 is as follows:

[0107] .

[0108] 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.

[0109] 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 a carbazole-indanone group, characterized in that, Selected from one or more of the following structural formulas: 、 、 、 、 。 2. An oxime ester photoinitiator containing a carbazole-indanone group, characterized in that, Selected from one or more of the following structural formulas: 、 、 、 、 、 、 、 。 3. A photocurable coating, characterized in that, Its raw materials include the oxime ester photoinitiator containing carbazole and indanone groups as described in claim 2.

4. The photocurable coating according to claim 3, characterized in that, The oxime ester photoinitiator containing the carbazole-indanone group is... .

5. The photocurable coating according to claim 4, characterized in that, The raw materials also include resins, solvents, and additives.

6. A cured film, characterized in that, Its raw materials include the photocurable coatings described in any one of claims 3-5.

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