Acridine-anthracene compound and photosensitizer or photoinitiator containing same

Abstract

The invention belongs to the technical field of photocuring, and particularly relates to an acridine-anthracene compound and a photosensitizer or photoinitiator containing the acridine-anthracene compound. Specifically, the structure of the compound disclosed by the invention is shown as a formula (I), and compared with the existing commercial sensitizer, the compound disclosed by the invention has the advantages of higher curing hardness, no frosting phenomenon and excellent solubility and photosensitive activity, and can be applied to the field of photocuring as a sensitizer or a photoinitiator.

Description

Technical Field

[0001] The invention belongs to the technical field of photocuring, and in particular relates to an acridine-anthracene compound and a photosensitizer or photoinitiator containing the compound. Background Art

[0002] As a light-responsive polymer material system, photocurable resin irradiates the photopolymerizable composition with energy sources such as ultraviolet radiation (UV) or electron beam (EB), triggering a photopolymerization reaction and forming a cross-linked network structure, ultimately obtaining a photocurable resin material with specific functions. This photocuring technology has been widely used in industrial coatings (wood coatings, metal protective coatings), printing processes (screen / offset printing inks), electronic manufacturing (dry film resists, semiconductor packaging materials) and advanced materials (holographic storage media, photocurable molding resins) and other fields.

[0003] The core components of a photopolymerizable composition generally include the following three functional components: (1) a photopolymerizable compound, i.e., a monomer or oligomer containing a polymerizable functional group; (2) a photoinitiator that generates active species (free radicals or cations) through photoexcitation; and (3) a photosensitizer (also known as a photopolymerization sensitizer) that improves the initiation efficiency through an energy transfer mechanism. The photosensitizer, as an auxiliary component to optimize the system's performance, can be selectively added based on actual needs (e.g., light source wavelength matching, initiation rate control, etc.).

[0004] Due to differences in polymerization mechanisms, industrial systems mainly use photoradical polymerization, photocationic polymerization, and their hybrid systems. When there is a light-shielding effect (such as the shielding of the characteristic absorption band of the initiator by fillers such as pigments, dyes, and stabilizers) or a mismatch between the emission spectrum of the light source and the absorption spectrum of the initiator, the introduction of a photosensitizer can significantly enhance the light response capability of the system. Typical application scenarios include: optimizing the adaptation of photocationic initiators (absorption peak <365nm) to long-wavelength light sources (380-405nm), and improving the efficiency of environmentally friendly benzyl methyl ketal / α-hydroxyalkyl phenone free radical initiators under long-wavelength light sources such as metal halide lamps / gallium lamps / UV-LED lamps.

[0005] Recent research has shown that the combination of photoinitiators and macromolecular conjugated photosensitizers has significantly improved photoinitiation efficiency and stability, attracting significant attention and showing great potential for application in photocuring. Acridine and anthracene compounds, as typical photosensitizers, have shown particular strength: these two compounds not only possess extended π-conjugated systems and rigid planar structures, but also achieve excellent photostability and photosensitivity through their extremely high fluorescence quantum efficiency.

[0006] Derivatives such as 9-phenylacridine (9PA) and 9,10-dibutoxyanthracene (DBA) effectively initiate crosslinking and curing of unsaturated resins and their monomers across a broad spectrum from ultraviolet light to X-rays, and have been successfully applied in UV-curable coatings, printing inks, and semiconductor photoresists. However, practical applications still face technical bottlenecks: acridine compounds are limited by strong intermolecular π-π stacking interactions caused by their molecular planar rigidity, resulting in poor solubility in conventional solvent systems. Furthermore, anthracene compounds are prone to surface sensitizer migration (e.g., blooming) during long-term storage of the cured product, leading to interfacial failures such as powdering or yellowing of the cured layer.

[0007] Therefore, how to solve the solubility and blooming problems of macrocyclic conjugated system sensitizers has become one of the current research directions of this type of sensitizers. Summary of the Invention

[0008] Problems to be solved by the invention

[0009] In view of the above problems existing in the prior art, the present invention provides a series of novel acridine-anthracene compounds and photosensitizers or photoinitiators containing the compounds, in order to solve the above problems.

[0010] Solutions for solving problems

[0011] In a first aspect, the present invention provides an acridine-anthracene compound as shown in formula (I),

[0012]

[0013] in,

[0014] Each R1 is independently selected from hydrogen, C 1-20 Alkyl and C 3-20 Cycloalkyl;

[0015] Each R2 is independently selected from hydrogen, C 1-20 Alkyl and C 3-20 Cycloalkyl;

[0016] R3 is selected from hydrogen, -C 1-20 Alkyl, -OC 1-20 Alkyl, -OC(=O)-C 1-20 Alkyl, -C(=O)OC 1-20 Alkyl and -OC(=O)-C 2-20 Alkenyl, the -C(=O)OC 1-20 Alkyl and -OC(=O)-C 1-20 Each alkyl group is independently optionally substituted with at least one -C(=O)OC 1-6 Alkyl or -OC(=O)-C 1-6 Alkyl substitution;

[0017] L is -(CH2) a -[C(=O)] b -O-, which is connected to the anthracene ring through an oxygen atom and to the acridine ring through a methylene group or a carbonyl group, wherein: a is any integer from 0 to 15, b is 0 or 1, and a and b are not 0 at the same time.

[0018] In a second aspect, the present invention provides a photosensitizer comprising the compound of the first aspect.

[0019] Preferably, the photosensitizer contains the compound in the first aspect as an active ingredient.

[0020] In a third aspect, the present invention provides a photoinitiator comprising the compound of the first aspect.

[0021] Preferably, the photoinitiator comprises the compound in the first aspect as an active ingredient.

[0022] In a fourth aspect, the present invention provides a photosensitive composition comprising the photosensitizer of the second aspect, a photoinitiator, and a polymerizable compound having an ethylenically unsaturated bond;

[0023] Alternatively, the photoinitiator according to the third aspect and a polymerizable compound having an ethylenically unsaturated bond are contained.

[0024] Preferably, the photosensitive composition further contains an inorganic compound.

[0025] In a fifth aspect, the present invention provides an alkali-developable photosensitive resin composition, which contains the photosensitizer of the second aspect, a photoinitiator, and an alkali-developable compound having an ethylenically unsaturated bond;

[0026] Alternatively, the photoinitiator according to the third aspect and an alkali-developable compound having an ethylenically unsaturated bond are contained.

[0027] In a sixth aspect, the present invention provides a colored alkali-developable photosensitive resin composition comprising the alkali-developable photosensitive resin composition of the fifth aspect and a colorant.

[0028] In a seventh aspect, the present invention provides a chemical for the electronic industry, comprising the photosensitive composition according to the fourth aspect.

[0029] Preferably, the electronic industry chemicals are anti-corrosion inks, solder resist inks, printing inks, inkjet inks, coatings or adhesives.

[0030] In an eighth aspect, the present invention provides a photoresist comprising at least one photosensitizer according to the second aspect; preferably, the photoresist further comprises a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin, an auxiliary agent, a colorant, and a solvent;

[0031] Or it contains at least one photoinitiator in the third aspect; preferably, the photoresist further contains a multifunctional acrylate monomer, an alkali-soluble resin, an auxiliary agent, a colorant and a solvent.

[0032] In a ninth aspect, the present invention provides an article obtained by processing using any of the electronic industry chemicals in the seventh aspect or the photoresist in the eighth aspect as a raw material.

[0033] Preferably, the article is a printed circuit board, an LCD display, an OLED display, a solar panel, a consumer electronic product or a semiconductor device.

[0034] More preferably, the consumer electronic product is a mobile phone, a television or a computer.

[0035] Effects of the Invention

[0036] The compounds of the present invention are based on an anthracene-acridine bifunctional synergistic design and have excellent photosensitivity. Compared with commercial sensitizers (especially single anthracene sensitizers), they have higher curing hardness. In addition, the introduction of an acridine ring effectively suppresses the photodimerization tendency of single anthracene sensitizers due to π-π stacking, thereby solving the problems of blooming, powdering, and coloring during photocuring. At the same time, the introduction of a flexible long alkyl chain structure solves the problem of poor solubility of acridine sensitizers. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 is the MS spectrum of compound 16;

[0038] Figure 2 This is the MS spectrum of compound 85. DETAILED DESCRIPTION

[0039] Various exemplary embodiments, features, and aspects of the present invention will be described in detail below. The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration." Any embodiment described herein as "exemplary" is not necessarily to be construed as superior or preferred over other embodiments.

[0040] In addition, numerous specific details are provided in the following detailed description to better illustrate the present invention. Those skilled in the art will appreciate that the present invention can be practiced without certain specific details. In other instances, methods, means, equipment, and steps well known to those skilled in the art are not described in detail in order to highlight the main points of the present invention.

[0041] Unless otherwise stated, the units used in this specification are international standard units, and the numerical values ​​and numerical ranges appearing in the present invention should be understood to include the inevitable systematic errors in industrial production.

[0042] In this specification, the use of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0043] In this specification, references to "some specific / preferred embodiments," "other specific / preferred embodiments," "embodiments," etc., mean that the specific elements (e.g., features, structures, properties, and / or characteristics) described in connection with the embodiments are included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it should be understood that the elements may be combined in various embodiments in any suitable manner.

[0044] In this specification, the numerical range expressed using "a numerical value A to a numerical value B" means a range including the endpoints A and B.

[0045] In this specification, "photoinitiator" or "photopolymerization initiator" refers to a type of compound that can absorb energy under light, thereby initiating polymerization, cross-linking and curing of monomers.

[0046] In this specification, "photosensitizer" or "photopolymerization sensitizer" refers to a class of compounds that improve the initiation efficiency through the energy transfer mechanism.

[0047] In a first aspect, the present invention provides an acridine-anthracene compound, the structure of which can be shown as formula (I):

[0048]

[0049] in,

[0050] Each R1 is independently selected from hydrogen, C 1-20 Alkyl and C 3-20 Cycloalkyl;

[0051] Each R2 is independently selected from hydrogen, C 1-20 Alkyl and C 3-20 Cycloalkyl;

[0052] R3 is selected from hydrogen, C 1-20 Alkyl, -OC 1-20 Alkyl, -OC(=O)-C 1-20 Alkyl, -C(=O)OC 1-20 Alkyl and -OC(=O)-C 2-20 Alkenyl, the -C(=O)OC 1-20Alkyl and -OC(=O)-C 1-20 Each alkyl group is independently optionally substituted with at least one -C(=O)OC 1-6 Alkyl or -OC(=O)-C 1-6 Alkyl substitution;

[0053] L is -(CH2) a -[C(=O)] b -O-, which is connected to the anthracene ring through an oxygen atom and to the acridine ring through a methylene group or a carbonyl group, wherein: a is any integer from 0 to 15, b is 0 or 1, and a and b are not 0 at the same time.

[0054] In some embodiments, the structure of the acridine-anthracene compound may be as shown in any one of Formula (I-1) to Formula (I-3):

[0055]

[0056] in,

[0057] R1, R2, R3 and L are as defined in formula (I).

[0058] In some embodiments, the structure of the acridine-anthracene compound may be as shown in Formula (IA) or Formula (IB):

[0059]

[0060] in,

[0061] R1, R2, R3 and L are as defined in any one of Formula (I) and Formula (I-1) to Formula (I-3).

[0062] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA), and Formula (IB), each R1 is independently selected from hydrogen and C 1-20 alkyl.

[0063] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA), and Formula (IB), each R1 is independently selected from hydrogen and C 1-9 alkyl.

[0064] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA) and Formula (IB), each R1 is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and isononyl.

[0065] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA) and Formula (IB), each R1 is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n-pentyl.

[0066] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA), and Formula (IB), each R2 is independently selected from hydrogen and C 1-20 alkyl.

[0067] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA), and Formula (IB), each R2 is independently selected from hydrogen and C 1-9 alkyl.

[0068] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA) and Formula (IB), each R2 is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and isononyl.

[0069] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA) and Formula (IB), each R2 is independently selected from hydrogen, methyl, ethyl, n-propyl and n-butyl.

[0070] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA) and Formula (IB), R3 is selected from -OC 1-20 Alkyl, -OC(=O)-C 1-20 Alkyl, -C(=O)OC 1-20 Alkyl and -OC(=O)-C 2-20 Alkenyl, the -C(=O)OC 1-20 Alkyl and -OC(=O)-C 1-20 Each alkyl group is independently optionally substituted with at least one -C(=O)OC 1-6 Alkyl or -OC(=O)-C 1-6 Alkyl substitution.

[0071] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA) and Formula (IB), R3 is selected from -OC 1-9 Alkyl, -OC(=O)-C 1-9 Alkyl, -C(=O)OC 1-9Alkyl and -OC(=O)-C 2-9 Alkenyl, the -C(=O)OC 1-9 The alkyl group is optionally substituted with one -C(=O)OC(CH3)3.

[0072] In some embodiments, in formula (I), formula (I-1), formula (I-2), formula (I-3), formula (IA) and formula (IB), R3 is selected from -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -OCH2CH2CH2CH3, -OCH2CH(CH3)2, -OCH(CH3)CH2CH3, -OC(CH3)3, -OCH2CH2CH2CH2CH3, -OCH2CH2CH(CH3)2, -OCH2C (CH3)3, -OCH2CH2CH2CH2CH2CH3, -OCH2CH2CH2CH2CH2CH2CH3, -OC(=O)CH3, -OC(=O)CH2CH3, -OC(=O)CH2CH2CH3 , -OC(=O)CH(CH3)2, -OC(=O)CH2CH2CH2CH3, -OC(=O)CH2CH(CH3)2, -OC(=O)CH2CH2CH2CH2CH3, -OC(=O)CH2CH2CH 2CH2CH2CH3, -OC(=O)CH2CH2CH2CH2CH2CH2CH3, -C(=O)OCH3, -C(=O)OCH2CH3, -C(=O)OCH2CH2CH3, -C(=O)OCH(C H3)2, -C(=O)OCH2CH2CH2CH3, -C(=O)OCH2CH(CH3)2, -C(=O)OCH(CH3)CH2CH3, -C(=O)OC(CH3)3, -C(=O)OCH2CH2C H2CH2CH3, -C(=O)OCH2CH2CH(CH3)2, -C(=O)OCH2C(CH3)3, -C(=O)OCH2CH2CH2CH2CH2CH3, -C(=O)OCH2C(=O)OC( CH3)3, -OC(=O)CH=CH2, -OC(=O)C(=CH2)CH3, -OC(=O)CH=CHCH3, -OC(=O)C(=CH2)CH2CH3 and -OC(=O)CH=CHCH2CH3.

[0073] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA) and Formula (IB), R3 is selected from -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH2CH2CH2CH3, -OCH2CH2CH2CH2CH3, -OCH2CH2CH2CH2CH2CH3, -OCH2CH2CH2CH2CH2CH3, -OC(=O)CH3, -OC(=O)CH2CH2CH2CH2CH2CH2CH3, -C(=O)OCH3, -C(=O)OCH2C(=O)OC(CH3)3 and -OC(=O)C(=CH2)CH3.

[0074] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA) and Formula (IB), when b is 0, a is any integer from 1 to 10, preferably any integer from 1 to 8.

[0075] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA) and Formula (IB), when b is 1, a is any integer from 0 to 10, preferably any integer from 0 to 7.

[0076] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA), and Formula (IB), L is

[0077] In some embodiments, in Formula (I), Formula (I-1), Formula (I-2), Formula (I-3), Formula (IA), and Formula (IB), L is

[0078] In some embodiments, the compounds of the present invention may be selected from the following compounds:

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090] In a second aspect, the present invention provides a photosensitizer comprising the compound described in the first aspect.

[0091] In some embodiments, the photosensitizer comprises the compound described in the first aspect as an active ingredient.

[0092] In a third aspect, the present invention provides a photoinitiator comprising the compound described in the first aspect.

[0093] In some embodiments, the photoinitiator comprises the compound described in the first aspect as an active ingredient.

[0094] In a fourth aspect, the present invention provides a photosensitive composition.

[0095] In some embodiments, the photosensitive composition contains the photosensitizer described in the second aspect, a photoinitiator, and a polymerizable compound having an ethylenically unsaturated bond.

[0096] In some embodiments, the photosensitive composition contains the photoinitiator described in the third aspect and a polymerizable compound having an ethylenically unsaturated bond.

[0097] In some embodiments, the photosensitive composition further contains an inorganic compound.

[0098] In some embodiments, the inorganic compound may include but is not limited to: metal oxides such as nickel oxide, iron oxide, iridium oxide, titanium oxide, zinc oxide, magnesium oxide, calcium oxide, potassium oxide, aluminum oxide; silicon dioxide, layered clay minerals, Milori blue, calcium carbonate, magnesium carbonate, cobalt series, manganese series, glass powder, mica, talc, kaolin, ferrocyanide, various metal sulfates, sulfides, selenides, aluminum silicate, calcium silicate, aluminum hydroxide, platinum, gold, silver, copper, etc.; among them, the inorganic compound is preferably titanium oxide, silicon dioxide, layered clay minerals, silver, etc.

[0099] In a fifth aspect, the present invention provides an alkali-developable photosensitive resin composition.

[0100] In some embodiments, the alkali-developable photosensitive resin composition contains the photosensitizer described in the second aspect, an alkali-developable compound having an ethylenically unsaturated bond, and a photoinitiator.

[0101] In some embodiments, the alkali-developable photosensitive resin composition contains the photoinitiator described in the third aspect and an alkali-developable compound having an ethylenically unsaturated bond.

[0102] In a sixth aspect, the present invention provides a colored alkali-developable photosensitive resin composition comprising the alkali-developable photosensitive resin composition described in the fifth aspect and a colorant.

[0103] In a seventh aspect, the present invention provides a chemical for the electronic industry, comprising the photosensitive composition described in the fourth aspect.

[0104] In some embodiments, the electronic industry chemical is an etch-resistant ink, a solder resist ink, a printing ink, an inkjet ink, a coating, or an adhesive.

[0105] In an eighth aspect, the present invention provides a photoresist.

[0106] In some embodiments, the photoresist contains at least one photosensitizer described in the second aspect.

[0107] In some embodiments, the photoresist further contains a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin, an auxiliary agent, a colorant, and a solvent.

[0108] In other embodiments, the photoresist contains at least one photoinitiator as described in the third aspect.

[0109] In other embodiments, the photoresist further contains a multifunctional acrylate monomer, an alkali-soluble resin, an auxiliary agent, a colorant, and a solvent.

[0110] In a ninth aspect, the present invention provides an article obtained by processing using any of the electronic industry chemicals described in the seventh aspect or the photoresist described in the eighth aspect as a raw material.

[0111] In some embodiments, the article is a printed circuit board (PCB), an LCD display, an OLED display, a solar panel, a consumer electronic product, or a semiconductor device.

[0112] In some embodiments, the consumer electronic product is a mobile phone, a television, or a computer.

[0113] Example

[0114] The embodiments of the present invention will be described in detail below with reference to the examples, but it will be understood by those skilled in the art that the following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention. Where specific conditions are not specified in the examples, the methods were performed according to conventional conditions or the conditions recommended by the manufacturer. Where the manufacturers of the reagents or instruments are not specified, they are all conventional products that can be obtained commercially.

[0115] Example 1: Synthesis of Compound 16

[0116] (1) Synthesis of compound S1:

[0117]

[0118] To a reaction flask, diphenylamine (40 g, approximately 0.236 mol) as Compound A, 4-bromobutyric acid (40 g, approximately 0.240 mol) as Compound B, p-toluenesulfonic acid (100 g), and N-methylpyrrolidone (200 g) were added. The mixture was stirred, heated to 180°C for 10 h, cooled, water was added, refluxed for 2 h, cooled, and the aqueous phase removed. The mixture was first washed with 220 g of liquid caustic soda, then heated to 70°C with 300 g of toluene, filtered, separated, concentrated, and crystallized by adding ethanol. The temperature was then cooled to obtain crystalline Compound S1 (60.3 g, 84.9% yield).

[0119] MS (ESI+): m / z 300.1 [M+H] +

[0120] (2) Synthesis of compound 16:

[0121]

[0122] Anthraquinone (34.6 g, approximately 0.166 mol), zinc powder (20 g), iron powder (1.5 g), tetrabutylammonium bromide (0.5 g), and water (60 g) were added to a reaction flask. The temperature was raised to 50-55°C, and 65 g of liquid caustic soda was added dropwise. The temperature was then raised to 65°C. Compound S1 (50 g, dissolved in toluene) was then added to the reaction system. Butane bromide (19.3 g, approximately 0.141 mol), compound D, was then added to the reaction system and allowed to react for 2 hours. After the reaction, the insoluble matter was removed by filtration, the liquids were separated, and toluene was distilled under reduced pressure. Ethanol was added for crystallization for 3 hours, filtered, and dried to obtain solid compound 16 (54.2 g, 67.1% yield).

[0123] The MS spectrum of compound 16 is shown in Figure 1 As shown, MS (ESI+): m / z 486.5 [M+H] + .

[0124] Examples 2-7: Synthesis of Compounds 28, 56, 85, 100, 126 and 143

[0125] Referring to the synthetic route in Example 1, corresponding compound A, compound B, compound C and compound D were selected to prepare the compounds of Examples 2-7 in Table 1, respectively. Among them, the MS spectrum of compound 85 is as follows: Figure 2shown.

[0126] Table 1

[0127]

[0128] <Photosensitizer performance test>

[0129] Example 8: Preparation of Photosensitive Composition 1

[0130] Trimethylolpropane triacrylate (36 g), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (2 g), compound 16 (1 g) and acrylic acid (5 g) were added to the acrylic copolymer (75.5 g) and stirred thoroughly to obtain a photosensitive composition 1.

[0131] The acrylic copolymer was obtained by dissolving 20 parts by mass of methacrylic acid, 15 parts by mass of hydroxyethyl methacrylate, 10 parts by mass of methyl methacrylate, and 55 parts by mass of butyl methacrylate in 300 parts by mass of ethyl cellosolve, adding 0.75 parts by mass of azobisisobutyronitrile under a nitrogen atmosphere, and reacting the mixture at 70°C for 5 hours to obtain the acrylic copolymer.

[0132] Examples 9-14: Preparation of Photosensitive Composition 2-7

[0133] Except that compound 16 was replaced by the compounds in Table 2, the photosensitive compositions of Examples 9-14 and Comparative Examples 1-5 were obtained by referring to the method in Example 8.

[0134] Table 2

[0135]

[0136] The structures of the compounds used in Comparative Examples 1-5 are shown below.

[0137]

[0138] <Solubility Test>

[0139] At 25° C., the solubility of the compounds in Examples 1-7 and Comparative Examples 2-5 in propylene glycol monomethyl ether acetate (PGMEA) was tested, with DBA as the reference and set to 1.0. The test results are shown in Table 3.

[0140] Table 3

[0141] Example Compound Solubility PGMEA@25℃ Example 1 Compound 16 1.20 Example 2 Compound 28 1.22 Example 3 Compound 56 1.31 Example 4 Compound 85 1.38 Example 5 Compound 100 1.15 Example 6 Compound 126 1.62 Example 7 Compound 143 1.55 Comparative Example 2 DPA 0.1 Comparative Example 3 9PA 0.02 Comparative Example 4 17PA 0.06 Comparative Example 5 DBA 1.0

[0142] As shown in Table 3, the solubility of the compounds of the present invention in Examples 1-7 in PGMEA is significantly higher than that of DPA, 9PA, 17PA and DBA in Comparative Examples 2-5, indicating that the acridine-anthracene compounds of the present invention have excellent solubility.

[0143] <Hardness test>

[0144] The photosensitive compositions of Examples 8-14 and Comparative Examples 1-5 were coated onto a 50 μm thick polyethylene terephthalate film using a #3 bar coater. Exposure was performed using a UV-LED caterpillar light source with a wavelength of 385 nm (at a light intensity of 500 mJ / cm 2 After curing, the film was placed at room temperature for 24 hours, and then the pencil hardness was measured using a pencil hardness tester at a load of 1 kg. The test results are shown in Table 4.

[0145] Table 4

[0146] Example Pencil hardness Is there frost? Example 8 3H no Example 9 3H no Example 10 3H no Example 11 3H no Example 12 3H no Example 13 3H no Example 14 3H no Comparative Example 1 1H no Comparative Example 2 2H yes Comparative Example 3 2H yes Comparative Example 4 2H yes Comparative Example 5 2H yes

[0147] As can be seen from Table 4, the curing hardness of the photosensitive compositions based on the compounds of the present invention in Examples 8-14 is significantly higher than that of the photosensitive compositions based on 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, DPA, 9PA, 17PA and DBA in Comparative Examples 1-5, indicating that the acridine-anthracene compounds of the present invention are suitable for use as photosensitizers in the field of photocuring.

[0148] Furthermore, the cured film provided by the present invention exhibited excellent stability during storage, with the designed compound exhibiting no blooming. By optimizing the molecular structure, the material's solubility was significantly improved and molecular mobility was effectively reduced. In contrast, significant blooming was observed in the DPA in Comparative Example 2, 9PA in Comparative Example 3, 17PA in Comparative Example 4, and DBA in Comparative Example 5 under the same storage conditions.

[0149] <Photoinitiator Performance Test>

[0150] Example 15: Preparation of polymerizable composition (photosensitive resin) 1

[0151] Acrylic resin prepolymer (96 g), compound 16 (3 g), tetraethyl Michler's ketone (0.05 g) and butanone (50 g) were added to a reaction vessel at 35° C., reacted for 6 hours, and stirred uniformly to obtain a polymerizable composition 1.

[0152] The above acrylic resin prepolymer is obtained by the following method: Dissolve 10 parts by mass of methacrylic acid, 10 parts by mass of methyl methacrylate, and 10 parts by mass of isobornyl methacrylate in 50 parts by mass of propylene glycol monomethyl ether acetate. Under the catalysis of 0.5 parts by mass of azobisisobutyronitrile (AIBN), the reaction system is kept at 70 - 80 °C for 2 h to obtain the acrylic resin prepolymer.

[0153] Examples 16 - 21: Preparation of Polymerizable Compositions 2 - 7

[0154] Except for replacing Compound 16 with each compound in Table 5, referring to the method in Reference Example 15, the polymerizable compositions in Examples 16 - 21 and Comparative Examples 6 - 10 were obtained.

[0155] Table 5

[0156] Example Acrylic resin prepolymer Compound Tetraethyl Michler's ketone Butanone Example 15 96g Compound 16 0.05g 50g Example 16 96g Compound 28 0.05g 50g Example 17 96g Compound 56 0.05g 50g Example 18 96g Compound 85 0.05g 50g Example 19 96g Compound 100 0.05g 50g Example 20 96g Compound 126 0.05g 50g Example 21 96g Compound 143 0.05g 50g Comparative Example 6 96g - 0.05g 50g Comparative Example 7 96g DPA 0.05g 50g Comparative Example 8 96g 9PA 0.05g 50g Comparative Example 9 96g 17PA 0.05g 50g Comparative Example 10 96g DBA 0.05g 50g

[0157] <Photocuring Activity Evaluation under UV - LED 405 nm Light Source>

[0158] According to the following method, the polymerizable compositions in Examples 15 - 21 and Comparative Examples 6 - 10 above were evaluated for photocuring activity.

[0159] Using a spin coater, the polymerizable compositions of Examples 15 - 21 and Comparative Examples 6 - 10 were coated on a glass substrate. Using a spin coater, at a rotation speed of 1500 rpm, it was heated to 100 °C and held for 2 min, then cooled to room temperature to form a coating film on the surface of the glass substrate. Then, under the irradiation of a UV - LED 405 nm light source, the polymerizable compositions in Examples 15 - 21 and Comparative Examples 6 - 10 were cured. Table 6 shows the exposure amount required for complete curing. The smaller this value is, the better the photocuring activity.

[0160] Table 6

[0161] Example Compound <![CDATA[Exposure dose (mJ / cm 2 ) under UV-LED 405nm light source irradiation Example 15 Compound 16 47 Example 16 Compound 28 52 Example 17 Compound 56 48 Example 18 Compound 85 55 Example 19 Compound 100 51 Example 20 Compound 126 57 Example 21 Compound 143 56 Comparative Example 6 - Uncured Comparative Example 7 DPA Uncured Comparative Example 8 9PA 81 Comparative Example 9 17PA 75 Comparative Example 10 DBA Uncured

[0162] As can be seen from Table 6, under the irradiation of a UV - LED 405 nm light source, the compounds used in Comparative Examples 6, 7, and 10 (no initiator, DPA, DBA) showed uncured phenomena. The energy required for the polymerizable compositions added with the compounds of the present invention to cure was significantly less than the energy required for the polymerizable compositions added with the compounds used in Comparative Examples 8 and 9 (9PA and 17PA) to cure. Compared with the compounds used in Comparative Examples 7 - 10 (DPA, 9PA, 17PA, and DBA), the photocuring activity of the acridine - anthracene compounds of the present invention is more excellent and is useful as a photoinitiator for optical applications.

[0163] In summary, DPA and DBA single anthracene compounds are only suitable for photosensitizers, while the acridine-anthracene compounds of the present invention have good effects as photosensitizers or photoinitiators.

[0164] It should be noted that, although the technical solutions of the present invention are described with specific examples, those skilled in the art will appreciate that the present invention should not be limited thereto.

[0165] While various embodiments of the present invention have been described above, the above descriptions are intended to be illustrative, non-exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those skilled in the art without departing from the scope and spirit of the described embodiments. The terminology used herein is selected to best explain the principles of the embodiments, their practical applications, or technological improvements in the marketplace, or to enable others skilled in the art to understand the embodiments disclosed herein.

Claims

1. A compound as shown in formula (I), in, Each R1 is independently selected from hydrogen, C 1-20 Alkyl and C 3-20 Cycloalkyl; Each R2 is independently selected from hydrogen, C 1-20 Alkyl and C 3-20 Cycloalkyl; R3 is selected from hydrogen, C 1-20 Alkyl, -OC 1-20 Alkyl, -OC(=O)-C 1-20 Alkyl, -C(=O)OC 1-20 Alkyl and -OC(=O)-C 2-20 Alkenyl, the -C(=O)OC 1-20 Alkyl and -OC(=O)-C 1-20 Each alkyl group is independently optionally substituted with at least one -C(=O)OC 1-6 Alkyl or -OC(=O)-C 1-6 Alkyl substitution; L is -(CH2) a -[C(=O)] b -O-, which is connected to the anthracene ring through an oxygen atom and to the acridine ring through a methylene group or a carbonyl group, wherein: a is any integer from 0 to 15, b is 0 or 1, and a and b are not 0 at the same time.

2. The compound according to claim 1, characterized in that The compound is represented by any one of formula (I-1) to formula (I-3): in, R1, R2, R3 and L are as defined in claim 1.

3. The compound according to claim 1 or 2, characterized in that The compound is represented by formula (IA) or formula (IB): in, R1, R2, R3 and L are as defined in claim 1 or 2.

4. The compound according to any one of claims 1 to 3, characterized in that Each R1 is independently selected from hydrogen and C 1-20 alkyl; Preferably, each R1 is independently selected from hydrogen and C 1-9 alkyl; More preferably, each R1 is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and isononyl; More preferably, each R1 is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and n-pentyl.

5. The compound according to any one of claims 1 to 4, characterized in that Each R2 is independently selected from hydrogen and C 1-20 alkyl; Preferably, each R2 is independently selected from hydrogen and C 1-9 alkyl; More preferably, each R2 is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, n-heptyl, n-octyl and isononyl; Further preferably, each R2 is independently selected from hydrogen, methyl, ethyl, n-propyl and n-butyl.

6. The compound according to any one of claims 1 to 5, characterized in that R3 is selected from -OC 1-20 Alkyl, -OC(=O)-C 1-20 Alkyl, -C(=O)OC 1-20 Alkyl and -OC(=O)-C 2-20 Alkenyl, the -C(=O)OC 1-20 Alkyl and -OC(=O)-C 1-20 Each alkyl group is independently optionally substituted with at least one -C(=O)OC 1-6 Alkyl or -OC(=O)-C 1-6 Alkyl substitution; Preferably, R3 is selected from -OC 1-9 Alkyl, -OC(=O)-C 1-9 Alkyl, -C(=O)OC 1-9 Alkyl and -OC(=O)-C 2-9 Alkenyl, the -C(=O)OC 1-9 The alkyl group is optionally substituted with one -C(=O)OC(CH3)3; More preferably, R3 is selected from -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH(CH3)2, -OCH2CH2CH2CH3, -OCH2CH(CH3)2, -OCH(CH3)CH2 CH3, -OC(CH3)3, -OCH2CH2CH2CH2CH3, -OCH2CH2CH(CH3)2, -OCH2C(CH3)3, -OCH2CH2CH2CH2CH2CH3, -OCH2 CH2CH2CH2CH2CH2CH3, -OC(=O)CH3, -OC(=O)CH2CH3, -OC(=O)CH2CH2CH3, -OC(=O)CH(CH3)2, -OC(=O)CH2C H2CH2CH3, -OC(=O)CH2CH(CH3)2, -OC(=O)CH2CH2CH2CH2CH3, -OC(=O)CH2CH2CH2CH2CH2CH3, -OC(=O)CH2C H2CH2CH2CH2CH2CH3, -C(=O)OCH3, -C(=O)OCH2CH3, -C(=O)OCH2CH2CH3, -C(=O)OCH(CH3)2, -C(=O)OCH2CH 2CH2CH3, -C(=O)OCH2CH(CH3)2, -C(=O)OCH(CH3)CH2CH3, -C(=O)OC(CH3)3, -C(=O)OCH2CH2CH2CH2CH3, -C (=O)OCH2CH2CH(CH3)2, -C(=O)OCH2C(CH3)3, -C(=O)OCH2CH2CH2CH2CH2CH3, -C(=O)OCH2C(=O)OC(CH3)3, -OC(=O)CH=CH2, -OC(=O)C(=CH2)CH3, -OC(=O)CH=CHCH3, -OC(=O)C(=CH2)CH2CH3 and -OC(=O)CH=CHCH2CH3; Further preferably, R3 is selected from -OCH3, -OCH2CH3, -OCH2CH2CH3, -OCH2CH2CH2CH3, -OCH2CH2CH2CH2CH3, -OCH2CH2CH2CH2CH2CH3, -OCH2CH2CH2CH2CH2CH3, -OC(=O)CH3, -OC(=O)CH2CH2CH2CH2CH2CH2CH3, -C(=O)OCH3, -C(=O)OCH2C(=O)OC(CH3)3 and -OC(=O)C(=CH2)CH3.

7. The compound according to any one of claims 1 to 6, characterized in that When b is 0, a is any integer from 1 to 10, preferably any integer from 1 to 8; When b is 1, a is any integer from 0 to 10, preferably any integer from 0 to 7.

8. A compound selected from the group consisting of:

9. A photosensitizer comprising the compound according to any one of claims 1 to 8; preferably, the photosensitizer comprises the compound according to any one of claims 1 to 8 as an active ingredient.

10. A photoinitiator comprising the compound according to any one of claims 1 to 8; preferably, the photoinitiator comprises the compound according to any one of claims 1 to 8 as an active ingredient.

11. A photosensitive composition comprising the photosensitizer according to claim 9, a photoinitiator, and a polymerizable compound having an ethylenically unsaturated bond; or containing the photoinitiator according to claim 10 and a polymerizable compound having an ethylenically unsaturated bond; Preferably, the photosensitive composition further contains an inorganic compound.

12. An alkali-developable photosensitive resin composition comprising the photosensitizer according to claim 9, a photoinitiator, and an alkali-developable compound having an ethylenically unsaturated bond; Alternatively, the photoinitiator according to claim 10 and an alkali-developable compound having an ethylenically unsaturated bond are contained. 13 . A colored alkali-developable photosensitive resin composition comprising the alkali-developable photosensitive resin composition according to claim 12 and a colorant.

14. A chemical for the electronic industry, comprising the photosensitive composition according to claim 11; preferably, the chemical for the electronic industry is an anti-corrosion ink, a solder resist ink, a printing ink, an inkjet ink, a coating or an adhesive.

15. A photoresist comprising at least one photosensitizer according to claim 9; preferably, the photoresist further comprises a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin, an auxiliary agent, a colorant and a solvent; Or it contains at least one photoinitiator according to claim 10; preferably, the photoresist further contains a multifunctional acrylate monomer, an alkali-soluble resin, an auxiliary agent, a colorant and a solvent.

16. An article obtained by processing any one of the electronic industry chemicals according to claim 14 or the photoresist according to claim 15 as a raw material; preferably, the article is a printed circuit board, an LCD display, an OLED display, a solar panel, a consumer electronic product or a semiconductor device; more preferably, the consumer electronic product is a mobile phone, a television or a computer.

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