Photosensitive resin composition containing anthryl chalcone photosensitizer and application

Abstract

The invention discloses a photosensitive resin composition containing an anthryl chalcone photosensitizer and application of the photosensitive resin composition. The photosensitive resin composition comprises an anthryl chalcone photosensitizer, and the anthryl chalcone photosensitizer at least comprises an anthracene derivative as shown in a general formula (III). Wherein R1 is one of straight chain or branched chain alkyl of C1 to C5, N-methylpyrrole-2-yl, furan-2-yl, benzofuran-2-yl, thiophene-2-yl, naphthalene-2-yl, phenyl and substituted aryl, and R2 is one of C1-C5 alkyl, N-methylpyrrole-2-yl, furan-2-yl, benzofuran-2-yl, thiophene-2-yl, naphthalene-2-yl, phenyl and substituted aryl; the anthryl chalcone is adopted as the photosensitizer of the photosensitive resin composition, the photosensitizer cannot migrate into a polyethylene (PE) film, and in the electroplating process after exposure and development, small molecular fragments cannot be separated out to pollute electroplating liquid, so that the undesirable phenomena of short circuit, open circuit and the like of a corrosion-resistant pattern are avoided, and the yield of a product is remarkably improved.

Description

[0001] This application is a divisional application of patent application number 2025105926550, titled "Photosensitive resin composition containing anthryl chalcone photosensitizer and application", filed on May 09, 2025. TECHNICAL FIELD

[0002] The present application belongs to the technical field of photosensitive resin composition, and specifically relates to a photosensitive resin composition containing an anthryl chalcone photosensitizer and application. BACKGROUND

[0003] Photosensitive resin composition is widely used in the manufacturing field of printed circuit board (PCB), lead frame (LF) and semiconductor packaging (IC) substrate printed circuit board as a key pattern transfer material. The photosensitive resin composition is usually coated on the surface of a PET support film, and after drying, a protective layer such as a polyethylene film (PE) protective layer is tightly attached to the surface, also known as photosensitive dry film, dry film resist, etc. In the process of realizing pattern transfer, first, the dry film resist is attached to the copper substrate, a mask with a certain pattern is covered on the dry film resist, and pattern exposure is performed; then, a weak alkaline aqueous solution is used as a developing solution to remove the unexposed part, and etching or electroplating treatment is used to form a pattern; finally, the dry film solidified part is removed by stripping with a film stripping solution, thereby realizing pattern transfer.

[0004] With the development of electronic devices towards miniaturization and high density, the fineness of the circuit is continuously improved. In order to meet the needs of fine line manufacturing, the photosensitive resin composition needs to have higher resolution. In order to improve the resolution, appropriate photosensitizer needs to be added to the photosensitive resin composition. For photosensitive resin composition, suitable photosensitizer has a direct impact on photosensitivity, resolution and production yield.

[0005] Currently, anthracene derivatives represented by 9,10-dibutoxyanthracene (DBA), 9,10-diphenylanthracene (DPHA) and 9,10-diacetoxyanthracene (DAcOA) are widely used as photosensitizers. However, there are some problems in the use of such photosensitizers; for example: 9,10-dibutoxyanthracene photosensitizer will break the 9,10 C-O bond during exposure, the anthracene ring will dimerize, and small molecule alkoxy fragments will be released, which will migrate from the solidified photosensitive resin composition to the plating solution in the subsequent plating process, causing pollution, affecting the service life of the plating solution and the plating effect; 9,10-diphenylanthracene photosensitizer has a rigid molecular structure, which greatly reduces its solubility, greatly affecting the uniformity and consistency of the product; 9,10-diacetoxyanthracene photosensitizer has an electron-withdrawing inductive effect due to the acetoxy group, which increases the electron cloud density of the 9,10 number of anthracene rings, thus reducing the efficiency of the catalytic curing reaction, and the solidified photosensitive resin composition has poor side wall perpendicularity and a large difference in line length between the top and bottom, forming an "inverted trapezoid", and the photosensitizer requires higher energy during exposure, resulting in reduced photobleaching efficiency.

[0006] Therefore, it is a technical problem to be solved in the art to develop a new anthracene photosensitizer with high light quantum yield, low migration characteristics and excellent development compatibility, and to construct a high-performance photo-curable resin composition based thereon. SUMMARY

[0007] To solve the above problems, the purpose of the present application is to provide a photosensitive resin composition containing an anthryl chalcone photosensitizer and its application.

[0008] In a first aspect, the present application provides an anthryl chalcone photosensitizer, which comprises at least one anthracene derivative represented by general formula (I)~(III); wherein: R 1 is one of C1-C5 straight-chain or branched alkyl, N-methyl pyrrole, furan, benzofuran, thiophene, naphthyl, phenyl, substituted aryl.

[0009] The anthryl chalcone photosensitizer comprises at least one anthracene derivative represented by formula D1~D11: In a second aspect, the present application provides a photosensitive resin composition comprising the aforementioned anthryl chalcone photosensitizer.

[0010] The photosensitive resin composition further comprises an alkali-soluble resin, a photopolymerization monomer and a photoinitiator. The photosensitive resin composition comprises, by weight fraction, 50-65 parts of alkali-soluble resin, 35-50 parts of photopolymerization monomer, 2-5 parts of photoinitiator, and 0.1-1 part of anthryl chalcone photosensitizer.

[0011] The alkali-soluble resin is obtained by polymerization of one or more monomers selected from (meth)acrylic acid, alkyl (meth)acrylate, benzyl (meth)acrylate, benzyl (meth)acrylate derivative, phenyl (meth)acrylate, styrene, and styrene derivative; preferably, the alkali-soluble resin is obtained by polymerization of one or more monomers selected from (meth)acrylic acid, alkyl (meth)acrylate, benzyl (meth)acrylate, and styrene; preferably, the monomer containing aromatic group accounts for 50-70% of the total monomer mass during the polymerization process.

[0012] The alkali-soluble resin has a weight average molecular weight of 20,000-60,000, an acid value of 160-220 mgKOH / g, and a molecular weight distribution of 1.0-3.0.

[0013] The photopolymerization monomer is a monomer having ethylenic unsaturated double bond, preferably an acrylate monomer, and further preferably one or more of methoxyl polyethylene glycol monoacrylate, ethoxy (propoxy) nonyl phenol acrylate, ethoxy (propoxy) bisphenol A di(meth)acrylate, ethoxy (propoxy) di(meth)acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxy (propoxy) trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, ethoxy (propoxy) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0014] The photoinitiator is 2,4,5-triaryl imidazole dimer, preferably one or more of 2-(2-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(2-chlorophenyl)-4,5-di(methoxyphenyl) imidazole dimer, 2-(2-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(2-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(4-methoxyphenyl)-4,5-diphenyl imidazole dimer, and 2,2’,4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4’,5’-diphenyl-1,1’-diimidazole.

[0015] The photosensitive resin composition further comprises an additive, which is one or more of dye, photochromic agent, plasticizer, adhesion promoter, polymerization inhibitor, defoaming agent, and coating aid; the additive is in a weight fraction of 0.5-5.0 parts.

[0016] The photosensitive resin composition further comprises a solvent, and the solvent is one or more of acetone, toluene and methanol; the weight of the solvent is 15-25 parts.

[0017] In a third aspect, the present application further provides a photosensitive dry film, which comprises a PET layer, a photosensitive etching agent layer and a PE layer from bottom to top, wherein the photosensitive etching agent layer is prepared from the photosensitive resin composition described above.

[0018] In a fourth aspect, the present application further provides an application of the photosensitive dry film in a printed circuit board, a lead frame or a semiconductor packaging substrate.

[0019] Compared with the prior art, one or more of the above technical solutions can achieve at least one of the following beneficial effects: (1) The anthryl chalcone photosensitizer provided by the present application has the characteristics of low migration before curing and low outgassing after curing.

[0020] (2) In the present application, anthryl chalcone is used as the photosensitizer of the photosensitive resin composition. The photosensitizer will not migrate into the polyethylene film (PE), and will not outgas small molecule fragments to contaminate the electroplating solution in the electroplating process after exposure and development, thereby avoiding adverse phenomena such as short circuit and open circuit of the resist pattern, and significantly improving the yield of the product.

[0021] (3) In the present application, the photosensitive resin composition comprises an alkali-soluble resin, a photopolymerization monomer, a photoinitiator and an anthryl chalcone photosensitizer. Through the synergistic effect between the components, the photosensitive resin composition obtained has excellent photosensitive properties and adhesion. After exposure, the resist circuit formed has uniform curing effect, the sidewall is flat, and the port presents an excellent right-angled rectangle, effectively solving the problem of poor resist form (i.e. "inverted trapezoidal problem") existing in the prior art. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 , Figure 2 are the nuclear magnetic hydrogen spectrum and the nuclear magnetic carbon spectrum of the anthryl chalcone photosensitizer D1 prepared in Example 1, respectively.

[0023] Figure 3 , Figure 4 are the nuclear magnetic hydrogen spectrum and the nuclear magnetic carbon spectrum of the anthryl chalcone photosensitizer D2 prepared in Example 2, respectively.

[0024] Figure 5 , Figure 6 are the nuclear magnetic hydrogen spectrum and the nuclear magnetic carbon spectrum of the anthryl chalcone photosensitizer D3 prepared in Example 3, respectively.

[0025] Figure 7 , Figure 8 are the nuclear magnetic hydrogen spectrum and the nuclear magnetic carbon spectrum of the anthryl chalcone photosensitizer D4 prepared in Example 4, respectively.

[0026] Figure 9 、 Figure 10 The figure is the nuclear magnetic hydrogen spectrum of anthryl chalcone photosensitizer D5 prepared in Example 5, and the figure is the nuclear magnetic carbon spectrum of anthryl chalcone photosensitizer D5 prepared in Example 5.

[0027] Figure 11 、 Figure 12 The figure is the nuclear magnetic hydrogen spectrum of anthryl chalcone photosensitizer D6 prepared in Example 6, and the figure is the nuclear magnetic carbon spectrum of anthryl chalcone photosensitizer D6 prepared in Example 6.

[0028] Figure 13 、 Figure 14 The figure is the nuclear magnetic hydrogen spectrum of anthryl chalcone photosensitizer D7 prepared in Example 7, and the figure is the nuclear magnetic carbon spectrum of anthryl chalcone photosensitizer D7 prepared in Example 7.

[0029] Figure 15 、 Figure 16 The figure is the nuclear magnetic hydrogen spectrum of anthryl chalcone photosensitizer D8 prepared in Example 8, and the figure is the nuclear magnetic carbon spectrum of anthryl chalcone photosensitizer D8 prepared in Example 8.

[0030] Figure 17 、 Figure 18 The figure is the nuclear magnetic hydrogen spectrum of anthryl chalcone photosensitizer D9 prepared in Example 9, and the figure is the nuclear magnetic carbon spectrum of anthryl chalcone photosensitizer D9 prepared in Example 9.

[0031] Figure 19 、 Figure 20 The figure is the nuclear magnetic hydrogen spectrum of anthryl chalcone photosensitizer D10 prepared in Example 10, and the figure is the nuclear magnetic carbon spectrum of anthryl chalcone photosensitizer D10 prepared in Example 10.

[0032] Figure 21 、 Figure 22 The figure is the nuclear magnetic hydrogen spectrum of anthryl chalcone photosensitizer D11 prepared in Example 11, and the figure is the nuclear magnetic carbon spectrum of anthryl chalcone photosensitizer D11 prepared in Example 11.

[0033] Figure 23 The figure is the ultraviolet-visible spectrum of anthryl chalcone photosensitizer D1~D5 dissolved in toluene (concentration 2×10 -5 mol / L).

[0034] Figure 24 The figure is the ultraviolet-visible spectrum of anthryl chalcone photosensitizer D6~D11 dissolved in toluene (concentration 2×10 -5 mol / L). DETAILED DESCRIPTION

[0035] As described above, in the first aspect, the present application provides an anthryl chalcone photosensitizer, which at least contains one anthracene derivative shown in general formula (I)~(III); Wherein: R 1one of C1-C5 straight chain or branched alkyl, N-methyl pyrrolyl, furanyl, benzofuranyl, thienyl, naphthyl, phenyl, substituted aryl.

[0036] In the anthracene-based chalcone photosensitizer of the present application, the chalcone structure is contained at 9 and / or 10 or 2, which can adjust the electronic arrangement of the anthracene group, improve the photosensitive properties, and the chalcone structure can improve the flexibility of the photosensitizer and the compatibility and dispersibility in the photosensitive resin composition, so as to avoid the migration and precipitation of the fragments cracked after exposure, and the pollution of the electroplating solution. Further, the anthracene-based chalcone photosensitizer of the present application can improve the photosensitivity of the photosensitive resin composition, and the formed resist pattern after curing has a flat side wall and a regular square cross section.

[0037] The anthracene-based chalcone photosensitizer contains one or more of (2E, 2'E)-3,3'-(9,10-anthracenediyl)bis[1-(N-methyl)-2-pyrrolyl]-1-propenone, (1E, 1'E)-1,1'-(9,10-anthracenediyl)bis-1-penten-3-one, (2E)-3-[(10-formyl)-9-anthryl]-1-(2-furanyl)-1-propenone, (2E)-3-[(10-formyl)-9-anthryl]-1-(2-benzofuranyl)-1-propenone, (2E)-3-[(10-formyl)-9-anthryl](1-phenyl)-1-propenone, (2E)-3-[(10-formyl)-9-anthryl]-1-(4-methoxy)phenyl-1-propenone, (2E)-3-[(10-formyl)-9-anthryl]-1-(2-naphthyl)-1-propenone, (2E)-1-(2-anthryl)-3-(2-thienyl)-1-propenone, (2E)-1-(2-anthryl)[3-(N-methyl)-2-pyrrolyl]-1-propenone, (2E)-1-(2-anthryl)[3-(4-isopropyl)phenyl]-1-propenone, (2E)-1-(2-anthryl)[3-(4-methoxy)phenyl]-1-propenone, and the specific structures thereof are shown in formulae D1-D11: .

[0038] In a second aspect, the present application provides a photosensitive resin composition comprising the anthracene-based chalcone photosensitizer described above.

[0039] The photosensitive resin composition further comprises an alkali-soluble resin, a photopolymerization monomer, and a photoinitiator. The photosensitive resin composition comprises the following components in terms of mass fraction: The alkali-soluble resin is 50-65 parts, preferably 55-60 parts, including but not limited to 50 parts, 52 parts, 54 parts, 55 parts, 57 parts, 59 parts, 60 parts, 62 parts, 64 parts, 65 parts, etc. The photopolymerization monomer is 35-50 parts, preferably 40-50 parts, including but not limited to 35 parts, 37 parts, 39 parts, 40 parts, 42 parts, 44 parts, 45 parts, 47 parts, 49 parts, 50 parts, etc. The photoinitiator is 2-5 parts, preferably 2-4 parts, including but not limited to 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts, etc. The anthryl chalcone photosensitizer is 0.1-1 part, preferably 0.1-0.8 part, including but not limited to 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1.0 part, etc.

[0040] The alkali-soluble resin in the photosensitive resin composition of the present application is 50-65 parts, if the content is less than 50 parts, it will cause the flow phenomenon of the resist layer; if the content exceeds 65 parts, it will cause the resolution of the photosensitive dry film to decrease.

[0041] The photopolymerization monomer in the photosensitive resin composition of the present application is 35-50 parts, if the content is less than 35 parts, it will cause the sensitivity and chemical resistance of the resist layer to decrease; if the content exceeds 50 parts, it will make the photosensitive resin composition not easy to be thin-filmized, and the resist layer appears the flow phenomenon.

[0042] The photoinitiator in the photosensitive resin composition of the present application is 2-5 parts, if the content is less than 2 parts, it will cause the sensitivity and resolution of the resist layer to decrease; if the content exceeds 5 parts, it will cause the development waste to increase.

[0043] The anthryl chalcone photosensitizer in the photosensitive resin composition of the present application is 0.1-1 part, if the content is less than 0.1 part, it will cause the sensitivity of the resist layer to decrease; if the content exceeds 1 part, it will make the resist bottom layer not completely cured, and then cause the resist cross-section shape to be "inverted trapezoidal", and the resolution to be poor.

[0044] The alkali-soluble resin is obtained by polymerization of one or more monomers selected from (meth)acrylic acid, (meth)acrylic alkyl ester, (meth)acrylic benzyl ester, (meth)acrylic benzyl ester derivative, (meth)acrylic phenyl ester, styrene, and styrene derivative; preferably, the alkali-soluble resin is obtained by polymerization of one or more monomers selected from (meth)acrylic acid, (meth)acrylic alkyl ester, (meth)acrylic benzyl ester, and styrene; preferably, in the polymerization process, the monomer containing aromatic group accounts for 50-70% of the total monomer mass.

[0045] The alkali-soluble resin has a weight average molecular weight of 20,000-60,000, an acid value of 160-220 mgKOH / g, and a molecular weight distribution of 1.0-3.0.

[0046] The photopolymerizable monomer is one or more of a monomer having an ethylenically unsaturated double bond, preferably an acrylate monomer, further preferably methoxypolyethylene glycol monoacrylate, ethoxy(propoxy) nonylphenol acrylate, ethoxy(propoxy) bisphenol A di(meth)acrylate, ethoxy(propoxy) di(meth)acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxy(propoxy) trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, ethoxy(propoxy) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate.

[0047] The photoinitiator is one or more of 2,4,5-triaryl imidazole dimer, preferably 2-(2-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(2-chlorophenyl)-4,5-di(methoxyphenyl) imidazole dimer, 2-(2-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(2-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(4-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole.

[0048] The photosensitive resin composition further comprises an additive, which is one or more of a dye, a photochromic agent, a plasticizer, an adhesion promoter, a polymerization inhibitor, an antifoaming agent, a coating aid; the weight fraction of the additive is 0.5-5.0 parts, including but not limited to 0.5 parts, 1.0 parts, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts, etc.

[0049] The photosensitive resin composition further comprises a solvent, which is one or more of acetone, toluene, methanol; the weight fraction of the solvent is 15-25 parts, including but not limited to 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, etc.

[0050] In a third aspect, the present application further provides a photosensitive dry film, comprising from bottom to top a PET layer, a photosensitive etching agent layer, and a PE layer, wherein the photosensitive etching agent layer is prepared from the aforementioned photosensitive resin composition.

[0051] In a fourth aspect, the present application further provides use of the photosensitive resin composition or the photosensitive dry film in a printed circuit board, a lead frame, or a semiconductor packaging substrate.

[0052] The photosensitive dry film has excellent resolution and adhesion, higher photosensitivity, and is beneficial to improving production efficiency and meeting the needs of high density and high fineness of printed circuit boards.

[0053] The application further provides a preparation method of the anthryl chalcone photosensitizer. The preparation method of the anthryl chalcone photosensitizer shown in the formula (I) comprises the following steps: Under the conditions of nitrogen atmosphere, ice water bath and stirring, an ethanol solution of 9,10-anthracene dialdehyde is added into a reaction bottle provided with a magnetic stirrer; then an aqueous NaOH solution is added into the solution; an ethanol solution of a methyl ketone compound is added dropwise into the reaction mixture; after a set time, the ice bath is removed, the temperature is slowly increased to room temperature, and the reaction is continued until the reaction is completed, to obtain the anthryl chalcone shown in the formula (I).

[0054] Preferably, the molar ratio of the 9,10-anthracene dialdehyde to the methyl ketone compound is 1: (2-3.5).

[0055] Preferably, the set time is 20-40 min, and the continuous reaction time is 4-6 h.

[0056] The preparation method of the anthryl chalcone photosensitizer shown in the formula (II) comprises the following steps: Under the conditions of nitrogen atmosphere, ice water bath and stirring, an ethanol solution of 9,10-anthracene dialdehyde is added into a reaction bottle provided with a magnetic stirrer; then an aqueous NaOH solution is added into the solution; an ethanol solution of a methyl ketone compound is added dropwise into the reaction mixture; after a set time, the ice bath is removed, the temperature is slowly increased to room temperature, and the reaction is continued until the reaction is completed, to obtain the anthryl chalcone shown in the formula (I).

[0057] Preferably, the molar ratio of the 9,10-anthracene dialdehyde to the methyl ketone compound is 1: (2-3.5).

[0058] Preferably, the set time is 20-40 min, and the continuous reaction time is 4-6 h.

[0059] The preparation method of the anthryl chalcone photosensitizer shown in the formula (III) comprises the following steps: Under the conditions of nitrogen atmosphere, ice water bath and stirring, an ethanol solution of 9,10-anthracene dialdehyde is added into a reaction bottle provided with a magnetic stirrer; then an aqueous NaOH solution is added into the solution; an ethanol solution of a methyl ketone compound is added dropwise into the reaction mixture; after a set time, the ice bath is removed, the temperature is slowly increased to room temperature, and the reaction is continued until the reaction is completed, to obtain the anthryl chalcone shown in the formula (I).

[0060] Preferably, the molar ratio of the 9,10-anthracene dialdehyde to the aldehyde compound is 1: (1~1.6).

[0061] Preferably, the setting time is 20~40 min, and the continuous reaction time is 4~6 h.

[0062] The preparation method of the anthryl chalcone photosensitizer in the application is simple, raw materials are easy to obtain, the yield is high, and industrialized production is easy to realize.

[0063] In order to facilitate understanding of the application, the application will be described more fully below with reference to the accompanying drawings and preferred embodiments, but the scope of protection of the application is not limited to the following specific embodiments.

[0064] Example 1 The anthryl chalcone photosensitizer in this example is (1E,1'E)-1,1'-(9,10-anthracene diyl) bis-1-penten-3-one (D1), and the specific synthesis route and preparation method are as follows: Under the conditions of nitrogen atmosphere, ice water bath and stirring, a solution of 9,10-anthracene dialdehyde (10 mmol, 2.34 g) in ethanol (10 mL) was added to a reaction bottle equipped with a magnetic stirrer; then, an aqueous solution of NaOH (6.0 equivalents, 2.4 g, 10% w / w) was added to the solution; then, a solution of 2-butanone (30 mmol) in ethanol (30 mL) was added dropwise to the reaction mixture, and after 30 min, the ice bath was removed, and the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography was used to monitor the consumption of anthracene dialdehyde); the obtained reaction mixture was sequentially neutralized to neutral with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phases were combined, and the crude product was obtained by rotary evaporation under reduced pressure, and then recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain D1 (2.7 g, yield: 78%).

[0065] The anthryl chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structure characterization, and the results are as follows: Figure 1 The anthryl chalcone photosensitizer in this example is (1E,1'E)-1,1'-(9,10-anthracene diyl) bis-1-penten-3-one (D1), and the specific synthesis route and preparation method are as follows: 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 8.48 (d, J = 16.32 Hz,2H), 8.22–8.20 (m, 4H), 7.53–7.51 (m, 4H), 6.69 (d, J = 16.27 Hz, 2H), 2.86 (q,J = 7.30 Hz, 4H), 1.28 (t, J = 7.41 Hz, 6H). Figure 2 is a D1 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 200.3, 139.3,135.4, 131.4, 129.0, 126.3, 125.9, 34.9, 8.3.

[0066] Example 2 The anthracene-based chalcone photosensitizer in this example is (2E,2'E)-3,3'-(9,10-anthracenediyl)bis[l-(N-methyl)-2-pyrrolyl]-l-propenone (D2), and the specific synthesis route and preparation method are as follows: Under the conditions of nitrogen atmosphere, ice water bath and stirring, a solution of 9,10-anthracene-dialdehyde (10 mmol, 2.34 g) in ethanol (10 mL) was added to a reaction bottle equipped with a magnetic stirrer; then a solution of NaOH aqueous solution (6.0 equivalents, 2.4 g, 10% w / w) was added to the solution; then a solution of 2-acetyl-l-methylpyrrole (30 mmol) in ethanol (30 mL) was added dropwise to the reaction mixture, and after 30 min, the ice bath was removed and slowly warmed to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitoring the consumption of anthracene dialdehyde); the obtained reaction mixture was sequentially neutralized to neutral with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phase was combined and concentrated under reduced pressure to obtain a crude product, which was recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain D2 (3.4 g, yield: 76%).

[0067] The anthracene-based chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structure characterization, and the results are as follows: Figure 3 is a D2 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 8.67 (d, J = 15.79 Hz,2H), 8.39 – 8.27 (m, 4H), 7.55 – 7.46 (m, 4H), 7.36 (d, J= 15.65 Hz, 2H), 7.07– 7.02 (m, 2H), 6.96 – 6.92 (m, 2H), 6.22 – 6.17 (m, 2H), 4.14 (s, 6H). Figure 4 is a D2 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 179.3, 138.9,133.5, 132.5, 132.4, 132.2, 129.5, 126.4, 126.3, 120.3, 108.8, 38.0.

[0068] Example 3 The anthryl chalcone photosensitizer in this example is (2E)-3-[(10- formyl)-9-anthryl](l-phenyl)-l-propen-l-one (D3), and the specific synthesis route and preparation method are as follows: Under the conditions of nitrogen atmosphere, ice water bath and stirring, a solution of 9,10-anthracene-dialdehyde (10 mmol) in ethanol (10 mL) was added to a reaction bottle equipped with a magnetic stirrer; then a solution of NaOH aqueous solution (3.0 equivalents, 10% w / w) was added to the solution; then a solution of phenylacetone (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 min, the ice bath was removed and the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitoring the consumption of anthracene dialdehyde); the obtained reaction mixture was sequentially neutralized to neutral with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phase was combined and concentrated under reduced pressure to obtain the crude product, which was recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain D3 pure product (2.4 g, yield: 72%).

[0069] The anthryl chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structure characterization, and the results are as follows: Figure 5 is a D3 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 11.50 (s, 1H), 8.93(d, J = 8.86 Hz, 2H), 8.70 (d, J = 15.96 Hz, 1H), 8.31 (d, J = 8.80 Hz, 2H), 8.09(d, J= 7.46 Hz, 2H), 7.69 (t, J = 7.94 Hz, 2H), 7.63 (t, J = 7.37 Hz, 1H), 7.61 –7.52 (m, 4H), 7.49 (d, J = 16.21 Hz, 1H). Figure 6 is the D3 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 193.5, 189.1,141.5, 138.8, 137.5, 133.6, 132.4, 131.3, 131.0, 129.1, 129.0, 128.9, 126.5,126.4, 126.1, 124.1.

[0070] Example 4 The anthracene-based chalcone photosensitizer in this example is (2E)-3-[(10- formyl)-9-anthryl]-1-(4-methoxy)phenyl-1-propenone (D4), and the specific synthesis route and preparation method are as follows: Under the conditions of nitrogen atmosphere, ice water bath and stirring, a solution of 9,10-anthracene-dialdehyde (10 mmol) in ethanol (10 mL) was added to a reaction bottle equipped with a magnetic stirrer; then a solution of NaOH aqueous solution (3.0 equivalents, 10% w / w) was added to the solution; then a solution of p-methoxyacetophenone (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 min, the ice bath was removed and the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitoring the consumption of anthracene dialdehyde); the obtained reaction mixture was sequentially neutralized to neutral with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phase was combined and concentrated under reduced pressure to obtain a crude product, which was recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain D4 pure product (2.6 g, yield: 70%).

[0071] The anthracene-based chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structure characterization, and the results are as follows: Figure 7 is the D4 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 11.48 (s, 1H), 8.92(d, J = 8.96 Hz, 2H), 8.66 (d,J = 15.89 Hz, 1H), 8.30 (d, J = 8.76 Hz, 2H), 8.08(d, J = 7.22 Hz, 2H), 7.68 (t, J = 7.24 Hz, 2H), 7.56 (t, J = 7.32 Hz, 2H), 7.48(d, J = 15.92 Hz, 1H), 6.99 (d, J = 7.20 Hz, 2H), 3.88 (s, 3H). Figure 8 is the D4 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 193.5, 187.3,164.0, 140.6, 139.2, 132.3, 131.3(5), 131.2(7), 130.5, 129.1, 128.9, 126.6,126.3, 125.9, 124.0, 114.2, 55.7.

[0072] Example 5 The anthryl chalcone photosensitizer in this example is (2E)-3-[(10- formyl)-9-anthryl]-1-(2-naphthyl)-1-propenone (D5), and the specific synthesis route and preparation method are as follows: Under the conditions of nitrogen atmosphere, ice water bath and stirring, a solution of 9,10-anthracene dialdehyde (10 mmol) in ethanol (10 mL) was added to a reaction bottle equipped with a magnetic stirrer; then a solution of NaOH aqueous solution (3.0 equivalents, 10% w / w) was added to the solution; then a solution of 2-naphthaldehyde (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 min, the ice bath was removed and the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitoring the consumption of anthracene dialdehyde); the obtained reaction mixture was sequentially neutralized to neutral with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phase was combined and concentrated under reduced pressure to obtain a crude product, which was recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain D5 pure product (3.0 g, yield: 78%).

[0073] The anthryl chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structure characterization, and the results are as follows: Figure 9 is the D5 photosensitizer1 H-NMR spectrum: 1 H NMR (400 MHz, CDC13): delta 11.53 (s, 1H), 8.96(d, J = 8.98 Hz, 2H), 8.78 (d, J = 15.99 Hz, 1H), 8.57 (s, 1H), 8.37 (d, J = 8.85Hz, 2H), 8.20 (d, J = 8.63 Hz, 1H), 8.01 - 7.87 (m, 3H), 7.74 - 7.55 (m, 7H). Figure 10 is a D5 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDC13): delta 193.6, 188.9, 141.5, 138.9, 135.9, 134.9, 132.7, 132.4, 131.4, 130.7, 129.8, 129.2, 129.1, 128.9, 128.0, 127.1, 126.6, 126.5, 126.0, 124.5, 124.1.

[0074] Example 6 The anthracene-based chalcone photosensitizer in this example is (2E)-3-[(10- formyl)-9-anthryl]-1-(2-furyl)-1-propenone (D6), and the specific synthesis route and preparation method are as follows: Under the conditions of nitrogen atmosphere, ice water bath and stirring, a solution of 9,10-anthracene-dialdehyde (10 mmol) in ethanol (10 mL) was added to a reaction bottle equipped with a magnetic stirrer; then a solution of NaOH aqueous solution (3.0 equivalents, 10% w / w) was added to the solution; then a solution of 2-acetylfuran (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 min, the ice bath was removed and the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitoring the consumption of anthracene dialdehyde); the obtained reaction mixture was sequentially neutralized to neutral with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phase was combined and concentrated under reduced pressure to obtain a crude product, which was recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain D6 pure product (2.2 g, yield: 68%).

[0075] The anthryl chalcone photosensitizer in the present embodiment was subjected to nuclear magnetic resonance structural characterization, and the results were as follows: Figure 11 is the D6 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 11.49 (s, 1H), 8.92(d, J = 8.95 Hz, 2H), 8.73 (d, J = 16.10 Hz, 1H), 8.28 (d, J = 8.81 Hz, 2H), 7.72 –7.64 (m, 3H), 7.56 (t, J = 7.66 Hz, 2H), 7.38 (d, J = 3.67 Hz, 1H), 7.35 (d, J =16.13 Hz, 1H), 6.63 (d, J = 4.01 Hz, 1H). Figure 12 is the D6 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 193.5, 176.9,153.5, 147.4, 140.9, 138.5, 131.8, 131.3, 129.1, 128.9, 126.5, 126.4, 126.1,124.0, 118.8, 113.0。

[0076] Example 7 The anthryl chalcone photosensitizer in the present embodiment is (2E)-3-[(10- formyl)-9-anthryl]-1-(2-benzofuranyl)-1-propenone (D7), and the specific synthesis route and preparation method are as follows: Under the conditions of nitrogen atmosphere, ice-water bath and stirring, a solution of 9,10-anthracene-dialdehyde (10 mmol) in ethanol (10 mL) was added into a reaction flask equipped with magnetic stirrer; then a solution of NaOH aqueous solution (3.0 equivalents, 10% w / w) was added into the solution; then a solution of 2-acetylbenzofuran (15 mmol) in ethanol (15 mL) was added dropwise into the reaction mixture, after 30 min, the ice bath was removed, and the temperature was slowly increased to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitoring the consumption of anthracene dialdehyde); the obtained reaction mixture was neutralized to neutral with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phase was combined, and concentrated under reduced pressure to obtain the crude product, which was recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain pure D7 product (2.7 g, yield: 71%).

[0077] The anthryl chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structure characterization, and the results were as follows: Figure 13 The anthryl chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structure characterization, and the results were as follows: 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 11.53 (s, 1H), 8.95(d, J = 8.94 Hz, 2H), 8.84 (d, J = 16.16 Hz, 1H), 8.34 (d, J = 8.79 Hz, 2H), 7.78 –7.67 (m, 4H), 7.62 – 7.58 (m, 3H), 7.55 – 7.48 (m, 2H), 7.35 (d, J = 7.06 Hz,1H). Figure 14 The anthryl chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structure characterization, and the results were as follows: 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 193.6, 178.7,156.2, 153.4, 141.5, 138.3, 131.8, 131.3, 129.2, 128.9, 127.3, 126.6, 126.5,126.4, 124.3, 124.1, 123.6, 114.6, 112.7.

[0078] Example 8 The anthryl chalcone photosensitizer in this example was (2E)-1-(2-anthryl)[3-(4- isopropyl)phenyl]-1-propenone (D8), and the specific synthesis route and preparation method were as follows: To a reaction flask equipped with a magnetic stirrer, was added a solution of 2-anthrylmethyl ketone (10 mmol) in ethanol (10 mL) under nitrogen atmosphere, ice-water bath and stirring condition; then, to the solution was added an aqueous solution of NaOH (3.0 eq, 10% w / w), followed by dropwise addition of a solution of p-isopropylbenzaldehyde (15 mmol) in ethanol (15 mL) to the reaction mixture, after 30 min, the ice bath was removed and the temperature was slowly increased to room temperature, the reaction was continued until the reaction was completed (monitored by thin layer chromatography until the consumption of 2-anthrylmethyl ketone was completed); the resulting reaction mixture was neutralized to neutral with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phase was combined, and concentrated under reduced pressure to obtain a crude product, which was recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain pure D8 (2.8 g, yield: 81%).

[0079] The anthryl chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structural characterization, and the results were as follows: Figure 15 is the 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 8.72 (s, 1H), 8.60(s, 1H), 8.45 (s, 1H), 8.07 – 8.02 (m, 4H), 7.92 (d, J = 15.64 Hz, 1H), 7.72(d, J = 15.64 Hz, 1H), 7.66 (d, J = 7.92 Hz, 2H), 7.61 – 7.50 (m, 2H), 7.33 (d, J =7.90 Hz, 2H), 2.98 (p, J = 6.93 Hz, 1H), 1.31 (d, J = 6.75 Hz, 6H). Figure 16 is the 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta190.9, 150.9, 146.5, 135.9, 133.3, 132.8, 132.7, 132.2, 131.3, 130.6, 129.5, 129.0, 128.8, 128.6, 128.4, 127.3, 126.8, 126.4, 126.1, 123.6, 121.2, 33.9, 24.7.

[0080] Example 9 The anthracenyl chalcone photosensitizer in this example is (2E)-1-(2- anthryl)[3-(4-methoxy)phenyl]-1-propenone (D9), the specific synthesis route and preparation method are as follows: Under the conditions of nitrogen atmosphere, ice water bath and stirring, a solution of 2-anthrylmethyl ketone (10 mmol) in ethanol (10 mL) was added to a reaction bottle equipped with a magnetic stirrer; then, an aqueous solution of NaOH (3.0 equivalents, 10% w / w) was added to the solution; then a solution of p-methoxybenzaldehyde (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, after 30 min, the ice bath was removed, and the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (monitored by thin layer chromatography until the 2-anthrylmethyl ketone was consumed); the obtained reaction mixture was neutralized to neutral with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phase was combined and concentrated under reduced pressure to obtain the crude product, which was recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain the pure D9 product (2.8 g, yield: 84%).

[0081] The anthracenyl chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structure characterization, and the results are as follows: Figure 17 The H-NMR spectrum of D9 photosensitizer is: 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 8.71 (s, 1H), 8.60(s, 1H), 8.45 (s, 1H), 8.05 (d, J = 13.13 Hz, 4H), 7.89 (d, J = 15.57 Hz, 1H),7.70 – 7.59 (m, 3H), 7.58 – 7.47 (m, 2H), 6.97 (d, J = 8.28 Hz, 2H), 3.87 (s,3H). Figure 18 The C-NMR spectrum of D9 photosensitizer is: 13 C-NMR spectrum;13 C NMR (100 MHz, CDCl3): delta 190.2, 161.8, 144.6, 135.5, 133.3, 132.7, 132.2, 131.1, 130.6, 130.4, 129.0, 128.9 128.6 128.4 127.9 126.7 126.4 126.0, 123.7, 119.8, 114.6, 55.6.

[0082] Example 10 The anthracenyl chalcone photosensitizer in this example is (2E)-1-(2-anthryl)[3-(N- methyl)-2-pyrrolyl]-1-propenone (D10), and the specific synthesis route and preparation method are as follows: Under the conditions of nitrogen atmosphere, ice water bath and stirring, a solution of 2-anthrylmethyl ketone (10 mmol) in ethanol (10 mL) was added to a reaction flask equipped with a magnetic stirrer; then, an aqueous NaOH solution (3.0 equivalents, 10% w / w) was added to the solution; then, a solution of N-methyl-2-pyrrole formaldehyde (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 min, the ice bath was removed, and the temperature was slowly raised to the set temperature, and the reaction was continued until the reaction was completed (monitored by thin layer chromatography that 2-anthrylmethyl ketone was consumed); the obtained reaction mixture was sequentially neutralized to neutral with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phases were combined, and the crude product was obtained by rotary evaporation under reduced pressure, and then recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain D10 pure product (2.5 g, yield: 80%).

[0083] The anthracenyl chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structure characterization, and the results are as follows: Figure 19 The H-NMR spectrum of D10 photosensitizer is as follows: 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 8.71 (s, 1H), 8.61(s, 1H), 8.45 (s, 1H), 8.13 – 8.01 (m, 4H), 7.90 (d, J = 15.10 Hz, 1H), 7.63 –7.48 (m, 3H), 6.94 (d, J = 3.58 Hz, 1H), 6.85 (s, 1H), 6.27 (t, J = 3.27 Hz, 1H),3.81 (s, 3H). Figure 20 is the D10 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 189.2, 135.7,133.2, 132.7, 132.2, 130.7 130.6, 129.0, 128.9, 128.6, 128.4, 128.0, 126.7,126.4, 126.0, 123.7, 116.8, 112.5, 110.0, 36.3.

[0084] Example 11 The anthryl chalcone photosensitizer in this example is (2E)-1-(2-anthryl)-3-(2- thienyl)-1-propen-1-one (D11), and the specific synthesis route and preparation method are as follows: Under the conditions of nitrogen atmosphere, ice water bath and stirring, a solution of 2-anthrylmethyl ketone (10 mmol) in ethanol (10 mL) was added to a reaction bottle equipped with a magnetic stirrer; then, an aqueous NaOH solution (3.0 equivalents, 10% w / w) was added to the solution; then a solution of 2-thiophene carboxaldehyde (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 min, the ice bath was removed and the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (monitored by thin layer chromatography that 2-anthrylmethyl ketone was consumed); the obtained reaction mixture was sequentially neutralized to neutral with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phase was combined and concentrated under reduced pressure to obtain a crude product, which was recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain D11 pure product (2.3 g, yield: 74%).

[0085] The anthryl chalcone photosensitizer in this example was subjected to nuclear magnetic resonance structure characterization, and the results are as follows: Figure 21 is the D11 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 8.69 (s, 1H), 8.60(s, 1H), 8.43 (s, 1H), 8.10 – 7.99 (m, 5H), 7.60 – 7.49 (m, 3H), 7.45 (d, J =5.11 Hz, 1H), 7.40 (d, J = 3.58 Hz, 1H), 7.11 (t, J= 4.49 Hz, 1H). Figure 22 D11 is the photosensitizer of 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 189.5, 140.7,137.1, 135.1, 133.3, 132.7, 132.3, 132.2, 131.3, 130.5, 129.1, 129.0, 128.9,128.6, 128.5, 128.4, 126.8, 126.4, 126.1, 123.5, 120.8.

[0086] Solubility test: The anthryl chalcone photosensitizers D1-D11 prepared by Examples 1-11 were subjected to solubility test; and 9,10-dibutoxyanthracene (DBA), 9,10-diphenylanthracene (DPHA) and 9,10-diacetoxyanthracene (DAcOA) were also subjected to solubility test, and the specific test method and evaluation method are as follows: acetone, toluene and methanol were used as solvents respectively; the solute was added into the solvent according to the ratio of 0.1 g solute / 1 g solvent (10% w / w), and the solubility was recorded according to the following grading standard: A (fast dissolution): under the condition of room temperature and stirring, within 1 minute, a clear and transparent uniform solution can be formed; B (slow dissolution): under the condition of room temperature and stirring, more than 5 minutes, a clear and transparent uniform solution can be formed; or under the condition of room temperature, it cannot be completely dissolved, but it can form a clear and transparent uniform solution when heated to 50-60°C, and there is no obvious phenomenon of turbidity after the temperature is restored to room temperature; C (partial dissolution): under the condition of room temperature and stirring, more than 5 minutes, it cannot be completely dissolved; or it can be completely dissolved when heated to 50-60°C, but it is obviously turbid after the temperature is restored to room temperature.

[0087] The test results are shown in Table 1: Table 1 UV-visible spectrum determination: The toluene solution of anthryl chalcone D1-D11 with a concentration of 2×10 -5 mol / L was subjected to UV full spectrum scanning respectively, the maximum absorption wavelength of anthryl chalcone D1-D11 was determined, the absorbance (A) was read, each sample was repeated for 3 times, and the average value was taken. The test UV spectrum is as follows: Figure 23 and 24As shown, it can be seen that anthracene chalcone photosensitizers D1-D11 have obvious absorption at 405 nm, and have potential to become photosensitizers.

[0088] Examples 12-17 and Comparative Examples 1-3 The compositions of the photosensitive resin compositions of Examples 12-17 and Comparative Examples 1-3 can be seen in Table 2.

[0089] Table 2 Alkali-soluble resin A: acrylate copolymer, solution polymerization method, polymerization of mass ratio of methacrylic acid monomer / butyl methacrylate monomer / benzyl methacrylate monomer = 25 / 10 / 65; solvent is acetone, solid content 46%, weight average molecular weight 40000, dispersity 2.1, acid value 163 mgKOH / g. (Hunan Chuyuan New Material Co., Ltd.) The photopolymerization monomer B is composed of the following ingredients (purchased from Shadoma Guangzhou Chemical Co., Ltd.): methoxy polyethylene glycol (350) monoacrylate 5 parts, 10 (ethoxy) bisphenol A dimethacrylate 20 parts, 6 (propoxy) bisphenol A dimethacrylate 5 parts, 3 (ethoxy) trimethylolpropane triacrylate 10 parts, di (trimethylolpropane) tetraacrylate 4 parts.

[0090] The photoinitiator C is 2,2'-bis (o-chlorophenyl)-4,4',5,5'-tetraphenyl-2,2'-dimethyl-1,1'-diimidazole (BCIM) The additive E is composed of the following ingredients (purchased from Anjieji Chemical): leuco crystal violet 0.5 parts, malachite green 0.05 parts, p-toluenesulfonamide 0.8 parts, 2,6-di-tert-butyl-4-methylphenol 0.03 parts.

[0091] The solvent is composed of the following ingredients: acetone 8 parts, toluene 10 parts, methanol 5 parts.

[0092] Preparation of photosensitive dry film The photosensitive resin compositions listed in Table 2 were prepared into photosensitive dry films, including the following steps: The photosensitive composition slurry prepared according to Table 2 was coated on a 15 μm thick polyethylene terephthalate (PET) support film using a coating machine (model: AB4220, TQC, Netherlands); baked at 80°C for 10 min to remove the solvent, and the thickness of the photosensitive layer after baking was controlled at 30 μm, then a polyethylene film (PE) was coated for protection, to obtain a photosensitive dry film.

[0093] Preparation of substrate with resist pattern Substrates with resist patterns were prepared using the photosensitive compositions of the inventive examples samples 12-17 and comparative samples 1-2 as shown in Table 2, with the following procedures: (1) Photosensitive layer forming step: forming a photosensitive layer on a substrate using a photosensitive composition; (2) Exposure step: irradiating active light to a part of the photosensitive layer to make the part photocured to form a cured product area; (3) Development step: removing the part of the photosensitive layer other than the cured product area from the substrate to form a resist pattern on the substrate.

[0094] Hereinafter, the operation conditions of each step will be described in detail.

[0095] Photosensitive layer forming step: A copper-clad laminate in which a 35-μm-thick rolled 1.2-mm-thick copper foil was laminated was used, and after the surface was adjusted and preheated to 80°C, the PE protective film of the photosensitive dry film obtained from each example or comparative example was peeled off while laminating the photosensitive resin composition layer on the copper-clad laminate using a hot roll laminator (Shinest Technology Co., Ltd., CSL-M25E) at a roll temperature of 110°C, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min to obtain a test substrate.

[0096] Exposure step: exposure was performed using a direct drawing exposure machine (Chipmicro, main wavelength 405 nm), and a Stouffer 41 step exposure ruler was used for photosensitivity test, and the exposure scale was controlled to 14-18 scales.

[0097] Development step: after exposure, the PET support film was peeled off, and an alkali developing machine (manufactured by Guangzhou Julong Printed Circuit Equipment Co., Ltd., dry film developing machine) was used to spray a 1 wt% Na2CO3 aqueous solution at 30°C for a time twice the minimum developing time to dissolve and remove the unexposed part of the photosensitive resin layer. After development, the photosensitive resin layer was washed with pure water for a time 1.5 times the developing time, and then water was removed using an air knife, and warm air drying was performed to obtain a substrate having an evaluation cured film. The shortest time required for complete dissolution of the unexposed part of the photosensitive resin layer was taken as the minimum developing time.

[0098] Evaluation items 1. Photosensitivity evaluation On the test substrate after the above film pasting, a Stouffer 41 step exposure ruler was placed for photosensitivity test. After the exposure step, the test substrate was left to stand for 20 min or more, and then the PET film layer was peeled off, and a 1.0 wt% sodium carbonate aqueous solution was sprayed at 30°C to remove the unexposed resist layer, and the developing time was 2.0 times the minimum developing time. After the above operation, a cured film obtained by curing the photosensitive resin composition was formed on the surface of the substrate. The exposure energy (mJ / cm 2), the smaller the value, the better the photosensitivity.

[0099] 2. Adhesion Evaluation On the above-mentioned post-laminating test substrate, exposure was performed using a photomask data having a line width / interval width of n:400 (unit: μm) wiring pattern so that the remaining stage number after development of the Stouffer 41 stage exposure ruler reached 16. After the development process, the resist pattern was observed using an optical microscope, and the value of the minimum line width at which a complete cured resist line was formed was used as the value of the adhesion (μm) to evaluate the adhesion. The smaller the value, the better the adhesion.

[0100] 3. Resist Shape Evaluation In the resist pattern used for the above-mentioned resolution evaluation, the best resolution part was observed using a SU1000 type scanning electron microscope (manufactured by Hitachi). Evaluation was performed according to the following evaluation criteria: ■: The difference between the top and bottom widths at the front end cross section of the resist is less than or equal to 0.8 μm, and the inverse trapezoid is basically not observed; O: The difference between the top and bottom widths at the front end cross section of the resist is greater than 0.8 μm and less than 1.2 μm, and the cross section is slightly inverse trapezoidal; X: The difference between the top and bottom widths at the front end cross section of the resist is greater than or equal to 1.2 μm, and the cross section is obviously inverse trapezoidal.

[0101] The test results of evaluation items 1-4 are summarized in Table 3 below.

[0102] Table 3 The results in Table 3 show that the anthryl chalcone photosensitizer of the present application is on par with DBA in terms of exposure energy (photosensitivity), and slightly lower than DPHA; but has obvious advantages in terms of adhesion and resist shape, solving the problem of easy formation of inverse trapezoids in the resist formed by curing the photosensitizers of DBA and DPHA; DOAcA has poor performance in terms of exposure energy, and has obvious inverse trapezoidal problems, and the comprehensive performance of the anthryl chalcone photosensitizer of the present application is obviously superior to DOAcA. The above results show that the photosensitizer of the present application has wide applicability.

[0103] The above-mentioned is only the preferred embodiment of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A photosensitive resin composition, characterized in that The invention comprises an anthracene-based chalcone photosensitizer, wherein the anthracene-based chalcone photosensitizer comprises at least one anthracene derivative represented by the general formula (III); Where: R 1 It is one of a C1-C5 straight-chain or branched alkyl group, N-methylpyrrol-2-yl, furan-2-yl, benzofuran-2-yl, thiophen-2-yl, naphthalene-2-yl, phenyl, and a substituted aryl group.

2. The photosensitive resin composition according to claim 1, wherein The anthracene-based chalcone photosensitizer comprises at least one anthracene derivative represented by formula D8 to D11: 。 3. The photosensitive resin composition according to claim 1, wherein The photosensitive resin composition further comprises an alkali-soluble resin, a photopolymerizable monomer and a photoinitiator.

4. The photosensitive resin composition according to claim 3, characterized in that The photosensitive resin composition comprises, by weight, 50-65 parts of an alkali-soluble resin, 35-50 parts of a photopolymerizable monomer, 2-5 parts of a photoinitiator, and 0.1-1 part of an anthracene chalcone photosensitizer.

5. The photosensitive resin composition according to claim 3 or 4, characterized in that: The alkali-soluble resin is obtained by polymerizing one or more monomers selected from the group consisting of (meth)acrylic acid, alkyl (meth)acrylate, benzyl (meth)acrylate, benzyl (meth)acrylate derivatives, phenyl (meth)acrylate, styrene, and styrene derivatives; wherein, during the polymerization process, monomers containing aromatic groups account for 50-70% of the total monomer mass; The alkali-soluble resin has a weight average molecular weight of 20,000 to 60,000, an acid value of 160 to 220 mgKOH / g, and a dispersion degree of 1.0 to 3.

0.

6. The photosensitive resin composition according to claim 3 or 4, characterized in that The photopolymerizable monomer is one or more of methoxy polyethylene glycol monoacrylate, ethoxy (propoxy) nonylphenol acrylate, ethoxy (propoxy) bisphenol A di(meth)acrylate, ethoxy (propoxy) di(meth)acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxy (propoxy) trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, ethoxy (propoxy) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

7. The photosensitive resin composition according to claim 3 or 4, characterized in that: The photoinitiator is a 2,4,5-triaryl imidazole dimer, specifically one or more of 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(2-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(4-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

8. The photosensitive resin composition according to claim 3 or 4, characterized in that The photosensitive resin composition further comprises additives, which are one or more of dyes, photochromic agents, plasticizers, adhesion promoters, polymerization inhibitors, defoaming agents, and coating aids; the weight portion of the additives is 0.5 to 5.0 parts.

9. A photosensitive dry film, characterized in that: From bottom to top, it comprises a PET layer, a photosensitive resist layer and a PE layer, wherein the photosensitive resist layer is prepared from the photosensitive resin composition according to any one of claims 3 to 8.

10. Use of the photosensitive dry film according to claim 9 in a printed circuit board, a lead frame or a semiconductor package substrate.

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