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 general formulas (I)-(III). In the imgabs0 #, R1 is one of a C1-C5 straight chain or branched chain alkyl group, an N-methylpyrrole-2-yl group, a furan-2-yl group, a benzofuran-2-yl group, a thiophene-2-yl group, a naphthalene-2-yl group, a phenyl group and a substituted aryl group; 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

Technical Field

[0001] The invention belongs to the technical field of photosensitive resin compositions, and in particular relates to a photosensitive resin composition comprising an anthracene chalcone photosensitizer and an application thereof. Background Art

[0002] Photosensitive resin compositions are widely used as key pattern transfer materials in the manufacturing fields of printed circuit boards (PCBs), lead frames (LFs), and semiconductor packaging (IC) substrate printed circuit boards. 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 a photosensitive dry film, dry film resist, etc. In the pattern transfer process, the dry film resist is first attached to the copper substrate, and a mask with a certain pattern is covered on the dry film resist to expose the pattern; then, a weak alkaline aqueous solution is used as a developer to remove the unexposed parts, and then etching or electroplating is used to form a pattern; finally, a film stripping solution is used to remove the solidified part of the dry film, thereby realizing the pattern transfer.

[0003] As electronic devices develop towards miniaturization and high density, the requirements for circuit fineness continue to increase. In order to meet the needs of fine circuit manufacturing, the photosensitive resin composition needs to have a higher resolution. In order to improve the resolution, it is necessary to add an appropriate photosensitizer to the photosensitive resin composition. For the photosensitive resin composition, a suitable photosensitizer has a direct impact on photosensitivity, resolution, and production yield.

[0004] 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 when using such photosensitizers; for example, when 9,10-dibutoxyanthracene photosensitizer is exposed, the CO bond at the 9,10 position will break, the anthracene ring will dimerize, and a small molecule alkoxy fragment will be released. This small molecule fragment will migrate from the cured photosensitive resin composition to the electroplating solution in the subsequent electroplating process, causing pollution, affecting the life of the plating solution and the electroplating effect; 9,10-diphenylanthracene photosensitizer, due to its rigid molecular structure, has greatly reduced solubility, which has a great impact on the uniformity and consistency of the product; 9,10-diacetoxyanthracene photosensitizer, due to the electron-pulling induction effect of the acyl group, leads to an increase in the electron cloud density of the 9,10 position of the anthracene ring, so that the efficiency of this photosensitizer in catalyzing the curing reaction is reduced, the side wall verticality of the cured photosensitive resin composition is poor, and the length difference between the top and bottom lines is large to form an "inverted trapezoid", and the energy required for exposure of this photosensitizer is increased, resulting in reduced photobleaching efficiency.

[0005] Therefore, developing a new anthracene photosensitizer with high photon yield, low migration characteristics and excellent development compatibility, and constructing a high-performance photocurable resin composition based on it, has become a technical problem to be solved urgently in this field. Summary of the invention

[0006] In view of the above problems, the object of the present invention is to provide a photosensitive resin composition comprising an anthracene chalcone photosensitizer and its application.

[0007] In a first aspect, the present invention provides a photosensitive resin composition, comprising an anthracene-based chalcone photosensitizer, wherein the anthracene-based chalcone photosensitizer comprises at least one anthracene derivative represented by general formula (I) to (III); Where: R 1 It is one of a C1-C5 straight chain or branched chain alkyl group, N-methylpyrrolyl group, furyl group, benzofuranyl group, thienyl group, naphthyl group, phenyl group, and a substituted aryl group.

[0008] The anthracene chalcone photosensitizer comprises at least one anthracene derivative represented by formula D1 to D11: The photosensitive resin composition also includes alkali-soluble resin, photopolymerizable monomer and photoinitiator. The photosensitive resin composition comprises, by weight fraction, 50-65 parts of alkali-soluble resin, 35-50 parts of photopolymerizable monomer, 2-5 parts of photoinitiator, and 0.1-1 part of anthracene chalcone photosensitizer.

[0009] 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; preferably, 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, and styrene; preferably, during the polymerization process, monomers containing aromatic groups account for 50-70% of the total monomer mass.

[0010] The weight average molecular weight of the alkali-soluble resin is 20,000 to 60,000, the acid value of the alkali-soluble resin is 160 to 220 mgKOH / g, and the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0011] The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond, preferably an acrylate monomer, and more preferably 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.

[0012] The photoinitiator 2,4,5-triaryl imidazole dimer is preferably 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-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

[0013] 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 proportion of the additives is 0.5 to 5.0 parts.

[0014] The photosensitive resin composition also includes a solvent, which is one or more of acetone, toluene and methanol; the weight proportion of the solvent is 15 to 25 parts.

[0015] In a second aspect, the present invention further provides a photosensitive dry film, which comprises a PET layer, a photosensitive resist layer and a PE layer from bottom to top, wherein the photosensitive resist layer is prepared from the aforementioned photosensitive resin composition.

[0016] In a third aspect, the present invention further provides an application of a photosensitive dry film in a printed circuit board, a lead frame or a semiconductor packaging substrate.

[0017] The chalcone mentioned in this article refers to a class of substances containing α, β-unsaturated ketone groups in the chemical structure formula.

[0018] 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 anthracene-based chalcone photosensitizer provided by the present invention has the characteristics of low migration before curing and low precipitation after curing.

[0019] (2) In the present invention, anthracene chalcone is used as a photosensitizer for the photosensitive resin composition. The photosensitizer will not migrate into the polyethylene film (PE), and in the electroplating process after exposure and development, small molecular fragments will not precipitate to pollute the electroplating solution, thereby avoiding undesirable phenomena such as short circuit and open circuit of the anti-etching pattern, and significantly improving the product yield.

[0020] (3) The photosensitive resin composition of the present invention includes an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator and an anthracene chalcone photosensitizer. Through the synergistic effect between the components, the obtained photosensitive resin composition has excellent photosensitivity and adhesion. After exposure, the formed resist circuit has a uniform curing effect, a flat side wall, and an excellent rectangular port, which effectively solves the problem of poor resist morphology (i.e., "inverted trapezoidal problem") existing in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 , Figure 2 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D1 prepared in Example 1.

[0022] Figure 3 , Figure 4 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D2 prepared in Example 2.

[0023] Figure 5 , Figure 6 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D3 prepared in Example 3.

[0024] Figure 7 , Figure 8 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D4 prepared in Example 4.

[0025] Fig. 9 , Fig.10 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D5 prepared in Example 5.

[0026] Fig.11 , Fig.12 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D6 prepared in Example 6.

[0027] Fig.13 , Fig.14 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D7 prepared in Example 7.

[0028] Fig.15 , Fig.16 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D8 prepared in Example 8.

[0029] Fig.17 , Fig.18 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D9 prepared in Example 9.

[0030] Fig.19 , Fig. 20 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D10 prepared in Example 10.

[0031] Fig.21 , Fig. 22 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D11 prepared in Example 11.

[0032] Fig.23 The anthracene chalcone photosensitizers D1 to D5 were dissolved in toluene (concentration 2×10 -5 mol / L) UV-visible spectrum.

[0033] Fig.24 The anthracene chalcone photosensitizers D6~D11 were dissolved in toluene (concentration 2×10 -5 mol / L) UV-visible spectrum. DETAILED DESCRIPTION

[0034] As mentioned above, in the first aspect, the present invention provides an anthracene-based chalcone photosensitizer, wherein the anthracene-based chalcone photosensitizer comprises at least one anthracene derivative represented by general formula (I) to (III); Where: R 1 It is one of a C1-C5 straight chain or branched chain alkyl group, N-methylpyrrolyl group, furyl group, benzofuranyl group, thienyl group, naphthyl group, phenyl group, and a substituted aryl group.

[0035] The anthracene-based chalcone photosensitizer of the present invention contains a chalcone structure at the 9 and / or 10 or 2 position, which can adjust the electronic configuration of the anthracene group and improve its photosensitivity. In addition, the chalcone structure can improve the softness of the photosensitizer and the compatibility and dispersibility in the photosensitive resin composition, and can prevent the fragments cleaved after exposure from migrating and precipitating to contaminate the electroplating solution. Furthermore, the anthracene-based chalcone photosensitizer of the present invention can improve the photosensitivity of the photoresist composition, and the sidewalls of the resist pattern formed after curing are flat and the cross section is a regular rectangular shape.

[0036] The anthracene chalcone photosensitizer includes (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-anthracenediyl]-1-(2-furanyl)-1-propenone, (2E)-3-[(10-formyl)-9-anthracenediyl]-1-(2-benzofuranyl)-1-propenone, (2E)-3-[(10-formyl)-9-anthracenediyl](1-phenyl)-1-propenone, (2E)-3-[(10-formyl)-9-anthracenediyl](1-phenyl)-1-propenone, and (2E)-3-[(10-formyl)-9-anthracenediyl](1-phenyl)-1-propenone. One or more of (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 corresponding specific structures are shown in Formulas D1 to D11: .

[0037] In a second aspect, the present invention provides a photosensitive resin composition comprising the aforementioned anthracene-based chalcone photosensitizer.

[0038] The photosensitive resin composition also includes alkali-soluble resin, photopolymerizable monomer and photoinitiator. The photosensitive resin composition comprises the following components in terms of mass fraction: The alkali-soluble resin is 50 to 65 parts, preferably 55 to 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 photopolymerizable monomer is 35 to 50 parts, preferably 40 to 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 to 5 parts, preferably 2 to 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 anthracene chalcone photosensitizer is 0.1 to 1 part, preferably 0.1 to 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.

[0039] The alkali-soluble resin in the photosensitive resin composition of the present invention is 50-65 parts. If the content is less than 50 parts, the resist layer will have a gel flow phenomenon; if the content exceeds 65 parts, the resolution of the photosensitive dry film will decrease.

[0040] The photosensitive resin composition of the present invention contains 35 to 50 parts of photopolymerizable monomers. If the content is less than 35 parts, the sensitivity and chemical resistance of the resist layer will be reduced. If the content exceeds 50 parts, the photosensitive resin composition will not be easily filmed and the resist layer will have a gel flow phenomenon.

[0041] The photoinitiator content in the photosensitive resin composition of the present invention is 2 to 5 parts. If the content is less than 2 parts, the sensitivity and resolution of the resist layer will be reduced; if the content exceeds 5 parts, the development waste will increase.

[0042] In the photosensitive resin composition of the present invention, the anthracene chalcone photosensitizer is 0.1 to 1 part. If the content is less than 0.1 part, the sensitivity of the resist layer will be reduced; if the content exceeds 1 part, the resist bottom layer will not be completely cured, which will cause the cross-sectional shape of the resist to be "inverted trapezoidal" and the resolution will be poor.

[0043] 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; preferably, 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, and styrene; preferably, during the polymerization process, monomers containing aromatic groups account for 50-70% of the total monomer mass.

[0044] The weight average molecular weight of the alkali-soluble resin is 20,000 to 60,000, the acid value of the alkali-soluble resin is 160 to 220 mgKOH / g, and the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0045] The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond, preferably an acrylate monomer, and more preferably 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.

[0046] The photoinitiator is a 2,4,5-triaryl imidazole dimer, preferably 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-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

[0047] The photosensitive resin composition also includes additives, which are one or more of dyes, photochromic agents, plasticizers, adhesion promoters, inhibitors, defoaming agents, and coating aids; the weight proportion of the additives is 0.5 to 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.

[0048] The photosensitive resin composition also includes a solvent, which is one or more of acetone, toluene, and methanol; the weight proportion of the solvent is 15 to 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.

[0049] In a third aspect, the present invention further provides a photosensitive dry film, which comprises a PET layer, a photosensitive resist layer and a PE layer from bottom to top, wherein the photosensitive resist layer is prepared from the aforementioned photosensitive resin composition.

[0050] In a fourth aspect, the present invention further provides an application of a photosensitive resin composition or a photosensitive dry film in a printed circuit board, a lead frame or a semiconductor packaging substrate.

[0051] The photosensitive dry film provided by the present invention has excellent resolution, adhesion, and higher sensitivity, which is beneficial to improving production efficiency and meeting the needs of high-density and high-precision printed circuit boards.

[0052] The present invention also provides a method for preparing anthracene chalcone photosensitizer: The preparation method of the anthracene chalcone photosensitizer represented by formula (I) comprises the following steps: Under nitrogen atmosphere, ice-water bath and stirring conditions, add an ethanol solution of 9,10-anthracenedialdehyde to a reaction bottle equipped with a magnetic stirrer; then add an aqueous NaOH solution to the solution; then add an ethanol solution of a methyl ketone compound dropwise to the reaction solution, remove the ice bath after the set reaction time, slowly warm to room temperature and continue the reaction until the reaction is completed, thereby obtaining anthracene chalcone represented by formula (I).

[0053] Preferably, the molar ratio of the 9,10-anthracene dialdehyde to the methyl ketone compound is 1:(2-3.5).

[0054] Preferably, the set time is 20 to 40 minutes, and the continued reaction time is 4 to 6 hours.

[0055] The preparation method of the anthracene chalcone photosensitizer represented by formula (II) comprises the following steps: Under nitrogen atmosphere, ice-water bath and stirring conditions, add an ethanol solution of 9,10-anthracenedialdehyde to a reaction bottle equipped with a magnetic stirrer; then add an aqueous NaOH solution to the solution; then add the ethanol solution of the methyl ketone compound dropwise to the reaction mixture, remove the ice bath after the set reaction time, slowly heat to room temperature, and continue the reaction until the reaction is completed to obtain anthracene chalcone represented by formula (II).

[0056] Preferably, the molar ratio of the 9,10-anthracene dialdehyde to the methyl ketone compound is 1:(1-1.6).

[0057] Preferably, the set time is 20 to 40 minutes, and the continued reaction time is 4 to 6 hours.

[0058] The preparation method of the anthracene chalcone photosensitizer represented by formula (III) comprises the following steps: Under nitrogen atmosphere, ice-water bath and stirring conditions, add an ethanol solution of 2-anthryl methyl ketone to a reaction bottle equipped with a magnetic stirrer; then add an aqueous NaOH solution to the solution; then add the ethanol solution of the aldehyde compound dropwise to the reaction solution, remove the ice bath after the set reaction time, slowly raise the temperature to room temperature, and continue the reaction until the reaction is completed to obtain a pure anthracenyl chalcone represented by formula (III).

[0059] Preferably, the molar ratio of the 9,10-anthracene dialdehyde to the aldehyde compound is 1:(1-1.6).

[0060] Preferably, the set time is 20 to 40 minutes, and the continued reaction time is 4 to 6 hours.

[0061] The preparation method of the anthracene chalcone photosensitizer of the present invention is simple, the raw materials are easy to obtain, the yield is high, and industrial production is easy to realize.

[0062] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively and meticulously below in conjunction with the accompanying drawings and preferred embodiments of the specification, but the protection scope of the present invention is not limited to the following specific embodiments.

[0063] Example 1 The anthracene chalcone photosensitizer in this embodiment is (1E, 1'E)-1,1'-(9,10-anthracenediyl)bis-1-penten-3-one (D1), and the specific synthesis route and preparation method are as follows: Under nitrogen atmosphere, ice-water bath and stirring conditions, a solution of 9,10-anthracenedialdehyde (10 mmol, 2.34 g) in ethanol (10 mL) was added to a reaction bottle equipped with a magnetic stirrer; then, an aqueous NaOH solution (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, the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitored the complete consumption of anthracenedialdehyde); the resulting reaction mixture was neutralized to neutrality with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and the organic phases were combined and evaporated under reduced pressure to obtain a crude product, which was then recrystallized from a mixed solvent of petroleum ether and ethyl acetate to obtain D1 (2.7 g, yield: 78%).

[0064] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results are as follows: Figure 1 It is a photosensitizer D1 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 8.48 (d, J = 16.32Hz, 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 It is a photosensitizer D1 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3 ): δ 200.3, 139.3,135.4, 131.4, 129.0, 126.3, 125.9, 34.9, 8.3.

[0065] Example 2 The anthracene chalcone photosensitizer in this embodiment is (2E, 2'E)-3,3'-(9,10-anthracenediyl)bis[1-(N-methyl)-2-pyrrolyl]-1-propenone (D2), and the specific synthesis route and preparation method are as follows: Under nitrogen atmosphere, ice-water bath and stirring conditions, 9,10-anthracenedialdehyde (10 mmol, 2.34 g) in ethanol (10 mL) was added to a reaction bottle equipped with a magnetic stirrer; then, an aqueous NaOH solution (6.0 equivalents, 2.4 g, 10% w / w) was added to the solution; then, an ethanol (30 mL) solution of 2-acetyl-1-methylpyrrole (30 mmol) 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 monitored that anthracenedialdehyde was completely consumed); the resulting reaction mixture was neutralized to neutrality with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and the organic phases were combined and evaporated under reduced pressure to obtain a crude product, which was then recrystallized from a mixed solvent of petroleum ether and ethyl acetate to obtain D2 (3.4 g, yield: 76%).

[0066] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows: Figure 3 It is a D2 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 8.67 (d, J = 15.79Hz, 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 It is a D2 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl 3 ): δ179.3, 138.9,133.5, 132.5, 132.4, 132.2, 129.5, 126.4, 126.3, 120.3, 108.8, 38.0.

[0067] Example 3 The anthracene chalcone photosensitizer in this example is (2E)-3-[(10-formyl)-9-anthracenyl](1-phenyl)-1-propenone (D3), and the specific synthesis route and preparation method are as follows: Under nitrogen atmosphere, ice-water bath and stirring conditions, a solution of 9,10-anthracenedialdehyde (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 an ethanol (15 mL) solution of acetophenone (15 mmol) was added dropwise to the reaction mixture, and after 30 min, the ice bath was removed, the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitored the complete consumption of anthracenedialdehyde); the resulting reaction mixture was neutralized with dilute hydrochloric acid to neutrality, washed with saturated brine, extracted with ethyl acetate, and the organic phases were combined and evaporated under reduced pressure to obtain a crude product, which was then recrystallized from a mixed solvent of petroleum ether and ethyl acetate to obtain pure D3 (2.4 g, yield: 72%).

[0068] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results are as follows: Figure 5 It is a D3 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 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 It is a D3 photosensitizer 13C-NMR spectrum; 13 C NMR (100 MHz, CDCl 3 ): δ 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.

[0069] Example 4 The anthracene chalcone photosensitizer in this example is (2E)-3-[(10-formyl)-9-anthracenyl]-1-(4-methoxy)phenyl-1-propenone (D4), and the specific synthesis route and preparation method are as follows: Under nitrogen atmosphere, ice-water bath and stirring conditions, a solution of 9,10-anthracenedialdehyde (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 p-methoxyacetophenone (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 minutes, the ice bath was removed, the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitored the complete consumption of anthracenedialdehyde); the resulting reaction mixture was neutralized to neutrality with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and the organic phases were combined and evaporated under reduced pressure to obtain a crude product, which was then recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain pure D4 (2.6 g, yield: 70%).

[0070] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows: Figure 7 It is a D4 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 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 It is a D4 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl 3 ): δ 93.5, 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.

[0071] Example 5 The anthracene chalcone photosensitizer in this example is (2E)-3-[(10-formyl)-9-anthracenyl]-1-(2-naphthyl)-1-propenone (D5), and the specific synthesis route and preparation method are as follows: Under nitrogen atmosphere, ice-water bath and stirring conditions, a solution of 9,10-anthracenedialdehyde (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-naphthacetone (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 minutes, the ice bath was removed, the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitored the complete consumption of anthracenedialdehyde); the resulting reaction mixture was neutralized to neutrality with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and the organic phases were combined and evaporated under reduced pressure to obtain a crude product, which was then recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain pure D5 (3.0 g, yield: 78%).

[0072] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results are as follows: Fig. 9 It is a photosensitizer D5 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 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). Fig.10 It is a photosensitizer D5 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl 3 ): δ 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.

[0073] Example 6 The anthracene chalcone photosensitizer in this example is (2E)-3-[(10-formyl)-9-anthracenyl]-1-(2-furyl)-1-propenone (D6), and the specific synthesis route and preparation method are as follows: Under nitrogen atmosphere, ice-water bath and stirring conditions, a solution of 9,10-anthracenedialdehyde (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-acetylfuran (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 min, the ice bath was removed, the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitored the complete consumption of anthracenedialdehyde); the resulting reaction mixture was neutralized with dilute hydrochloric acid to neutrality, washed with saturated brine, extracted with ethyl acetate, and the organic phases were combined and evaporated under reduced pressure to obtain a crude product, which was then recrystallized from a mixed solvent of petroleum ether and ethyl acetate to obtain pure D6 (2.2 g, yield: 68%).

[0074] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows: Fig.11 It is a D6 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ11.49 (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). Fig.12 It is a D6 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl 3 ): δ 8.8, 113.0.

[0075] Example 7 The anthracene chalcone photosensitizer in this example is (2E)-3-[(10-formyl)-9-anthracenyl]-1-(2-benzofuranyl)-1-propenone (D7), and the specific synthesis route and preparation method are as follows: Under nitrogen atmosphere, ice-water bath and stirring conditions, a solution of 9,10-anthracenedialdehyde (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 an ethanol (15 mL) solution of 2-acetylbenzofuran (15 mmol) was added dropwise to the reaction mixture, and after 30 minutes, the ice bath was removed, the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitored the complete consumption of anthracenedialdehyde); the resulting reaction mixture was neutralized to neutrality with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and the organic phases were combined and evaporated under reduced pressure to obtain a crude product, which was then recrystallized from a mixed solvent of petroleum ether and ethyl acetate to obtain pure D7 (2.7 g, yield: 71%).

[0076] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows: Fig.13 It is D7 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 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). Fig.14 It is D7 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl 3 ): δ 8.8, 127.3, 126.6, 126.5, 126.4, 124.3, 124.1, 123.6, 114.6, 112.7.

[0077] Example 8 The anthracene chalcone photosensitizer in this example is (2E)-1-(2-anthracenyl)[3-(4-isopropyl)phenyl]-1-propenone (D8), and the specific synthesis route and preparation method are as follows: Under nitrogen atmosphere, ice-water bath and stirring conditions, 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 p-isopropylbenzaldehyde (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 minutes, the ice bath was removed, the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitored that 2-anthrylmethyl ketone was completely consumed); the resulting reaction mixture was neutralized with dilute hydrochloric acid to neutrality, washed with saturated brine, extracted with ethyl acetate, and the organic phases were combined and evaporated under reduced pressure to obtain a crude product, which was then recrystallized from a mixed solvent of petroleum ether and ethyl acetate to obtain pure D8 (2.8 g, yield: 81%).

[0078] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results are as follows: Fig.15 It is D8 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 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). Fig.16 It is D8 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl 3 ): δ 9.8, 126.4, 126.1, 123.6, 121.2, 33.9, 24.7.

[0079] Example 9 The anthracene chalcone photosensitizer in this example is (2E)-1-(2-anthracenyl)[3-(4-methoxy)phenyl]-1-propenone (D9), and the specific synthesis route and preparation method are as follows: Under nitrogen atmosphere, ice-water bath and stirring conditions, 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 p-methoxybenzaldehyde (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 minutes, the ice bath was removed, the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitored that 2-anthrylmethyl ketone was completely consumed); the resulting reaction mixture was neutralized with dilute hydrochloric acid to neutrality, washed with saturated brine, extracted with ethyl acetate, and the organic phases were combined and evaporated under reduced pressure to obtain a crude product, which was then recrystallized from a mixed solvent of petroleum ether and ethyl acetate to obtain pure D9 (2.8 g, yield: 84%).

[0080] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows: Fig.17 It is a D9 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 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). Fig.18 It is a D9 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl 3 ): δ 7, 119.8, 114.6, 55.6, 129.0, 128.9, 128.6, 128.4, 127.9, 126.7, 126.4, 126.0, 123.7, 119.8, 114.6, 55.6.

[0081] Example 10 The anthracene chalcone photosensitizer in this example is (2E)-1-(2-anthracenyl)[3-(N-methyl)-2-pyrrolyl]-1-propenone (D10), and the specific synthesis route and preparation method are as follows: Under nitrogen atmosphere, ice-water bath and stirring conditions, 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, an ethanol (15 mL) solution of N-methyl-2-pyrrolecarboxaldehyde (15 mmol) was added dropwise to the reaction mixture, and the ice bath was removed after 30 minutes. After slowly heating to the set temperature, the reaction was continued until the reaction was completed (thin layer chromatography monitored that 2-anthrylmethyl ketone was completely consumed); the resulting reaction mixture was neutralized to neutrality with dilute hydrochloric acid, washed with saturated brine, extracted with ethyl acetate, and then the organic phases were combined and evaporated under reduced pressure to obtain a crude product, which was then recrystallized with a mixed solvent of petroleum ether and ethyl acetate to obtain pure D10 (2.5 g, yield: 80%).

[0082] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows: Fig.19 It is D10 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 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 = 3.27Hz, 1H), 3.81 (s, 3H). Fig. 20 It is D10 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl 3 ): δ36.3, 116.8, 112.5, 110.0, 36.3.

[0083] Embodiment 11 The anthracene chalcone photosensitizer in this example is (2E)-1-(2-anthracenyl)-3-(2-thienyl)-1-propenone (D11), and the specific synthesis route and preparation method are as follows: Under nitrogen atmosphere, ice-water bath and stirring conditions, 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-thiophenecarboxaldehyde (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture, and after 30 minutes, the ice bath was removed, the temperature was slowly raised to room temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitored that 2-anthrylmethyl ketone was completely consumed); the resulting reaction mixture was neutralized with dilute hydrochloric acid to neutrality, washed with saturated brine, extracted with ethyl acetate, and the organic phases were combined and evaporated under reduced pressure to obtain a crude product, which was then recrystallized from a mixed solvent of petroleum ether and ethyl acetate to obtain pure D11 (2.3 g, yield: 74%).

[0084] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results are as follows: Fig.21 It is D11 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl 3 ): δ 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). Fig. 22 It is D11 photosensitizer 13 C-NMR spectrum; 13C NMR (100 MHz, CDCl 3 ): δ 89.5, 189.7, 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.

[0085] Solubility test: The solubility test was performed on D1 to D11 prepared from the anthracene chalcone photosensitizers prepared in Examples 1 to 11; and the solubility test was also performed using 9,10-dibutoxyanthracene (DBA), 9,10-diphenylanthracene (DPHA) and 9,10-diacetoxyanthracene (DAcOA). The specific test method and evaluation method are as follows: acetone, toluene and methanol were used as solvents respectively; the solute was added to the solvent at a ratio of 0.1 g solute / 1 g solvent (10% w / w), and the dissolution was recorded according to the following classification standard: A (fast dissolution): Under room temperature and stirring conditions, a clear, transparent and uniform solution can be formed within 1 minute; B (slow dissolution): Under room temperature and stirring conditions, a clear, transparent and uniform solution can be formed in more than 5 minutes; or it cannot be completely dissolved at room temperature, but a clear, transparent and uniform solution can be formed when the temperature is raised to 50-60℃, and there is no obvious turbidity after returning to room temperature; C (partially dissolved): It cannot be completely dissolved at room temperature and under stirring conditions for more than 5 minutes; or it can be completely dissolved when heated to 50-60℃, but becomes obviously turbid after returning to room temperature.

[0086] The test results are shown in Table 1: UV-Vis spectroscopy: The concentration is 2×10 -5 mol / L toluene solutions of anthracene chalcone D1-D11 were scanned by UV spectrum to determine the maximum absorption wavelength of anthracene chalcone D1-D11, and the absorbance (A) was read. Each sample was repeated 3 times and the average value was taken. The test UV spectrum is shown in the figure below: Fig.23 and 24 As shown, it can be seen that anthracene chalcone photosensitizers D1-D11 have obvious absorption at 405nm and have the potential to become photosensitizers.

[0087] Examples 12 to 17 and Comparative Examples 1 to 3 The compositions of the photosensitive resin compositions of Examples 12 to 17 and Comparative Examples 1 to 3 can be seen in Table 2.

[0088] Alkali-soluble resin A: acrylate copolymer, solution polymerization method, according to the mass ratio, methacrylic acid monomer / butyl methacrylate monomer / benzyl methacrylate monomer = 25 / 10 / 65 polymerization; the solvent is acetone, the solid content is 46%, the weight average molecular weight is 40000, the dispersion degree is 2.1, and the acid value is 163mgKOH / g. (Hunan Chuyuan New Materials Co., Ltd.) Photopolymerizable monomer B is composed of the following components (purchased from Sartomer Guangzhou Chemical Co., Ltd.): 5 parts of methoxy polyethylene glycol (350) monoacrylate, 20 parts of 10 (ethoxy) bisphenol A dimethacrylate, 5 parts of 6 (propoxy) bisphenol A dimethacrylate, 10 parts of 3 (ethoxy) trimethylolpropane triacrylate, and 4 parts of di(trimethylolpropane) tetraacrylate.

[0089] Photoinitiator C is 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole (BCIM) Additive E was composed of the following ingredients (purchased from Anaiji Chemical): 0.5 parts of leuco crystal violet, 0.05 parts of malachite green, 0.8 parts of p-toluenesulfonamide, and 0.03 parts of 2,6-di-tert-butyl-4-methylphenol.

[0090] The solvent consists of the following components: 8 parts of acetone, 10 parts of toluene, and 5 parts of methanol.

[0091] Preparation of photosensitive dry film The photosensitive resin composition listed in Table 2 is used to prepare a photosensitive dry film, comprising 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, the Netherlands); the solvent was removed at 80°C for 10 min, and the thickness of the photosensitive layer was controlled to be 30 μm after baking, and then covered with a polyethylene film (PE) for protection to obtain a photosensitive dry film.

[0092] Preparation of substrate with resist pattern The photosensitive compositions of Example Samples 12-17 of the present invention and Comparative Samples 1-2 shown in Table 2 were used to prepare substrates with resist patterns, and the process was as follows: (1) Photosensitive layer forming step: forming a photosensitive layer on a substrate using a photosensitive composition; (2) an exposure step of irradiating a portion of the photosensitive layer with active light to photocuring the portion to form a cured product region; (3) Development step: removing the portion of the photosensitive layer other than the cured product region from the substrate to form a resist pattern on the substrate.

[0093] The operating conditions of each process are described in detail below.

[0094] Photosensitive layer forming process: A copper-clad laminate laminated with a 35μm thick rolled 1.2mm thick copper foil is used. After surface adjustment and preheating to 80°C, the PE protective film of the photosensitive dry film obtained by each embodiment or comparative example is peeled off, and the above-mentioned photosensitive resin composition layer is laminated on the copper-clad laminate using a hot roller laminator (Zhisheng Technology Co., Ltd., CSL-M25E) at a roller temperature of 110°C, an air pressure of 0.35MPa, and a lamination speed of 1.5m / min to obtain a test substrate.

[0095] Exposure process: Use a direct drawing exposure machine (Core Micro, main wavelength 405nm) for exposure, use a Stouffer 41-level stage exposure ruler for sensitivity testing, and control the number of exposure grids at 14-18 grids.

[0096] Development process: After exposure, the PET support film was peeled off and an alkali developer (manufactured by Guangzhou Julong Printed Circuit Equipment Co., Ltd., a dry film developer) was used to spray 1wt% Na at 30°C for twice the minimum development time. 2 CO 3 The unexposed part of the photosensitive resin layer is dissolved and removed by an aqueous solution. After development, the substrate is washed with pure water for 1.5 times the development time, dewatered with an air knife, and then dried with warm air to obtain a substrate with a cured film for evaluation. The shortest time required for the unexposed part of the photosensitive resin layer to be completely dissolved is the minimum development time.

[0097] Evaluation Project 1. Sensitivity evaluation A Stouffer 41-level step exposure scale was placed on the above-mentioned film-attached test substrate for sensitivity testing. After the exposure process, the test substrate was left to stand for more than 20 minutes, and then the PET film layer was peeled off, and a 1.0wt% sodium carbonate aqueous solution was sprayed at 30°C to remove the unexposed resist layer. The development time was 2.0 times the minimum development 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 sensitivity of the photosensitive resin composition was evaluated, and the smaller the value, the better the sensitivity.

[0098] 2. Adhesion evaluation On the above-mentioned post-filming test substrate, a photomask data with a wiring pattern of line width / space width of n:400 (unit: μm) was used to expose the energy so that the number of residual stages 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 adhesion (μm) was evaluated by taking the minimum line width of the complete cured resist line as the adhesion value. The smaller the value, the better the adhesion.

[0099] 3. Resist shape evaluation In the resist pattern used for the above-mentioned resolution evaluation, the portion with the best resolution was observed using a SU1000 scanning electron microscope (manufactured by Hitachi). Evaluation was performed according to the following evaluation criteria: ■: The width difference between the top and bottom of the resist front cross section is less than or equal to 0.8 μm, and the inverted trapezoid is basically not observed; ○: The difference between the top and bottom widths of the front cross section of the resist is greater than 0.8 μm and less than 1.2 μm, and the cross section is slightly inverted trapezoidal; ×: The difference in width between the top and bottom of the cross section of the front end of the resist is greater than or equal to 1.2 μm, and the cross section is a clear inverted trapezoid.

[0100] The test results of evaluation items 1-4 are summarized in Table 3 below.

[0101] The results in Table 3 show that the anthracene-based chalcone photosensitizer of the present invention is equal to DBA in terms of exposure energy (sensitivity) and slightly lower than DPHA; however, it has obvious advantages in terms of adhesion and resist shape, solving the problem that the resist formed by curing DBA and DPHA photosensitizers is easy to form an inverted trapezoid; DOAcA has poor performance in terms of exposure energy and has an obvious inverted trapezoid problem, and the comprehensive performance of the anthracene-based chalcone photosensitizer of the present invention is significantly better than DOAcA. The above results show that the photosensitizer of the present invention has a wide range of applicability.

[0102] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A photosensitive resin composition, characterized in that: It includes an anthracene chalcone photosensitizer, wherein the anthracene chalcone photosensitizer comprises at least one anthracene derivative represented by general formula (I) to (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, characterized in that: The anthracene chalcone photosensitizer comprises at least one anthracene derivative represented by formula D1 to D11: 。 3. The photosensitive resin composition according to claim 1, characterized in that: The photosensitive resin composition also includes 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 fraction, 50-65 parts of alkali-soluble resin, 35-50 parts of photopolymerizable monomer, 2-5 parts of photoinitiator, and 0.1-1 part of 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, (meth)acrylic acid alkyl ester, (meth)acrylic acid benzyl ester, (meth)acrylic acid benzyl ester derivative, (meth)acrylic acid phenyl ester, styrene, and styrene derivatives; wherein: during the polymerization process, the monomer containing an aromatic group accounts for 50-70% of the total monomer mass; The weight average molecular weight of the alkali-soluble resin is 20,000 to 60,000, the acid value of the alkali-soluble resin is 160 to 220 mgKOH / g, and the dispersion degree of the alkali-soluble resin is 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; 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-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

7. 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 proportion of the additives is 0.5 to 5.0 parts.

8. A photosensitive dry film, characterized in that: From bottom to top, it includes 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 7.

9. Use of the photosensitive dry film according to claim 8 in a printed circuit board, a lead frame or a semiconductor packaging substrate.

Images