Photosensitive Resin Composition Containing Anthryl Chalcones Photosensitizer and Application

Abstract

The present invention discloses a photosensitive resin composition containing an anthracene-based chalcone photosensitizer and its application. The photosensitive resin composition includes an anthracene-based chalcone photosensitizer, and the anthracene-based chalcone photosensitizer includes at least one anthracene derivative represented by general formula (I) to (III); #imgabs0# wherein: R 1 The anthracene chalcone is selected from the group consisting of a C1-C5 straight-chain or branched 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. In the present invention, anthracene chalcone is used as a photosensitizer for the photosensitive resin composition. The photosensitizer does not migrate into the polyethylene film (PE), and in the electroplating process after exposure and development, small molecular fragments are not precipitated to contaminate the electroplating solution, thereby avoiding adverse phenomena such as short circuit and open circuit of the resist pattern and significantly improving the yield rate of the product.

Description

Technical Field

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

[0002] Photosensitive resin compositions, as key pattern transfer materials, are widely used in the manufacturing of printed circuit boards (PCBs), lead frames (LFs), and semiconductor package (IC) substrates. The photosensitive resin composition is typically coated on a PET support film surface. After drying, a protective layer, such as a polyethylene film (PE) protective layer, is tightly adhered to the surface. This layer is also known as a photosensitive dry film or dry film resist. The pattern transfer process involves first applying the dry film resist to a copper substrate, then covering the dry film resist with a mask having a specific pattern, and exposing the pattern. A weakly alkaline aqueous solution is then used as a developer to remove the unexposed areas, followed by etching or electroplating to form the pattern. Finally, a stripping solution is used to remove the solidified dry film, thereby achieving pattern transfer.

[0003] As electronic devices progress toward miniaturization and higher density, the demand for circuit fineness continues to increase. To meet the demands of fine circuit manufacturing, photosensitive resin compositions must exhibit higher resolution. To improve resolution, it is necessary to add an appropriate photosensitizer to the photosensitive resin composition. The appropriate 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 exposed to light, the CO bond at the 9,10 position of the 9,10-dibutoxyanthracene photosensitizer breaks, the anthracene ring dimerizes, and a small molecule alkoxy fragment is released. This small molecule fragment migrates from the cured photosensitive resin composition to the plating solution during the subsequent electroplating process, causing contamination and affecting the life of the plating solution and the electroplating effect. Due to its rigid molecular structure, the solubility of the 9,10-diphenylanthracene photosensitizer is greatly reduced, which has a great impact on the uniformity and consistency of the product. Due to the electron-withdrawing induction effect of the acyl group of the 9,10-diacetoxyanthracene photosensitizer, the electron cloud density at the 9,10 positions of the anthracene ring increases, resulting in a decrease in the efficiency of this photosensitizer in catalyzing the curing reaction. The sidewall verticality of the cured photosensitive resin composition is poor, and the length difference between the top and bottom lines is large, forming an "inverted trapezoid". In addition, the energy required for exposure of this photosensitizer is increased, resulting in a decrease in photobleaching efficiency.

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

[0006] In view of the above problems, the present invention aims to provide a photosensitive resin composition comprising an anthracene-based 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);

[0008]

[0009] Where: R 1 It is one of a C1-C5 straight-chain or branched alkyl group, N-methylpyrrolyl, furyl, benzofuranyl, thienyl, naphthyl, phenyl, and substituted aryl group.

[0010] The anthracene-based chalcone photosensitizer comprises at least one anthracene derivative represented by formula D1 to D11:

[0011]

[0012] The photosensitive resin composition also includes an alkali-soluble resin, a photopolymerizable monomer, and a photoinitiator.

[0013] 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.

[0014] 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.

[0015] 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 molecular weight distribution of 1.0 to 3.0.

[0016] The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond, preferably an acrylate monomer, 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.

[0017] 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-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

[0018] 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.

[0019] The photosensitive resin composition further comprises a solvent, which is one or more of acetone, toluene, and methanol; the weight proportion of the solvent is 15 to 25 parts.

[0020] In a second aspect, the present invention further provides a photosensitive dry film comprising, from bottom to top, a PET layer, a photosensitive resist layer and a PE layer, wherein the photosensitive resist layer is prepared from the aforementioned photosensitive resin composition.

[0021] 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.

[0022] The chalcone mentioned in this article refers to a class of substances containing α,β-unsaturated ketone groups in their chemical structure.

[0023] Compared with the prior art, one or more of the above technical solutions can achieve at least one of the following beneficial effects:

[0024] (1) The anthracene-based chalcone photosensitizer provided by the present invention has the characteristics of low migration before curing and low precipitation after curing.

[0025] (2) In the present invention, anthracene-based chalcone is used as a photosensitizer for the photosensitive resin composition. The photosensitizer will not migrate into the polyethylene film (PE), and will not precipitate small molecular fragments to contaminate the plating solution during the electroplating process after exposure and development, thereby avoiding adverse phenomena such as short circuit and open circuit of the anti-etching pattern and significantly improving the product yield.

[0026] (3) The photosensitive resin composition of the present invention includes an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, and an anthracene-based chalcone photosensitizer. Through the synergistic effect of the components, the resulting photosensitive resin composition has excellent photosensitivity and adhesion. After exposure, the formed resist circuit has a uniform curing effect, flat sidewalls, and the ports exhibit excellent rectangular shapes, effectively solving the problem of poor resist morphology (i.e., the "inverted trapezoidal problem") existing in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] Figure 9 、 Figure 10 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D5 prepared in Example 5.

[0032] Figure 11 、 Figure 12 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D6 prepared in Example 6.

[0033] Figure 13 、 Figure 14 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D7 prepared in Example 7.

[0034] Figure 15 、 Figure 16 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D8 prepared in Example 8.

[0035] Figure 17 、 Figure 18 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D9 prepared in Example 9.

[0036] Figure 19 、 Figure 20 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D10 prepared in Example 10.

[0037] Figure 21 、 Figure 22 They are respectively the H NMR spectrum and C NMR spectrum of the anthracene chalcone photosensitizer D11 prepared in Example 11.

[0038] Figure 23 The anthracene chalcone photosensitizers D1 to D5 were dissolved in toluene (concentration 2×10 -5 mol / L) UV-visible spectrum.

[0039] Figure 24 The anthracene chalcone photosensitizers D6~D11 were dissolved in toluene (concentration 2×10 -5 mol / L) UV-visible spectrum. DETAILED DESCRIPTION

[0040] 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);

[0041]

[0042] Where: R 1 It is one of a C1-C5 straight-chain or branched alkyl group, N-methylpyrrolyl, furyl, benzofuranyl, thienyl, naphthyl, phenyl, and substituted aryl group.

[0043] The anthracene-based chalcone photosensitizer of the present invention contains a chalcone structure at positions 9 and / or 10 or 2, which can adjust the electron configuration of the anthracene group and enhance its photosensitivity. Furthermore, the chalcone structure enhances the photosensitizer's flexibility, compatibility, and dispersibility in photosensitive resin compositions, preventing the migration and precipitation of fragments generated after exposure and contamination of the electroplating solution. Furthermore, the anthracene-based chalcone photosensitizer of the present invention can enhance the photosensitivity of the photoresist composition, and the resist pattern formed after curing has smooth sidewalls and a regular rectangular cross-section.

[0044] 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-furyl)-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- 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, and (2E)-1-(2-anthryl)[3-(4-methoxy)phenyl]-1-propenone, and the corresponding specific structures are shown in Formulas D1 to D11:

[0045] .

[0046] In a second aspect, the present invention provides a photosensitive resin composition comprising the aforementioned anthracene-based chalcone photosensitizer.

[0047] The photosensitive resin composition also includes an alkali-soluble resin, a photopolymerizable monomer, and a photoinitiator.

[0048] The photosensitive resin composition comprises the following components in parts by mass:

[0049] 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.;

[0050] 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.;

[0051] 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.;

[0052] The anthracene chalcone photosensitizer is 0.1 to 1 parts, preferably 0.1 to 0.8 parts, including but not limited to 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, etc.

[0053] The alkali-soluble resin in the photosensitive resin composition of the present invention is 50 to 65 parts. If the content is less than 50 parts, the resist layer may experience gel flow; if the content exceeds 65 parts, the resolution of the photosensitive dry film may decrease.

[0054] The photopolymerizable monomer in the photosensitive resin composition of the present invention is 35 to 50 parts. 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 easy to be filmed, and the resist layer will have a gel flow phenomenon.

[0055] 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.

[0056] The content of the anthracene chalcone photosensitizer in the photosensitive resin composition of the present invention 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, resulting in the cross-sectional shape of the resist being "inverted trapezoidal" and the resolution being deteriorated.

[0057] 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.

[0058] 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 molecular weight distribution of 1.0 to 3.0.

[0059] The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond, preferably an acrylate monomer, 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.

[0060] 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-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

[0061] The photosensitive resin composition also includes additives, which are one or more of a dye, a photochromic agent, a plasticizer, an adhesion promoter, an inhibitor, a defoaming agent, and a coating aid; 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.

[0062] 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.

[0063] In a third aspect, the present invention further provides a photosensitive dry film comprising, from bottom to top, a PET layer, a photosensitive resist layer and a PE layer, wherein the photosensitive resist layer is prepared from the aforementioned photosensitive resin composition.

[0064] 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 package substrate.

[0065] The photosensitive dry film provided by the present invention has excellent resolution and adhesion, and higher sensitivity, which is conducive to improving production efficiency and meeting the needs of high density and high precision of printed circuit boards.

[0066] The present invention also provides a method for preparing anthracene-based chalcone photosensitizer:

[0067] The preparation method of the anthracene chalcone photosensitizer represented by formula (I) comprises the following steps:

[0068]

[0069] Under nitrogen atmosphere, ice-water bath and stirring conditions, an ethanol solution of 9,10-anthracenedialdehyde is added to a reaction flask equipped with a magnetic stirrer; then an aqueous NaOH solution is added to the solution; then an ethanol solution of a methyl ketone compound is added dropwise to the reaction solution. After the reaction time is set, the ice bath is removed, and the temperature is slowly raised to room temperature and the reaction is continued until the reaction is completed to obtain an anthracene chalcone represented by formula (I).

[0070] Preferably, the molar ratio of the 9,10-anthracene dialdehyde to the methyl ketone compound is 1:(2-3.5).

[0071] Preferably, the set time is 20 to 40 minutes, and the continued reaction time is 4 to 6 hours.

[0072] The preparation method of the anthracene chalcone photosensitizer represented by formula (II) comprises the following steps:

[0073]

[0074] Under nitrogen atmosphere, ice-water bath and stirring conditions, an ethanol solution of 9,10-anthracenedialdehyde is added to a reaction flask equipped with a magnetic stirrer; then, a NaOH aqueous solution is added to the solution; and then, an ethanol solution of a methyl ketone compound is added dropwise to the reaction mixture. After the reaction is allowed to proceed for a set time, the ice bath is removed, the temperature is slowly raised to room temperature, and the reaction is continued until the reaction is completed to obtain an anthracene chalcone represented by formula (II).

[0075] Preferably, the molar ratio of the 9,10-anthracene dialdehyde to the methyl ketone compound is 1:(1-1.6).

[0076] Preferably, the set time is 20 to 40 minutes, and the continued reaction time is 4 to 6 hours.

[0077] The preparation method of the anthracene chalcone photosensitizer represented by formula (III) comprises the following steps:

[0078] Under nitrogen atmosphere, ice-water bath and stirring conditions, an ethanol solution of 2-anthryl methyl ketone is added to a reaction flask equipped with a magnetic stirrer; then, a NaOH aqueous solution is added to the solution; and then, the ethanol solution of the aldehyde compound is added dropwise to the reaction solution. After the set reaction time, the ice bath is removed, the temperature is slowly raised to room temperature, and the reaction is continued until the reaction is completed to obtain a pure anthracenyl chalcone represented by formula (III).

[0079]

[0080] Preferably, the molar ratio of the 9,10-anthracene dialdehyde to the aldehyde compound is 1:(1-1.6).

[0081] Preferably, the set time is 20 to 40 minutes, and the continued reaction time is 4 to 6 hours.

[0082] The preparation method of the anthracene-based chalcone photosensitizer of the present invention is simple, the raw materials are easily obtained, the yield is high, and industrial production can be easily realized.

[0083] To facilitate understanding of the present invention, the present invention will be described in more comprehensive and detailed form below in conjunction with the accompanying drawings and preferred embodiments. However, the scope of protection of the present invention is not limited to the following specific embodiments.

[0084] Example 1

[0085] The anthracene chalcone photosensitizer in this embodiment is (1E,1'E)-1,1'-(9,10-anthracenediyl)bis-1-penten-3-one (D1). The specific synthesis route and preparation method are as follows:

[0086]

[0087] 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 flask equipped with a magnetic stirrer. Subsequently, an aqueous NaOH solution (6.0 equivalents, 2.4 g, 10% w / w) was added to the solution. A solution of 2-butanone (30 mmol) in ethanol (30 mL) was then added dropwise to the reaction mixture. 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 monitoring of anthracenedialdehyde consumption). 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 D1 (2.7 g, yield: 78%).

[0088] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows:

[0089] Figure 1 It is D1 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): 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).

[0090] Figure 2 It is D1 photosensitizer 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.

[0091] Example 2

[0092] 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). The specific synthesis route and preparation method are as follows:

[0093]

[0094] 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 flask 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-acetyl-1-methylpyrrole (30 mmol) in ethanol (30 mL) was added dropwise to the reaction mixture. 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 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 D2 (3.4 g, yield: 76%).

[0095] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows:

[0096] Figure 3 It is a D2 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): 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).

[0097] Figure 4 It is a D2 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ 179.3, 138.9,133.5, 132.5, 132.4, 132.2, 129.5, 126.4, 126.3, 120.3, 108.8, 38.0.

[0098] Example 3

[0099] The anthracene chalcone photosensitizer in this example is (2E)-3-[(10-formyl)-9-anthracenyl](1-phenyl)-1-propenone (D3). The specific synthesis route and preparation method are as follows:

[0100]

[0101] 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 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 acetophenone (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture. 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 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%).

[0102] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows:

[0103] Figure 5 It is a D3 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): 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).

[0104] Figure 6 It is a D3 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): 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.

[0105] Example 4

[0106] The anthracene chalcone photosensitizer in this example is (2E)-3-[(10-formyl)-9-anthracenyl]-1-(4-methoxy)phenyl-1-propenone (D4). The specific synthesis route and preparation method are as follows:

[0107]

[0108] 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 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 p-methoxyacetophenone (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture. 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 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 D4 (2.6 g, yield: 70%).

[0109] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows:

[0110] Figure 7 It is a D4 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): 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).

[0111] Figure 8 It is a D4 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ 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.

[0112] Example 5

[0113] The anthracene chalcone photosensitizer in this example is (2E)-3-[(10-formyl)-9-anthracenyl]-1-(2-naphthyl)-1-propenone (D5). The specific synthesis route and preparation method are as follows:

[0114]

[0115] 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 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 2-naphthylacetonone (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture. 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 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 D5 (3.0 g, yield: 78%).

[0116] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows:

[0117] Figure 9 It is D5 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): 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).

[0118] Figure 10 It is D5 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ193.6, 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.

[0119] Example 6

[0120] The anthracene chalcone photosensitizer in this example is (2E)-3-[(10-formyl)-9-anthracenyl]-1-(2-furyl)-1-propenone (D6). The specific synthesis route and preparation method are as follows:

[0121]

[0122] 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 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 2-acetylfuran (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture. 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 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%).

[0123] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows:

[0124] Figure 11 It is a D6 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): δ 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).

[0125] Figure 12 It is a D6 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ 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.

[0126] Example 7

[0127] The anthracene chalcone photosensitizer in this example is (2E)-3-[(10-formyl)-9-anthracenyl]-1-(2-benzofuranyl)-1-propenone (D7). The specific synthesis route and preparation method are as follows:

[0128]

[0129] 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 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 2-acetylbenzofuran (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture. 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 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 D7 (2.7 g, yield: 71%).

[0130] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows:

[0131] Figure 13 It is D7 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): 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).

[0132] Figure 14 It is D7 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ 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.

[0133] Example 8

[0134] The anthracene chalcone photosensitizer in this example is (2E)-1-(2-anthracenyl)[3-(4-isopropyl)phenyl]-1-propenone (D8). The specific synthesis route and preparation method are as follows:

[0135]

[0136] 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 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 p-isopropylbenzaldehyde (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture. 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 2-anthrylmethyl ketone); 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%).

[0137] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows:

[0138] Figure 15 It is D8 photosensitizer1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): 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).

[0139] Figure 16 It is D8 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ .8, 126.4, 126.1, 123.6, 121.2, 33.9, 24.7.

[0140] Example 9

[0141] 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:

[0142]

[0143] 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 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 p-anisaldehyde (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture. 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 2-anthrylmethyl ketone); 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%).

[0144] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows:

[0145] Figure 17 It is D9 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): 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).

[0146] Figure 18 It is D9 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ 90.2, 161.8,144.6, 135.5, 133.3, 132.7, 132.2, 131.1, 130.6, 130.4, 129.0, 128.9 128.6128.4 127.9 126.7 126.4 126.0,123.7, 119.8, 114.6, 55.6.

[0147] Example 10

[0148] The anthracene chalcone photosensitizer in this example is (2E)-1-(2-anthryl)[3-(N-methyl)-2-pyrrolyl]-1-propenone (D10). The specific synthesis route and preparation method are as follows:

[0149]

[0150] 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 flask equipped with a magnetic stirrer; then, NaOH aqueous solution (3.0 equivalents, 10% w / w) was added to the solution; then, a solution of N-methyl-2-pyrrolecarboxaldehyde (15 mmol) in ethanol (15 mL) was added dropwise to the reaction mixture. After 30 minutes, the ice bath was removed, the temperature was slowly raised to the set temperature, and the reaction was continued until the reaction was completed (thin layer chromatography monitored the complete consumption of 2-anthrylmethyl ketone); 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 D10 (2.5 g, yield: 80%).

[0151] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows:

[0152] Figure 19 It is D10 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): 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).

[0153] Figure 20 It is D10 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ189.2, 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.

[0154] Example 11

[0155] The anthracene chalcone photosensitizer in this example is (2E)-1-(2-anthracenyl)-3-(2-thienyl)-1-propenone (D11). The specific synthesis route and preparation method are as follows:

[0156]

[0157] 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 flask equipped with a magnetic stirrer; then, 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. 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 monitoring of 2-anthrylmethyl ketone consumption was complete); 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%).

[0158] The anthracene chalcone photosensitizer in this example was characterized by nuclear magnetic resonance structure, and the results were as follows:

[0159] Figure 21 It is D11 photosensitizer 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): 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).

[0160] Figure 22It is D11 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): 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.

[0161] Solubility test:

[0162] The solubility of D1 to D11 prepared from the anthracene-based chalcone photosensitizers prepared in Examples 1 to 11 was tested. Solubility tests were also conducted using 9,10-dibutoxyanthracene (DBA), 9,10-diphenylanthracene (DPHA), and 9,10-diacetoxyanthracene (DAcOA). The specific testing and evaluation methods were as follows: acetone, toluene, and methanol were used as solvents, respectively; the solutes were added to the solvents at a ratio of 0.1 g solute / 1 g solvent (10% w / w), and the dissolution was recorded according to the following grading standard:

[0163] A (fast dissolution): Under room temperature and stirring conditions, a clear, transparent and uniform solution can be formed within 1 minute;

[0164] B (slow dissolution): At room temperature and under 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 heated to 50-60°C, and there is no obvious turbidity after returning to room temperature;

[0165] C (partially dissolved): It cannot be completely dissolved at room temperature with stirring 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.

[0166] The test results are shown in Table 1:

[0167]

[0168] UV-visible spectrometry:

[0169] The concentration is 2×10 -5 mol / L anthracene chalcone D1-D11 toluene solutions were subjected to full UV spectrum scanning to determine the maximum absorption wavelength of anthracene chalcone D1-D11 and read the absorbance (A). Each sample was repeated 3 times and the average value was taken. The test UV spectrum is shown in the figure below. Figure 23 and 24As shown, it can be seen that anthracene chalcone photosensitizers D1-D11 have obvious absorption at 405 nm and have the potential to become photosensitizers.

[0170] Examples 12 to 17 and Comparative Examples 1 to 3

[0171] The compositions of the photosensitive resin compositions of Examples 12 to 17 and Comparative Examples 1 to 3 can be seen in Table 2.

[0172]

[0173] Alkali-soluble resin A: Acrylate copolymer, solution polymerization, methacrylic acid monomer / butyl methacrylate monomer / benzyl methacrylate monomer = 25 / 10 / 65 by mass; solvent: acetone. Solids content: 46%, weight-average molecular weight: 40,000, dispersity: 2.1, acid value: 163 mgKOH / g. (Hunan Chuyuan New Materials Co., Ltd.)

[0174] Photopolymerizable monomer B consisted of the following ingredients (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.

[0175] Photoinitiator C is 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole (BCIM)

[0176] Additive E consists 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.

[0177] The solvent consists of the following components: 8 parts of acetone, 10 parts of toluene, and 5 parts of methanol.

[0178] Preparation of photosensitive dry film

[0179] The photosensitive resin composition listed in Table 2 is used to prepare a photosensitive dry film, comprising the following steps:

[0180] 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 film was baked at 80°C for 10 min to remove the solvent. After baking, the thickness of the photosensitive layer was controlled to 30 μm. The film was then covered with a polyethylene film (PE) for protection to obtain a photosensitive dry film.

[0181] Preparation of substrate with resist pattern

[0182] 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:

[0183] (1) Photosensitive layer forming step: forming a photosensitive layer on a substrate using a photosensitive composition;

[0184] (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;

[0185] (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.

[0186] The operating conditions of each step are described in detail below.

[0187] Photosensitive layer formation process: A copper-clad laminate laminated with a 35 μm thick rolled 1.2 mm thick copper foil was used. After surface conditioning and preheating to 80°C, the PE protective film of the photosensitive dry film obtained in each embodiment or comparative example was peeled off, and the above-mentioned photosensitive resin composition layer was laminated to 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 0.35 MPa, and a lamination speed of 1.5 m / min to obtain a test substrate.

[0188] Exposure process: Exposure is performed using a direct-drawing exposure machine (Core Micro, main wavelength 405nm). A Stouffer 41-level stage exposure scale is used for sensitivity testing, and the number of exposure grids is controlled at 14-18 grids.

[0189] Development Process: After exposure, the PET support film is peeled off and an alkali developer (manufactured by Guangzhou Julong Printed Circuit Equipment Co., Ltd., a dry film developer) is used to spray a 1wt% Na2CO3 aqueous solution at 30°C for twice the minimum development time to dissolve and remove the unexposed portions of the photosensitive resin layer. After development, the substrate is rinsed with pure water for 1.5 times the development time, dehydrated with an air knife, and then dried with warm air to obtain a substrate with a cured film for evaluation. The minimum development time is the shortest time required to completely dissolve the unexposed portion of the photosensitive resin layer.

[0190] Evaluation Project

[0191] 1. Sensitivity evaluation

[0192] A Stouffer 41-step 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, 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) when the number of remaining segments of the scale obtained by curing the film was 16 2 ), the sensitivity of the photosensitive resin composition was evaluated, and the smaller the value, the better the sensitivity.

[0193] 2. Adhesion evaluation

[0194] On the above-described post-filming test substrate, exposure was performed using a photomask with a line / space width of n:400 (unit: μm) at an energy level that resulted in 16 remaining steps after development using a Stouffer 41-step scale. After development, the resist pattern was observed using an optical microscope, and adhesion (μm) was evaluated using the minimum line width resulting in a complete, cured resist line. A smaller value indicates better adhesion.

[0195] 3. Resist shape evaluation

[0196] The resist pattern used for the resolution evaluation was observed with a SU1000 scanning electron microscope (manufactured by Hitachi) for the portion with the best resolution. Evaluation was performed based on the following criteria:

[0197] ■: The difference in width 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;

[0198] ○: The difference in width between the top and bottom of the resist front cross section is greater than 0.8 μm and less than 1.2 μm, and the cross section is slightly inverted trapezoidal;

[0199] ×: The difference in width between the top and bottom of the resist front end cross section is greater than or equal to 1.2 μm, and the cross section is clearly inverted trapezoidal.

[0200] The test results of evaluation items 1-4 are summarized in Table 3 below.

[0201]

[0202] The results in Table 3 show that the anthracene-based chalcone photosensitizer of the present invention performs on par with DBA in terms of exposure energy (sensitivity) and slightly below DPHA. However, it has significant advantages in terms of adhesion and resist shape, resolving the problem of inverted trapezoidal shapes in resists formed by curing DBA and DPHA photosensitizers. DOAcA performs poorly in terms of exposure energy and exhibits a significant inverted trapezoidal shape problem. The anthracene-based chalcone photosensitizer of the present invention has significantly better overall performance than DOAcA. These results demonstrate the broad applicability of the photosensitizer of the present invention.

[0203] 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 principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A photosensitive resin composition, 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 parts of an anthracene-based chalcone photosensitizer. The anthracene-based chalcone photosensitizer is one or two of the anthracene derivatives shown in D1 and D2. ； The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond; and the photoinitiator is a 2,4,5-triaryl imidazole dimer.

2. The photosensitive resin composition according to claim 1, wherein 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.

3. The photosensitive resin composition according to claim 2, characterized in that 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.

4. The photosensitive resin composition according to claim 1, wherein 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.

5. The photosensitive resin composition according to claim 1, wherein The 2,4,5-triaryl imidazole dimer is 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.

6. The photosensitive resin composition according to claim 1, wherein 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.

7. 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 1 to 6.

8. Use of the photosensitive dry film according to claim 7 in a printed circuit board, a lead frame or a semiconductor package substrate.

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