Diepoxy alkoxy anthracene photosensitizer, light-cured resin composition, light-sensitive dry film and application

Abstract

The invention provides a diepoxy alkoxy anthracene photosensitizer, and relates to the field of photopolymerization. The invention further comprises a light-cured resin composition containing the diepoxy alkoxy anthracene photosensitizer, a light-sensitive dry film containing the diepoxy alkoxy anthracene photosensitizer and application of the light-cured resin composition and the light-sensitive dry film. The photosensitizer provided by the invention has the characteristics of low migration before curing and low precipitation after curing, and is excellent in photosensitive property and high in photobleaching efficiency; the polymer can be widely applied to the fields of photopolymerization and photocuring of dry films, paints, coatings, printing ink, forming materials and the like; in a photosensitive dry film, the photosensitizer cannot migrate to a polyethylene film, and when an electroplating process is carried out after exposure and development, fragments cannot be separated out to pollute electroplating liquid, so that undesirable phenomena of short circuit, open circuit and the like of an anti-corrosion pattern are avoided, and the yield of a product is remarkably improved.

Description

Technical Field

[0001] The present invention relates to the field of photopolymerization, and specifically relates to a diepoxyalkoxyanthracene photosensitizer, a photocurable resin composition containing the photosensitizer, a photosensitive dry film, and applications thereof. Background Art

[0002] The photosensitive resin composition is a key pattern transfer material in the fields of printed circuit board (PCB), lead frame (LF), and semiconductor package (IC) substrate printed circuit board manufacturing, etc. The usage method is usually to coat it on the surface of a PET support film, and after drying, a protective layer is closely attached to its surface, which is also called a photosensitive dry film, a dry film resist, etc. When realizing the pattern transfer process, first, the dry film resist is attached to the copper substrate, a mask with a certain pattern is covered on the dry film resist, and graphic exposure is carried out; then, a weak alkaline aqueous solution is used as the developer to remove the unexposed part, and then etching or electroplating treatment is carried out to form a pattern; finally, the cured part of the dry film is peeled off with a stripping solution to realize pattern transfer.

[0003] For the photosensitive resin composition, a suitable photoinitiating system has a direct impact on photosensitivity, resolution, and production yield. As electronic devices develop towards miniaturization and high density, the requirement for the fineness of circuits is continuously increasing. In order to meet the needs of manufacturing fine circuits, the photosensitive resin composition needs to have higher resolution. In order to improve the resolution, an appropriate photosensitizer needs to be added to the photosensitive resin composition.

[0004] Anthracene photosensitizers generally have good resolution and adhesion. For example, patent CN101218538A discloses 9,10-dialkoxyanthracene photosensitizers, CN110446976A discloses alkoxyanthracene or phenylanthracene photosensitizers, and CN116300313A discloses 9,10-diacyloxyanthracene or 9,10-diphenoxyanthracene photosensitizers. However, on the other hand, the problem that 9,10-dialkoxyanthracene photosensitizers have a large impact on the electroplating solution, affecting the life of the plating solution and the electroplating effect, has not been solved. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to overcome the above-mentioned defects existing in the prior art, and provide a diepoxyalkoxyanthracene photosensitizer, a photocurable resin composition, a photosensitive dry film, and applications thereof, which have less electroplating pollution and good dispersion stability.

[0006] The technical solution adopted by the present invention to solve its technical problems is as follows: A diepoxyalkoxyanthracene photosensitizer, the chemical structure of which can be represented as: ; wherein, R 1 represents hydrogen, ethyl or chlorine, R 2 represents an alkylene group of C2-C6, R3 represents hydrogen, methyl or ethyl; Its components include one or more combinations of the following: (abbreviation: TM-1), (abbreviation: TM-2), (abbreviation: TM-3), (abbreviation: TM-4), (abbreviation: TM-5), (abbreviation: TM-6), (abbreviation: TM-7), (abbreviation: TM-8), (abbreviation: TM-9).

[0007] The above structural formulas represent in sequence: 9,10-bis-(1,2-epoxypropoxy)anthracene, 9,10-bis-(1,2-epoxypropoxy)-2-ethylanthracene, 9,10-bis-(1,2-epoxypropoxy)-2-chloroanthracene, 9,10-bis-(1,2-epoxypentanyloxy)anthracene, 9,10-bis-(1,2-epoxyhexyloxy)anthracene, 9,10-bis-(1,2-epoxyheptyloxy)anthracene, 9,10-bis-(1,2-epoxyoctyloxy)anthracene, 9,10-bis-(2,3-epoxyhexyloxy)anthracene, 9,10-bis-(2,3-epoxybutyloxy)anthracene; and are abbreviated as TM-1, TM-2, TM-3, TM-4, TM-5, TM-6, TM-7, TM-8, TM-9 in the above order.

[0008] Based on the same inventive concept, the present invention also provides a photocurable resin composition, which, by mass parts, includes 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 a photosensitizer; the photosensitizer is the bis-epoxyalkyloxyanthracene photosensitizer; The alkali-soluble resin is obtained by copolymerization of one or more of methacrylic acid, acrylic acid, alkyl methacrylate, alkyl acrylate, benzyl methacrylate, benzyl acrylate, benzyl methacrylate derivatives, benzyl acrylate derivatives, phenyl methacrylate, phenyl acrylate, styrene, and styrene derivatives; The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond.

[0009] Preferably, by mass parts, the photocurable resin composition contains 55 - 60 parts of an alkali-soluble resin.

[0010] Preferably, by mass parts, the photocurable resin composition contains 40 - 49 parts of a photopolymerizable monomer; more preferably 45 - 48 parts.

[0011] Preferably, the photocurable resin composition contains 2.2 to 4 parts by mass of a photoinitiator; more preferably 2.5 to 3.5 parts by mass.

[0012] Preferably, the photocurable resin composition contains 0.2 to 0.8 parts by mass of a photosensitizer, more preferably 0.3 to 0.5 parts by mass.

[0013] Preferably, the alkali-soluble resin is obtained by copolymerization of one or more of methacrylic acid, acrylic acid, alkyl methacrylate, alkyl acrylate, benzyl methacrylate, benzyl acrylate, and styrene.

[0014] The photopolymerizable monomer is a methacrylate monomer and / or an acrylate monomer.

[0015] Preferably, the photoinitiator is 2,4,5-triaryl imidazole dimer.

[0016] Preferably, the weight-average molecular weight of the alkali-soluble resin is 20,000 to 60,000.

[0017] Preferably, the acid value of the alkali-soluble resin is 160 to 220 mg KOH / g.

[0018] Preferably, the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0019] Preferably, among the comonomers used to synthesize the alkali-soluble resin, the comonomer having an aromatic group accounts for 50 to 70% by mass.

[0020] Preferably, the photopolymerizable monomer is one or more of methoxypolyethylene glycol monoacrylate, ethoxy(propoxy)nonylphenol acrylate, ethoxy(propoxy)bisphenol A di(meth)acrylate, ethoxy(propoxy)di(meth)acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxy(propoxy)trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tetraacrylate, ethoxy(propoxy)pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0021] Preferably, the photoinitiator is one or more of 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2-chlorophenyl)-4,5-bis(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.

[0022] Preferably, the photocurable resin composition further contains 0.5 to 5.0 parts by mass of an additive; the additive is one or more of a dye, a photosensitizer, a plasticizer, an adhesion promoter, a polymerization inhibitor, an antifoaming agent, and a coating aid.

[0023] Based on the same inventive concept, the present invention also provides a photosensitive dry film, including a substrate layer, a photosensitive resist layer, and a protective layer arranged in sequence; the composition of the photosensitive resist layer includes the bis(epoxyalkyloxy)anthracene photosensitizer and / or the photocurable resin composition.

[0024] Based on the same inventive concept, the present invention also provides the application of one or more of the bis(epoxyalkyloxy)anthracene photosensitizer, the photocurable resin composition, and the photosensitive dry film in a substrate with a resist pattern, a printed circuit board, a lead frame, or a semiconductor package substrate.

[0025] The present invention has the following beneficial effects: (1) The photosensitizer provided by the present invention has the characteristics of low migration before curing and low precipitation after curing, excellent photosensitive characteristics, and high photo-bleaching efficiency; it can be widely applied to the fields of photopolymerization and photocuring such as dry films, paints, coatings, inks, and molding materials; (2) In the photosensitive dry film, the photosensitizer will not migrate to the polyethylene film (PE), and during the electroplating process after exposure and development, it will not cause fragment precipitation to contaminate the electroplating solution, thereby avoiding defects such as short circuits and open circuits in the resist pattern, and significantly improving the yield of the product; (3) Based on the above specific parts by mass of the alkali-soluble resin, the photopolymerizable monomer, the photoinitiator, and the photosensitizer, the synergistic effect is better, and the obtained photosensitive resin composition has excellent photosensitive characteristics, resolution, and adhesion; after exposure, the formed resist circuit has a uniform curing effect, a flat side wall, and an excellent positive rectangle at the port, effectively solving the problem of poor resist morphology (i.e., the "inverted trapezoid problem") existing in the prior art.

[0026] In addition to the purposes, features and advantages described above, the present invention has other purposes, features and advantages. The following will further elaborate on the present invention with reference to the accompanying drawings. Description of the Drawings

[0027] The accompanying drawings that form a part of this application are used to provide a further understanding of the present invention. The schematic embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings: Figure 1 is the 1 H-NMR spectrum of the TM-1 photosensitizer in the embodiment of the present invention; Figure 2 is the 13 C-NMR spectrum of the TM-1 photosensitizer in the embodiment of the present invention; Figure 3 is the 1 H-NMR spectrum of the TM-2 photosensitizer in the embodiment of the present invention; Figure 4 is the 13 C-NMR spectrum of the TM-2 photosensitizer in the embodiment of the present invention; Figure 5 is the 1 H-NMR spectrum of the TM-3 photosensitizer in the embodiment of the present invention; Figure 6 is the 13 C-NMR spectrum of the TM-3 photosensitizer in the embodiment of the present invention; Figure 7 is the 1 H-NMR spectrum of the TM-4 photosensitizer in the embodiment of the present invention; Figure 8 is the 13 C-NMR spectrum of the TM-4 photosensitizer in the embodiment of the present invention; Figure 9 is the 1 H-NMR spectrum of the TM-5 photosensitizer in the embodiment of the present invention; Figure 10 is the 13 C-NMR spectrum of the TM-5 photosensitizer in the embodiment of the present invention; Figure 11 is the 1 H-NMR spectrum of the TM-6 photosensitizer in the embodiment of the present invention; Figure 12 is the 13 C-NMR spectrum of the TM-6 photosensitizer in the embodiment of the present invention; Figure 13 is the 1 H-NMR spectrum of the TM-7 photosensitizer in the embodiment of the present invention; Figure 14 The 13 C-NMR spectrum of the TM-7 photosensitizer according to an embodiment of the present invention; Figure 15 The 1 H-NMR spectrum of the TM-8 photosensitizer according to an embodiment of the present invention; Figure 16 The 13 C-NMR spectrum of the TM-8 photosensitizer according to an embodiment of the present invention; Figure 17 The 1 H-NMR spectrum of the TM-9 photosensitizer according to an embodiment of the present invention; Figure 18 The 13 C-NMR spectrum of the TM-9 photosensitizer according to an embodiment of the present invention; Figure 19 The ultraviolet absorption spectra of TM-1, TM-2, and TM-3 according to an embodiment of the present invention; Figure 20 The ultraviolet absorption spectra of TM-4, TM-5, TM-6, and TM-7 according to an embodiment of the present invention; Figure 21 The ultraviolet absorption spectra of TM-8 and TM-9 according to an embodiment of the present invention. Detailed implementation manners

[0028] In order to make the objectives, solutions, and beneficial technical effects of the present invention clearer, the present invention will be further described in detail below with reference to embodiments and the accompanying drawings. It should be noted that the embodiments described in this specification are only for explaining the present invention and are not intended to limit the present invention.

[0029] For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recited; and any lower limit can be combined with other lower limits to form a range not explicitly recited, and similarly any upper limit can be combined with any other upper limit to form a range not explicitly recited. In addition, although not explicitly recited, each point or single value between the range endpoints is included in the range. Thus, each point or single value can be used as its own lower or upper limit and combined with any other point or single value or combined with other lower or upper limits to form a range not explicitly recited.

[0030] In the description herein, it should be noted that unless otherwise specified, "above" and "below" include the recited number, "multiple" in "one or more" means two or more, and "plural" in "one or more" means two or more.

[0031] An embodiment of the present invention provides a diepoxyalkoxy anthracene photosensitizer, the chemical structure of which can be represented as: ; Among them, R 1 represents hydrogen, ethyl or chlorine, and R 2 represents an alkylene group with 2 to 6 carbon atoms, and R 3 represents hydrogen, methyl or ethyl; Its components include one or more combinations of the following: (abbreviation: TM-1), (abbreviation: TM-2), (abbreviation: TM-3), (abbreviation: TM-4), (abbreviation: TM-5), (abbreviation: TM-6), (abbreviation: TM-7), (abbreviation: TM-8), (abbreviation: TM-9).

[0032] The above structural formulas represent in sequence: 9,10-bis-(1,2-epoxypropoxy)anthracene, 9,10-bis-(1,2-epoxypropoxy)-2-ethylanthracene, 9,10-bis-(1,2-epoxypropoxy)-2-chloroanthracene, 9,10-bis-(1,2-epoxypentyloxy)anthracene, 9,10-bis-(1,2-epoxyhexyloxy)anthracene, 9,10-bis-(1,2-epoxyheptyloxy)anthracene, 9,10-bis-(1,2-epoxyoctyloxy)anthracene, 9,10-bis-(2,3-epoxyhexyloxy)anthracene, 9,10-bis-(2,3-epoxybutyloxy)anthracene; they are abbreviated as TM-1, TM-2, TM-3, TM-4, TM-5, TM-6, TM-7, TM-8, TM-9 in the above order.

[0033] Among them, the preparation method of TM-1 is: ; Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0034] Place anthraquinone (1.0 eq, 2.0 mmol, 470 mg), sodium dithionite (3.0 eq, 6.0 mmol, 1040 mg), and methyltrioctylammonium chloride (0.1 eq, 0.2 mmol, 80 mg) in a 20 mL Schlenk tube with a side arm, and displace argon 3 times; then add 3.2 mL of toluene to the reaction system, and while stirring, add a 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) dropwise to the reaction system, and heat up to 35 oReact for 30 min. Then, slowly add 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) to the reaction system, complete the addition within 10 min, and raise the temperature to 45 °C and react for 1 h. Slowly add epibromohydrin (4.0 eq, 8.0 mmol, 1080 mg) to the reaction system, raise the temperature to 60 °C and react for 12 h. After the reaction is completed (monitor the reaction by thin-layer chromatography until the anthraquinone raw material spot disappears), add 10 ml of deionized water to the reaction system, transfer the reaction solution to a separatory funnel and extract it 3 times with DCM (dichloromethane). The organic phase is dried with anhydrous Na 2 SO 4 and the solvent is removed by distillation under reduced pressure; the crude product is separated by column chromatography to obtain 9,10-bis-(1,2-epoxypropoxy)anthracene (490 mg, yield 77%).

[0035] Figure 1 is the 1 1H-NMR spectrum of the TM-1 photosensitizer; 1 1H NMR (400 MHz, CDCl 3 3): δ δ = 8.34 (d, J J = 10.4 Hz, 4H), 7.51 (d, J J = 10.5 Hz 4H), 4.47 (d, J J = 11.3 Hz, 2H), 4.11 (dd, J J = 11.3, 6.3 Hz, 2H), 3.61 – 3.52 (m, 2H), 2.97 (t, J J = 4.6 Hz, 2H), 2.85 – 2.77 (m, 2H) (ppm). Figure 2 is the 13 13C-NMR spectrum of the TM-1 photosensitizer; 13 13C NMR (100 MHz, CDCl 3 3): δ δ 147.0, 125.8, 125.0, 122.6, 76.3, 50.8, 44.7. The preparation method of TM-2 is as follows: ; Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0036] 2-Ethylanthraquinone (1.0 eq, 2.0 mmol, 470 mg), sodium dithionite (3.0 eq, 6.0 mmol, 1040 mg), and methyltrioctylammonium chloride (0.1 eq, 0.2 mmol, 80 mg) were placed in a 20 mL Schlenk tube with a side arm, and the argon was replaced three times. 3.2 mL of toluene was added to the reaction system, and a 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) was added dropwise to the reaction system with stirring, and the temperature was raised to 35 °C and reacted for 30 min. Then, a 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) was slowly added dropwise to the reaction system, and the addition was completed within 10 min. The temperature was raised to 45 °C and reacted for 1 h. Epibromohydrin (4.0 eq, 8.0 mmol, 1080 mg) was slowly added dropwise to the reaction system, and the temperature was raised to 60 °C and reacted for 12 h. After the reaction was completed (monitored by thin-layer chromatography until the anthraquinone raw material spot disappeared), 10 ml of deionized water was added to the reaction system, and the reaction solution was transferred to a separatory funnel and extracted three times with DCM. The organic phase was dried with anhydrous Na 2 SO 4 and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to obtain 9,10-bis-(1,2-epoxypropoxy)-2-ethylanthracene (600 mg, yield 87%).

[0037] Figure 3 is the 1 1H-NMR spectrum of the TM-2 photosensitizer; 1 1H NMR (400 MHz, CDCl 3 ): δ 8.32 (d, J J = 6.67Hz, 2H), 8.27 (d, J J = 8.93 Hz, 1H), 8.09 (s, 1H), 7.52 – 7.46 (m, 2H), 7.39 (d, J J = 8.89 Hz, 1H), 4.49 – 4.38 (m, 2H), 4.16 – 4.03 (m, 2H), 3.62 – 3.52 (m,2H), 3.03 – 2.93 (m, 2H), 2.88 (q, J J = 7.59 Hz, 2H), 2.84 – 2.78 (m, 2H), 1.39(t, J J = 7.55 Hz, 3H). Figure 4of the TM-2 photosensitizer 13 C-NMR spectrum; 13 C NMR(100 MHz, CDCl 3 ): δ 147.0, 146.4,141.7, 127.6, 125.6, 125.4, 125.3, 125.2, 124.5, 124.0, 122.6, 122.5, 122.4,76.3, 76.2, 50.8, 44.8, 44.7, 29.5, 15.3 . The preparation method of TM-3 is as follows: ; Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0038] Place 2-chloroanthraquinone (1.0 eq, 2.0 mmol, 490 mg), sodium dithionite (3.0 eq, 6.0 mmol, 1040 mg), and methyltrioctylammonium chloride (0.1 eq, 0.2 mmol, 80 mg) into a 20 mL Schlenk tube with a side arm, and displace argon 3 times. Add 3.2 mL of toluene to the reaction system, and while stirring, slowly add a 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) to the reaction system, and heat the temperature to 35 °C and react for 30 min. Then slowly add a 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) to the reaction system, finish the addition within 10 min, heat the temperature to 45 °C and react for 1 h. Slowly add epibromohydrin (4.0 eq, 8.0 mmol, 1080 mg) to the reaction system, heat the temperature to 60 °C and react for 12 h. After the reaction is completed (monitor the reaction by thin-layer chromatography until the anthraquinone raw material spot disappears), add 10 ml of deionized water to the reaction system, transfer the reaction solution to a separatory funnel and extract it 3 times with DCM. The organic phase is dried with anhydrous Na 2 SO 4 and the solvent is removed by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 9,10-bis-(1,2-epoxypropoxy)-2-chloroanthracene (524.5 mg, with a yield of 78%).

[0039] Figure 5 of the TM-3 photosensitizer 1 H-NMR spectrum; 1 H NMR(400 MHz, CDCl 3 ): δ8.36 – 8.22 (m, 4H), 7.57 – 7.46 (m, 2H), 7.40 (d, J = 9.57 Hz, 1H), 4.50 – 4.41 (m, 2H), 4.12– 4.01 (m, 2H), 3.62 – 3.47 (m, 2H), 3.01 – 2.90 (m, 2H), 2.87 – 2.77 (m, 2H) (ppm). Figure 6 It is the 13 C-NMR spectrum of the photosensitizer TM-3; 13 C NMR (100 MHz, CDCl 3 ): δ 147.3, 146.2, 132.0, 126.9, 126.4, 126.1, 125.9, 125.3, 125.2, 124.7, 123.2, 122.6, 122.6(5), 121.1, 76.5, 76.4, 50.7, 44.6, 44.5. The preparation method of TM-4 is as follows: ; Aliquat 336 refers to trioctylmethylammonium chloride, and toluene refers to toluene.

[0040] Step 1: Add m-chloroperbenzoic acid (2 eq, 4 mmol, 0.81 g) to a 50 mL round-bottom flask, displace Ar three times, add 6 mL of anhydrous DCM, stir until the solid dissolves, then dropwise add 5-bromo-1-pentene (1 eq, 2 mmol, 0.3 g). After reacting at room temperature for 12 h, concentrate and distill the reaction solution to obtain epoxy bromopentane.

[0041] Step 2: Place anthraquinone (1.0 eq, 2.0 mmol, 490 mg), sodium dithionite (3.0 eq, 6.0 mmol, 1040 mg), and methyltrioctylammonium chloride (0.1 eq, 0.2 mmol, 80 mg) in a 20 mL Schlenk tube with a side arm, and displace argon three times. Add 3.2 mL of toluene to the reaction system. While stirring, slowly add 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) to the reaction system, and heat the reaction system to 35 °C and react for 30 min. Then slowly add 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) to the reaction system, complete the addition within 10 min, heat the reaction system to 45 °C and react for 1 h. Slowly add 1,2-epoxypentane bromide (4.0 eq, 8.0 mmol, 1320 mg) to the reaction system, heat the reaction system to 60 °C and react for 12 h. After the reaction is completed, add 10 mL of deionized water to the reaction system, transfer the reaction solution to a separatory funnel, and extract it three times with DCM. The organic phase is dried with anhydrous Na 2 SO 4 and the solvent is removed by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 9,10-bis-(1,2-epoxypentyloxy)anthracene (660 mg, yield 87%).

[0042] Figure 7 is the 1 1H-NMR spectrum of the TM-4 photosensitizer; 1 1H NMR (400 MHz, CDCl 3 ): δ 8.27 (d, J J = 7.1 Hz, 4H), 7.49 (d, J J = 7.2 Hz, 4H), 4.20 (t, J J = 6.7 Hz, 4H), 3.11 – 3.05 (m, 2H), 2.85 – 2.79 (m, 2H), 2.62 – 2.56 (m, 2H), 2.26 – 2.14 (m, 4H), 2.08 – 1.95 (m, 2H), 1.94 – 1.80 (m, 2H). Figure 8 is the 13 13C-NMR spectrum of the TM-4 photosensitizer; 13 13C NMR (100 MHz, CDCl 3 ): δ147.3, 125.3, 125.1, 122.6, 75.4, 52.1, 47.2, 29.4, 27.2. The preparation method of TM-5 is as follows: ; Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0043] Step 1: Add m-chloroperbenzoic acid (2 eq, 4 mmol, 0.81 g) to a 50 mL round-bottom flask, displace Ar three times, add 6 mL of anhydrous DCM, stir until the solid dissolves, and then add 6-bromo-1-hexene (1 eq, 2 mmol, 0.3 g) dropwise. After reacting at room temperature for 12 h, concentrate and distill the reaction solution to obtain epoxy bromohexane.

[0044] Step 2: Place anthraquinone (1.0 eq, 2.0 mmol, 490 mg), sodium dithionite (3.0 eq, 6.0 mmol, 1040 mg), and methyltrioctylammonium chloride (0.1 eq, 0.2 mmol, 80 mg) in a 20 mL Schlenk tube with a side arm, and displace Ar three times. Add 3.2 mL of toluene to the reaction system, and while stirring, add a 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) dropwise to the reaction system, and heat to 35 °C and react for 30 min. Then slowly add a 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) dropwise to the reaction system, complete the addition within 10 min, heat to 45 °C and react for 1 h. Slowly add epoxy bromohexane (4.0 eq, 8.0 mmol, 1432 mg) dropwise to the reaction system, heat to 60 °C and react for 12 h. After the reaction is completed, add 10 mL of deionized water to the reaction system, transfer the reaction solution to a separatory funnel, extract it 3 times with DCM, and dry the organic phase with anhydrous Na 2 SO 4 Dry, and remove the solvent by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 9,10-bis-(1,2-epoxy-n-hexyloxy)anthracene (615 mg, yield 76%).

[0045] Figure 9 is the 1 1H-NMR spectrum of the TM-5 photosensitizer; 1 1H NMR (400 MHz, CDCl 3 ): δ 8.27 (d, J= 10.18 Hz, 4H), 7.49 (d, J = 7.2 Hz, 4H), 4.18 (t, J = 6.45 Hz, 4H), 3.02 (t, J = 5.70 Hz, 2H), 2.81 (t, J = 4.35 Hz, 2H), 2.56 – 2.51 (m, 2H), 2.11 (p, J = 7.22 Hz, 4H), 1.93 – 1.83 (m, 4H), 1.79 – 1.64 (m, 4H). Figure 10 is the 13 C-NMR spectrum of the TM-5 photosensitizer; 13 C NMR (100 MHz, CDCl 3 ): δ 147.5, 125.3, 125.2, 122.7, 75.8, 52.3, 47.3, 32.6, 30.6, 23.0 . The preparation method of TM-6 is as follows: ; Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0046] Step 1: Add m-chloroperoxybenzoic acid (2 eq, 4 mmol, 0.81 g) to a 50 mL round-bottom flask, displace Ar three times, add 6 mL of anhydrous DCM, stir until the solid dissolves, then add 7-bromo-1-heptene (1 eq, 2 mmol, 0.35 g). After reacting at room temperature for 12 h, concentrate and distill the reaction solution to obtain epoxy bromoheptane.

[0047] Step 2: Place anthraquinone (1.0 eq, 2.0 mmol, 490 mg), sodium dithionite (3.0 eq, 6.0 mmol, 1040 mg), and methyltrioctylammonium chloride (0.1 eq, 0.2 mmol, 80 mg) into a 20 mL Schlenk tube with a side arm, and displace argon three times. Add 3.2 mL of toluene to the reaction system. While stirring, slowly add 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) to the reaction system, and heat the mixture to 35 °C and react for 30 min. Then slowly add 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) to the reaction system, complete the addition within 10 min, heat the mixture to 45 °C and react for 1 h. Slowly add epoxy bromoheptane (4.0 eq, 8.0 mmol, 1544 mg) to the reaction system, heat the mixture to 60 °C and react for 12 h. After the reaction is completed, add 10 mL of deionized water to the reaction system, transfer the reaction solution to a separatory funnel, and extract it three times with DCM. The organic phase is dried with anhydrous Na 2 SO 4 and the solvent is removed by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 9,10-bis-(1,2-epoxyheptyloxy)anthracene (615 mg, yield 76%).

[0048] Figure 11 is the 1 1H-NMR spectrum of the TM-6 photosensitizer; 1 1H NMR (400 MHz, CDCl 3 3): δ 8.28 (d, J J = 10.01 Hz, 4H), 7.49 (d, J J = 7.2 Hz, 4H), 4.17 (t, J J = 6.59 Hz, 4H), 3.03 – 2.91 (m, 2H), 2.77 (t, J J = 4.53 Hz, 2H), 2.55 – 2.44 (m, 2H), 2.06 (p, J J = 6.86 Hz, 4H), 1.79 – 1.56 (m, 12H). Figure 12 is the 13 13C-NMR spectrum of the TM-6 photosensitizer; 13 13C NMR (100 MHz, CDCl 3 3): δ147.5, 125.2, 125.1, 122.7, 75.9, 52.3, 47.2, 32.5, 30.6, 26.2, 26.1 . The preparation method of TM-7 is as follows: ; Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0049] Step 1: Add m-chloroperbenzoic acid (2 eq, 4 mmol, 0.81 g) to a 50 mL round-bottom flask, displace Ar three times, add 6 mL of anhydrous DCM, stir until the solid dissolves, and then dropwise add 8-bromo-1-octene (1 eq, 2 mmol, 0.38 g). After reacting at room temperature for 12 h, concentrate and distill the reaction solution to obtain epoxy bromooctane.

[0050] Step 2: Place anthraquinone (1.0 eq, 2.0 mmol, 490 mg), sodium dithionite (3.0 eq, 6.0 mmol, 1040 mg), and methyltrioctylammonium chloride (0.1 eq, 0.2 mmol, 80 mg) in a 20 mL Schlenk tube with a side arm, and displace Ar three times. Add 3.2 mL of toluene to the reaction system, and while stirring, dropwise add 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) to the reaction system, and heat to 35 °C and react for 30 min. Then slowly dropwise add 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) to the reaction system, complete the dropwise addition within 10 min, heat to 45 °C and react for 1 h. Slowly dropwise add epoxy bromooctane (4 eq, 8 mmol, 1657 mg) to the reaction system, heat to 60 °C and react for 12 h. After the reaction is completed, add 10 mL of deionized water to the reaction system, transfer the reaction solution to a separatory funnel, extract with DCM three times, and dry the organic phase with anhydrous Na 2 SO 4 Dry, and remove the solvent by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 9,10-bis-(1,2-epoxyoctyloxy)anthracene (586 mg, yield 63%).

[0051] Figure 13 is the 1 1H-NMR spectrum of the TM-7 photosensitizer; 1 1H NMR (400 MHz, CDCl 3 ): δ 8.29 (d, J= 10.11Hz, 4H), 7.51 – 7.45 (m, 4H), 4.16 (t, J = 6.58 Hz, 4H), 2.93 (t, J = 3.88 Hz,2H), 2.75 (t, J = 4.51 Hz, 2H), 2.48 (t, J = 3.90 Hz, 2H), 2.05 (p, J = 6.89 Hz,4H), 1.75 – 1.62 (m, 4H), 1.63 – 1.46 (m, 12H). Figure 14 is the 13 C-NMR spectrum of the TM-7 photosensitizer; 13 C NMR(100 MHz, CDCl 3 ): δ 147.5, 125.2,125.1, 122.7, 76.0, 52.4, 47.1, 32.5, 30.6, 29.4, 26.2, 26.0 . The preparation method of TM-8 is as follows: ; Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0052] Step 1: Add m-chloroperoxybenzoic acid (2 eq, 4 mmol, 0.81 g) to a 50 mL round-bottom flask, displace Ar three times, add 6 mL of anhydrous DCM, stir until the solid dissolves, then dropwise add 1-bromohex-3-ene (1 eq, 2 mmol, 0.33 g). After reacting at room temperature for 12 h, concentrate and distill the reaction solution to obtain 2-(bromomethyl)-3-propyloxirane.

[0053] Step 2: Place anthraquinone (1.0 eq, 2.0 mmol, 490 mg), sodium dithionite (3.0 eq, 6.0 mmol, 1040 mg), and methyltrioctylammonium chloride (0.1 eq, 0.2 mmol, 80 mg) in a 20 mL Schlenk tube with a side arm, and displace argon three times. Add 3.2 mL of toluene to the reaction system, and while stirring, slowly drip 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) into the reaction system, and then heat the mixture to 35 °C and react for 30 min. Then slowly drip 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) into the reaction system, complete the dripping within 10 min, and heat the mixture to 45 °C and react for 1 h. Slowly drip 2-(bromomethyl)-3-propyloxirane (4 eq, 8 mmol, 1432 mg) into the reaction system, heat the mixture to 60 °C and react for 12 h. After the reaction is completed, add 10 mL of deionized water to the reaction system, transfer the reaction solution to a separatory funnel, and extract it three times with DCM. The organic phase is dried with anhydrous Na 2 SO 4 and the solvent is removed by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 9,10-bis(1,2-2-(bromomethyl)-3-propyloxirane)oxy)anthracene (652 mg, yield 80%).

[0054] Figure 15 is the 1 1H-NMR spectrum of the TM-8 photosensitizer; 1 1H NMR (400 MHz, CDCl 3 ) δ 8.29 (d, J J = 8.9 Hz, 4H), 7.49 (d, J J = 7.0 Hz, 4H), 4.31 (dt, J J = 11.4, 6.3 Hz, 4H), 3.20 (s, 2H), 2.89 (s, 2H), 2.44 – 2.29 (m, 2H), 2.13 (dt, J J = 13.6, 6.9 Hz, 2H), 1.69 (dt, J J = 14.5, 7.3 Hz, 4H), 1.17 – 1.03 (m, 6H). Figure 16 is the 13 13C-NMR spectrum of the TM-8 photosensitizer; 13 13C NMR (100 MHz, CDCl 3) δ 147.4, 125.5, 125.2, 122.7, 72.7, 60.3, 56.0, 33.5, 25.2, 10.1. The preparation method of TM-9 is as follows: ; Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0055] Step 1: Add m-chloroperbenzoic acid (2 eq, 4 mmol, 0.81 g) to a 50 mL round-bottom flask, displace Ar three times, add 6 mL of anhydrous DCM, stir until the solid dissolves, and then dropwise add 1-bromo-2-pentene (1 eq, 2 mmol, 0.30 g). After reacting at room temperature for 12 h, concentrate and distill the reaction solution to obtain 2-(bromomethyl)-3-ethyloxirane.

[0056] Step 2: Place anthraquinone (1.0 eq, 2.0 mmol, 490 mg), sodium dithionite (3.0 eq, 6.0 mmol, 1040 mg), and methyltrioctylammonium chloride (0.1 eq, 0.2 mmol, 80 mg) in a 20 mL Schlenk tube with a side arm, and displace Ar three times. Add 3.2 mL of toluene to the reaction system, and while stirring, dropwise add 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) to the reaction system, and heat to 35 °C and react for 30 min. Then slowly dropwise add 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) to the reaction system, complete the dropwise addition within 10 min, and heat to 45 °C and react for 1 h. Slowly dropwise add 2-(bromomethyl)-3-ethyloxirane (4 eq, 8 mmol, 1296 mg) to the reaction system, and heat to 60 °C and react for 12 h. After the reaction is completed, add 10 mL of deionized water to the reaction system, transfer the reaction solution to a separatory funnel, extract it 3 times with DCM, and dry the organic phase with anhydrous Na 2 SO 4 Dry, and remove the solvent by distillation under reduced pressure. The crude product is separated by column chromatography to obtain 9,10-bis(1,2-2-(bromomethyl)-3-ethyloxirane)oxy)anthracene (573 mg, yield 76%).

[0057] Figure 17 is the 1 1H-NMR spectrum of the TM-9 photosensitizer; 1 1H NMR (400 MHz, CDCl 3 ) δ 8.33 (dd,J = 6.7, 3.1 Hz, 4H), 7.50 (dd, J = 6.7, 3.0 Hz, 4H), 4.44 – 4.35 (m, 2H), 4.17 (dd, J = 11.3, 6.1 Hz, 2H), 3.29 (d, J = 2.9 Hz, 2H), 3.10 – 3.01 (m, 2H), 1.39 (d, J = 5.4 Hz, 6H). Figure 18 is the 13 C-NMR spectrum of the TM-9 photosensitizer; 13 C NMR(100 MHz, CDCl 3 ) δ 147.0, 125.7, 125.0, 122.6, 76.0, 57.7, 52.6, 17.5. Figure 19 is the ultraviolet absorption spectrum of TM-1, TM-2, and TM-3; Figure 20 is the ultraviolet absorption spectrum of TM-4, TM-5, TM-6, and TM-7; Figure 21 is the ultraviolet absorption spectrum of TM-8 and TM-9. It can be seen from the figure that the ultraviolet absorption wavelength of the diepoxyalkoxy anthracene photosensitizer is around 365 nm and 405 nm, indicating that this photosensitizer has the potential to improve the photosensitivity of the photosensitive resin composition to the 365 nm and 405 nm exposure light sources.

[0058] The embodiments of the present invention also provide a photocurable resin composition, which includes, by mass, 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 a photosensitizer; the photosensitizer is the diepoxyalkoxy anthracene photosensitizer; The alkali-soluble resin is copolymerized from one or more of methacrylic acid, acrylic acid, alkyl methacrylate, alkyl acrylate, benzyl methacrylate, benzyl acrylate, benzyl methacrylate derivatives, benzyl acrylate derivatives, phenyl methacrylate, phenyl acrylate, styrene, and styrene derivatives; The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond.

[0059] Based on this formulation, if the content of the alkali-soluble resin is less than 50 parts by mass, there is a tendency for the resist layer to flow; if the content exceeds 65 parts by mass, there is a tendency for the resolution to decrease.

[0060] Based on this formulation, if the content of the photopolymerizable monomer is less than 35 parts by mass, there is a tendency for the sensitivity and chemical resistance of the resist to decrease; if the content exceeds 50 parts by mass, there is a tendency for the photosensitive resin composition to be difficult to form into a thin film and for the resist layer to flow.

[0061] Based on this formulation, if the content of the photoinitiator is less than 2 parts by mass, there is a tendency for the sensitivity and resolution of the resist to decrease; if the content exceeds 5 parts by mass, there is a tendency for the development waste to increase.

[0062] Based on this formulation, if the content of the photosensitizer is less than 0.1 parts by mass, the sensitivity of the resist tends to decrease; if the content exceeds 1 part by mass, there is a tendency for the bottom layer of the resist to cure incompletely, resulting in a "reverse trapezoidal" cross-sectional shape of the resist and poor resolution.

[0063] In the embodiments of the present invention, by mass, the photocurable resin composition contains 55 - 60 parts of an alkali-soluble resin.

[0064] In the embodiments of the present invention, by mass, the photocurable resin composition contains 40 - 49 parts of a photopolymerizable monomer.

[0065] In some embodiments of the present invention, by mass, the photocurable resin composition contains 45 - 48 parts of a photopolymerizable monomer.

[0066] In the embodiments of the present invention, by mass, the photocurable resin composition contains 2.2 - 4 parts of a photoinitiator.

[0067] In some embodiments of the present invention, by mass, the photocurable resin composition contains 2.5 - 3.5 parts of a photoinitiator.

[0068] In the embodiments of the present invention, by mass, the photocurable resin composition contains 0.2 - 0.8 parts of a photosensitizer.

[0069] In some embodiments of the present invention, by mass, the photocurable resin composition contains 0.3 - 0.5 parts of a photosensitizer.

[0070] In the embodiments of the present invention, the alkali-soluble resin is obtained by copolymerization of one or more of methacrylic acid, acrylic acid, alkyl methacrylate, alkyl acrylate, benzyl methacrylate, benzyl acrylate, and styrene.

[0071] In the embodiments of the present invention, the photopolymerizable monomer is a methacrylate monomer and / or an acrylate monomer.

[0072] In the embodiments of the present invention, the photoinitiator is 2,4,5 - triarylimidazole dimer.

[0073] In the embodiments of the present invention, the weight-average molecular weight of the alkali-soluble resin is 20,000 to 60,000.

[0074] In the embodiments of the present invention, the acid value of the alkali-soluble resin is 160 to 220 mg KOH / g.

[0075] In the embodiments of the present invention, the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0076] In the embodiments of the present invention, among the comonomers used for synthesizing the alkali-soluble resin, by mass, the comonomer having an aromatic group accounts for 50 to 70%. Under this condition, the resolution and chemical resistance of the product can be improved to a certain extent.

[0077] In the embodiments of the present invention, the photopolymerizable monomer is one or more of methoxypolyethylene glycol monoacrylate, ethoxy(propoxy)nonylphenol acrylate, ethoxy(propoxy)bisphenol A di(meth)acrylate, ethoxy(propoxy)di(meth)acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxy(propoxy)trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tetraacrylate, ethoxy(propoxy)pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0078] In the embodiments of the present invention, the photoinitiator is one or more of 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2-chlorophenyl)-4,5-bis(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.

[0079] In the embodiments of the present invention, the photocurable resin composition further contains 0.5 to 5.0 parts by mass of an additive; the additive is one or more of a dye, a photochromic agent, a plasticizer, an adhesion promoter, a polymerization inhibitor, an antifoaming agent, and a coating aid.

[0080] The embodiments of the present invention further provide a photosensitive dry film, including a substrate layer, a photosensitive resist layer, and a protective layer arranged in sequence; the composition of the photosensitive resist layer includes the bis(epoxyalkyloxy)anthracene photosensitizer and / or the photocurable resin composition.

[0081] In some embodiments of the present invention, the substrate layer is a PET layer.

[0082] In some embodiments of the present invention, the protective layer is a PE layer.

[0083] Embodiments of the present invention also provide the application of one or more of the dioxiranyloxyanthracene photosensitizer, the photocurable resin composition, and the photosensitive dry film in a substrate with a resist pattern, a printed circuit board, a lead frame, or a semiconductor package substrate.

[0084] Anthracene compounds or anthracene derivatives, due to their unique structures, can undergo dimerization reactions under light irradiation and thus be photo-bleached. This property effectively avoids the problem of excessive energy absorption by the upper-layer photosensitizer during the exposure process, enabling the underlying photosensitive resin composition to receive light more fully, so that the photosensitive resin composition can achieve uniform curing during the exposure process and reach a better resolution. However, the present invention has found that when 9,10-dialkoxyanthracene photosensitizers are exposed, the C-O bonds at the 9,10 positions will break, the anthracene ring will dimerize, and at the same time, small-molecule alkoxy fragments will be released; these small-molecule fragments will migrate from the cured photosensitive resin composition to the electroplating solution during the subsequent electroplating process, causing pollution and affecting the life of the plating solution and the electroplating effect.

[0085] Based on the parent structure of alkoxyanthracene of the present invention, an epoxyethyl functional group is introduced. This functional group can undergo ring-opening curing in the presence of imidazole compounds, thereby greatly reducing the possibility of migration of photosensitizer fragments after photo-initiation and reducing the pollution of the electroplating solution by the precipitates after curing; thus improving the yield of downstream products.

[0086] The photosensitizer provided by the present invention has an anthracene ring structure main body and an alkoxy group with an ethylene oxide substituent at the 9,10 positions. Compared with the existing 9,10-dibutoxyanthracene (DBA) type photoinitiators, the introduction of the ethylene oxide functional group in the present invention enables the photosensitizer to undergo ring-opening polymerization at a certain temperature, so that small-molecule alkoxy fragments are not released. Therefore, while not reducing the efficiency of the photosensitizer in the catalytic curing reaction, the migration of initiator fragments can be greatly reduced, avoiding pollution of the electroplating solution. It can be widely applied in the field of photocuring such as dry films, paints, coatings, inks, and molding materials.

[0087] According to the embodiments of the present application, in the compound used as a photosensitizer, the photosensitive characteristics are improved by introducing an oxygen atom at the 9,10-positions of the anthracene ring, and the R 3 group can improve the flexibility of the photosensitizer and the dispersion stability in the photosensitive resin composition, while avoiding the R 2 group from affecting the electrical properties of the oxygen atom at the 9,10 positions of the anthracene ring. The R 2 group has high compatibility with the alkali-soluble resin and the photopolymerizable monomer, and the fragments cleaved after exposure are not easily migrated and precipitated. In addition, due to the rigid planar structure of the anthracene ring, by introducing R 1Group, which can further improve its solubility.

[0088] Based on the above specific R 1 , R 2 and R 3 synergistic effect, the photosensitizer of the present invention can effectively improve the photosensitivity of the photosensitive resin composition. The side walls of the resist pattern formed after curing are flat, and the cross-section is a regular rectangle. It has little pollution to the electroplating solution in the electroplating process.

[0089] For the reasons described above, the photosensitive dry film provided by the present invention has excellent resolution and adhesion, and has a higher photosensitivity than the photosensitive resin composition added with photosensitizers such as benzophenone or Michler's ketone, which is beneficial to improving the production efficiency of the client and meeting the requirements of high density and high precision of printed circuit boards.

[0090] Examples The following examples more specifically describe the content disclosed in the present invention. These examples are only for illustrative purposes, because various modifications and changes within the scope of the present invention are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are based on weight. Unless otherwise stated, all reagents used in the examples can be obtained through conventional commercial channels or synthesized according to conventional methods, and can be used directly without further treatment. Unless otherwise stated, the instruments used in the examples can be obtained through conventional commercial channels.

[0091] (I) Preparation of photocurable resin composition Set 7 examples and 3 comparative examples. Referring to the formula shown in Table 1, each component was mixed evenly to prepare a photocurable resin composition. The data units in Table 1 are parts by mass, and "-" indicates not added.

[0092] The components and specific information of each component code in Table 1 are as follows: Alkali-soluble resin (A) A1: Acrylate copolymer, solution polymerization method, polymerized according to the mass ratio of methacrylic acid / butyl methacrylate / benzyl methacrylate = 25 / 10 / 65; the solvent is acetone, the solid content is 46%, the weight average molecular weight is 40,000, the dispersion degree is 2.1, and the acid value is 163 mgKOH / g (Hunan Chuyuan New Materials Co., Ltd.); A2: Acrylate copolymer, solution polymerization method, polymerized according to the mass ratio of methacrylic acid / ethyl methacrylate / styrene = 30 / 20 / 50; the solvent is acetone, the solid content is 47%, the weight average molecular weight is 55,000, the dispersion degree is 2.3, and the acid value is 195 mgKOH / g (Hunan Chuyuan New Materials Co., Ltd.); A3: Acrylate copolymer, solution polymerization method, by mass ratio, methacrylic acid / ethyl methacrylate / benzyl methacrylate / styrene = 32 / 9 / 34 / 25 polymerization; the solvent is acetone, the solid content is 47%, the weight average molecular weight is 25000, the dispersity is 1.9, and the acid value is 208mgKOH / g (Hunan Chuyuan New Materials Co., Ltd.).

[0093] Photopolymerizable monomer (B) B1: 2 (propyloxy) nonylphenol acrylate (Sartomer Guangzhou Chemical Co., Ltd.); B2: 8 (ethoxy) nonylphenol acrylate (Sartomer Guangzhou Chemical Co., Ltd.); B3: 10 (ethoxy) bisphenol A dimethacrylate (Sartomer Guangzhou Chemical Co., Ltd.); B4: 20 (ethoxy) bisphenol A diacrylate (Sartomer Guangzhou Chemical Co., Ltd.); B5: polypropylene glycol (400) diacrylate (Sartomer Guangzhou Chemical Co., Ltd.); B6: 3(ethoxy)trimethylolpropane triacrylate (Sartomer Guangzhou Chemical Co., Ltd.); B7: 4 (ethoxy) pentaerythritol tetraacrylate (Sartomer Guangzhou Chemical Co., Ltd.).

[0094] Photoinitiator (C) C: 2,2'-Bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole (BCIM).

[0095] Photosensitizer (D) D1: 9,10-di-(1,2-epoxypropoxy)anthracene (TM-1); D2: 9,10-di-(1,2-epoxypropoxy)-2-ethylanthracene (TM-2); D3: 9,10-di-(1,2-epoxypropoxy)-2-chloroanthracene (TM-3); D4: 9,10-di-(1,2-epoxypentyloxy)anthracene (TM-4); D5: 9,10-dibutoxyanthracene (Shanghai Haohong Biopharmaceutical Technology Co., Ltd.); D6: 9,10-diphenylanthracene (Shanghai Haohong Biopharmaceutical Technology Co., Ltd.).

[0096] Additives (E) E1: Leuco crystal violet (Annaiji Chemical); E2: Malachite green (Annaiji Chemical); E3 p-Toluenesulfonamide (Annaiji Chemical); E4: 2,6 - Di - tert - butyl - 4 - methylphenol (Aladdin Chemistry); E4: 5 - Carboxybenzotriazole (Aladdin Chemistry).

[0097] Table 1 Formulations of the photocurable resin compositions for each example and comparative example ;

[0098] (II) Preparation of the photosensitive dry film Using the photocurable resin compositions of Examples 1 - 7 and Comparative Examples 1 - 3 as raw materials, the photosensitive dry films were prepared respectively, including the following steps: Using experimental equipment (Model: AB4220, TQC, Netherlands), the prepared slurry of the photocurable resin composition was coated on a 15 - μm - thick polyethylene terephthalate (PET) support film; baked at 80 °C for 10 min to remove the solvent, and after baking, the thickness of the photosensitive layer was controlled at 30 μm, and then covered with a polyethylene film (PE) for protection to obtain the photosensitive dry film.

[0099] Before coating, acetone can be added to the photocurable resin composition to adjust its viscosity to an appropriate value for coating. The solvent will be removed after baking and has no effect on the composition of the photosensitive dry film.

[0100] (III) Preparation of the substrate with an anti - resist pattern Using the photocurable resin compositions of Examples 1 - 7 and Comparative Examples 1 - 3 as raw materials, the substrates with anti - resist patterns were prepared respectively, and the procedures are as follows: (1) Photosensitive layer formation step: A photosensitive layer was formed on the substrate using a photosensitive composition; (2) Exposure step: At least a part of the above - mentioned photosensitive layer was irradiated with actinic rays to photocure the above - mentioned area to form a cured - product area; (3) Development step: At least a part of the above - mentioned photosensitive layer except the cured - product area was removed from the substrate to form an anti - resist pattern on the substrate.

[0101] Hereinafter, the operating conditions of each step will be specifically described.

[0102] Photosensitive layer formation step: Using a copper - clad laminate laminated with a 35 - μm - thick rolled 1.2 - mm - thick copper foil, after surface conditioning and pre - heating to 80 °C, while peeling off the PE protective film of the photosensitive dry film obtained from each example or comparative example, the above - mentioned photosensitive resin composition layer was laminated on the copper - clad laminate using a hot - roll laminator (Zisheng Technology Co., Ltd., CSL - M25E) under the conditions of a roll temperature of 110 °C, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min to obtain a test substrate.

[0103] Exposure process: Use a direct drawing exposure machine (Xinqi Micro, main wavelength 405 nm) for exposure. Use a Stouffer 41-step exposure scale for sensitivity testing, and control the number of exposure grids at 14 - 18 grids.

[0104] Development process: After exposure, peel off the PET support film. Use an alkaline developer (manufactured by Guangzhou Julong Printed Circuit Board Equipment Co., Ltd., a developer for dry film), and spray a 1wt% Na 2 CO 3 aqueous solution at 30 °C for twice the minimum development time to dissolve and remove the unexposed part of the photosensitive resin layer. After development, wash with pure water for 1.5 times the development time, perform water removal treatment with an air knife, and then perform warm air drying to obtain a substrate with a cured film for evaluation. The shortest time required to completely dissolve the unexposed part of the photosensitive resin layer is defined as the minimum development time.

[0105] (IV) Testing and Evaluation (1) Solubility test of photosensitizer Using acetone and toluene as representative solvents, test the solubility of photosensitizers D1 - D4 in Examples 1 - 4 in each gram of the corresponding solvent, and use D5 - D6 in Comparative Examples 1 - 2 as a comparison. The test results are shown in Table 2.

[0106] Table 2 Solubility test results of photosensitizers

[0107] (2) Sensitivity evaluation Place a Stouffer 41-step exposure scale on the test substrate after laminating for sensitivity testing. After the exposure process, let the test substrate stand for more than 20 minutes, then peel off the PET film layer, spray a 1.0wt% sodium carbonate aqueous solution at 30 °C to remove the unexposed resist layer, and the development time is 2.0 times the minimum development time. After the above operations, a cured film obtained by curing the photosensitive resin composition is formed on the substrate surface. The exposure energy (mJ / cm 2 ) when the remaining number of segments of the step exposure scale obtained through the cured film is 16 segments is used to evaluate the sensitivity of the photosensitive resin composition. The smaller this value, the better the sensitivity.

[0108] (3) Adhesion evaluation On the above-mentioned test substrate after film lamination, using photomask data with a line width / spacing width of n:400 (unit: μm) wiring pattern, exposure is carried out with an energy such that the remaining step number after developing the Stouffer 41-step stepwise exposure scale reaches 16. After the developing process, the photoresist pattern is observed using an optical microscope, and the value of the minimum line width forming a complete cured photoresist line is used as the adhesion value to evaluate the adhesion (μm). The smaller this value, the better the adhesion indicates.

[0109] (4)Resolution evaluation On the above-mentioned test substrate after film lamination, using photomask data with a line width / spacing width of n:n (unit: μm) wiring pattern, exposure is carried out with an energy such that the remaining step number after developing the Stouffer 41-step stepwise exposure scale reaches 16. After the developing process, the photoresist pattern is observed using an optical microscope, and the value of the minimum line width forming a complete cured photoresist line is used as the adhesion value to evaluate the adhesion (μm). The smaller this value, the better the resolution indicates.

[0110] (5)Electroplating resistance evaluation On the above-mentioned test substrate after film lamination, using photomask data with a line width / spacing width of 2 / 2~6 / 6 (unit: mil) wiring pattern, exposure is carried out with an energy such that the remaining step number after developing the Stouffer 41-step stepwise exposure scale reaches 16. After the developing process, pre-treatment before copper plating is carried out in the order of dipping in a degreasing solution (Baikal M404, 10%) for 10 min (40 °C) → water washing for 1 min → micro-etching (4% sodium thiosulfate solution) for 1 min → pickling in dilute sulfuric acid (10%) for 1 min, and then it is put into a copper sulfate electroplating solution (copper sulfate 75 g / L, sulfuric acid 110 g / L, chloride ion 50 ppm, bath conditioner 680 7 mL / L), and copper plating is carried out at room temperature, 3.0 A / dm 2 for 30 minutes. Then, water washing for 1 min → pickling in methanesulfonic acid (10%) for 1 min is carried out in the order of pre-treatment before tin plating, and then it is put into a stannous methanesulfonate electroplating solution (stannous methanesulfonate 170 mL / L, B14WA14 wetting agent 70 mL / L, B14 BR14 wetting agent 3 mL / L, B14 RX14 wetting agent 3 mL / L, SB stabilizer), and tin plating is carried out at 22 °C, 2.0 A / dm 2 for 20 minutes. Then, water washing → film stripping (4.0% sodium hydroxide solution, 55 °C) → water washing → drying are carried out. In addition, after the photoresist is peeled off, the presence or absence of copper plating metal penetration is observed from above using an optical microscope, a section is made, and it is confirmed by scanning electron microscopy whether there is plating penetration. The evaluation result is expressed as: ■ represents no plating penetration phenomenon; ○ represents slight overplating; × represents severe overplating.

[0111] (6)Evaluation of electroplating pollution The exposed dry film resist sample (with 16 exposure grids) is dissolved in a copper sulfate electroplating solution at a ratio of 0.8 m 2 / L. After soaking at room temperature for 24 h, the dry film resist is filtered off to obtain the sample to be tested. Using the high-temperature catalytic combustion oxidation method, measure the organic carbon content (TOC) of the electroplating solution sample to be tested, with the electroplating solution sample without the resist sample as the blank sample. The larger the measured organic carbon content (TOC) value, the greater the pollution of the electroplating solution. The evaluation results are expressed as: ■ represents that after deducting the blank, the TOC value < 500 ppm; ○ represents that after deducting the blank, 500 ppm > TOC value < 1000 ppm; × represents that after deducting the blank, the TOC value > 1000 ppm.

[0112] (7)Evaluation of resist shape In the resist pattern used for the above resolution evaluation, observe the part with the best resolution using a SU1000 type scanning electron microscope (manufactured by Hitachi). The evaluation results are expressed as: ■ represents that the difference between the top and bottom widths at the front end cross-section of the resist is less than or equal to 0.8 μm, and basically no inverted trapezoid can be observed; ○ represents that the difference between the top and bottom widths at the front end cross-section of the resist is greater than 0.8 μm and less than 1.2 μm, and the cross-section is slightly inverted trapezoidal; × represents that the difference between the top and bottom widths at the front end cross-section of the resist is greater than or equal to 1.2 μm, and the cross-section is significantly inverted trapezoidal.

[0113] (8)Evaluation of the dispersion stability of photosensitizer Store the above-prepared photosensitive dry film in the dark at 25 °C for 2 weeks. Observe the surface of the photosensitive layer using a microscope and classify it as follows: ■ represents that the surface of the photosensitive layer is uniform; × represents that undissolved substances precipitate on the surface of the photosensitive layer.

[0114] The test results of evaluation items 2 to 8 are summarized in Table 3 below.

[0115] Table 3 Test results of evaluation items 2 to 8 in the examples and comparative examples

[0116] As can be seen from the test results in Table 2, the photosensitizers D1 - D4 of the present invention have significantly better solubility in different solvents than 9,10 - dibutoxyanthracene and 9,10 - diphenylanthracene, and have lower migration properties, enabling them to be more evenly dispersed in the photosensitive resin composition and more easily form fine circuits during exposure. The test results in Table 3 further prove this trend. The photosensitive resin compositions prepared in Examples 1 - 7 exhibit excellent performance in terms of photosensitivity, adhesion, resolution, electroplating pollution resistance, resist shape, and dispersion stability, etc. Among them, in Examples 5 - 7, the types and proportions of each component were adjusted, and good performance could still be obtained, indicating that the photosensitizer of the present invention has wide applicability and can be used in combination with different raw materials.

[0117] In contrast, 9,10 - dibutoxyanthracene used in Comparative Example 1 and Comparative Example 3 has poor solubility and poor photosensitive performance. To achieve a photosensitivity equivalent to that of the examples, at least 25% additional photosensitizer needs to be added. In addition, the small - molecule fragments generated after exposure are prone to migration, resulting in serious pollution of the electroplating solution during the electroplating process. Although 9,10 - diphenylanthracene used in Comparative Example 2 does not have the problem of electroplating solution pollution, its solubility is even worse. Due to its rigid structure, its dispersion stability in the photosensitive resin composition is poor. In Comparative Examples 1 - 3, there is incomplete curing at the bottom during exposure, and it is easy to form an inverted - trapezoid resist shape. The photosensitizer of the present invention clearly overcomes these problems.

[0118] The above content is only the preferred embodiment of the present invention and is not used to limit the present invention. Those skilled in the art can make various modifications and changes within the spirit and principle of the present invention. Any modification, equivalent substitution, or improvement within this scope shall be regarded as covered by the protection scope of the present invention.

Claims

1. A diepoxyalkoxyanthracene photosensitizer, characterized in that: The chemical structure can be expressed as: ； Among them, R 1 represents hydrogen, ethyl or chlorine, R 2 represents a C2~C6 alkylene group, R 3 represents hydrogen, methyl or ethyl; Its ingredients include one or a combination of two or more of the following: 、 、 、 、 、 、 、 、 。 2. A photocurable resin composition, characterized in that: In parts by mass, it comprises 50-65 parts of alkali-soluble resin, 35-50 parts of photopolymerizable monomer, 2-5 parts of photoinitiator, and 0.1-1 parts of photosensitizer; the photosensitizer is the diepoxyalkoxyanthracene photosensitizer according to claim 1 or 2; The alkali-soluble resin is obtained by copolymerizing one or more of methacrylic acid, acrylic acid, alkyl methacrylate, alkyl acrylate, benzyl methacrylate, benzyl acrylate, benzyl methacrylate derivatives, benzyl acrylate derivatives, phenyl methacrylate, phenyl acrylate, styrene, and styrene derivatives; The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond.

3. The photocurable resin composition according to claim 2, characterized in that: The photocurable resin composition contains 55 to 60 parts of alkali-soluble resin by weight; the photocurable resin composition contains 40 to 49 parts of photopolymerizable monomer by weight; the photocurable resin composition contains 2.2 to 4 parts of photoinitiator by weight; the photocurable resin composition contains 0.2 to 0.8 parts of photosensitizer by weight; The alkali-soluble resin is obtained by copolymerizing one or more of methacrylic acid, acrylic acid, alkyl methacrylate, alkyl acrylate, benzyl methacrylate, benzyl acrylate, and styrene; The photopolymerizable monomer is a methacrylate monomer and / or an acrylate monomer; The photoinitiator is a 2,4,5-triaryl imidazole dimer.

4. The photocurable resin composition according to claim 2 or 3, characterized in that: 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 mg KOH / g; the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0; in the comonomers used to synthesize the alkali-soluble resin, the comonomers having aromatic groups account for 50 to 70% by mass.

5. The photocurable resin composition according to claim 2 or 3, 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.

6. The photocurable resin composition according to claim 2 or 3, characterized in that: The photoinitiator 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.

7. The photocurable resin composition according to claim 2 or 3, characterized in that: The invention also contains 0.5 to 5.0 parts by weight of additives; the additives are one or more of a dye, a photochromic agent, a plasticizer, an adhesion promoter, an inhibitor, a defoaming agent, and a coating aid.

8. A photosensitive dry film, characterized in that: The invention comprises a base layer, a photoresist layer and a protective layer arranged in sequence; the components of the photoresist layer include the diepoxyalkoxyanthracene photosensitizer according to claim 1 and / or the photocurable resin composition according to any one of claims 2 to 7.

9. Use of one or more of the diepoxyalkoxyanthracene photosensitizer according to claim 1, the photocurable resin composition according to any one of claims 2 to 7, and the photosensitive dry film according to claim 8 in a substrate with a resist pattern, a printed circuit board, a lead frame, or a semiconductor packaging substrate.

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