Diepoxyalkoxyanthracene photosensitizer, photocurable resin composition, photosensitive dry film and applications thereof

Abstract

The present invention provides a diepoxyalkoxy anthracene photosensitizer, which relates to the field of photopolymerization. The present invention also includes a photocurable resin composition containing the diepoxyalkoxy anthracene photosensitizer, a photosensitive dry film containing the diepoxyalkoxy anthracene photosensitizer, and applications thereof. The photosensitizer provided by the present invention has the characteristics of low migration before curing and low precipitation after curing, excellent photosensitivity, and high photobleaching efficiency; it can be widely used in the fields of photopolymerization and photocuring of dry films, paints, coatings, inks, and molding materials; in the photosensitive dry film, the photosensitizer will not migrate to the polyethylene film, and when the electroplating process is performed after exposure and development, it will not cause fragment precipitation to contaminate the electroplating solution, thereby avoiding adverse phenomena such as short circuits and open circuits in the resist pattern, and significantly improving the product yield.

Description

Technical Field

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

[0002] Photosensitive resin compositions are key pattern transfer materials used in the manufacture of printed circuit boards (PCBs), lead frames (LFs), and semiconductor package (IC) substrates. They are typically applied to a PET support film, dried, and then tightly bonded with a protective layer. These materials are also known as photosensitive dry film or dry film resist. The pattern transfer process involves first applying the dry film resist to a copper substrate, then covering it with a patterned mask to expose 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 cured dry film, achieving pattern transfer.

[0003] For photosensitive resin compositions, a suitable photoinitiator system has a direct impact on photosensitivity, resolution, and production yield. As electronic devices progress toward miniaturization and higher density, the demand for circuit sophistication continues to increase. To meet the demands of fine circuit manufacturing, photosensitive resin compositions must exhibit higher resolution. To improve resolution, a suitable photosensitizer must 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-diphenyloxyanthracene photosensitizers. However, 9,10-dialkoxyanthracene photosensitizers also pose significant risks to the plating solution, impacting the plating solution life and plating results. This issue remains unresolved. Summary of the Invention

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

[0006] The technical solution adopted by the present invention to solve the technical problem is as follows: a diepoxyalkoxyanthracene photosensitizer, the chemical structure of which can be expressed as:

[0007] ;

[0008] Among them, R 1 represents hydrogen, ethyl or chlorine, R2 represents a C2~C6 alkylene group, R 3 represents hydrogen, methyl or ethyl;

[0009] Its ingredients include one or a combination of two or more of the following:

[0010] (TM-1 for short), (TM-2 for short), (TM-3 for short), (TM-4 for short), (TM-5 for short), (TM-6 for short), (TM-7 for short), (TM-8 for short), (abbreviated as TM-9).

[0011] The above structural formulas represent in sequence: 9,10-bis-(1,2-epoxypropyloxy)anthracene, 9,10-bis-(1,2-epoxypropyloxy)-2-ethylanthracene, 9,10-bis-(1,2-epoxypropyloxy)-2-chloroanthracene, 9,10-bis-(1,2-epoxypentaneoxy)anthracene, 9,10-bis-(1,2-epoxyhexaneoxy)anthracene, 9,10-bis-(1,2-epoxyheptanoxy)anthracene, 9,10-bis-(1,2-epoxyoctaneoxy)anthracene, 9,10-bis-(2,3-epoxyhexaneoxy)anthracene, and 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, and TM-9 in the above order.

[0012] Based on the same inventive concept, the present invention also provides a photocurable resin composition, which comprises, by mass, 50 to 65 parts of an alkali-soluble resin, 35 to 50 parts of a photopolymerizable monomer, 2 to 5 parts of a photoinitiator, and 0.1 to 1 part of a photosensitizer; the photosensitizer is the diepoxyalkoxyanthracene photosensitizer;

[0013] 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;

[0014] The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond.

[0015] Preferably, the photocurable resin composition contains 55 to 60 parts by mass of alkali-soluble resin.

[0016] Preferably, the photocurable resin composition contains 40 to 49 parts by mass of the photopolymerizable monomer; more preferably 45 to 48 parts by mass.

[0017] Preferably, the photocurable resin composition contains 2.2 to 4 parts by mass of the photoinitiator; more preferably 2.5 to 3.5 parts by mass.

[0018] Preferably, the photocurable resin composition contains 0.2 to 0.8 parts by mass of the photosensitizer, more preferably 0.3 to 0.5 parts by mass.

[0019] Preferably, 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.

[0020] The photopolymerizable monomer is a methacrylate monomer and / or an acrylate monomer.

[0021] Preferably, the photoinitiator is a 2,4,5-triaryl imidazole dimer.

[0022] Preferably, the weight average molecular weight of the alkali-soluble resin is 20,000 to 60,000.

[0023] Preferably, the acid value of the alkali-soluble resin is 160 to 220 mg KOH / g.

[0024] Preferably, the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0025] Preferably, among the comonomers used to synthesize the alkali-soluble resin, the comonomers having aromatic groups account for 50 to 70% by mass.

[0026] Preferably, 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.

[0027] Preferably, 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.

[0028] 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 photochromic agent, a plasticizer, an adhesion promoter, a polymerization inhibitor, a defoaming agent, and a coating aid.

[0029] Based on the same inventive concept, the present invention also provides a photosensitive dry film, comprising a base layer, a photosensitive resist layer and a protective layer arranged in sequence; the components of the photosensitive resist layer include the diepoxyalkoxyanthracene photosensitizer and / or the photocurable resin composition.

[0030] Based on the same inventive concept, the present invention also provides the use of one or more of the diepoxyalkoxyanthracene 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 packaging substrate.

[0031] The present invention has the following beneficial effects:

[0032] (1) The photosensitizer provided by the present invention has the characteristics of low migration before curing and low precipitation after curing, excellent photosensitivity, and high photobleaching efficiency; it can be widely used in the fields of photopolymerization and photocuring of dry films, paints, coatings, inks, and molding materials;

[0033] (2) In the photosensitive dry film, the photosensitizer will not migrate to the polyethylene film (PE), and when the electroplating process is carried out after exposure and development, it will not cause fragments to precipitate and contaminate the electroplating solution, thereby avoiding adverse phenomena such as short circuit and open circuit of the resist pattern, and significantly improving the product yield;

[0034] (3) Based on the above-mentioned specific mass parts of alkali-soluble resin, photopolymerizable monomer, photoinitiator and photosensitizer, the synergistic effect is better, and the obtained photosensitive resin composition has excellent photosensitivity, resolution and adhesion; after exposure, the formed resist circuit has a uniform curing effect, flat side walls, and the port presents an excellent rectangular shape, which effectively solves the problem of poor resist morphology (i.e., "inverted trapezoidal problem") existing in the prior art.

[0035] In addition to the above-described objects, features and advantages, the present invention has other objects, features and advantages. The present invention will be further described in detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The accompanying drawings, which constitute part of this application, are intended to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are intended to explain the present invention and do not constitute an undue limitation of the present invention. In the accompanying drawings:

[0037] Figure 1 is the TM-1 photosensitizer of the embodiment of the present invention 1 H-NMR spectrum;

[0038] Figure 2 is the TM-1 photosensitizer of the embodiment of the present invention 13 C-NMR spectrum;

[0039] Figure 3 is the TM-2 photosensitizer of the embodiment of the present invention 1 H-NMR spectrum;

[0040] Figure 4 is the TM-2 photosensitizer of the embodiment of the present invention 13 C-NMR spectrum;

[0041] Figure 5 is the TM-3 photosensitizer of the embodiment of the present invention 1 H-NMR spectrum;

[0042] Figure 6 is the TM-3 photosensitizer of the embodiment of the present invention 13 C-NMR spectrum;

[0043] Figure 7 is the TM-4 photosensitizer of the embodiment of the present invention 1 H-NMR spectrum;

[0044] Figure 8 is the TM-4 photosensitizer of the embodiment of the present invention 13 C-NMR spectrum;

[0045] Figure 9 is the TM-5 photosensitizer of the embodiment of the present invention 1 H-NMR spectrum;

[0046] Figure 10 is the TM-5 photosensitizer of the embodiment of the present invention 13 C-NMR spectrum;

[0047] Figure 11 is the TM-6 photosensitizer of the embodiment of the present invention 1H-NMR spectrum;

[0048] Figure 12 is the TM-6 photosensitizer of the embodiment of the present invention 13 C-NMR spectrum;

[0049] Figure 13 is the TM-7 photosensitizer of the embodiment of the present invention 1 H-NMR spectrum;

[0050] Figure 14 is the TM-7 photosensitizer of the embodiment of the present invention 13 C-NMR spectrum;

[0051] Figure 15 is the TM-8 photosensitizer of the embodiment of the present invention 1 H-NMR spectrum;

[0052] Figure 16 is the TM-8 photosensitizer of the embodiment of the present invention 13 C-NMR spectrum;

[0053] Figure 17 is the TM-9 photosensitizer of the embodiment of the present invention 1 H-NMR spectrum;

[0054] Figure 18 is the TM-9 photosensitizer of the embodiment of the present invention 13 C-NMR spectrum;

[0055] Figure 19 1 is the ultraviolet absorption spectrum of TM-1, TM-2 and TM-3 of the embodiment of the present invention;

[0056] Figure 20 1 is the ultraviolet absorption spectrum of TM-4, TM-5, TM-6 and TM-7 of the embodiment of the present invention;

[0057] Figure 21 It is the ultraviolet absorption spectrum of TM-8 and TM-9 of the embodiment of the present invention. DETAILED DESCRIPTION

[0058] In order to make the purpose, scheme and beneficial technology of the present invention clearer, the present invention is further described in detail below with reference to the embodiments and 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.

[0059] For simplicity, only some numerical ranges are explicitly disclosed herein. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, and similarly, any upper limit can be combined with any other upper limit to form an unspecified range. In addition, although not explicitly stated, each point or individual value between the endpoints of a range is included in the range. Thus, each point or individual value can serve as its own lower limit or upper limit and be combined with any other point or individual value, or with other lower limits or upper limits, to form an unspecified range.

[0060] In the description of this article, it should be noted that, unless otherwise specified, "above" and "below" are inclusive of the number itself, and the "multiple" in "one or more" means two or more, and the "multiple" in "one or more" means two or more.

[0061] An embodiment of the present invention provides a diepoxyalkoxyanthracene photosensitizer, the chemical structure of which can be represented as follows:

[0062] ;

[0063] Among them, R 1 represents hydrogen, ethyl or chlorine, R 2 represents a C2~C6 alkylene group, R 3 represents hydrogen, methyl or ethyl;

[0064] Its ingredients include one or a combination of two or more of the following:

[0065] (TM-1 for short), (TM-2 for short), (TM-3 for short), (TM-4 for short), (TM-5 for short), (TM-6 for short), (TM-7 for short), (TM-8 for short), (abbreviated as TM-9).

[0066] The above structural formulas represent in sequence: 9,10-bis-(1,2-epoxypropyloxy)anthracene, 9,10-bis-(1,2-epoxypropyloxy)-2-ethylanthracene, 9,10-bis-(1,2-epoxypropyloxy)-2-chloroanthracene, 9,10-bis-(1,2-epoxypentaneoxy)anthracene, 9,10-bis-(1,2-epoxyhexaneoxy)anthracene, 9,10-bis-(1,2-epoxyheptanoxy)anthracene, 9,10-bis-(1,2-epoxyoctaneoxy)anthracene, 9,10-bis-(2,3-epoxyhexaneoxy)anthracene, and 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, and TM-9 in the above order.

[0067] The preparation method of TM-1 is as follows:

[0068] ;

[0069] Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0070] 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) were placed in a 20 mL Schlenk tube with a branch pipe, and the argon atmosphere was replaced three times. Then, 3.2 mL of toluene was added to the reaction system, and 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) was added dropwise to the reaction system under stirring, and the temperature was raised to 35 ℃. o C for 30 min. Then, 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) was slowly added dropwise to the reaction system over 10 min, and the temperature was raised to 45°C 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 for 12 h. After the reaction was complete (monitored by thin-layer chromatography until the anthraquinone starting material spot disappeared), 10 ml of deionized water was added to the reaction system. The reaction solution was transferred to a separatory funnel and extracted three times with dichloromethane (DCM). The organic phase was dried over anhydrous Na2SO4 and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to obtain 9,10-di-(1,2-epoxypropyloxy)anthracene (490 mg, 77% yield).

[0071] Figure 1 It is TM-1 photosensitizer 1 H-NMR spectrum;1 H NMR (400 MHz, CDCl3): δ = 8.34 (d, J = 10.4Hz, 4H), 7.51 (d, J = 10.5 Hz 4H), 4.47 (d, J = 11.3 Hz, 2H), 4.11 (dd, J = 11.3,6.3 Hz, 2H), 3.61 – 3.52 (m, 2H), 2.97 (t, J = 4.6 Hz, 2H), 2.85 – 2.77 (m, 2H)(ppm).

[0072] Figure 2 It is TM-1 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3,): δ 147.0, 125.8,125.0, 122.6, 76.3, 50.8, 44.7.

[0073] The preparation method of TM-2 is:

[0074] ;

[0075] Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0076] 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 branched tube and the atmosphere was replaced with argon three times. 3.2 mL of toluene was added to the reaction system, and 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) was added dropwise while stirring. The temperature was raised to 35°C and the reaction was continued for 30 min. Then, 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) was slowly added dropwise to the reaction system over 10 min. The temperature was then raised to 45°C and the reaction was continued 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 for 12 h. After the reaction was complete (monitored by thin-layer chromatography until the anthraquinone starting material disappeared), 10 ml of deionized water was added to the reaction system. The reaction solution was transferred to a separatory funnel and extracted three times with dichloromethane. The organic phase was dried over anhydrous Na₂SO₄ and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to yield 9,10-di-(1,2-epoxypropoxy)-2-ethylanthracene (600 mg, 87% yield).

[0077] Figure 3 It is TM-2 photosensitizer 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): δ 8.32 (d, J = 6.67Hz, 2H), 8.27 (d, J = 8.93 Hz, 1H), 8.09 (s, 1H), 7.52 – 7.46 (m, 2H), 7.39 (d, 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 = 7.59 Hz, 2H), 2.84 – 2.78 (m, 2H), 1.39(t, J = 7.55 Hz, 3H) .

[0078] Figure 4 It is TM-2 photosensitizer 13C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): 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 .

[0079] The preparation method of TM-3 is:

[0080] ;

[0081] Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0082] 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) were placed in a 20 mL Schlenk tube with a branched tube and the atmosphere was replaced with argon three times. 3.2 mL of toluene was added to the reaction system. A 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) was added dropwise while stirring. The temperature was raised to 35°C and the reaction was continued for 30 min. Subsequently, a 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) was slowly added dropwise to the reaction system over 10 min. The temperature was then raised to 45°C and the reaction was continued 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 for 12 h. After the reaction was complete (monitored by thin-layer chromatography until the anthraquinone starting material disappeared), 10 ml of deionized water was added to the reaction system. The reaction solution was transferred to a separatory funnel and extracted three times with dichloromethane. The organic phase was dried over anhydrous Na₂SO₄ and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to yield 9,10-di-(1,2-epoxypropoxy)-2-chloroanthracene (524.5 mg, 78% yield).

[0083] Figure 5 It is TM-3 photosensitizer 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): 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).

[0084] Figure 6 It is TM-3 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): 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.

[0085] The preparation method of TM-4 is:

[0086] ;

[0087] Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0088] Step 1: To a 50 mL handle flask, add m-chloroperbenzoic acid (2 eq, 4 mmol, 0.81 g) and replace Ar three times. Add 6 mL of anhydrous DCM and stir until the solid dissolves. Then add 5-bromo-1-pentene (1 eq, 2 mmol, 0.3 g) dropwise. After reacting at room temperature for 12 h, the reaction solution is concentrated and distilled to obtain epoxy bromopentane.

[0089] Step 2: 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) were placed in a 20 mL Schlenk tube with a branched tube and the atmosphere was replaced with argon three times. 3.2 mL of toluene was added to the reaction system. A 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) was added dropwise while stirring. The temperature was raised to 35°C and the reaction was continued for 30 min. Subsequently, a 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) was slowly added dropwise to the reaction system over 10 min. The temperature was then raised to 45°C and the reaction was continued for 1 h. Epoxybromopentane (4.0 eq, 8.0 mmol, 1320 mg) was slowly added dropwise to the reaction system, and the temperature was raised to 60°C for 12 h. After the reaction, 10 mL of deionized water was added to the reaction system. The reaction solution was transferred to a separatory funnel and extracted three times with dichloromethane. The organic phase was dried over anhydrous Na₂SO₄ and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to yield 9,10-di-(1,2-epoxypentyloxy)anthracene (660 mg, 87% yield).

[0090] Figure 7 It is TM-4 photosensitizer 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): δ 8.27 (d, J = 7.1 Hz,4H), 7.49 (d, J = 7.2 Hz, 4H), 4.20 (t, 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).

[0091] Figure 8 It is TM-4 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ 147.3, 125.3,125.1, 122.6, 75.4, 52.1, 47.2, 29.4, 27.2.

[0092] The preparation method of TM-5 is:

[0093] ;

[0094] Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0095] Step 1: To a 50 mL handle flask, add m-chloroperbenzoic acid (2 eq, 4 mmol, 0.81 g) and replace Ar three times. Add 6 mL of anhydrous DCM and stir until the solid dissolves. Then add 6-bromo-1-hexene (1 eq, 2 mmol, 0.3 g) dropwise. After reacting at room temperature for 12 h, the reaction solution is concentrated and distilled to obtain epoxy bromhexane.

[0096] Step 2: 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) were placed in a 20 mL Schlenk tube with a branched tube and the atmosphere was replaced with argon three times. 3.2 mL of toluene was added to the reaction system. A 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) was added dropwise while stirring. The temperature was raised to 35°C and the reaction was continued for 30 min. Subsequently, a 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) was slowly added dropwise to the reaction system over 10 min. The temperature was then raised to 45°C and the reaction was continued for 1 h. Epoxybromohexane (4.0 eq, 8.0 mmol, 1432 mg) was slowly added dropwise to the reaction system, and the temperature was raised to 60°C for 12 h. After the reaction, 10 mL of deionized water was added to the reaction system. The reaction solution was transferred to a separatory funnel and extracted three times with dichloromethane. The organic phase was dried over anhydrous Na₂SO₄ and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to yield 9,10-di-(1,2-epoxyhexyloxy)anthracene (615 mg, 76% yield).

[0097] Figure 9 It is TM-5 photosensitizer 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): δ 8.27 (d, J = 10.18Hz, 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).

[0098] Figure 10 It is TM-5 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ 147.5, 125.3,125.2, 122.7, 75.8, 52.3, 47.3, 32.6, 30.6, 23.0 .

[0099] The preparation method of TM-6 is:

[0100] ;

[0101] Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0102] Step 1: To a 50 mL handle flask, add m-chloroperbenzoic acid (2 eq, 4 mmol, 0.81 g) and replace Ar three times. Add 6 mL of anhydrous DCM and stir until the solid dissolves. Then add 7-bromo-1-heptene (1 eq, 2 mmol, 0.35 g) dropwise. After reacting at room temperature for 12 h, the reaction solution is concentrated and distilled to obtain epoxy bromide heptane.

[0103] Step 2: 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) were placed in a 20 mL Schlenk tube with a branched tube and the atmosphere was replaced with argon three times. 3.2 mL of toluene was added to the reaction system. A 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) was added dropwise while stirring. The temperature was raised to 35°C and the reaction was continued for 30 min. Subsequently, a 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) was slowly added dropwise to the reaction system over 10 min. The temperature was then raised to 45°C and the reaction was continued for 1 h. Epoxybromoheptane (4.0 eq, 8.0 mmol, 1544 mg) was slowly added dropwise to the reaction system, and the temperature was raised to 60°C for 12 h. After the reaction, 10 mL of deionized water was added to the reaction system. The reaction solution was transferred to a separatory funnel and extracted three times with dichloromethane. The organic phase was dried over anhydrous Na₂SO₄ and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to yield 9,10-di-(1,2-epoxy-n-heptyloxy)anthracene (615 mg, 76% yield).

[0104] Figure 11 It is TM-6 photosensitizer 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): δ 8.28 (d, J = 10.01Hz, 4H), 7.49 (d, J = 7.2 Hz, 4H), 4.17 (t, J = 6.59 Hz, 4H), 3.03 – 2.91 (m,2H), 2.77 (t, J = 4.53 Hz, 2H), 2.55 – 2.44 (m, 2H), 2.06 (p, J = 6.86 Hz, 4H),1.79 – 1.56 (m, 12H).

[0105] Figure 12 It is TM-6 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ147.5, 125.2,125.1, 122.7, 75.9, 52.3, 47.2, 32.5, 30.6, 26.2, 26.1 .

[0106] The preparation method of TM-7 is:

[0107] ;

[0108] Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0109] Step 1: To a 50 mL handle flask, add m-chloroperbenzoic acid (2 eq, 4 mmol, 0.81 g) and replace Ar three times. Add 6 mL of anhydrous DCM and stir until the solid dissolves. Then add 8-bromo-1-octene (1 eq, 2 mmol, 0.38 g) dropwise. After reacting at room temperature for 12 h, the reaction solution is concentrated and distilled to obtain epoxy bromide octane.

[0110] Step 2: 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) were placed in a 20 mL Schlenk tube with a branched tube and the atmosphere was replaced with argon three times. 3.2 mL of toluene was added to the reaction system. A 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) was added dropwise while stirring. The temperature was raised to 35°C and the reaction was continued for 30 min. Subsequently, a 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) was slowly added dropwise to the reaction system over 10 min. The temperature was then raised to 45°C and the reaction was continued for 1 h. Epoxyoctane (4 eq, 8 mmol, 1657 mg) was slowly added dropwise to the reaction system, and the temperature was raised to 60°C for 12 h. After the reaction was complete, 10 mL of deionized water was added to the reaction system. The reaction solution was transferred to a separatory funnel and extracted three times with dichloromethane (DCM). The organic phase was dried over anhydrous Na₂SO₄ and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to yield 9,10-di-(1,2-epoxyoctyloxy)anthracene (586 mg, 63% yield).

[0111] Figure 13 It is TM-7 photosensitizer 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): 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).

[0112] Figure 14 It is TM-7 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): 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 .

[0113] The preparation method of TM-8 is:

[0114] ;

[0115] Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0116] Step 1: To a 50 mL handle flask, add m-chloroperbenzoic acid (2 eq, 4 mmol, 0.81 g) and replace Ar three times. Add 6 ml of anhydrous DCM and stir until the solid dissolves. Then add 1-bromohex-3-ene (1 eq, 2 mmol, 0.33 g) dropwise. After reacting at room temperature for 12 h, the reaction solution is concentrated and distilled to obtain 2-(bromomethyl)-3-propyloxirane.

[0117] Step 2: 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) were placed in a 20 mL Schlenk tube with a branched tube and the atmosphere was replaced with argon three times. 3.2 mL of toluene was added to the reaction system. A 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) was added dropwise while stirring. The temperature was raised to 35°C and the reaction was continued for 30 min. Subsequently, a 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) was slowly added dropwise to the reaction system over 10 min. The temperature was then raised to 45°C and the reaction was continued for 1 h. 2-(Bromomethyl)-3-propyloxirane (4 eq, 8 mmol, 1432 mg) was slowly added dropwise to the reaction system, and the temperature was raised to 60°C for 12 h. After the reaction, 10 mL of deionized water was added to the reaction system. The reaction solution was transferred to a separatory funnel and extracted three times with dichloromethane (DCM). The organic phase was dried over anhydrous Na₂SO₄, and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to yield 9,10-bis(1,2-2-(bromomethyl)-3-propyloxirane)oxy)anthracene (652 mg, 80% yield).

[0118] Figure 15 It is TM-8 photosensitizer 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3) δ 8.29 (d, J = 8.9Hz, 4H), 7.49 (d, J = 7.0 Hz, 4H), 4.31 (dt, 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 = 13.6, 6.9 Hz, 2H), 1.69 (dt, J =14.5, 7.3 Hz, 4H), 1.17 – 1.03 (m, 6H).

[0119] Figure 16 It is TM-8 photosensitizer 13 C-NMR spectrum; 13C NMR (100 MHz, CDCl3) δ 147.4, 125.5, 125.2, 122.7, 72.7, 60.3, 56.0, 33.5, 25.2, 10.1.

[0120] The preparation method of TM-9 is:

[0121] ;

[0122] Aliquat 336 represents trioctylmethylammonium chloride, and toluene represents toluene.

[0123] Step 1: To a 50 mL handle flask, add m-chloroperbenzoic acid (2 eq, 4 mmol, 0.81 g) and replace Ar three times. Add 6 ml of anhydrous DCM and stir until the solid is dissolved. Then add 1-bromo-2-pentene (1 eq, 2 mmol, 0.30 g) dropwise. After reacting at room temperature for 12 h, the reaction solution is concentrated and distilled to obtain 2-(bromomethyl)-3-ethyloxirane.

[0124] Step 2: 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) were placed in a 20 mL Schlenk tube with a branched tube and the atmosphere was replaced with argon three times. 3.2 mL of toluene was added to the reaction system. A 35 wt% NaOH solution (0.9 eq, 1.8 mmol, 210 mg) was added dropwise while stirring. The temperature was raised to 35°C and the reaction was continued for 30 min. Subsequently, a 35 wt% NaOH solution (9.1 eq, 18.2 mmol, 2080 mg) was slowly added dropwise to the reaction system over 10 min. The temperature was then raised to 45°C and the reaction was continued for 1 h. 2-(Bromomethyl)-3-ethyloxirane (4 eq, 8 mmol, 1296 mg) was slowly added dropwise to the reaction system, and the temperature was raised to 60°C for 12 h. After the reaction, 10 mL of deionized water was added to the reaction system. The reaction solution was transferred to a separatory funnel and extracted three times with dichloromethane (DCM). The organic phase was dried over anhydrous Na₂SO₄, and the solvent was removed by distillation under reduced pressure. The crude product was separated by column chromatography to yield 9,10-bis(1,2-(bromomethyl)-3-ethyloxirane)oxy)anthracene (573 mg, 76% yield).

[0125] Figure 17 It is TM-9 photosensitizer 1 H-NMR spectrum; 1H NMR (400 MHz, CDCl3) 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).

[0126] Figure 18 It is TM-9 photosensitizer 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3) δ 147.0, 125.7, 125.0, 122.6, 76.0, 57.7, 52.6, 17.5.

[0127] Figure 19 is the UV absorption spectrum of TM-1, TM-2, and TM-3; Figure 20 It is the UV absorption spectrum of TM-4, TM-5, TM-6 and TM-7; Figure 21 The UV absorption spectra of TM-8 and TM-9 show that the UV absorption wavelengths of the diepoxyalkoxyanthracene photosensitizer are around 365nm and 405nm, indicating that this photosensitizer has the potential to enhance the photosensitivity of the photosensitive resin composition to 365nm and 405nm exposure light sources.

[0128] An embodiment of the present invention further provides a photocurable resin composition, comprising, by mass, 50 to 65 parts of an alkali-soluble resin, 35 to 50 parts of a photopolymerizable monomer, 2 to 5 parts of a photoinitiator, and 0.1 to 1 part of a photosensitizer; the photosensitizer is the diepoxyalkoxyanthracene photosensitizer;

[0129] 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;

[0130] The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond.

[0131] Based on this formulation, if the content of the alkali-soluble resin is less than 50 parts by mass, the resist layer tends to become smeared; and if the content exceeds 65 parts by mass, the resolution tends to decrease.

[0132] Based on this formulation, if the content of the photopolymerizable monomer is less than 35 parts by mass, the sensitivity and chemical resistance of the resist tend to decrease; if the content exceeds 50 parts by mass, the photosensitive resin composition is difficult to form into a thin film, and the resist tends to have laminar flow.

[0133] Based on this formulation, if the content of the photoinitiator is less than 2 parts by mass, the sensitivity and resolution of the resist tend to decrease; if the content exceeds 5 parts by mass, the amount of development waste tends to increase.

[0134] Based on this formula, 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, the bottom layer of the resist tends to be incompletely cured, resulting in an "inverted trapezoidal" cross-sectional shape of the resist and poor resolution.

[0135] In an embodiment of the present invention, the photocurable resin composition contains 55 to 60 parts by mass of an alkali-soluble resin.

[0136] In an embodiment of the present invention, the photocurable resin composition contains 40 to 49 parts by mass of a photopolymerizable monomer.

[0137] In some embodiments of the present invention, the photocurable resin composition contains 45 to 48 parts by mass of a photopolymerizable monomer.

[0138] In an embodiment of the present invention, the photocurable resin composition contains 2.2 to 4 parts by mass of a photoinitiator.

[0139] In some embodiments of the present invention, the photocurable resin composition contains 2.5 to 3.5 parts by mass of a photoinitiator.

[0140] In an embodiment of the present invention, the photocurable resin composition contains 0.2 to 0.8 parts by mass of a photosensitizer.

[0141] In some embodiments of the present invention, the photocurable resin composition contains 0.3 to 0.5 parts by mass of a photosensitizer.

[0142] In an embodiment of the present invention, 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.

[0143] In an embodiment of the present invention, the photopolymerizable monomer is a methacrylate monomer and / or an acrylate monomer.

[0144] In an embodiment of the present invention, the photoinitiator is a 2,4,5-triaryl imidazole dimer.

[0145] In an embodiment of the present invention, the weight average molecular weight of the alkali-soluble resin is 20,000 to 60,000.

[0146] In an embodiment of the present invention, the acid value of the alkali-soluble resin is 160-220 mg KOH / g.

[0147] In an embodiment of the present invention, the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0148] In an embodiment of the present invention, the comonomers used to synthesize the alkali-soluble resin contain 50-70% by mass of comonomers having aromatic groups. Under such conditions, the resolution and chemical resistance of the product can be improved to a certain extent.

[0149] In an embodiment of the present invention, 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.

[0150] In an embodiment of the present invention, 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.

[0151] In an embodiment 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, an inhibitor, a defoaming agent, and a coating aid.

[0152] An embodiment of the present invention further provides a photosensitive dry film comprising a base layer, a photosensitive resist layer and a protective layer arranged in sequence; the photosensitive resist layer comprises the diepoxyalkoxyanthracene photosensitizer and / or the photocurable resin composition.

[0153] In some embodiments of the present invention, the base layer is a PET layer.

[0154] In some embodiments of the present invention, the protective layer is a PE layer.

[0155] The embodiments of the present invention also provide the use of one or more of the diepoxyalkoxyanthracene 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 packaging substrate.

[0156] Due to their unique structure, anthracene compounds or anthracene derivatives can dimerize under the influence of light, resulting in photobleaching. This property effectively avoids the problem of excessive energy absorption by the upper photosensitizer during exposure, allowing the underlying photosensitive resin composition to more fully absorb light, resulting in uniform curing of the photosensitive resin composition during exposure and achieving superior resolution. However, the present invention discovered that the CO bond at the 9,10 position of the 9,10-dialkoxyanthracene photosensitizer breaks upon exposure, causing the anthracene ring to dimerize and release small alkoxy fragments. These small fragments can migrate from the cured photosensitive resin composition into the plating solution during the subsequent electroplating process, causing contamination and affecting the plating solution life and plating results.

[0157] Based on the parent structure of the alkoxyanthracene of the present invention, an ethylene oxide functional group is introduced. This functional group can undergo ring-opening curing in the presence of an imidazole compound, thereby greatly reducing the possibility of photosensitizer fragment migration after photoinitiation and reducing the contamination of the electroplating solution by precipitates after curing; thereby improving the yield of downstream products.

[0158] The photosensitizer provided by this invention has an anthracene ring structure with alkoxy groups containing ethylene oxide substituents at the 9 and 10 positions. Compared to existing 9,10-dibutyloxyanthracene (DBA) photoinitiators, the introduction of ethylene oxide functional groups in this invention allows the photosensitizer to undergo ring-opening polymerization at a certain temperature, preventing the release of small alkoxy fragments. This significantly reduces the migration of initiator fragments and contamination of electroplating solutions while maintaining the efficiency of the photosensitizer in catalytic curing reactions. It can be widely used in photocuring applications such as dry films, paints, coatings, inks, and molding materials.

[0159] According to the embodiments of the present application, in the compound used as a photosensitizer, oxygen atoms are introduced into the 9,10-positions of the anthracene ring to enhance the photosensitivity. 3The group can improve the flexibility of the photosensitizer and the dispersion stability in the photosensitive resin composition, while avoiding the R 2 The group affects the electrical properties of the oxygen atoms at positions 9 and 10 of the anthracene ring. 2 The group has high compatibility with alkali-soluble resins and photopolymerizable monomers. The fragments cleaved after exposure are not easy to migrate and precipitate. In addition, due to the rigid planar structure of the anthracene ring, by introducing R 1 groups, which can further enhance its solubility.

[0160] Based on the above specific R 1 , R 2 and R 3 The photosensitizer of the present invention can effectively improve the photosensitivity of the photosensitive resin composition through the synergistic effect. The sidewalls of the resist pattern formed after curing are smooth and the cross section is a regular rectangular shape, which causes little pollution to the plating solution during the electroplating process.

[0161] Based on the reasons mentioned above, the photosensitive dry film provided by the present invention has excellent resolution and adhesion. Compared with the photosensitive resin composition with the addition of photosensitizers such as benzophenone or Michler's ketone, it has higher sensitivity, which is beneficial to improving client production efficiency and meeting the needs of high-density and high-precision printed circuit boards.

[0162] Example

[0163] The following examples describe the present disclosure in more detail and are intended to be illustrative only, as various modifications and variations within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise stated, all parts, percentages, and ratios reported in the following examples are by weight. Unless otherwise stated, all reagents used in the examples are available through conventional commercial sources or synthesized according to conventional methods and can be used directly without further processing. Unless otherwise stated, all instruments used in the examples are available through conventional commercial sources.

[0164] (1) Preparation of photocurable resin composition

[0165] Seven examples and three comparative examples were provided. Referring to the formulation shown in Table 1, the components were uniformly mixed to prepare a photocurable resin composition. The data in Table 1 are in parts by mass, and "-" means no addition.

[0166] The composition and specific information of each component code in Table 1 are as follows:

[0167] Alkali-soluble resin (A)

[0168] A1: Acrylate copolymer, solution polymerization, methacrylic acid / butyl methacrylate / benzyl methacrylate = 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.);

[0169] A2: Acrylate copolymer, solution polymerization, methacrylic acid / ethyl methacrylate / styrene = 30 / 20 / 50 by mass; solvent: acetone; solids content: 47%, weight-average molecular weight: 55,000, dispersity: 2.3, acid value: 195 mgKOH / g (Hunan Chuyuan New Materials Co., Ltd.);

[0170] A3: Acrylate copolymer, solution polymerization, mass ratio of methacrylic acid / ethyl methacrylate / benzyl methacrylate / styrene = 32 / 9 / 34 / 25; solvent: acetone, solid content 47%, weight-average molecular weight 25,000, dispersity 1.9, acid value 208 mgKOH / g (Hunan Chuyuan New Materials Co., Ltd.).

[0171] Photopolymerizable monomer (B)

[0172] B1: 2-(Propoxy)nonylphenol acrylate (Sartomer Guangzhou Chemical Co., Ltd.);

[0173] B2: 8-(ethoxy)nonylphenol acrylate (Sartomer Guangzhou Chemical Co., Ltd.);

[0174] B3: 10-(ethoxy)bisphenol A dimethacrylate (Sartomer Guangzhou Chemical Co., Ltd.);

[0175] B4: 20 (ethoxy) bisphenol A diacrylate (Sartomer Guangzhou Chemical Co., Ltd.);

[0176] B5: polypropylene glycol (400) diacrylate (Sartomer Guangzhou Chemical Co., Ltd.);

[0177] B6: 3(ethoxy)trimethylolpropane triacrylate (Sartomer Guangzhou Chemical Co., Ltd.);

[0178] B7: 4-(Ethoxy)pentaerythritol tetraacrylate (Sartomer Guangzhou Chemical Co., Ltd.).

[0179] Photoinitiator (C)

[0180] C: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-biimidazole (BCIM).

[0181] Photosensitizer (D)

[0182] D1: 9,10-di-(1,2-epoxypropoxy)anthracene (TM-1);

[0183] D2: 9,10-di-(1,2-epoxypropoxy)-2-ethylanthracene (TM-2);

[0184] D3: 9,10-di-(1,2-epoxypropoxy)-2-chloroanthracene (TM-3);

[0185] D4: 9,10-di-(1,2-epoxypentyloxy)anthracene (TM-4);

[0186] D5: 9,10-dibutoxyanthracene (Shanghai Haohong Biopharmaceutical Technology Co., Ltd.);

[0187] D6: 9,10-diphenylanthracene (Shanghai Haohong Biopharmaceutical Technology Co., Ltd.).

[0188] Additives (E)

[0189] E1: Leuco crystal violet (Annaiji Chemical);

[0190] E2: Malachite green (Annaiji Chemical);

[0191] E3 p-toluenesulfonamide (Annaiji Chemical);

[0192] E4: 2,6-di-tert-butyl-4-methylphenol (Annaiji Chemical);

[0193] E4: 5-Carboxybenzotriazole (Annaiji Chemical).

[0194] Table 1 Formulations of the photocurable resin compositions of various examples and comparative examples

[0195] ;

[0196] (2) Preparation of photosensitive dry film

[0197] The photosensitive dry films were prepared using the photocurable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 as raw materials, respectively, including the following steps:

[0198] The prepared photocurable resin composition slurry was coated on a 15 μm thick polyethylene terephthalate (PET) support film using experimental equipment (model: AB4220, TQC, the Netherlands). The film was baked at 80°C for 10 minutes to remove the solvent. 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 a photosensitive dry film.

[0199] Before coating, acetone solvent can be added to the photocurable resin composition to adjust it to an appropriate viscosity for coating. The solvent will be removed after baking and will not affect the composition of the photosensitive dry film.

[0200] (3) Preparation of substrate with resist pattern

[0201] Substrates with resist patterns were prepared using the photocurable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 as raw materials, respectively, in the following steps:

[0202] (1) Photosensitive layer forming step: forming a photosensitive layer on a substrate using a photosensitive composition;

[0203] (2) Exposure step: irradiating at least a portion of the photosensitive layer with active light to photocuring the region to form a cured product region;

[0204] (3) Development step: removing at least a portion of the photosensitive layer except for the cured product region from the substrate to form a resist pattern on the substrate.

[0205] The operating conditions of each step are described in detail below.

[0206] 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.

[0207] 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.

[0208] 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.

[0209] (IV) Testing and Evaluation

[0210] (1) Photosensitizer solubility test

[0211] Using acetone and toluene as representative solvents, the solubility of photosensitizers D1-D4 in Examples 1-4 in each gram of the corresponding solvents was tested, and D5-D6 in Comparative Examples 1-2 were used as comparisons. The test results are shown in Table 2.

[0212] Table 2 Test results of photosensitizer solubility performance

[0213]

[0214] (2) Sensitivity evaluation

[0215] 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.

[0216] (3) Adhesion evaluation

[0217] 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.

[0218] (4) Resolution evaluation

[0219] On the above-described post-filming test substrate, using photomask data with a wiring pattern with a line / space width of n:n (unit: μm), exposure was performed at an energy level that resulted in 16 remaining steps after development using a Stouffer 41-step scale. After the development process, the resist pattern was observed using an optical microscope, and adhesion (μm) was evaluated using the minimum line width that formed a complete cured resist line. A smaller value indicates better resolution.

[0220] (5) Evaluation of electroplating resistance

[0221] On the above-mentioned film-attached test substrate, a photomask with a wiring pattern of line / space widths of 2 / 2 to 6 / 6 (unit: mil) was used, and exposure was performed at an energy level that resulted in 16 residual steps after development of the Stouffer 41-step exposure scale. After the development process, copper plating pretreatment was performed in the following order: immersion in a degreasing solution (Baikal M404, 10%) for 10 minutes (40°C) → water washing for 1 minute → micro-etching (4% sodium thiosulfate solution) for 1 minute → pickling in dilute sulfuric acid (10%) for 1 minute. The substrate was then placed in a copper sulfate electroplating solution (copper sulfate 75g / L, sulfuric acid 110g / L, chloride ion 50ppm, tank opener 680 7mL / L) at room temperature and 3.0 A / dm 2 Copper plating was performed for 30 minutes under 40°C. Afterwards, the tin plating pre-treatment was carried out in the order of water washing for 1 minute → methanesulfonic acid (10%) pickling for 1 minute. Then, the tin plating was carried out in a stannous methanesulfonate electroplating solution (stannous methanesulfonate 170mL / L, B14WA14 wetting agent 70mL / L, B14 BR14 wetting agent 3mL / L, B14 RX14 wetting agent 3mL / L, SB stabilizer) at 22°C and 2.0 A / dm 2 Tin plating was performed for 20 minutes at room temperature, followed by water washing → film stripping (4.0% sodium hydroxide solution, 55°C) → water washing → drying. Furthermore, after the resist was stripped, the copper plated metal was observed from above using an optical microscope to see if it had penetrated. A section was prepared and confirmed using a scanning electron microscope to see if there had been any penetration. The evaluation results are shown as follows:

[0222] ■ Represents no permeation phenomenon;

[0223] ○ represents slight permeation;

[0224] × indicates severe permeation.

[0225] (6) Evaluation of electroplating pollution

[0226] The dry film resist sample after exposure (exposure grid number 16 grids) was measured at 0.8m 2 / L is dissolved in copper sulfate electroplating solution, soaked at room temperature for 24 hours, and the dry film resist is filtered out to obtain the sample to be tested. The organic carbon content (TOC) of the electroplating solution sample to be tested is measured using the high-temperature catalytic combustion oxidation method, and the electroplating solution sample without the resist sample is used as a blank sample. The larger the measured organic carbon content (TOC) value, the greater the contamination of the electroplating solution. The evaluation results are expressed as:

[0227] ■ Indicates that after deducting blank, TOC value is less than 500ppm;

[0228] ○ means after deducting blank, 500ppm>TOC value<1000ppm;

[0229] × indicates that after deducting the blank, the TOC value is greater than 1000 ppm.

[0230] (7) Resist shape evaluation

[0231] In the resist pattern used for the above resolution evaluation, the portion with the best resolution was observed using a SU1000 scanning electron microscope (manufactured by Hitachi). The evaluation results are shown as follows:

[0232] ■ The difference between the top and bottom widths of the resist front cross section is less than or equal to 0.8 μm, and the inverted trapezoid is basically not observed;

[0233] ○ represents that the difference between the top and bottom widths 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;

[0234] × represents that the difference between the top and bottom widths of the resist front cross section is greater than or equal to 1.2 μm, and the cross section is clearly inverted trapezoidal.

[0235] (8) Evaluation of photosensitizer dispersion stability

[0236] The prepared photosensitive dry film was stored in a dark place at 25°C for 2 weeks. The surface of the photosensitive layer was observed under a microscope and graded as follows:

[0237] ■ represents a uniform surface of the photosensitive layer;

[0238] × represents undissolved matter precipitated on the surface of the photosensitive layer.

[0239] The test results of evaluation items 2 to 8 are summarized in Table 3 below.

[0240] Table 3 Test results of evaluation items 2 to 8 of the examples and comparative examples

[0241]

[0242] The test results in Table 2 show that the solubility of the photosensitizers D1-D4 in various solvents is significantly superior to that of 9,10-dibutoxyanthracene and 9,10-diphenylanthracene, and their low mobility allows for more uniform dispersion in the photosensitive resin composition, making it easier to form fine circuits during exposure. The test results in Table 3 further demonstrate this trend. The photosensitive resin compositions prepared in Examples 1-7 exhibit excellent performance in various aspects, including sensitivity, adhesion, resolution, electroplating contamination resistance, resist shape, and dispersion stability. Examples 5-7, despite adjusting the types and proportions of the components, still achieve good performance, demonstrating the broad applicability of the photosensitizers of the present invention and their ability to be used with a variety of raw materials.

[0243] In contrast, the 9,10-dibutoxyanthracene used in Comparative Examples 1 and 3 has poor solubility and poor photosensitivity. In order to achieve a sensitivity comparable to that of the embodiment, at least 25% of photosensitizer needs to be added. In addition, the small molecule fragments generated after exposure are easy to migrate, resulting in serious contamination of the electroplating solution during the electroplating process. Although the 9,10-diphenylanthracene used in Comparative Example 2 does not have the problem of electroplating solution contamination, its solubility is even worse. Due to its rigid structure, its dispersion stability in the photosensitive resin composition is poor. Comparative Examples 1 to 3 all have incomplete bottom curing during exposure, and are prone to forming an inverted trapezoidal resist shape. The photosensitizer of the present invention significantly overcomes these problems.

[0244] The above contents are only preferred embodiments of the present invention and are not intended to limit the present invention. Those skilled in the art may make various modifications and changes within the spirit and principles of the present invention. Any changes, equivalent substitutions or improvements within this scope shall be deemed to be covered by the scope of protection of the present invention.

Claims

1. A photocurable resin composition, characterized in that Calculated by mass, it includes 50-65 parts of alkali-soluble resin, 35-50 parts of photopolymerizable monomer, 2-5 parts of photoinitiator, and 0.1-1 part of photosensitizer; The alkali-soluble resin is obtained by copolymerizing one or more of methacrylic acid, acrylic acid, alkyl methacrylate, alkyl acrylate, benzyl methacrylate, benzyl acrylate, phenyl methacrylate, phenyl acrylate, and styrene; The photopolymerizable monomer is a monomer having an ethylenically unsaturated double bond; The photoinitiator is a 2,4,5-triaryl imidazole dimer; The photosensitizer is a diepoxyalkoxyanthracene photosensitizer comprising one or a combination of two or more of the following components: 、 、 、 。 2. The photocurable resin composition according to claim 1, wherein The photocurable resin composition contains 55 to 60 parts of alkali-soluble resin by mass; the photocurable resin composition contains 40 to 49 parts of photopolymerizable monomer by mass; the photocurable resin composition contains 2.2 to 4 parts of photoinitiator by mass; and the photocurable resin composition contains 0.2 to 0.8 parts of photosensitizer by mass. 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.

3. The photocurable resin composition according to claim 1 or 2, wherein 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; and among the comonomers used to synthesize the alkali-soluble resin, the comonomers having aromatic groups account for 50 to 70% by mass.

4. The photocurable resin composition according to claim 1 or 2, 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.

5. The photocurable resin composition according to claim 1 or 2, wherein 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.

6. The photocurable resin composition according to claim 1 or 2, characterized in that The invention also contains 0.5 to 5.0 parts by mass of additives, wherein the additives are one or more of a dye, a photochromic agent, a plasticizer, an adhesion promoter, a polymerization inhibitor, a defoaming agent, and a coating auxiliary agent.

7. A photosensitive dry film, characterized in that: The invention comprises a base layer, a photosensitive resist layer and a protective layer arranged in sequence; the photosensitive resist layer comprises the photocurable resin composition according to any one of claims 1 to 6.

8. Use of one or more of the photocurable resin composition according to any one of claims 1 to 6 and the photosensitive dry film according to claim 7 in a substrate with a resist pattern, a printed circuit board, a lead frame, or a semiconductor package substrate.

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