Anthracene methylphenthiazide for use in photosensitive resin compositions and its applications

Abstract

This invention provides anthracene methylphenthiazide for use in photosensitive resin compositions, relating to the field of photopolymerization. The invention also includes photosensitive resin compositions containing the anthracene methylphenthiazide, photosensitive dry films containing the anthracene methylphenthiazide, and their applications. The anthracene methylphenthiazide of this invention is photosensitizing and can be used as a photosensitizer in photosensitive resin compositions. It also enhances the adhesion of photosensitive resin compositions to various metal surfaces and exhibits low migration characteristics; it can be widely used in photocuring fields such as dry films, paints, coatings, inks, and molding materials.

Description

Technical Field

[0001] This invention relates to the field of photopolymerization, and more specifically to anthracene methylphenthiazide for use in photosensitive resins and its applications. Background Technology

[0002] Photosensitive resin compositions are key materials for pattern transfer and are an important component of photosensitive dry films (or dry film resists). In pattern transfer, the dry film resist is first bonded to a copper substrate, and a mask with a specific pattern is used to cover the resist for exposure. Then, a weakly alkaline aqueous solution is used as a developer to remove unexposed areas, followed by etching or electroplating to form the pattern. Finally, a stripping solution is used to remove the cured dry film, thus achieving pattern transfer. This technology is widely used in the manufacture of printed circuit boards (PCBs), lead frames (LFs), and semiconductor packaging (IC) substrates.

[0003] For photosensitive resin compositions, a suitable photoinitiation system directly impacts photosensitivity, resolution, and production yield. As electronic devices become increasingly miniaturized and denser, the precision requirements for circuitry are constantly rising. To meet the demands of fine-line manufacturing, photosensitive resin compositions need to possess higher resolution and excellent adhesion to copper substrates. This ensures that the dry film remains intact on the copper-clad laminate substrate even after harsh processes such as development, electroplating, or etching, which involve high-pressure spraying and prolonged contact with corrosive chemicals. Therefore, effectively improving the resolution and adhesion of photosensitive resin compositions is of paramount importance. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the above-mentioned defects of the prior art and provide anthraquinone with photosensitivity that can improve the adhesion of photosensitive resin compositions to metal foil surfaces and its application.

[0005] The technical solution adopted by the present invention to solve its technical problem is as follows: an anthracene methylphenthiazide for use in photosensitive resin compositions, comprising...

[0006] , , ,

[0007] One or more of them.

[0008] Based on the same inventive concept, the present invention also provides a photosensitive resin composition, comprising, by weight, 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; wherein the photosensitizer comprises the aforementioned anthracene methylphenthiazide.

[0009] More preferably, the photosensitizer further includes one or more of 9,10-dibutoxyanthracene, 9,10-diacetoxyanthracene, and 9,10-diphenylanthracene.

[0010] Preferably, the alkali-soluble resin is an acrylate copolymer containing aromatic groups.

[0011] Preferably, the photopolymerization monomer is an olefinic unsaturated carboxylic acid and / or an olefinic unsaturated carboxylic acid ester.

[0012] Preferably, the photoinitiator is a diimidazole compound.

[0013] Preferably, in the comonomers used to synthesize the alkali-soluble resin, the comonomers having aromatic groups account for 50-70% by mass.

[0014] Preferably, the weight-average molecular weight of the alkali-soluble resin is 20,000 to 60,000.

[0015] Preferably, the acid value of the alkali-soluble resin is 160-220 mg KOH / g.

[0016] Preferably, the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0017] Preferably, the photopolymerization monomer is a methacrylate monomer and / or an acrylate monomer.

[0018] Preferably, the photoinitiator is a 2,4,5-triarylimidazolium dimer.

[0019] Preferably, the alkali-soluble resin is obtained by copolymerization of one or more of the following: acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, benzyl acrylate, benzyl methacrylate, benzyl acrylate derivatives, benzyl methacrylate derivatives, phenyl acrylate, phenyl methacrylate, styrene, and styrene derivatives.

[0020] Preferably, the photopolymerizable monomer is one or more of the following: 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.

[0021] Preferably, the photoinitiator is one or more of 2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(2-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(2-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2-methoxyphenyl)-4,5-diphenylimidazolium dimer, 2-(4-methoxyphenyl)-4,5-diphenylimidazolium dimer, and 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

[0022] Preferably, by weight, it comprises 55-60 parts of alkali-soluble resin, 40-49 parts of photopolymerizable monomer, 2.2-4 parts of photoinitiator, and 0.1-1 parts of photosensitizer.

[0023] Preferably, it also contains 0.5 to 5.0 parts by weight of additives; the additives are one or more of dyes, photochromic agents, plasticizers, adhesion promoters, polymerization inhibitors, defoamers, and coating aids.

[0024] Based on the same inventive concept, the present invention also provides a photosensitive dry film, comprising a support layer, a photosensitive resist layer and a protective layer disposed sequentially; the photosensitive resist layer comprises at least one of the anthracene methyl phenothiazine and the photosensitive resin composition.

[0025] Based on the same inventive concept, the present invention also provides the application of one or more of the anthraquinone phenothiazine, the photosensitive resin composition, and the photosensitive dry film in substrates with resist patterns, printed circuit boards, lead frames, semiconductor packaging substrates, solar cells, and photocurable inks.

[0026] The present invention has the following beneficial effects: the anthracene methyl phenothiazine of the present invention has photosensitivity and can be used as a photosensitizer in photosensitive resin compositions, and can improve the adhesion of photosensitive resin compositions to various metal surfaces, and has low migration characteristics; it can be widely used in the field of photocuring such as dry films, paints, coatings, inks and molding materials.

[0027] In addition to the objectives, features, and advantages described above, the present invention has other objectives, features, and advantages. The invention will now be described in further detail with reference to the accompanying drawings. Attached Figure Description

[0028] The accompanying drawings, which form part of this application, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0029] Figure 1 The TM1 manufactured in the embodiments of the present invention 1H-NMR spectrum;

[0030] Figure 2 The TM1 manufactured in the embodiments of the present invention 13 C-NMR spectrum;

[0031] Figure 3 It is the TM2 manufactured in the embodiment of the present invention. 1 H-NMR spectrum;

[0032] Figure 4 It is the TM2 manufactured in the embodiment of the present invention. 13 C-NMR spectrum;

[0033] Figure 5 It is the TM3 manufactured in the embodiment of the present invention. 1 H-NMR spectrum;

[0034] Figure 6 It is the TM3 manufactured in the embodiment of the present invention. 13 C-NMR spectrum:

[0035] Figure 7 It is the TM4 manufactured in the embodiment of the present invention. 1 H-NMR spectrum;

[0036] Figure 8 It is the TM4 manufactured in the embodiment of the present invention. 13 C-NMR spectrum:

[0037] Figure 9 These are the ultraviolet-visible absorption spectra of TM1~TM4 prepared according to the embodiments of the present invention. Detailed Implementation

[0038] To make the objectives, solutions, and beneficial technologies of this invention clearer, the invention will be further described in detail below with reference to embodiments and accompanying drawings. It should be noted that the embodiments described in this specification are merely illustrative of the invention and are not intended to limit the invention.

[0039] For simplicity, this paper only explicitly discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an undefined range; and any lower limit can be combined with other lower limits to form an undefined range, just as any upper limit can be combined with any other upper limit to form an undefined range. Furthermore, although not explicitly stated, every point or individual value between the endpoints of a range is included within that range. Therefore, each point or individual value can serve as its own lower or upper limit and be combined with any other point or individual value, or with other lower or upper limits, to form an undefined range.

[0040] In this description, it should be noted that, unless otherwise stated, "above" and "below" include the stated number, "multiple" in "one or more" means two or more, and "more than" in "one or more" means two or more.

[0041] Embodiments of the present invention provide anthracene methylphenthiazide for use in photosensitive resin compositions, comprising: (abbreviated as TM1) (abbreviated as TM2)

[0042] (abbreviated as TM3) (abbreviated as TM4)

[0043] One or more of them.

[0044] This invention discloses a photosensitive resin composition, comprising, by weight, 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 includes the aforementioned anthracene methylphenthiazide. The anthracene methylphenthiazide is photosensitizing and can be used as a photosensitizer. The "0.1-1 parts" of photosensitizer in the photosensitive resin composition refers to the total amount of anthracene methylphenthiazide and other photosensitizers.

[0045] When the content of alkali-soluble resin is too low, there is a tendency for the resist to flow into a laminar flow; when the content is too high, there is a tendency for the resolution to decrease.

[0046] When the content of photopolymer monomers is too low, there is a tendency for the sensitivity and chemical resistance of the photoresist to decrease. When the content is too high, the photosensitive resin composition is not easy to form a thin film, and the photoresist tends to flow into a laminar adhesive.

[0047] When the photoinitiator content is too low, there is a tendency for the sensitivity and resolution of the resist to decrease; when the content is too high, there is a tendency for more development debris to appear.

[0048] When the photosensitizer content is too low, the sensitivity of the resist tends to decrease. When the content is too high, the resist substrate tends to be incompletely cured, resulting in an "inverted trapezoidal" cross-sectional shape and poor resolution.

[0049] In some embodiments of the present invention, the photosensitizer further includes one or more of 9,10-dibutoxyanthracene, 9,10-diacetoxyanthracene, and 9,10-diphenylanthracene.

[0050] In an embodiment of the present invention, the alkali-soluble resin is an acrylate copolymer containing aromatic groups.

[0051] In embodiments of the present invention, the photopolymerization monomer is an olefinic unsaturated carboxylic acid and / or an olefinic unsaturated carboxylic acid ester.

[0052] In an embodiment of the present invention, the photoinitiator is a diimidazole compound.

[0053] In embodiments of the present invention, the comonomers used to synthesize the alkali-soluble resin contain 50-70% by mass of comonomers having aromatic groups.

[0054] In an embodiment of the present invention, the weight-average molecular weight of the alkali-soluble resin is 20,000 to 60,000.

[0055] In an embodiment of the present invention, the acid value of the alkali-soluble resin is 160-220 mg KOH / g.

[0056] In an embodiment of the present invention, the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0057] In embodiments of the present invention, the photopolymerization monomer is a methacrylate monomer and / or an acrylate monomer.

[0058] In an embodiment of the present invention, the photoinitiator is a 2,4,5-triarylimidazolium dimer.

[0059] In embodiments of the present invention, the alkali-soluble resin is obtained by copolymerization of one or more of the following: acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, benzyl acrylate, benzyl methacrylate, benzyl acrylate derivatives, benzyl methacrylate derivatives, phenyl acrylate, phenyl methacrylate, styrene, and styrene derivatives.

[0060] In embodiments of the present invention, the photopolymerizable monomer is one or more of the following: 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.

[0061] In embodiments of the present invention, the photoinitiator is one or more of 2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(2-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(2-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2-methoxyphenyl)-4,5-diphenylimidazolium dimer, 2-(4-methoxyphenyl)-4,5-diphenylimidazolium dimer, and 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

[0062] Typical diimidazole compounds, such as hexaaryldiimidazole (HABI), are representative of diimidazole photoinitiators. Their maximum absorption peak is located at 255–275 nm, and they are insensitive to long-wave ultraviolet light (such as 365 nm) and visible light. Another example is 2-(2-hydroxyphenyl)benzimidazole, which has absorption at 320–380 nm and can be matched with UV-A light sources (such as 365 nm LEDs), but is insensitive in the visible light region at 405 nm. This invention uses a photosensitizer to adjust the operating wavelength of diimidazole photoinitiators to around 405 nm.

[0063] In embodiments of the present invention, the product comprises, by weight, 55-60 parts of alkali-soluble resin, 40-49 parts of photopolymerizable monomer, 2.2-4 parts of photoinitiator, and 0.1-1 parts of photosensitizer.

[0064] In some embodiments of the present invention, the photosensitive resin composition containing the anthraquinone methylphenthiazide comprises 45 to 48 parts by weight of a photopolymerizable monomer (corresponding to 55 to 60 parts by weight of an alkali-soluble resin).

[0065] In some embodiments of the present invention, the photosensitive resin composition containing the anthraquinone phenothiazine comprises 2.5 to 3.5 parts by weight of a photoinitiator (corresponding to 55 to 60 parts by weight of an alkali-soluble resin).

[0066] In some embodiments of the present invention, the photosensitive resin composition containing the anthraquinone phenothiazine comprises 0.2 to 0.8 parts by weight of photosensitizer (corresponding to 55 to 60 parts by weight of alkali-soluble resin).

[0067] In embodiments of the present invention, it further contains 0.5 to 5.0 parts by weight of additives; the additives are one or more of dyes, photochromic agents, plasticizers, adhesion promoters, polymerization inhibitors, defoamers, and coating aids (corresponding to 50 to 65 parts by weight of alkali-soluble resin).

[0068] An embodiment of the present invention provides a photosensitive dry film, comprising a support layer, a photosensitive resist layer, and a protective layer disposed sequentially; the photosensitive resist layer comprises at least one of the anthracene methyl phenothiazine and the photosensitive resin composition.

[0069] The support layer material of the photosensitive dry film is PET.

[0070] The protective layer material of the photosensitive dry film is PE.

[0071] The application of one or more of the anthraquinone methyl phenothiazine, the photosensitive resin composition, and the photosensitive dry film described in the embodiments of the present invention in substrates with resist patterns, printed circuit boards, lead frames, semiconductor packaging substrates, solar cells, and photocurable inks.

[0072] Currently, the most commercially available anthracene photosensitizers are mainly of three types: 9,10-dibutoxyanthracene (DBA), 9,10-diphenylanthracene (DPHA), and 9,10-diacetoxyanthracene (DAcOA). Extensive experimental records and reports indicate that, in addition to the significant defect of insufficient adhesion, these photosensitizers also have the following shortcomings:

[0073] (1) 9,10-Dibutoxyanthracene photosensitizers, although they have advantages in solubility, will break the CO bond at the 9,10 position during exposure, and the anthracene ring will dimerize, releasing small molecule alkoxy fragments. These small molecule fragments will migrate from the cured photosensitive resin composition to the electroplating solution in the subsequent electroplating process, causing pollution, affecting the life of the plating solution and the electroplating effect.

[0074] (2) Although DPHA has the advantage of high photon yield, its solubility is poor due to the large size of the conjugated system, high molecular rigidity;

[0075] (3) Due to the electron-withdrawing induction effect of acyl groups, DAcOA leads to an increase in the electron cloud density of the 9th and 10th electrons of the anthracene ring. As a result, the efficiency of this type of photosensitizer decreases during the catalytic curing reaction. The sidewall verticality of the cured photosensitive resin composition is poor, and the difference in line length between the top and bottom is large, forming an "inverted trapezoid" problem. It cannot meet the needs of fine circuit manufacturing.

[0076] Compared to conventional anthracene photosensitizers, the anthracene methylphenthiazine of the present invention has the following advantages:

[0077] (1) Inhibit migration and crystallization: The anthracene group is flexibly linked by methyl groups, avoiding p-π conjugation caused by direct bonding and avoiding the breaking of carbon heterobonds, thereby inhibiting the migration of small molecule fragments and reducing the risk of penetration and diffusion into the PE film;

[0078] (2) Excellent adhesion: Phenothiazine is a five-membered ring containing nitrogen and sulfur atoms, which can exhibit excellent affinity with a variety of transition metals such as Pd, Pt, Cu, etc. This affinity can also greatly enhance the adhesion of such photosensitizers on metal foils, especially copper foils.

[0079] This invention achieves low migration and excellent adhesion simultaneously through molecular structure innovation, meeting the needs of high-precision, high-density, and multi-layered high-density circuit manufacturing.

[0080] Example

[0081] The following examples describe the disclosure of this invention in more detail. These examples are merely illustrative, as various modifications and variations will be apparent to those skilled in the art within the scope of this disclosure. 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 are available commercially or synthesized using conventional methods and are ready for use without further processing. Unless otherwise stated, all instruments used in the examples are available commercially.

[0082] (I) Preparation and detection of anthracene methylphenthiazide

[0083] (1) Preparation of TM1

[0084] The reaction formula for preparing TM1 can be written as:

[0085]

[0086] The specific preparation method of TM1 is as follows:

[0087] Under a nitrogen atmosphere, phenothiazine (1.5 mmol, 299 mg), 9-bromomethylanthracene (1 mmol, 271 mg), potassium carbonate (2 mmol, 276 mg), and tetrabutylammonium bromide (0.2 mmol, 64 mg) were added sequentially to a round-bottom flask equipped with a magnetic stirrer. Then, 5 mL of dry toluene was added to dissolve the mixture, and the mixture was stirred at room temperature until TLC monitoring showed that the 9-bromomethylanthracene feedstock was almost completely consumed. The reaction mixture was washed with water and extracted with dichloromethane, and the combined organic phases were dried over anhydrous Na2SO4. The crude product was separated by column chromatography to obtain a pale yellow solid TM1 (233 mg, yield 60%).

[0088] Figure 1 It's TM1. 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): δ 8.59 (s, 1H), 8.56 (s,1H), 8.48 (s, 1H), 8.21 (d, J = 8.59 Hz, 1H), 8.13 – 8.07 (m, 4H), 8.04 (d, J=9.21 Hz, 1H), 7.78 (d, J = 7.71 Hz, 2H), 7.59 – 7.44 (m, 5H), 7.35 (t, J = 8.72Hz, 2H).

[0089] Figure 2 It's TM1. 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ 131.8, 131.7, 130.6, 129.3, 127.4, 127.1, 126.7, 126.5, 126.1, 125.1, 124.8, 114.6, 32.7.

[0090] (2) Preparation of TM2

[0091] The reaction formula for preparing TM2 can be written as:

[0092]

[0093] The specific preparation method of TM2 is as follows:

[0094] Under a nitrogen atmosphere, 2-cyanophithiazine (1.5 mmol, 336 mg), 9-bromomethylanthracene (1 mmol, 271 mg), potassium carbonate (2 mmol, 276 mg), and tetrabutylammonium bromide (0.2 mmol, 64 mg) were added to a round-bottom flask equipped with a magnetic stirrer. Then, 5 mL of dry toluene was added to dissolve the mixture, and the mixture was stirred at room temperature until the 9-bromomethylanthracene feedstock was almost completely consumed by TLC. The reaction mixture was washed with water and extracted with dichloromethane. The organic phases were combined and dried over anhydrous Na2SO4. The crude product was separated by column chromatography to obtain a yellow solid TM2 (289 mg, yield 70%).

[0095] Figure 3 It's TM2. 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): δ 8.52 (d, J = 8.91 Hz, 2H),8.39 (s, 1H), 7.98 (d, J = 8.49 Hz, 2H), 7.58 (t, J = 6.84 Hz, 2H), 7.47 (t, J =8.08 Hz, 2H), 7.17 (d,J = 1.57 Hz, 1H), 7.13 – 6.95 (m, 5H), 6.91 (t, J = 7.56Hz, 1H).

[0096] Figure 4 It's TM2. 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ 145.2, 144.3, 133.5, 131.4, 131.0, 129.7, 129.1, 127.9, 127.8, 127.8, 127.0, 126.3, 125.7, 125.2, 124.8, 123.7, 123.6, 119.5, 118.6, 117.0, 110.3, 45.8.

[0097] (3) Preparation of TM3

[0098] The reaction formula for preparing TM3 can be written as:

[0099]

[0100] The specific preparation method of TM3 is as follows:

[0101] Under a nitrogen atmosphere, 2-acetylphenothiazine (1.5 mmol, 362 mg), 9-bromomethylanthracene (1 mmol, 271 mg), potassium carbonate (2 mmol, 276 mg), and tetrabutylammonium bromide (0.2 mmol, 64 mg) were added to a round-bottom flask equipped with a magnetic stirrer. Then, 5 mL of dry toluene was added to dissolve the mixture, and the mixture was stirred at room temperature until the 9-bromomethylanthracene feedstock was almost completely consumed by TLC. The reaction mixture was washed with water and extracted with dichloromethane. The organic phases were combined and dried over anhydrous Na2SO4. The crude product was separated by column chromatography to obtain a yellow solid TM3 (258 mg, yield 60%).

[0102] Figure 5 It's TM3. 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): δ 8.50 (s, 1H), 8.11 –8.04 (m, 4H), 7.57 – 7.46 (m, 4H), 7.37 (d, J = 8.01 Hz, 1H), 7.01 (d, J= 7.96Hz, 1H), 6.89 (s, 1H), 6.80 (d, J = 7.61 Hz, 1H), 6.54 (t, J = 7.69 Hz, 1H), 6.36(s, 1H), 6.30 (d, J = 7.65 Hz, 1H), 4.80 (s, 2H), 2.49 (s, 3H).

[0103] Figure 6 It's TM3. 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ 197.0, 141.5, 138.8, 136.3, 131.7, 130.6, 129.4, 128.4, 127.4, 126.5, 126.3, 126.0, 125.2, 125.0, 124.5, 124.2, 123.2, 122.5, 113.5, 29.7, 26.5.

[0104] (4) Preparation of TM4

[0105] The reaction formula for preparing TM4 can be written as:

[0106]

[0107] The specific preparation method of TM4 is as follows:

[0108] Under a nitrogen atmosphere, benzophenthiazide (1.5 mmol, 373 mg), 9-bromomethylanthracene (1 mmol, 271 mg), potassium hydroxide (2 mmol, 112 mg), and tetrabutylammonium bromide (0.2 mmol, 64 mg) were added to a round-bottom flask equipped with a magnetic stirrer. Then, 5 mL of dry toluene was added to dissolve the mixture, and the mixture was stirred at room temperature until the 9-bromomethylanthracene feedstock was almost completely consumed by TLC. The reaction mixture was washed with water and extracted with dichloromethane. The organic phases were combined and dried over anhydrous Na2SO4. The crude product was separated by column chromatography to obtain a yellow solid TM4 (307 mg, yield 70%).

[0109] Figure 7 It's TM4. 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): δ 8.65 (d, J= 8.99 Hz, 2H),8.31 (s, 1H), 7.93 (d, J = 8.46 Hz, 2H), 7.60 – 7.50 (m, 4H), 7.45 (t, J = 7.88Hz, 2H), 7.34 (s, 1H), 7.31 (d, J = 7.47 Hz, 1H), 7.25 – 7.18 (m, 2H), 7.17 (d, J = 7.51 Hz, 1H), 7.11 (d, J = 8.12 Hz, 1H), 6.98 (t, J = 6.98 Hz, 1H), 6.85 (t, J =7.39 Hz, 1H), 6.04 (s, 2H).

[0110] Figure 8 It's TM4. 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): δ 144.5, 142.8, 132.9, 131.3, 130.9, 130.1, 129.4, 128.6, 128.0, 127.6, 127.1, 127.0, 126.7, 126.4, 126.4, 125.8, 125.5, 125.3, 124.9, 124.2, 124.1, 122.6, 116.9, 112.5, 45.9.

[0111] (5) Ultraviolet-visible spectrum

[0112] The UV-Vis absorption spectra were measured on a Shimadzu UV-1900 UV-Vis spectrophotometer, using toluene as the solvent (photosensitizer concentration: 4). 10 -5 (mol / L). Calculate the molar extinction coefficient ε = A according to Beer-Lambert law. bn / c, where A bn ρ represents the absorbance of the UV-Vis absorption spectrum, and c represents the concentration (mol / L). The results are shown in Table 1. The UV-Vis spectra of the prepared TM1~TM4 are shown below. Figure 9 As shown.

[0113] Table 1. Molar extinction coefficients of TM1~TM4 and DBA

[0114]

[0115] As can be seen from the molar extinction coefficients in Table 1, the molar extinction coefficients of the anthraquinone methylphenthiazide of the present invention are comparable to those of DBA, proving that this type of photosensitizer has excellent photo-radical conversion ability.

[0116] (II) Preparation of photosensitive resin composition

[0117] Examples and comparative examples were set up. Examples 1-16 used TM1-TM4 as photosensitizers, while the comparative examples used DBA, DPHA, and DAcOA as photosensitizers, respectively. Referring to the formulations shown in Tables 2 and 3, the components were mixed evenly to prepare photosensitive resin compositions. The data in Tables 2 and 3 are in parts by mass; "-" indicates that no components were added.

[0118] The components and specific information of each component code in Tables 2 and 3 are as follows:

[0119] A: Alkali-soluble resin: acrylate copolymer, solution polymerization, by mass ratio, methacrylic acid / butyl methacrylate / benzyl methacrylate = 25 / 10 / 65; solvent is acetone, solid content 46%, weight average molecular weight 40000, dispersity 2.1, acid value 163mgKOH / g (Hunan Chuyuan New Materials Co., Ltd.).

[0120] B: The photopolymer monomer is composed of the following components (purchased from Sartoma Guangzhou Chemical Co., Ltd.): 5 parts of methoxy polyethylene glycol (350) monoacrylate, 20 parts of 10 (ethoxy) bisphenol A dimethacrylate, 5 parts of 6 (propoxy) bisphenol A dimethacrylate, 10 parts of 3 (ethoxy) trimethylolpropane triacrylate, and 4 parts of di (trimethylolpropane) tetraacrylate.

[0121] C: Photoinitiator: 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-diimidazole (BCIM), purchased from Jiuding Chemical;

[0122] D: Photosensitizers: DBA is 9,10-dibutoxyanthracene, DPHA is 9,10-diphenylanthracene, and DAcOA is 9,10-diacetoxyanthracene, all purchased from Leyan;

[0123] E: Additives: Composed of the following ingredients (purchased from Anaiji Chemical): 0.5 parts of leuco crystal violet, 0.05 parts of malachite green, 0.8 parts of p-toluenesulfonamide, and 0.03 parts of 2,6-di-tert-butyl-4-methylphenol;

[0124] Solvent: Composed of the following components: 8 parts acetone, 10 parts toluene, and 5 parts methanol.

[0125] Table 2 Formulations of the photosensitive resin compositions in Examples 1-12

[0126]

[0127] Table 3 Formulations of the photosensitive resin compositions of Examples 13-16 and Comparative Examples 1-3

[0128]

[0129] (III) Preparation of photosensitive dry film

[0130] Photosensitive dry films were prepared using the photosensitive resin compositions of Examples 1-16 and Comparative Examples 1-3 as raw materials, including the following steps:

[0131] Using experimental equipment (model: AB4220, TQC, Netherlands), the prepared photosensitive resin composition slurry was coated onto a 15μm thick polyethylene terephthalate (PET) support film; the solvent was removed by baking at 80℃ for 10min; after baking, the thickness of the photosensitive layer was controlled at 30μm, and then a polyethylene film (PE) was applied for protection to obtain a photosensitive dry film.

[0132] Before coating, acetone solvent can be added to the photosensitive resin composition to adjust it to a suitable viscosity for coating. The solvent will be removed after baking and will not affect the composition of the photosensitive dry film.

[0133] (iv) Preparation of substrates with resist patterns

[0134] Substrates with resist patterns were prepared using the photosensitive resin compositions of Examples 1-16 and Comparative Examples 1-3 as raw materials, and the procedures are as follows:

[0135] (1) Photosensitive layer formation process: A photosensitive layer is formed on a substrate using a photosensitive composition;

[0136] (2) Exposure process: At least a portion of the above photosensitive layer is irradiated with active light to photocur the above area to form a cured area;

[0137] (3) Development process: Remove at least a portion of the above photosensitive layer, excluding the cured area, from the substrate to form a resist pattern on the substrate.

[0138] The operating conditions for each process are explained in detail below.

[0139] Photosensitive layer formation process: Using a copper-clad laminate with a 35μm thick rolled 1.2mm thick copper foil, after surface adjustment and preheating to 80°C, while peeling off the PE protective film of the photosensitive dry film obtained from each embodiment or comparative example, the above-mentioned photosensitive resin composition is laminated onto the copper-clad laminate using a hot roller laminator (Zhisheng Technology Co., Ltd., CSL-M25E) at a roller temperature of 110°C, an air pressure of 0.35MPa, and a lamination speed of 1.5m / min to obtain a test substrate.

[0140] Exposure process: Exposure is performed using a direct drawing exposure machine (Xinge Microelectronics, main wavelength 405nm), and the sensitivity is tested using a Stouffer 41-level step exposure scale, with the number of exposure frames controlled between 14 and 18.

[0141] Development Process: After exposure, the PET support film is peeled off. Using an alkaline developer (manufactured by Guangzhou Julong Printed Circuit Board Equipment Co., Ltd., a dry film developer), a 1wt% Na₂CO₃ aqueous solution at 30°C is sprayed 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 using 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 for complete dissolution of the unexposed photosensitive resin layer.

[0142] (v) Evaluation Items

[0143] (1) Evaluation of photosensitivity

[0144] Photosensitivity evaluation tests were conducted on Examples 1-16 and Comparative Examples 1-3. A Stouffer 41-level segmented exposure scale was placed on the test substrate after the film was applied for photosensitivity testing. After the exposure process, the test substrate was left to stand for at least 20 minutes, then the PET film layer was peeled off, and a 1.0 wt% sodium carbonate aqueous solution was sprayed at 30°C to remove the unexposed resist layer. The development time was 2.0 times the minimum development time. After the above operations, a cured film obtained by curing the photosensitive resin composition was formed on the substrate surface. The exposure energy (mJ / cm²) when the number of residual segments on the segmented exposure scale obtained through the cured film was 16 segments was measured. 2 The photosensitivity of the photosensitive resin composition was evaluated, with a smaller value indicating better photosensitivity.

[0145] (2) Adhesion evaluation

[0146] Adhesion evaluation tests were conducted on Examples 1-16 and Comparative Examples 1-3. On the test substrates after film application, photomask data with a wiring pattern of linewidth / spacing width n:400 (unit: μm) was used to expose the substrates at an energy level that ensured a residual stage number of 16 after development using a Stouffer 41-stage exposure ruler. After the development process, the resist pattern was observed using an optical microscope. The minimum linewidth at which a complete cured resist line was formed was used as the adhesion value to evaluate adhesion (μm). The smaller this value, the better the adhesion.

[0147] (3) Evaluation of corrosion resist migration

[0148] The photoresist migration of Examples 1-16 and Comparative Examples 1-3 was evaluated. After the prepared three-layer photosensitive dry film was completed, the UV absorption spectrum of the dry film was detected using a UV spectrophotometer to obtain the absorbance A1 of the maximum absorption peak in the 350-450 nm range. The dry film was then placed at 30°C for 72 hours. After removing the PE film layer from the surface of the photosensitive dry film, the UV absorption spectra of the PET layer and the photoresist layer were detected using a UV spectrophotometer to obtain the absorbance A2 of the maximum absorption peak in the 350-450 nm range. If the sensitizer migrates to the surface of the PE layer, the absorbance of the maximum absorption peak in the 350-450 nm range of the PET layer and the photoresist layer will decrease, i.e., the absorbance of the sensitizer that migrated to the PE layer is (A1). - A2). Calculate the migration rate of the photosensitizer, i.e., migration rate A = (A1) / (A2). - The larger the value of A2 / A1, the greater the migration amount.

[0149] Basis for judgment:

[0150] ○: Mobility A < 0.01;

[0151] ×: Mobility A > 0.01.

[0152] The test results for each evaluation item are summarized in Tables 4 and 5 below.

[0153] Examples 1-12 used TM1-TM4 as photosensitizers and conducted experiments under different dosages.

[0154] The results in Table 4 show that TM1~TM4 exhibit excellent adhesion enhancement while significantly reducing migration rate.

[0155] Table 4 Test results of each evaluation item in Examples 1-12

[0156]

[0157] Examples 13-16 used TM1-TM4 as photosensitizers, while Comparative Examples 1-3 used DBA, DPHA, and DAcOA as photosensitizers, respectively, and the amount of photosensitizer used in the above cases was the same.

[0158] The results in Table 5 show that the photosensitive resin composition using anthraquinone phenothiazine as a photosensitizer of the present invention has lower exposure energy under the same mass concentration conditions, indicating that its photosensitivity is superior to DBA and DAcOA; in addition, the anthraquinone phenothiazine of the present invention shows advantages in terms of adhesion and migration.

[0159] Table 5. Test results of each evaluation item in Examples 13-16 and Comparative Examples 1-3

[0160]

[0161] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Those skilled in the art can make various modifications and alterations within the spirit and principles of the present invention, and any modifications, equivalent substitutions, or improvements within this scope should be considered as covered by the protection scope of the present invention.

Claims

1. Anthracene methylphenthiazide for use in photosensitive resin compositions, characterized in that: include , , , One or more of them.

2. A photosensitive resin composition, characterized in that, The product comprises, by weight, 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; wherein the photosensitizer comprises anthracene methylphenthiazide as described in claim 1.

3. The photosensitive resin composition according to claim 2, characterized in that, The photosensitizer also includes one or more of 9,10-dibutoxyanthracene, 9,10-diacetoxyanthracene, and 9,10-diphenylanthracene.

4. The photosensitive resin composition according to claim 2 or 3, characterized in that, The alkali-soluble resin is an acrylate copolymer containing aromatic groups; the photopolymerization monomer is an olefin unsaturated carboxylic acid and / or an olefin unsaturated carboxylic acid ester; and the photoinitiator is a diimidazole compound.

5. The photosensitive resin composition according to claim 2 or 3, characterized in that, In the comonomers used to synthesize the alkali-soluble resin, the comonomers having aromatic groups account for 50-70% by mass; the weight-average molecular weight of the alkali-soluble resin is 20,000-60,000; the acid value of the alkali-soluble resin is 160-220 mg KOH / g; and the molecular weight distribution of the alkali-soluble resin is 1.0-3.

0. The photopolymerization monomer is a methacrylate monomer and / or an acrylate monomer; The photoinitiator is a 2,4,5-triarylimidazolium dimer.

6. The photosensitive resin composition according to claim 2 or 3, characterized in that, The alkali-soluble resin is obtained by copolymerization of two or more of the following: acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, and styrene. The photopolymerizable monomer is one or more of the following: methoxy polyethylene glycol monoacrylate, ethoxy(propoxy)nonylphenol acrylate, ethoxy(propoxy)bisphenol A di(meth)acrylate, ethoxy(propoxy)di(meth)acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxy(propoxy)trimethylolpropane tri(meth)acrylate, di(trimethylolpropane)tetraacrylate, ethoxy(propoxy)pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate. The photoinitiator is one or more of the following: 2-(2-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(2-chlorophenyl)-4,5-di(methoxyphenyl)imidazolium dimer, 2-(2-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2-methoxyphenyl)-4,5-diphenylimidazolium dimer, 2-(4-methoxyphenyl)-4,5-diphenylimidazolium dimer, and 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

7. The photosensitive resin composition according to claim 2 or 3, characterized in that, By weight, it includes 55-60 parts of alkali-soluble resin, 40-49 parts of photopolymerizable monomer, 2.2-4 parts of photoinitiator, and 0.1-1 parts of photosensitizer.

8. The photosensitive resin composition according to claim 2 or 3, characterized in that, It also contains 0.5 to 5.0 parts by weight of additives; the additives are one or more of dyes, photochromic agents, plasticizers, adhesion promoters, polymerization inhibitors, and defoamers.

9. A photosensitive dry film, characterized in that, It includes a support layer, a photoresist layer and a protective layer arranged sequentially; the photoresist layer comprises at least one of the anthracene methyl phenothiazine as described in claim 1 or the photosensitive resin composition as described in any one of claims 2 to 8.

10. The use of one or more of the anthracene methyl phenothiazine as claimed in claim 1, the photosensitive resin composition of any one of claims 2 to 8, or the photosensitive dry film as claimed in claim 9 in substrates with resist patterns, printed circuit boards, lead frames, semiconductor packaging substrates, solar cells, and photocurable inks.

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