Anthracene methyl phenothiazine for photosensitive resin composition and application

Abstract

The invention provides anthracene methyl phenothiazine for a photosensitive resin composition, and relates to the field of photopolymerization. The invention further comprises a photosensitive resin composition containing the anthracene methyl phenothiazine, a photosensitive dry film containing the anthracene methyl phenothiazine and application of the photosensitive resin composition and the photosensitive dry film. The anthracene methyl phenothiazine disclosed by the invention has photosensitivity, can be used as a photosensitizer in the photosensitive resin composition, can improve the adhesive force of the photosensitive resin composition on various metal surfaces, and has the characteristic of low migration; the method can be widely applied to the photo-curing fields of dry films, paints, coatings, printing ink, forming materials and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of photopolymerization, in particular to an anthrylmethyl phenothiazine for photosensitive resin and application thereof. BACKGROUND

[0002] Photosensitive resin composition is a key material for pattern transfer; it is an important component of photosensitive dry film (or dry film resist). In the process of pattern transfer, first, the dry film resist is attached to the copper substrate, and a mask with a certain pattern is covered on the dry film resist for pattern exposure; then the unexposed part is removed by using weak alkaline aqueous solution as the developing solution, and etching or plating treatment is carried out to form a pattern; finally, the dry film solidified part is removed by stripping with a stripping solution, thereby realizing pattern transfer. This technology is widely used in the fields of printed circuit board (PCB), lead frame (LF) and semiconductor packaging (IC) substrate printed circuit board manufacturing.

[0003] For photosensitive resin composition, a suitable photoinitiating system has a direct impact on photosensitivity, resolution and production yield. With the development of electronic devices towards miniaturization and high density, the fineness of the circuit is continuously improved. In order to meet the needs of fine line manufacturing, photosensitive resin composition needs to have higher resolution and excellent adhesion on copper substrate to ensure that the dry film remains intact after the harsh process of developing, plating or etching, which involves high-pressure spraying and long-time contact with corrosive chemicals. Therefore, how to effectively improve the resolution and adhesion of photosensitive resin composition is of great significance. SUMMARY

[0004] The technical problem to be solved by the present application is to overcome the above-mentioned defects existing in the prior art, and to provide an anthrylmethyl phenothiazine with photosensitivity and adhesion on metal foil surface and application thereof.

[0005] The technical scheme adopted by the present application to solve the technical problem is as follows: an anthrylmethyl phenothiazine for photosensitive resin composition, comprising 、 、 、

[0006] one or more of the above.

[0007] Based on the same inventive concept, the present application also provides a photosensitive resin composition, comprising, by mass fraction, 50-65 parts of alkali-soluble resin, 35-50 parts of photopolymerization monomer, 2-5 parts of photoinitiator, and 0.1-1 part of photosensitizer; the photosensitizer comprises the anthrylmethyl phenothiazine.

[0008] More preferably, the photosensitizer further includes one or two or more of 9,10-dibutoxyanthracene, 9,10-diacetoxyanthracene, 9,10-diphenylanthracene.

[0009] Preferably, the alkali-soluble resin is an acrylic ester copolymer including an aromatic group.

[0010] Preferably, the photopolymerization monomer is an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid ester.

[0011] Preferably, the photoinitiator is a bis-imidazole compound.

[0012] Preferably, among the comonomers used to synthesize the alkali-soluble resin, the comonomer having an aromatic group accounts for 50 to 70% by mass.

[0013] Preferably, the weight average molecular weight of the alkali-soluble resin is 20,000 to 60,000.

[0014] Preferably, the acid value of the alkali-soluble resin is 160 to 220 mg KOH / g.

[0015] Preferably, the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0016] Preferably, the photopolymerization monomer is a methacrylate monomer and / or an acrylate monomer.

[0017] Preferably, the photoinitiator is a 2,4,5-triaryl imidazole dimer.

[0018] Preferably, the alkali-soluble resin is obtained by copolymerization of one or two or more of acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, benzyl acrylate, benzyl methacrylate, benzyl acrylate derivative, benzyl methacrylate derivative, phenyl acrylate, phenyl methacrylate, styrene, and styrene derivative.

[0019] Preferably, the photopolymerization monomer is one or two or more of methoxypolyethylene glycol monoacrylate, ethoxy(propoxy) nonylphenol acrylate, ethoxy(propoxy) bisphenol A di(meth)acrylate, ethoxy(propoxy) di(meth)acrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, ethoxy(propoxy) trimethylolpropane tri(meth)acrylate, di(trimethylolpropane) tetraacrylate, ethoxy(propoxy) pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0020] 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, 2,2',4-tri(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole.

[0021] Preferably, the composition comprises 55-60 parts by mass of the alkali-soluble resin, 40-49 parts by mass of the photopolymerizable monomer, 2.2-4 parts by mass of the photoinitiator, and 0.1-1 part by mass of the photosensitizer.

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

[0023] Based on the same inventive concept, the present application further provides a photosensitive dry film comprising a support layer, a photosensitive resist layer, and a protective layer arranged in sequence; the photosensitive resist layer comprises at least one of the anthrylmethylphenothiazine and the photosensitive resin composition.

[0024] Based on the same inventive concept, the present application further provides the use of one or more of the anthrylmethylphenothiazine, the photosensitive resin composition, and the photosensitive dry film in a substrate with a resist pattern, a printed circuit board, a lead frame, a semiconductor packaging substrate, a solar cell, and a photocured ink.

[0025] The anthrylmethylphenothiazine of the present application has photosensitivity, can be used as a photosensitizer in a photosensitive resin composition, and can improve the adhesion of the photosensitive resin composition to various metal surfaces and has low migration characteristics, and can be widely used in the field of photocuring such as dry films, paints, coatings, inks, and molding materials.

[0026] In addition to the objects, features, and advantages described above, the present application has other objects, features, and advantages. The present application will be further described in detail with reference to the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0027] The accompanying drawings, which form a part of this application, are included to provide a further understanding of the application, illustrate embodiments of the present application and assist in Figure 1 is a H-NMR chart of TM1 prepared in an embodiment of the present application 1 H-NMR chart Figure 2 is the UV-Vis absorption spectrum of TM1 prepared in the embodiment of the present application. 13 H-NMR chart of TM1 prepared in the embodiment of the present application. Figure 3 is the UV-Vis absorption spectrum of TM2 prepared in the embodiment of the present application. 1 H-NMR chart of TM2 prepared in the embodiment of the present application. Figure 4 is the UV-Vis absorption spectrum of TM2 prepared in the embodiment of the present application. 13 H-NMR chart of TM2 prepared in the embodiment of the present application. Figure 5 is the UV-Vis absorption spectrum of TM3 prepared in the embodiment of the present application. 1 H-NMR chart of TM3 prepared in the embodiment of the present application. Figure 6 is the UV-Vis absorption spectrum of TM3 prepared in the embodiment of the present application. 13 H-NMR chart of TM3 prepared in the embodiment of the present application. Figure 7 is the UV-Vis absorption spectrum of TM4 prepared in the embodiment of the present application. 1 H-NMR chart of TM4 prepared in the embodiment of the present application. Figure 8 is the UV-Vis absorption spectrum of TM4 prepared in the embodiment of the present application. 13 H-NMR chart of TM4 prepared in the embodiment of the present application. Figure 9 is the UV-Vis absorption spectrum of TM1~TM4 prepared in the embodiment of the present application. DETAILED DESCRIPTION

[0028] In order to make the objects, technical schemes and beneficial technical of the present application clearer, the present application will be further described in detail below with embodiments and drawings. It should be pointed out that the embodiments described in the present specification are only for explaining the present application, and are not intended to limit the present application.

[0029] For the sake of simplicity, only some numerical ranges are explicitly recited herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recited; and any lower limit can be combined with any other lower limit to form a range not explicitly recited, as can any upper limit with any other upper limit. Further, although not explicitly recited, every point or individual number within a range is included in the range. Thus, every point or individual number can serve as its own lower or upper limit to form a range not explicitly recited.

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

[0031] The embodiment of the present application provides an anthrylmethyl phenothiazine for a photosensitive resin composition, comprising TM1, TM2, TM3, TM4 one or more of 9,10-dibutoxyanthracene, 9,10-diacetoxyanthracene, and 9,10-diphenylanthracene.

[0032] The photosensitive resin composition according to an embodiment of the present application comprises, by mass, 50-65 parts of alkali-soluble resin, 35-50 parts of photopolymerization monomer, 2-5 parts of photoinitiator, and 0.1-1 part of photosensitizer. The photosensitizer comprises anthrylmethylphenothiazine. The anthrylmethylphenothiazine has photosensitivity and can be used as a photosensitizer. The "0.1-1 part" of photosensitizer contained in the photosensitive resin composition refers to the total amount of anthrylmethylphenothiazine and other photosensitizers.

[0033] When the content of alkali-soluble resin is too low, the resist layer tends to flow. When the content is too high, the resolution tends to decrease.

[0034] When the content of photopolymerization monomer is too low, the sensitivity and chemical resistance of the resist tend to decrease. When the content is too high, the photosensitive resin composition tends to be difficult to filmize and the resist layer tends to flow.

[0035] When the content of photoinitiator is too low, the sensitivity and resolution of the resist tend to decrease. When the content is too high, the amount of development waste tends to increase.

[0036] When the content of photosensitizer is too low, the sensitivity of the resist tends to decrease. When the content is too high, the bottom layer of the resist tends to be incompletely cured, resulting in a "reversed trapezoidal" cross-sectional shape of the resist and poor resolution.

[0037] In some embodiments of the present application, the photosensitizer further comprises one or more of 9,10-dibutoxyanthracene, 9,10-diacetoxyanthracene, and 9,10-diphenylanthracene.

[0038] In embodiments of the present application, the alkali-soluble resin is an acrylic ester copolymer comprising aromatic groups.

[0039] In embodiments of the present application, the photopolymerization monomer is an olefinically unsaturated carboxylic acid and / or an olefinically unsaturated carboxylic acid ester.

[0040] In embodiments of the present application, the photoinitiator is a bis-imidazole compound.

[0041] In embodiments of the present application, the copolymerization monomer used to synthesize the alkali-soluble resin comprises, by mass, 50-70% of copolymerization monomers having aromatic groups.

[0042] In the embodiment of the present application, the weight average molecular weight of the alkali-soluble resin is 20,000 to 60,000.

[0043] In the embodiment of the present application, the acid value of the alkali-soluble resin is 160 to 220 mg KOH / g.

[0044] In the embodiment of the present application, the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0045] In the embodiment of the present application, the photopolymerization monomer is a methacrylate monomer and / or an acrylate monomer.

[0046] In the embodiment of the present application, the photoinitiator is a 2,4,5-triaryl imidazole dimer.

[0047] In the embodiment of the present application, the alkali-soluble resin is obtained by copolymerization of one or two or more of acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, benzyl acrylate, benzyl methacrylate, benzyl acrylate derivative, benzyl methacrylate derivative, phenyl acrylate, phenyl methacrylate, styrene, and styrene derivative.

[0048] In the embodiment of the present application, the photopolymerization monomer is one or two or more of methoxy polyethylene glycol monoacrylate, ethoxy (propoxy) nonyl phenol 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.

[0049] In the embodiment of the present application, the photoinitiator is one or two or more of 2-(2-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(2-chlorophenyl)-4,5-di(methoxyphenyl) imidazole dimer, 2-(2-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(2-methoxyphenyl)-4,5-diphenyl imidazole dimer, 2-(4-methoxyphenyl)-4,5-diphenyl imidazole dimer, and 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole.

[0050] A typical bis-imidazole compound, such as hexaarylbiimidazole (HABI): as a representative of bis-imidazole photoinitiators, its maximum absorption peak is located at 255-275 nm, which is not sensitive to long-wave ultraviolet light (such as 365 nm) and visible light; for example, 2-(2-hydroxyphenyl) benzimidazole has an absorption at 320-380 nm, which can be matched with UV-A light sources (such as 365 nm LED), but is not sensitive in the visible light region at 405 nm. The present application can adjust the working wavelength of bis-imidazole photoinitiators to about 405 nm by using photosensitizer.

[0051] In an embodiment of the present application, the photosensitive resin composition contains 55-60 parts by mass of alkali-soluble resin, 40-49 parts by mass of photopolymerizable monomer, 2.2-4 parts by mass of photoinitiator, and 0.1-1 part by mass of photosensitizer.

[0052] In some embodiments of the present application, the photosensitive resin composition containing the anthrylmethylphenothiazine contains 45-48 parts by mass of photopolymerizable monomer (corresponding to 55-60 parts by mass of alkali-soluble resin).

[0053] In some embodiments of the present application, the photosensitive resin composition containing the anthrylmethylphenothiazine contains 2.5-3.5 parts by mass of photoinitiator (corresponding to 55-60 parts by mass of alkali-soluble resin).

[0054] In some embodiments of the present application, the photosensitive resin composition containing the anthrylmethylphenothiazine contains 0.2-0.8 parts by mass of photosensitizer (corresponding to 55-60 parts by mass of alkali-soluble resin).

[0055] In an embodiment of the present application, 0.5-5.0 parts by mass of additives are further contained; the additives are one or more of dyes, phototriggers, plasticizers, adhesion promoters, polymerization inhibitors, defoamers, and coating aids (corresponding to 50-65 parts by mass of alkali-soluble resin).

[0056] In an embodiment of the present application, a photosensitive dry film contains a support layer, a photosensitive resist layer, and a protective layer arranged in sequence; the photosensitive resist layer contains at least one of the anthrylmethylphenothiazine and the photosensitive resin composition.

[0057] The support layer material of the photosensitive dry film is PET.

[0058] The protective layer material of the photosensitive dry film is PE.

[0059] One or more of the anthrylmethylphenothiazine, the photosensitive resin composition, and the photosensitive dry film of the present application are used in substrates with resist patterns, printed circuit boards, lead frames, semiconductor packaging substrates, solar cells, and photocurable inks.

[0060] The products with high marketization degree of the existing anthracene photosensitizer mainly include 9,10-dibutoxyanthracene (DBA), 9,10-diphenylanthracene (DPHA) and 9,10-diacetoxyanthracene (DAcOA). A large number of experimental records and reports show that, in addition to the obvious defect of insufficient adhesion, the photosensitizers of the above-mentioned types also have the following defects: (1) The 9,10-dibutoxyanthracene photosensitizer, although having an advantage in solubility, the 9,10 C-O bond thereof will be broken during exposure, the anthracene ring will be dimerized, and small molecule alkoxy fragments will be released at the same time. The small molecule fragments will migrate from the solidified photosensitive resin composition to the plating solution in the subsequent plating process, causing pollution, affecting the service life of the plating solution and the plating effect; (2) The DPHA has the advantage of high light quantum yield, but due to the too large conjugated system and high rigidity of the molecule, the solubility is poor; (3) The DAcOA has the problem of decreased efficiency in catalytic curing reaction due to the electron-withdrawing induction effect of acyloxy group, and the solidified photosensitive resin composition has poor verticality of side wall and large difference between the length of top and bottom lines to form an inverted trapezoidal shape, which cannot meet the needs of fine line manufacturing; Compared with the conventional anthracene photosensitizer, the anthracene methyl phenothiazine of the present application has the following advantages: (1) Inhibition of migration and crystallization: the anthracene group is connected by a methyl group, avoiding p-π conjugation caused by direct bonding, avoiding the breakage of carbon hetero bond, thereby inhibiting the migration of small molecule fragments and reducing the risk of penetration and diffusion to the PE film; (2) Excellent adhesion: the phenothiazine system contains a five-membered ring of nitrogen and sulfur atoms, which can exhibit excellent affinity with various transition metals such as Pd, Pt, Cu, etc., and the affinity can greatly improve the adhesion of the photosensitizer on the surface of metal foil, especially copper foil; The present application simultaneously realizes low migration and excellent adhesion through molecular structure innovation, and meets the needs of high-density line manufacturing, high fineness, high density and multi-layer.

[0061] Examples The following examples more specifically describe the disclosure of the present application, which are only used for illustrative purposes, because various modifications and changes within the scope of the present disclosure are obvious to those skilled in the art. Unless otherwise stated, all parts, percentages and ratios reported in the following examples are based on weight. Unless otherwise stated, all reagents used in the examples can be obtained by conventional commercial channels or synthesized according to conventional methods, and can be used directly without further treatment. Unless otherwise stated, the instruments used in the examples can be obtained by conventional commercial channels.

[0062] (I) Preparation and detection of anthrylmethylphenothiazine (1) Preparation of TM1 The reaction formula for preparing TM1 can be written as:

[0063] The specific preparation method of TM1 is as follows: Under a nitrogen atmosphere, a round-bottom flask equipped with a magnetic stirrer was added 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) in sequence, and then dry toluene (5 mL) was added to dissolve the mixture, which was stirred at room temperature until the TLC monitoring showed that the 9-bromomethylanthracene raw material was substantially consumed completely. The reaction mixture was washed with water and dichloromethane in sequence, and the combined organic phase was dried over anhydrous Na2SO4. The crude product was separated by column chromatography to obtain a light yellow solid TM1 (233 mg, yield 60%).

[0064] Figure 1 TM1 is 1 H-NMR spectrum; 1 H NMR (400 MHz, CDCl3): delta 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)。

[0065] Figure 2 TM1 is 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 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。

[0066] (2) Preparation of TM2 The reaction formula for preparing TM2 can be written as:

[0067] The specific preparation method of TM2 is as follows: Under a nitrogen atmosphere, a round-bottom flask equipped with a magnetic stirrer was charged with 2-cyanophenothiazine (1.5 mmol, 336 mg), 9-bromomethylanthracene (1 mmol, 271 mg), potassium carbonate (2 mmol, 276 mg), tetrabutylammonium bromide (0.2 mmol, 64 mg), dry toluene (5 mL) was added to dissolve the mixture, and the mixture was stirred at room temperature until the 9-bromomethylanthracene starting material was substantially consumed according to TLC monitoring; the reaction mixture was washed with water in turn, extracted with dichloromethane, and the combined organic phase was dried over anhydrous Na2SO4; the crude product was separated by column chromatography to obtain yellow solid TM2 (289 mg, yield 70%).

[0068] Figure 3 TM2 is 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 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)。

[0069] Figure 4 TM2 is 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 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。

[0070] (3) Preparation of TM3 The reaction formula for preparing TM3 can be written as:

[0071] A specific preparation method of TM3 is as follows: Into a round bottom flask equipped with a magnetic stirrer, 2-acetylphenothiazine (1.5 mmol, 362 mg), 9-bromomethylanthracene (1 mmol, 271 mg), potassium carbonate (2 mmol, 276 mg), tetrabutylammonium bromide (0.2 mmol, 64 mg) were added under nitrogen atmosphere, and then dry toluene (5 mL) was added to dissolve the mixture, which was stirred at room temperature until the starting material of 9-bromomethylanthracene was consumed completely according to TLC monitoring. The reaction mixture was washed with water in turn, and extracted with dichloromethane, and the combined organic phase was dried over anhydrous Na2SO4. The crude product was separated by column chromatography to obtain yellow solid TM3 (258 mg, yield 60%).

[0072] Figure 5 TM3 is 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 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)。

[0073] Figure 6 TM3 is 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 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。

[0074] (4) Preparation of TM4 The reaction for preparing TM4 can be written as:

[0075] The specific preparation method of TM4 is as follows: In a nitrogen atmosphere, a round-bottom flask was charged with benzothiophene (1.5 mmol, 373 mg), 9-bromomethylanthracene (1 mmol, 271 mg), potassium hydroxide (2 mmol, 112 mg), tetrabutylammonium bromide (0.2 mmol, 64 mg), and dry toluene (5 mL) was added to dissolve the mixture, and stirred at room temperature until the TLC monitoring of 9-bromomethylanthracene raw material was substantially consumed; the reaction mixture was washed with water in turn, extracted with dichloromethane, and the combined organic phase was dried over anhydrous Na2SO4; the crude product was separated by column chromatography to obtain yellow solid TM4 (307 mg, yield 70%).

[0076] Figure 7 TM4 is 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 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).

[0077] Figure 8 TM4 is 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta144.5, 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.

[0078] (5) UV-Vis spectrum UV-Vis absorption spectrum was tested on Shimadzu UV-1900 UV-Vis spectrophotometer, with toluene as solvent (photosensitizer concentration: 4 10 -5 mol / L). According to Lambert Beer law, the molar extinction coefficient ε = A bn / c was calculated, where A bn is the absorbance of UV-Vis absorption spectrum, and c is the concentration (mol / L), and the results are shown in Table 1. The UV-Vis spectrum of TM1~TM4 prepared is shown in Figure 9 .

[0079] Table 1 Molar extinction coefficient of TM1~TM4 and DBA

[0080] From the molar extinction coefficient in Table 1, it can be seen that the molar extinction coefficient of anthrylmethyl phenothiazine of the present application is comparable to that of DBA, proving that such photosensitizer has good photo-radical conversion ability.

[0081] (II) Preparation of photosensitive resin composition Examples and comparative examples were set, examples 1~16 used TM1~TM4 as photosensitizer, and comparative examples used DBA, DPHA, DAcOA as photosensitizer respectively. Referring to the formulations shown in Table 2 and Table 3, each component was mixed uniformly to prepare a photosensitive resin composition. The data in Table 2 and Table 3 are in mass parts, and "-" means not added.

[0082] The components and specific information of each component code in Table 2 and Table 3 are as follows: A: alkali-soluble resin: acrylate copolymer, solution polymerization method, polymerized according to mass ratio, methacrylic acid / butyl methacrylate / benzyl methacrylate = 25 / 10 / 65; solvent is acetone, solid content is 46%, weight average molecular weight is 40000, dispersity is 2.1, acid value is 163 mgKOH / g (Hunan Chuyuan New Material Co., Ltd.); B: Photopolymerization monomer consists of the following ingredients (purchased from Shadoma Guangzhou Chemical Co., Ltd.): 5 parts of methoxypolyethylene 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, 4 parts of di (trimethylolpropane) tetraacrylate; C: Photoinitiator: 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetraphenyl-2,2'-dimethyl-1,1'-diimidazole (BCIM) purchased from Jiuding Chemical; D: Photosensitizer: DBA is 9,10-dibutoxyanthracene, DPHA is 9,10-diphenylanthracene, DAcOA is 9,10-diacetyloxyanthracene, all purchased from Leyan; E: Additives: consists of the following ingredients (purchased from Anjier Chemical): 0.5 parts of leuco crystal violet, 0.05 parts of malachite green, 0.8 parts of p-toluenesulfonamide, 0.03 parts of 2,6-di-tert-butyl-4-methylphenol; Solvent: consists of the following ingredients: 8 parts of acetone, 10 parts of toluene, 5 parts of methanol.

[0083] Table 2 Formulation of the photosensitive resin composition of Examples 1-12

[0084] Table 3 Formulation of the photosensitive resin composition of Examples 13-16 and Comparative Examples 1-3

[0085] (III) Preparation of photosensitive dry film The photosensitive resin composition of Examples 1-16 and Comparative Examples 1-3 was used as raw material to prepare the photosensitive dry film, including the following steps: The experiment equipment (model: AB4220, TQC, Netherlands) was used to coat the photosensitive resin composition slurry according to the formulation on a 15 μm thick polyethylene terephthalate (PET) support film; bake at 80°C for 10 min to remove the solvent, the photosensitive layer thickness is controlled at 30 μm after baking, then cover with a polyethylene film (PE) for protection, to get the photosensitive dry film.

[0086] The solvent acetone can be added to the photosensitive resin composition before coating the film to adjust its viscosity to a suitable viscosity for coating. The solvent will be removed after baking and has no effect on the composition of the photosensitive dry film.

[0087] (IV) Preparation of substrate with resist pattern The photosensitive resin composition of Examples 1-16 and Comparative Examples 1-3 was used as raw material to prepare the substrate with resist pattern, the process is as follows: (1) Photosensitive layer forming step: forming a photosensitive layer on a substrate using a photosensitive composition; (2) Exposure step: irradiating active light to at least a part of the photosensitive layer to make the irradiated part photocured to form a cured product area; (3) Development step: removing at least a part of the photosensitive layer other than the cured product area from the substrate to form a resist pattern on the substrate.

[0088] Hereinafter, the operation conditions of each step will be described in detail.

[0089] Photosensitive layer forming step: using a copper-clad laminate in which a 35 μm thick rolled 1.2 mm thick copper foil was laminated, after surface adjustment and preheating to 80°C, the PE protective film of the photosensitive dry film obtained from each example or comparative example was peeled off while laminating the photosensitive resin composition layer on the copper-clad laminate using a hot roll laminator (Zhisheng Technology Co., Ltd., CSL-M25E) at a roll temperature of 110°C, an air pressure of 0.35 MPa, and a lamination speed of 1.5 m / min to obtain a test substrate.

[0090] Exposure step: exposure was performed using a direct drawing exposure machine (Chiptronics, main wavelength 405 nm), and a Stouffer 41 step exposure ruler was used for photosensitivity test, and the exposure scale was controlled to be 14-18 scales.

[0091] Development step: after exposure, the PET support film was peeled off, and an alkali developing machine (manufactured by Guangzhou Julong Printed Circuit Equipment Co., Ltd., dry film developing machine) was used to spray a 1 wt% Na2CO3 aqueous solution at 30°C for a time twice the minimum developing time to dissolve and remove the unexposed part of the photosensitive resin layer. After development, the photosensitive resin layer was washed with pure water for 1.5 times the developing time, and then water was removed by air knife, and then warm air drying was performed to obtain a substrate with an evaluation cured film. The shortest time required for complete dissolution of the unexposed part of the photosensitive resin layer was taken as the minimum developing time.

[0092] (Five) Evaluation Items (1) Photosensitivity Evaluation Photosensitivity evaluation tests were performed on Examples 1-16 and Comparative Examples 1-3. On the above-mentioned test substrate after film pasting, a Stouffer 41 step exposure ruler was placed for photosensitivity test. After the exposure step, the test substrate was left to stand for more than 20 min, and 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, and the developing time was 2.0 times the minimum developing time. After the above operation, a cured film obtained by curing the photosensitive resin composition was formed on the surface of the substrate. The exposure energy (mJ / cm 2), the smaller the value, the better the photosensitivity.

[0093] (2) Adhesion evaluation Adhesion evaluation tests were performed on Examples 1 to 16 and Comparative Examples 1 to 3, and the above-mentioned test substrate after the film was attached, using a photomask data having a line width / interval width of n:400 (unit: pm) wiring pattern to expose with an energy that makes the remaining stage number after the Stouffer 41 stage type exposure ruler development 16. After the development process, the resist pattern was observed using an optical microscope, and the value of the minimum line width at which a complete cured resist line was formed was used as the value of the adhesion (pm) to evaluate the adhesion. The smaller the value, the better the adhesion.

[0094] (3) Resist migration evaluation Resist migration evaluation tests were performed on Examples 1 to 16 and Comparative Examples 1 to 3, and after the above-mentioned 3-layer structure of the photosensitive dry film was prepared, the ultraviolet absorption spectrum of the dry film was detected using a UV spectrophotometer to obtain the absorbance A1 of the maximum absorption peak in 350-450 nm; then the dry film was placed at 30°C for 72 h, and the PE film layer on the surface of the photosensitive dry film was removed, and the ultraviolet absorption spectrum of the PET layer and the photosensitive resist layer was detected using a UV spectrophotometer to obtain the absorbance A2 of the maximum absorption peak in 350-450 nm. If the sensitizer migrates to the surface of the PE layer, the absorbance of the maximum absorption peak of the PET layer and the photosensitive resist layer in the wavelength range of 350-450 nm will decrease, i.e. the absorbance of the sensitizer migrated to the PE layer is (A1 - A2). The migration degree of the photosensitizer, i.e. the migration rate A = (A1 - A2) / A1, was calculated, and the larger the value, the greater the migration amount.

[0095] Judgment basis: O: migration rate A < 0.01; X: migration rate A > 0.01.

[0096] The test results of each evaluation item are summarized in Tables 4 and 5 below.

[0097] Examples 1 to 12 used TM1 to TM4 as photosensitizers, and tests were performed under different amounts.

[0098] The results of Table 4 show that TM1 to TM4 not only greatly reduce the migration rate, but also exhibit excellent adhesion enhancement effect.

[0099] Table 4 Test results of each evaluation item of Examples 1 to 12

[0100] Examples 13~16 use TM1~TM4 as photosensitizer, Comparative Examples 1~3 use DBA, DPHA and DAcOA as photosensitizer respectively, and the photosensitizer dosage is the same in the above cases.

[0101] The results in Table 5 show that the photosensitive resin composition using anthrylmethylphenothiazine as photosensitizer in the present application has lower exposure energy under the same mass concentration, which indicates that the photosensitivity is superior to DBA and DAcOA; in addition, the anthrylmethylphenothiazine in the present application has advantages in adhesion and migration.

[0102] Table 5 Test results of each evaluation item of Examples 13~16 and Comparative Examples 1~3

[0103] The above is only the preferred embodiment of the present application, not for limiting the present application. Those skilled in the art can make various modifications and changes under the spirit and principles of the present application, any modification, equivalent replacement or improvement within the scope should be considered as covered by the protection scope of the present application.

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 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. 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 the following: dyes, light developers, plasticizers, adhesion promoters, polymerization inhibitors, defoamers, and coating aids.

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 and 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, and 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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