Diaminophosphate anthracene ester for photosensitive resin composition, photosensitive resin composition, photosensitive dry film and application

Abstract

The invention provides anthracene diaminophosphate for a photosensitive resin composition, and relates to the field of photopolymerization. The invention also comprises a photosensitive resin composition containing the anthracene diphosphoramidate, a photosensitive dry film containing the anthracene diphosphoramidate, and applications of the photosensitive resin composition and the photosensitive dry film. The anthracene diaminophosphate provided 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 a diaminoanthracene phosphate ester for photosensitive resin, a photosensitive resin composition, a photosensitive dry film and application thereof. BACKGROUND

[0002] Photosensitive resin composition is a key pattern transfer material; usually coated on the surface of PET support film, after drying, a layer of protective layer such as polyethylene film (PE) protective layer is closely attached to the surface to form a photosensitive dry film (or dry film resist). In the process of realizing pattern transfer, first, the dry film resist is attached to the copper substrate, a mask with a certain pattern is covered on the dry film resist, and pattern exposure is performed; then, the unexposed part is removed by using weak alkaline aqueous solution as developer, and etching or plating treatment is performed 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 is still intact and attached to the copper-clad plate substrate after the harsh process of development, 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 a diaminoanthracene phosphate ester with photosensitivity and capable of improving the adhesion of photosensitive resin composition on metal foil surface, a photosensitive resin composition, a photosensitive dry film and application thereof.

[0005] The technical solution adopted by the present application to solve the technical problem is as follows: a diaminoanthracene phosphate ester for photosensitive resin composition, comprising , , one or more of the above.

[0006] 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 diaminoanthracene phosphate ester.

[0007] More preferably, the photosensitizer further includes one or two or more of 9,10-dibutoxyanthracene, 9,10-diacetoxyanthracene, 9,10-diphenylanthracene.

[0008] Preferably, the alkali-soluble resin is an acrylic ester copolymer including an aromatic group.

[0009] Preferably, the photopolymerization monomer is an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid ester.

[0010] Preferably, the photoinitiator is a bis-imidazole compound.

[0011] Preferably, among the comonomers used to synthesize the alkali-soluble resin, the comonomer having an aromatic group accounts for 50 to 70% by mass.

[0012] Preferably, the alkali-soluble resin has a weight average molecular weight of 20,000 to 60,000.

[0013] Preferably, the alkali-soluble resin has an acid value of 160 to 220 mg KOH / g.

[0014] Preferably, the alkali-soluble resin has a molecular weight distribution of 1.0 to 3.0.

[0015] Preferably, the photopolymerization monomer is a methacrylate monomer and / or an acrylate monomer.

[0016] Preferably, the photoinitiator is a 2,4,5-triaryl imidazole dimer.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] Based on the same inventive concept, the 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 anthracene diamino phosphate and the photosensitive resin composition.

[0023] Based on the same inventive concept, the application further provides applications of one or more of the anthracene diamino phosphate, 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.

[0024] The anthracene diamino phosphate of the 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 applied to the photocuring field of dry films, paints, coatings, inks, and molding materials.

[0025] In addition to the objects, features, and advantages described above, the application has other objects, features, and advantages. The application will be described in further detail below with reference to the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0026] The accompanying drawings, which form a part of this application, are included to provide a further understanding of the application, illustrate preferred embodiments of the application, and assist in Figure 1 is a H-NMR chart of TM1 prepared in an embodiment of the application 1 H-NMR chart Figure 2 UV-Vis spectrum of TM1 prepared in an embodiment of the present application 13 C-NMR chart Figure 3 UV-Vis spectrum of TM1 prepared in an embodiment of the present application 31 P-NMR chart Figure 4 UV-Vis spectrum of TM2 prepared in an embodiment of the present application 1 H-NMR chart Figure 5 UV-Vis spectrum of TM2 prepared in an embodiment of the present application 13 C-NMR chart Figure 6 UV-Vis spectrum of TM2 prepared in an embodiment of the present application 31 P-NMR chart Figure 7 UV-Vis spectrum of TM3 prepared in an embodiment of the present application 1 H-NMR chart Figure 8 UV-Vis spectrum of TM3 prepared in an embodiment of the present application 13 C-NMR chart Figure 9 UV-Vis spectrum of TM3 prepared in an embodiment of the present application 31 P-NMR chart Figure 10 UV-Vis spectrum of TM1-TM3 and DBA prepared in an embodiment of the present application DETAILED DESCRIPTION

[0027] 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 in combination with embodiments and drawings. It should be pointed out that the embodiments described in the specification are only for explaining the present application, and are not intended to limit the present application.

[0028] 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 that range. Thus, every point or individual number can serve as its own lower or upper limit to form a range not explicitly recited.

[0029] 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, and "multiple" in "one or more" means two or more.

[0030] An anthracene diamino phosphate ester for a photosensitive resin composition according to an embodiment of the present application includes one or more of: (TM1), (TM2), (TM3)

[0031] A photosensitive resin composition according to an embodiment of the present application includes, by mass, 50 to 65 parts of an alkali-soluble resin, 35 to 50 parts of a photopolymerization monomer, 2 to 5 parts of a photoinitiator, and 0.1 to 1 part of a photosensitizer, wherein the photosensitizer includes the anthracene diamino phosphate ester. The anthracene diamino phosphate ester has photosensitivity and can be used as a photosensitizer. The "0.1 to 1 part" of the photosensitizer contained in the photosensitive resin composition refers to the total amount of the anthracene diamino phosphate ester and other photosensitizers.

[0032] When the content of the alkali-soluble resin is too low, there is a tendency for the resist layer to flow. When the content is too high, there is a tendency for the resolution to decrease.

[0033] When the content of the photopolymerization monomer is too low, there is a tendency for the sensitivity and the chemical resistance of the resist to decrease. When the content is too high, there is a tendency for the photosensitive resin composition to be difficult to filmize and for the resist layer to flow.

[0034] When the content of the photoinitiator is too low, there is a tendency for the sensitivity and the resolution of the resist to decrease. When the content is too high, there is a tendency for the amount of development waste to increase.

[0035] When the content of the photosensitizer is too low, there is a tendency for the sensitivity of the resist to decrease. When the content is too high, there is a tendency for the bottom layer of the resist to be incompletely cured, resulting in a "reversed trapezoidal" cross-sectional shape of the resist and poor resolution.

[0036] In some embodiments of the present application, the photosensitizer further includes one or more of 9,10-dibutoxyanthracene, 9,10-diacetoxyanthracene, and 9,10-diphenylanthracene.

[0037] In embodiments of the present application, the alkali-soluble resin is an acrylate copolymer including an aromatic group.

[0038] In embodiments of the present application, the photopolymerization monomer is an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid ester.

[0039] In embodiments of the present application, the photoinitiator is a bis-imidazole compound.

[0040] In embodiments of the present application, among the comonomers used to synthesize the alkali-soluble resin, the comonomer having an aromatic group accounts for 50 to 70% by mass.

[0041] ​In the embodiment of the present application, the weight average molecular weight of the alkali-soluble resin is 20,000 to 60,000.

[0042] In the embodiment of the present application, the acid value of the alkali-soluble resin is 160 to 220 mg KOH / g.

[0043] In the embodiment of the present application, the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0044] In the embodiment of the present application, the photopolymerization monomer is a methacrylate monomer and / or an acrylate monomer.

[0045] In the embodiment of the present application, the photoinitiator is a 2,4,5-triaryl imidazole dimer.

[0046] 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.

[0047] In the embodiment of the present application, 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.

[0048] 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.

[0049] 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 match the UV-A light source (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.

[0050] In an embodiment of the present application, the photosensitive resin composition containing the anthracene diamidophosphate includes 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.

[0051] In some embodiments of the present application, the photosensitive resin composition containing the anthracene diamidophosphate includes 45-48 parts by mass of photopolymerizable monomer (corresponding to 55-60 parts by mass of alkali-soluble resin).

[0052] In some embodiments of the present application, the photosensitive resin composition containing the anthracene diamidophosphate includes 2.5-3.5 parts by mass of photoinitiator (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 anthracene diamidophosphate includes 0.2-0.8 parts by mass of photosensitizer (corresponding to 55-60 parts by mass of alkali-soluble resin).

[0054] In an embodiment of the present application, 0.5-5.0 parts by mass of additives are further included; 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).

[0055] In an embodiment of the present application, a photosensitive dry film includes a support layer, a photosensitive resist layer, and a protective layer arranged in sequence; the composition of the photosensitive resist layer includes at least one of the anthracene diamidophosphate and the photosensitive resin composition.

[0056] The support layer material of the photosensitive dry film is PET.

[0057] The protective layer material of the photosensitive dry film is PE.

[0058] One or more of the anthracene diamidophosphate, the photosensitive resin composition, and the photosensitive dry film according to the embodiments of the present application are used in substrates with resist patterns, printed circuit boards, lead frames, semiconductor packaging substrates, solar cells, and photocurable inks.

[0059] 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 several types also have the following defects: (1) The 9,10-dibutoxyanthracene photosensitizer, although has advantages in solubility, the 9,10 C-O bond will break during exposure, the anthracene ring will dimerize, and small molecule alkoxy fragments will be released, which 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) 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) DAcOA has the problem of decreased efficiency in catalytic curing reaction due to the electron-withdrawing induction effect of acyloxy group, the verticality of the photosensitive resin composition after curing is poor, and the length difference between the top and bottom lines is large to form an inverted trapezoidal shape, which cannot meet the needs of fine line manufacturing; The present application provides a diamino phosphoric acid anthracene ester, which has the following technical advantages: (1) Reduce migration risk: the anthracene group is directly connected to a large polar and large size group, which can greatly inhibit the migration of small molecule fragments, hinder the penetration and diffusion of photosensitizer molecules to the PE film, and improve the yield of the product; (2) Excellent adhesion: the amino phosphate derivative can form stable complexes with various transition metals, such as Pd, Pt, Cu, etc., which can greatly improve the adhesion of the photosensitizer on the surface of the copper foil; The diamino phosphoric acid anthracene ester of the present application has photosensitivity and can replace the existing anthracene photosensitizer as a photosensitizer in photosensitive resin, while enhancing the adhesion on the surface of the metal foil. Through molecular structure innovation, the present application simultaneously realizes low migration, excellent adhesion, and meets the needs of high-density line manufacturing, high precision, high density and multi-layer.

[0060] Example The present disclosure is more particularly described in the following examples that are intended to be illustrative only since modifications and variations from the details given can be made within the scope of the present disclosure. All percentages, parts by weight and ratios reported in the following examples are based on weight unless otherwise stated. All reagents used in the examples were obtained from common commercial sources and used without further purification unless otherwise stated. All instruments used in the examples were obtained from common commercial sources unless otherwise stated.

[0061] (I) Preparation and detection of diamino phosphoric anthracene ester (1) Preparation of TM1 The reaction equation for preparing TM1 can be written as: .

[0062] The specific preparation method of TM1 is as follows: Under a nitrogen atmosphere, a round-bottom flask equipped with a magnetic stirrer was charged with anthrone (2 mmol) and potassium hydroxide (2 mmol) in a molar ratio of 1:2, and dissolved in 6 mL of dry acetone, and then bis(dimethylamino)phosphoryl chloride (8 mmol) was slowly added dropwise; after the dropwise addition was completed, the reaction mixture was reacted at 60°C until the consumption of the raw material anthrone was monitored by TLC; the reaction mixture was sequentially washed with water and extracted with dichloromethane, and the combined organic phase was dried; the crude product was purified by column chromatography (yield 80%).

[0063] Figure 1 is the 1 H-NMR spectrum of TM1; 1 H NMR (400 MHz, CDCl3): delta 8.40 (d, J = 8.7 Hz, 2H), 8.27 (s, 1H), 7.97 (d, J = 8.4 Hz, 2H), 7.51 (t, J = 8.3 Hz, 2H), 7.45 (t, J = 6.8 Hz, 2H), 2.75 (d, J = 10.0 Hz, 12H).

[0064] Figure 2 is the 13 C-NMR spectrum of TM1; 13 C NMR (100 MHz, CDCl3): delta 143.4 ( J C-P= 8.8 Hz), 132.3 ( J C-P = 2.2 Hz), 128.2, 125.6 ( J C-P = 5.6 Hz), 124.4 ( J C-P = 3.6 Hz), 123.4( J C-P = 2.8 Hz), 123.0 ( J C-P = 1.8 Hz), 37.2 ( J C-P = 4.0 Hz)。

[0065] Figure 3 is the H-NMR spectrum of TM1 31 P-NMR spectrum; 31 P NMR (162 MHz, CDCl3) delta 16.4 ( J = 19.6, 10.1 Hz)。

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

[0067] The specific preparation method of TM2 is as follows: Under a nitrogen atmosphere, 2-chloroanthraquinone (2 mmol), sodium hydrosulfite (6 mmol), and methyltrioctylammonium bromide (0.2 mmol) were added to a round-bottom flask equipped with a magnetic stirrer in a molar ratio of 1:3:0.1, followed by dropwise addition of 6 mL of dry toluene solvent. After the dropwise addition was completed, 35% NaOH aqueous solution (NaOH total 0.9 mmol) was slowly added dropwise. After 30 min of reaction, 35% NaOH aqueous solution (NaOH total 9.1 mmol) was slowly added dropwise. After the temperature was raised to 45°C for 1 h, bis(dimethylamino)phosphoryl chloride (8 mmol) was added dropwise, and the temperature was raised to 60°C for 16 h. After the reaction was completed by TLC monitoring, dichloromethane was used for extraction, and the obtained oily crude product was purified by column chromatography (yield 65%).

[0068] Figure 4 is the H-NMR spectrum of TM2 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 8.37 (d, J= 8.6 Hz, 1H),8.30 (s, 1H), 8.22 (s, 1H), 7.94 (d, J = 8.4 Hz, 1H), 7.89 (d, J = 9.0 Hz, 1H),7.54 (t, J = 7.2 Hz, 1H), 7.46 (t, J = 6.9 Hz, 1H), 7.37 (d, J = 2.1 Hz, 1H), 7.35(d, J = 2.1 Hz, 1H), 2.80 (d, J = 9.9 Hz, 12H)。

[0069] Figure 5 is TM2 of 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 142.5 ( J C-P = 8.7 Hz),132.5 ( J C-P = 2.2 Hz), 130.1 ( J C-P = 2.2 Hz), 128.3, 126.7, 126.3, 125.9, 125.1( J C-P = 3.3 Hz), 124.5 ( J C-P = 3.7 Hz), 123.6 ( J C-P = 2.9 Hz), 123.0 ( J C-P = 1.7 Hz),121.4 ( J C-P = 1.7 Hz), 37.1 ( J C-P = 4.1 Hz), 29.8。

[0070] Figure 6 is TM2 of 31 P-NMR spectrum; 31 P NMR (162 MHz, CDCl3) delta 16.2 ( J = 19.7, 9.8 Hz).

[0071] (3) Preparation of TM3 The reaction equation for preparing TM3 can be written as: .

[0072] The specific preparation method of TM3 is as follows: Under a nitrogen atmosphere, 2-ethylanthraquinone (2 mmol), sodium hydrosulfite (6 mmol) and methyltrioctylammonium bromide (0.2 mmol) were added to a round-bottom flask equipped with a magnetic stirrer in a molar ratio of 1:3:0.1, followed by dropwise addition of 6 mL of dry toluene solvent. After the dropwise addition was completed, 35% NaOH aqueous solution (NaOH total 0.9 mmol) was slowly added dropwise. After 30 min of reaction, 35% NaOH aqueous solution (NaOH total 9.1 mmol) was slowly added dropwise. After being warmed to 45°C for 1 h, bis(dimethylamino)phosphoryl chloride (8 mmol) was added dropwise. After being warmed to 60°C for 16 h, the reaction was monitored by TLC. After the reaction was completed, dichloromethane was used for extraction, and the obtained oily crude product was purified by column chromatography (yield 78%).

[0073] Figure 7 is the 1 H-NMR spectrum: 1 H NMR (400 MHz, CDCl3): delta 8.3 – 8.3 (m, 3H), 8.1(s, 1H), 7.5 – 7.4 (m,2H), 7.4 (dd, J = 9.01, 1.66 Hz, 1H), 2.9 – 2.8 (m, 2H),2.7 (d, J = 9.96 Hz, 32H), 1.3 (s, 3H)。

[0074] Figure 8 is the 13 C-NMR spectrum; 13 C NMR (100 MHz, CDCl3): delta 141.4, 127.5, 125.5,125.2, 122.9, 122.8, 122.7, 37.0, 29.3, 15.0。

[0075] Figure 9 is the 31 P-NMR spectrum; 31 P NMR (162 MHz, CDCl3) delta 16.7(dd, J = 24.7, 4.0Hz).

[0076] (4) UV-Vis spectrum The UV-Vis absorption spectra of TM1-TM3 were tested on a Shimadzu UV-1900 UV-Vis spectrophotometer, with toluene as the solvent, and the photosensitizer concentration being 8 x 10 -5 mol / L; the test solvent of DBA was toluene, and the photosensitizer concentration was 4 x 10 -5 mol / L (Table 1). According to the Lambert-Beer law, the molar extinction coefficient ε = A bn / c was calculated, where A bn is the absorbance of the UV-Vis absorption spectrum, and c is the concentration (mol / L). The results are shown in Table 1. The UV-Vis spectra of the prepared TM1-TM3 and DBA are shown in Figure 10 .

[0077] As can be seen from the molar extinction coefficients in Table 1, the molar extinction coefficients of the anthracene diamino phosphate photosensitizers of the present application are comparable to those of DBA, proving that such photosensitizers have good photo-radical conversion ability.

[0078] Table 1 Molar extinction coefficients of TM1-TM3 and DBA

[0079] (II) Preparation of the photosensitive resin composition Examples and comparative examples were set up. Examples 1-12 used TM1-TM3 as the photosensitizer, and comparative examples used DBA, DPHA, and DAcOA as the photosensitizer, respectively. The components were mixed uniformly to prepare the photosensitive resin composition according to the formulations shown in Tables 2 and 3. The data in Tables 2 and 3 are in parts by mass, and "-" indicates that the component was not added.

[0080] Table 2 Formulations of the photosensitive resin compositions of Examples 1-9

[0081] The components and specific information of the component codes in Tables 2 and 3 are as follows: Alkali-soluble resin (A): acrylate copolymer, solution polymerization, polymerized according to the mass ratio of methyl methacrylate / butyl methacrylate / benzyl methacrylate = 25 / 10 / 65; the solvent was acetone, the solid content was 46%, the weight average molecular weight was 40000, the dispersity was 2.1, and the acid value was 163 mgKOH / g (Hunan Chuyuan New Material Co., Ltd.); The photopolymerization monomer (B) is composed 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; The photoinitiator (C): 2,2'-bis (o-chlorophenyl) -4,4', 5, 5'-tetraphenyl-2,2'-dimethyl-1,1'-dihydroxy-1,1'-diimidazole (BCIM) is purchased from Jiuding Chemical; The photosensitizer (D): DBA is 9,10-dibutoxyanthracene, DPHA is 9,10-diphenylanthracene, and DAcOA is 9,10-diacetyloxyanthracene, all purchased from Leyan; The additive (E) is composed 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, and 0.03 parts of 2,6-di-tert-butyl-4-methylphenol; The solvent is composed of the following ingredients: 8 parts of acetone, 10 parts of toluene, and 5 parts of methanol.

[0082] Table 3 Formulation of the photosensitive resin composition of Examples 10-12 and Comparative Examples

[0083] (III) Preparation of photosensitive dry film The photosensitive resin composition of Examples 1-12 and Comparative Examples 1-3 is used as raw material to prepare the photosensitive dry film, including the following steps: The experiment equipment (model: AB4220, TQC, Netherlands) is 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, and the thickness of the photosensitive layer after baking is controlled at 30 μm, then cover with a polyethylene film (PE) for protection, to obtain the photosensitive dry film.

[0084] The solvent acetone can be added to the photosensitive resin composition before coating the film to adjust its viscosity to a suitable value for coating. The solvent will be removed after baking, and has no effect on the composition of the photosensitive dry film.

[0085] (IV) Preparation of substrate with resist pattern The photosensitive resin composition of Examples 1-12 and Comparative Examples 1-3 is used as raw material to prepare the substrate with resist pattern, and the process is as follows: (1) Photosensitive layer forming process: form a photosensitive layer on the substrate using the photosensitive composition; (2) Exposure process: irradiate at least one part of the above photosensitive layer with active light to make the above area photocured to form a cured area; (3) Developing step: removing at least a part of the photosensitive layer except the cured product region from the substrate to form a resist pattern on the substrate.

[0086] Hereinafter, the operation conditions of each step are described in detail.

[0087] 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 (Shinest 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.

[0088] Exposure step: exposure was performed using a direct drawing exposure machine (Chipmos, main wavelength 405 nm), and a Stouffer 41-step exposure ruler was used for photosensitivity test, and the exposure number was controlled to be in the range of 14-18.

[0089] Developing 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 substrate was washed with pure water for a time 1.5 times the developing time, and then water was removed using an 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 photosensitive resin layer in the unexposed part was taken as the minimum developing time.

[0090] (Five) Evaluation Items (1) Photosensitivity Evaluation The photosensitivity evaluation test was performed on Examples 1-12 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 allowed 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 ) at which the number of remaining segments of the step exposure ruler obtained by the cured film was 16 segments was determined, and the photosensitivity of the photosensitive resin composition was evaluated, and the smaller the value, the better the photosensitivity.

[0091] (2) Adhesion Evaluation The adhesion evaluation test was performed on the test substrate after the above-mentioned film pasting, using a photomask data having a line width / interval width of n:400 (unit: μm) wiring pattern to expose with an energy to make the remaining stage number after the Stouffer 41 stage type exposure ruler development reach 16. After the development process treatment, 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 adhesion value to evaluate the adhesion (μm). The smaller the value, the better the adhesion.

[0092] (3) Evaluation of resist migration The resist migration evaluation test was performed on Examples 1-12 and Comparative Examples 1-3. 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. After the dry film was placed at 30°C for 72 h, 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.

[0093] Judgment basis: O: migration rate A < 0.01; X: migration rate A > 0.01.

[0094] The test results of each evaluation item are summarized in Tables 4 and 5 below.

[0095] Table 4 Test results of each evaluation item of Examples 1-9

[0096] Examples 1-9 used TM1-TM3 as photosensitizers and were tested at different amounts. The results in Table 4 show that TM1-TM3 not only greatly reduced the migration rate, but also exhibited excellent adhesion enhancement effect.

[0097] Table 5 Test results of each evaluation item of Examples 10-12 and Comparative Examples 1-3

[0098] The results in Table 5 show that the photosensitive resin composition using the anthracene diamino phosphate ester of the present application as photosensitizer has lower exposure energy than DBA and DAcOA under the same mass concentration, indicating that the photosensitivity is superior to DBA and DAcOA; and is obviously superior to DBA, DPHA and DAcOA in adhesion; and the anthracene diamino phosphate ester of the present application also has advantages in migration.

[0099] The above merely illustrates the preferred embodiments of the present application, and is not intended to limit the present application. Any modification, equivalent replacement or improvement made by those skilled in the art within the spirit and principle of the present application shall be considered as falling within the protection scope of the present application.

Claims

1. An anthracene diamino phosphate ester for a photosensitive resin composition, characterized in that: 50-65 parts by mass of an alkali-soluble resin, 35-50 parts by mass of a photopolymerization monomer, 2-5 parts by mass of a photoinitiator, and 0.1-1 parts by mass of a photosensitizer are included; and the photosensitizer includes the anthracene diamino phosphate ester of claim 1. including one or more of , , .

2. A photosensitive resin composition, characterized by comprising: The photosensitizer further includes one or two or more of 9,10-dibutoxyanthracene, 9,10-diacetoxyanthracene, and 9,10-diphenylanthracene.

3. The photosensitive resin composition according to claim 2, characterized by The alkali-soluble resin is an acrylate copolymer including an aromatic group; the photopolymerization monomer is an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid ester; and the photoinitiator is a bis-imidazole compound.

4. The photosensitive resin composition according to claim 2 or 3, characterized by In the comonomers used to synthesize the alkali-soluble resin, the comonomer having an aromatic group accounts 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.

5. The photosensitive resin composition according to claim 2 or 3, characterized by The photopolymerization monomer is a methacrylate monomer and / or an acrylate monomer. The photoinitiator is a 2,4,5-triaryl imidazole dimer. 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 derivatives, benzyl methacrylate derivatives, phenyl acrylate, phenyl methacrylate, styrene, and styrene derivatives.

6. The photosensitive resin composition according to claim 2 or 3, characterized by The photopolymerization monomer is one or two 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. 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. 55-60 parts by mass of an alkali-soluble resin, 40-49 parts by mass of a photopolymerization monomer, 2.2-4 parts by mass of a photoinitiator, and 0.1-1 parts by mass of a photosensitizer are included.

7. The photosensitive resin composition according to claim 2 or 3, characterized by ​ 8. The photosensitive resin composition according to claim 2 or 3, characterized by Further, 0.5 to 5.0 parts by mass of an additive is contained; the additive is one or two or more of a dye, a phototoner, a plasticizer, an adhesion promoter, a polymerization inhibitor, an antifoaming agent, and a coating aid.

9. A photosensitive dry film characterized by comprising: The photofreezing resin composition comprises the anthracene diamino phosphate of claim 1 and at least one of the photosensitive resin compositions of any one of claims 2 to 8.

10. Use of one or two or more of the anthracene diamino phosphate of claim 1, the photosensitive resin composition of any one of claims 2 to 8, and the photosensitive dry film of claim 9 in a substrate with a resist pattern, a printed circuit board, a lead frame, a semiconductor package substrate, a solar cell, and a light-cured ink.

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