An anthracene diamino phosphate for a photosensitive resin composition, a photosensitive resin composition, a photosensitive dry film, and an application thereof

Abstract

The present application provides a kind of anthracene diamino phosphate for photosensitive resin composition, it is related to the field of photopolymerization.The present application also includes the photosensitive resin composition containing the anthracene diamino phosphate, the photosensitive dry film containing the anthracene diamino phosphate, and its application.The anthracene diamino phosphate of the present application has photosensitivity, can be used as photosensitizer in photosensitive resin composition, and can improve the adhesion of photosensitive resin composition on various metal surfaces, with low migration characteristics;It can be widely used in dry film, paint, coating, ink and molding material and other light curing fields.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of photopolymerization, in particular to a diamino phosphate anthracene ester for photosensitive resin, a photosensitive resin composition thereof, a photosensitive dry film and application. 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 its 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 carried out to form a pattern; finally, the dry film solidified part is removed by stripping with film 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 influence 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 diamino phosphate anthracene ester with photosensitivity, which can improve the adhesion of photosensitive resin composition on metal foil surface, a photosensitive resin composition thereof, a photosensitive dry film and application.

[0005] The technical solution adopted by the present application to solve the technical problem is as follows: a diamino phosphate anthracene ester 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 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; the photosensitizer comprises the anthracene diamino phosphate.

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

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

[0010] Preferably, the photopolymerization monomer is an olefinically unsaturated carboxylic acid and / or an olefinically 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 aromatic groups accounts for 50-70% by mass.

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

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

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

[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 more than two 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 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, and 2,2',4-tris(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 photopolymerization 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, wherein 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, in sequence, a support layer, a photosensitive resist layer, and a protective layer, wherein the photosensitive resist layer comprises at least one of the anthracene diamino phosphate 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 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 package substrate, a solar cell, and a photocuring ink.

[0025] The anthracene diamino phosphate of the present application has photosensitivity and 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 above described objects, features and advantages, the present application has other objects, features and advantages. These will become apparent from the following detailed description of the application, when read in conjunction with the accompanying drawings. BRIEF DESCRIPTION OF DRAWINGS

[0027] The accompanying drawings, which form a part of this specification, are included to provide a further understanding of the application, illustrate preferred embodiments of the present application and assist in

[0028] Figure 1 H-NMR chart of TM1 made by an embodiment of the present application 1 H-NMR chart of TM1 made by an embodiment of the present application

[0029] Figure 2 C-NMR chart of TM1 made by an embodiment of the present application 13 C-NMR chart of TM1 made by an embodiment of the present application

[0030] Figure 3 P-NMR chart of TM1 made by an embodiment of the present application 31 P-NMR chart of TM1 made by an embodiment of the present application

[0031] Figure 4 H-NMR chart of TM2 made by an embodiment of the present application 1 H-NMR chart of TM2 made by an embodiment of the present application

[0032] Figure 5 C-NMR chart of TM2 made by an embodiment of the present application 13 C-NMR chart of TM2 made by an embodiment of the present application

[0033] Figure 6 P-NMR chart of TM2 made by an embodiment of the present application 31 P-NMR chart of TM2 made by an embodiment of the present application

[0034] Figure 7 H-NMR chart of TM3 made by an embodiment of the present application 1 H-NMR chart of TM3 made by an embodiment of the present application

[0035] Figure 8 C-NMR chart of TM3 made by an embodiment of the present application 13 C-NMR chart of TM3 made by an embodiment of the present application

[0036] Figure 9 P-NMR chart of TM3 made by an embodiment of the present application 31 P-NMR chart of TM3 made by an embodiment of the present application

[0037] Figure 10 UV-Vis absorption spectrum chart of TM1~TM3 and DBA made by an embodiment of the present application DETAILED DESCRIPTION

[0038] In order to make the purposes, schemes and beneficial techniques of the present application clearer, the following further describes the present application in conjunction with the embodiments and drawings. It should be noted that the embodiments described in the present specification are merely for explaining the present application, and are not intended to limit the present application.

[0039] For 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 to form a range not explicitly recited. Furthermore, 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 limit or upper limit to combine with any other point or individual number or to combine with other lower limits or upper limits to form a range not explicitly recited.

[0040] In the description herein, it should be noted that, unless otherwise specified, "above", "below" are inclusive of the number, and the meaning of "multiple" in "one or more" is two or more, and the meaning of "multiple" in "one or more" is two or more.

[0041] The embodiment of the present application provides a diamino phosphoric acid anthracene ester for a photosensitive resin composition, comprising: (TM1), (TM2), (TM3)

[0042] one or two or more of them.

[0043] The photosensitive resin composition of the embodiment of the present application comprises, in parts 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 the diamino phosphoric acid anthracene ester. The diamino phosphoric acid anthracene ester 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 the diamino phosphoric acid anthracene ester and other photosensitizers.

[0044] When the content of the alkali-soluble resin is too low, there is a tendency of the resist layer to flow; when the content is too high, there is a tendency of resolution to decrease.

[0045] When the content of the photopolymerization monomer is too low, there is a tendency of the sensitivity and chemical resistance of the resist to decrease; when the content is too high, there is a tendency of the photosensitive resin composition to be difficult to filmize and the resist layer to flow.

[0046] When the content of the photoinitiator is too low, there is a tendency of the sensitivity and resolution of the resist to decrease; when the content is too high, there is a tendency of the development garbage to increase.

[0047] When the photosensitizer content is too low, the sensitivity of the resist tends to decrease, and 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 a poor resolution.

[0048] 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.

[0049] In embodiments of the present application, the alkali-soluble resin is an acrylate copolymer including an aromatic group.

[0050] In embodiments of the present application, the photopolymerization monomer is an ethylenically unsaturated carboxylic acid and / or an ethylenically unsaturated carboxylic acid ester.

[0051] In embodiments of the present application, the photoinitiator is a bis-imidazole compound.

[0052] 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.

[0053] In embodiments of the present application, the alkali-soluble resin has a weight average molecular weight of 20,000 to 60,000.

[0054] In embodiments of the present application, the alkali-soluble resin has an acid value of 160 to 220 mg KOH / g.

[0055] In embodiments of the present application, the alkali-soluble resin has a molecular weight distribution of 1.0 to 3.0.

[0056] In embodiments of the present application, the photopolymerization monomer is a methacrylate monomer and / or an acrylate monomer.

[0057] In embodiments of the present application, the photoinitiator is a 2,4,5-triaryl imidazole dimer.

[0058] In embodiments of the present application, the alkali-soluble resin is obtained by copolymerization of one or more of acrylic acid, methacrylic acid, an alkyl acrylate, an alkyl methacrylate, a hydroxyalkyl acrylate, a hydroxyalkyl methacrylate, a benzyl acrylate, a benzyl methacrylate, a benzyl acrylate derivative, a benzyl methacrylate derivative, a phenyl acrylate, a phenyl methacrylate, styrene, and a styrene derivative.

[0059] In embodiments 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, dipentaerythritol hexaacrylate.

[0060] In embodiments of the present application, the photoinitiator is one or two 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-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-biimidazole.

[0061] Typical biimidazole compounds, such as hexaarylbiimidazole (HABI): as a representative of biimidazole photoinitiators, its maximum absorption peak is at 255-275 nm, and it 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 the biimidazole photoinitiator to about 405 nm by the photosensitizer.

[0062] In embodiments of the present application, the photosensitive resin composition containing the anthracene diamino phosphate includes 55-60 parts by mass of alkali-soluble resin, 40-49 parts by mass of photopolymerization monomer, 2.2-4 parts by mass of photoinitiator, and 0.1-1 part by mass of photosensitizer.

[0063] In some embodiments of the present application, the photosensitive resin composition containing the anthracene diamino phosphate includes 45-48 parts by mass of photopolymerization monomer (corresponding to 55-60 parts by mass of alkali-soluble resin).

[0064] In some embodiments of the present application, the photosensitive resin composition containing the anthracene diamino phosphate includes 2.5-3.5 parts by mass of photoinitiator (corresponding to 55-60 parts by mass of alkali-soluble resin).

[0065] In some embodiments of the present application, the photosensitive resin composition containing the anthracene diamino phosphate ester includes 0.2-0.8 parts by mass of a photosensitizer (corresponding to 55-60 parts by mass of alkali-soluble resin per 1).

[0066] In embodiments of the present application, 0.5-5.0 parts by mass of an additive is further included; the additive is one or two or more of a dye, a phototoning agent, a plasticizer, an adhesion promoter, a polymerization inhibitor, an antifoaming agent, and a coating aid (corresponding to 50-65 parts by mass of alkali-soluble resin per 1).

[0067] In embodiments of the present application, a photosensitive dry film includes a support layer, a photosensitive resist layer, and a protective layer arranged in this order; the photosensitive resist layer includes at least one of the anthracene diamino phosphate ester and the photosensitive resin composition.

[0068] The support layer material of the photosensitive dry film is PET.

[0069] The protective layer material of the photosensitive dry film is PE.

[0070] One or two or more of the anthracene diamino phosphate ester, the photosensitive resin composition, and the photosensitive dry film in embodiments of the present application are used in a substrate with a resist pattern, a printed circuit board, a lead frame, a semiconductor package substrate, a solar cell, and a photocured ink.

[0071] The products that are currently highly marketable in the anthracene photosensitizer market 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, these photosensitizers also have the following shortcomings:

[0072] (1) The 9,10-dibutoxyanthracene photosensitizer, although having an advantage in solubility, the 9,10 C-O bond thereof will break during exposure, the anthracene ring will dimerize, and small molecule alkoxy fragments will be released, which will migrate from the cured photosensitive resin composition to the plating solution in the subsequent plating process, causing pollution and affecting the plating solution life and plating effect;

[0073] (2) DPHA, although having the advantage of high light quantum yield, has poor solubility due to the large conjugated system and high rigidity of the molecule;

[0074] (3) DAcOA, due to the electron-withdrawing induction effect of the acetoxy group, the electron cloud density of the anthracene ring at No. 9,10 is increased, so that the curing efficiency of this type of photosensitizer is reduced, the verticality of the side wall of the cured photosensitive resin composition is poor, and the length difference between the top and bottom lines is large, forming an "inverted trapezoidal" problem; it cannot meet the needs of fine line manufacturing;

[0075] The present application provides a diamino phosphoric acid anthracene, which has the following technical advantages:

[0076] (1) Reduce the risk of migration: anthracene group and large polar, large size group is directly connected, can greatly inhibit small molecular fragments migration, hinder the photosensitizer molecules to PE film penetration diffusion, improve product yield;

[0077] (2) Excellent adhesion: amino phosphate derivatives can form stable complex with a variety of transition metals, such as Pd, Pt, Cu and so on, also can greatly improve the adhesion of such photosensitizer on the surface of copper foil;

[0078] The diamino phosphoric acid anthracene of the present application has photosensitivity, which can replace the existing anthracene photosensitizer in photosensitive resin as photosensitizer, and at the same time, it can enhance the adhesion on the surface of metal foil. Through the innovation of molecular structure, the present application simultaneously realizes low migration, excellent adhesion, and meets the needs of high density line manufacturing, high fineness, high density and multi-layer.

[0079] Examples

[0080] The following examples more specifically describe the present application, which are only used for illustrative purposes, because various modifications and changes within the scope of the present application 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 are available through conventional commercial channels or are synthesized according to conventional methods, and can be used directly without further treatment. Unless otherwise stated, the instruments used in the examples are available through conventional commercial channels.

[0081] (I) Preparation and detection of diamino phosphoric acid anthracene

[0082] (1) Preparation of TM1

[0083] The reaction formula for preparing TM1 can be written as:

[0084] .

[0085] The specific preparation method of TM1 is as follows:

[0086] In a round bottom flask equipped with magnetic stirring, under nitrogen atmosphere, the material anthrone (2 mmol) and potassium hydroxide (2 mmol) were added in a 1 :2 molar ratio and dissolved in 6 mL of dry acetone, then bis(dimethylamino)phosphoryl chloride (8 mmol) was slowly added dropwise; after the addition was complete, the reaction mixture was left to react at 60°C until TLC monitored the consumption of the starting material anthrone; the reaction mixture was washed with water, extracted with dichloromethane, and the organic phases were combined and dried; the crude product was purified by column chromatography (yield 80%).

[0087] Figure 1 is TM1 1 H-NMR spectrum; 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 = 6.8Hz, 2H), 2.75 (d, J = 10.0 Hz, 12H)。

[0088] Figure 2 is TM1 13 C-NMR spectrum; 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)。

[0089] Figure 3 is TM1 31 P-NMR spectrum; 31P NMR (162 MHz, CDCl3) delta 16.4 ( J = 19.6, 10.1 Hz)。

[0090] (2) Preparation of TM2

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

[0092] .

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

[0094] 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 of reaction, bis(dimethylamino)phosphoryl chloride (8 mmol) was added dropwise. After the temperature was raised to 60°C for 16 h of reaction, 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 65%).

[0095] Figure 4 is 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).

[0096] Figure 5 is TM2 13C-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.

[0097] Figure 6 It's TM2. 31 P-NMR spectrum; 31 p NMR (162 MHz, CDCl3) delta 16.2 ( J = 19.7, 9.8 Hz).

[0098] (3) Preparation of TM3

[0099] The reaction formula for preparing TM3 can be written as:

[0100] .

[0101] The specific preparation method of TM3 is as follows:

[0102] Under nitrogen atmosphere, 2-ethylanthraquinone (2 mmol), sodium hydrosulfite (6 mmol) and methyltrioctylammonium bromide (0.2 mmol) were added into a round bottom flask equipped with magnetic stirring in a molar ratio of 1:3:0.1, followed by dropwise addition of 6 mL of dry toluene solvent, after dropwise addition was completed, 35% NaOH aqueous solution (NaOH total 0.9 mmol) was slowly added, after reaction for 30 min, 35% NaOH aqueous solution (NaOH total 9.1 mmol) was slowly added, after warming to 45°C for 1 h, bis(dimethylamino)phosphoryl chloride (8 mmol) was added, and after warming to 60°C for 16 h, the reaction was monitored by TLC, after extraction with dichloromethane, the obtained oily crude product was purified by column chromatography (yield 78%).

[0103] Figure 7 TM3 is 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)。

[0104] Figure 8 TM3 is 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。

[0105] Figure 9 TM3 is 31 P-NMR spectrum; 31 P NMR (162 MHz, CDCl3) delta 16.7(dd, J = 24.7, 4.0Hz)。

[0106] (4) UV-Vis spectrum

[0107] 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: 8 x 10 -5mol / 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 was the absorbance of the UV-Vis absorption spectrum, and c was the concentration (mol / L), and the results are shown in Table 1. The UV-Vis spectra of TM1-TM3 and DBA prepared are shown in Figure 10

[0108] As can be seen from the molar extinction coefficient in Table 1, the molar extinction coefficient of the anthracene diamino phosphate of the present application is comparable to that of DBA, proving that such a photosensitizer has good photo-radical conversion ability.

[0109] Table 1 Molar extinction coefficient of TM1-TM3 and DBA

[0110]

[0111] (B) Preparation of the photosensitive resin composition

[0112] Examples and comparative examples were set up, and examples 1-12 used TM1-TM3 as photosensitizers, and comparative examples used DBA, DPHA, and DAcOA as photosensitizers, respectively. Referring to the formulations shown in Tables 2 and 3, the components were mixed uniformly to prepare the photosensitive resin composition. The data in Tables 2 and 3 are in mass parts, and "-" indicates that no component was added.

[0113] Table 2 Formulation of the photosensitive resin composition of examples 1-9

[0114]

[0115] The components and specific information of each component in Tables 2 and 3 are as follows:

[0116] The alkali-soluble resin (A) was an acrylate copolymer prepared by solution polymerization, and the monomers were polymerized in a 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.);

[0117] The photopolymerization monomer (B) was composed of the following components (purchased from Sartomer Guangzhou Chemical Co., Ltd.): 5 parts of methoxypolyethylene glycol (350) monoacrylate, 20 parts of 10 (ethoxyl) bisphenol A dimethacrylate, 5 parts of 6 (propoxy) bisphenol A dimethacrylate, 10 parts of 3 (ethoxyl) trimethylolpropane triacrylate, and 4 parts of di (trimethylolpropane) tetraacrylate;

[0118] ​Photoinitiator (C): 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-2,2'- diimidazole (BCIM) was purchased from Jiuding Chemical;

[0119] Photosensitizer (D): DBA is 9,10-dibutoxyanthracene, DPHA is 9,10- diphenylanthracene, DAcOA is 9,10-diacetoxyanthracene, all purchased from Lejian;

[0120] Additive (E) consists of the following ingredients (purchased from Anjieji 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;

[0121] The solvent consists of the following ingredients: 8 parts of acetone, 10 parts of toluene, 5 parts of methanol.

[0122] Table 3 Formulation of photosensitive resin composition of Examples 10~12 and Comparative Examples

[0123]

[0124] (III) Preparation of photosensitive dry film

[0125] The photosensitive resin composition of Examples 1~12 and Comparative Examples 1~3 was used as raw material to prepare the photosensitive dry film, including the following steps:

[0126] The prepared photosensitive resin composition slurry was coated on a 15 μm thick polyethylene terephthalate (PET) support film using an experimental device (model: AB4220, TQC, Netherlands); the solvent was removed by baking at 80°C for 10 min, and the thickness of the photosensitive layer after baking was controlled at 30 μm, then a polyethylene film (PE) was coated for protection, to obtain the photosensitive dry film.

[0127] Before coating the film, the photosensitive resin composition can be adjusted to an appropriate viscosity by adding a solvent, acetone, so as to coat the film. The solvent will be removed after baking, and has no effect on the composition of the photosensitive dry film.

[0128] (IV) Preparation of substrate with resist pattern

[0129] The photosensitive resin composition of Examples 1~12 and Comparative Examples 1~3 was used as raw material to prepare the substrate with resist pattern, and the process was as follows:

[0130] (1) Photosensitive layer forming process: a photosensitive layer was formed on the substrate using the photosensitive composition;

[0131] (2) Exposure process: active light was irradiated on at least a part of the above photosensitive layer, so that the above area was photocured to form a cured area;

[0132] (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.

[0133] Hereinafter, the operation conditions of each step will be described in detail.

[0134] Photosensitive layer forming step: using a copper-clad laminate on 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.

[0135] 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 step number was controlled to be 14-18 steps.

[0136] 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 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.

[0137] (Five) Evaluation Items

[0138] (1) Photosensitivity Evaluation

[0139] Photosensitivity evaluation tests were 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 20 min or more, 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. When the number of remaining steps of the step exposure ruler obtained by the cured film was 16 steps, the exposure energy (mJ / cm 2 ) was evaluated, and the smaller the value, the better the photosensitivity.

[0140] (2) Adhesion Evaluation

[0141] The adhesion evaluation test was performed on the above-mentioned post-film-attached test substrate using a photomask data having a line width / interval width of n:400 (unit: μm) to expose with an energy that makes the residual stage number after developing the Stouffer 41 stage exposure ruler to be 16. After the developing 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 (μm) to evaluate the adhesion. The smaller the value, the better the adhesion.

[0142] (3) Evaluation of resist migration

[0143] The resist migration evaluation test was performed on Examples 1~12 and Comparative Examples 1~3 after the 3-layer structure of the photosensitive dry film was prepared. 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 350-450 nm. After the dry film was placed at 30℃ for 72 h, the PE film layer on the surface of the photosensitive dry film was removed, and the UV 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 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.

[0144] Judgment basis:

[0145] ○: migration rate A<0.01;

[0146] ×: migration rate A>0.01.

[0147] The test results of each evaluation item are summarized in Tables 4 and 5 below.

[0148] Table 4 Test results of each evaluation item of Examples 1~9

[0149]

[0150] Examples 1~9 used TM1~TM3 as photosensitizers and were tested at different dosages. The results in Table 4 show that TM1~TM3 not only greatly reduced the migration rate, but also exhibited excellent adhesion-enhancing effect.

[0151] Table 5 Test results of each evaluation item of Examples 10~12 and Comparative Examples 1~3

[0152]

[0153] Examples 10~12 use TM1~TM3 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; the results in Table 5 show that the photosensitive resin composition using the anthracene diamino phosphate 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; in terms of migration, the anthracene diamino phosphate of the present application also shows advantages.

[0154] The above only describes the preferred embodiments of the present application, and is not intended to limit the present application. Those skilled in the art can make various modifications and changes within the spirit and principle of the present application, and any modification, equivalent replacement or improvement within the scope should 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 two or more of acrylic acid, methacrylic acid, alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate, hydroxyalkyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, and styrene.

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-tri(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 0.5-5.0 parts by mass of an additive is further included; the additive is one or two or more of a dye, a phototoning agent, a plasticizer, an adhesion promoter, a polymerization inhibitor, and an antifoaming agent.

8. The photosensitive resin composition according to claim 2 or 3, characterized by ​ 9. A photosensitive dry film characterized by comprising: A photosensitive dry film comprising, in order, a support layer, a photosensitive resist layer, and a protective layer; the photosensitive resist layer comprising a composition comprising at least one of the anthracene diamino phosphate of claim 1 and the photosensitive resin composition of any one of claims 2 to 8.

10. Use of one or more of the anthracene diamino phosphate of claim 1, the photosensitive resin composition of any one of claims 2 to 8, or 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.

Images