Sensitizer, photosensitive resin composition, photosensitive dry film and preparation method thereof

Abstract

The invention provides a sensitizer, a photosensitive resin composition, a photosensitive dry film and a preparation method thereof, the structure of the sensitizer is as shown in formula (I): # imgabs0 # (I), M1 is selected from-O-or-NR4-, and R4 is selected from H or methyl; q is a single bond or-(CHCH) n-, and n is an integer of 1 or more; r1 is selected from aryl and heteroaryl, or R1 is selected from aryl or heteroaryl substituted by at least one substituent group of halogen, nitryl, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester group, C1-C8 alkyl, C1-C4 alkoxy and # imgabs 1 #, or R1 is selected from aryl or heteroaryl substituted by at least one substituent group of halogen, nitryl, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester group, C1-C8 alkyl, C1-C4 alkoxy and # imgabs 1 #; and R3 is selected from H, halogen, C1-C8 alkyl groups or C1-C4 alkoxy groups. Based on the sensitizer provided by the invention, the problems of low resolution, high sensitivity and low adhesive ability of a photosensitive resin composition in the prior art are solved.

Description

Technical Field

[0001] The present invention relates to the field of semiconductor technology, and in particular, to a sensitizer, a photosensitive resin composition, a photosensitive dry film, and a preparation method thereof. Background Art

[0002] In fine electronic circuits such as printed circuit boards, lead frames, solar cells, conductor packages, BGA (Ball Grid Array), and CPS (Chip Size Package) packages, they are generally manufactured by a process of forming a photoresist pattern through an optical etching method. For example, when manufacturing a printed circuit board, first, a photosensitive layer is formed on a substrate, covered with a mask having a certain pattern on the photosensitive layer, and subjected to pattern exposure. Then, after developing with a developer having different solubilities between the exposed part and the unexposed part, etching or electroplating treatment is performed to form a pattern, and finally, the cured part of the dry film is peeled off with a remover to achieve pattern transfer.

[0003] As electronic devices develop towards being thinner, lighter, shorter, and smaller, there are corresponding requirements for PCBs to be more highly refined, high-density, and multi-layered. For example, for high-precision HDI multi-layer boards (high-density interconnect printed circuit boards), there are higher requirements for the resolution, sensitivity, and adhesion on the substrate of the photosensitive resin composition used in the optical etching method. Therefore, it is of great significance to develop a photosensitive resin composition with high resolution, high photosensitivity, and high adhesion ability. Summary of the Invention

[0004] The main object of the present invention is to provide a sensitizer, a photosensitive resin composition, a photosensitive dry film, and a preparation method thereof to solve the problems of low resolution, high photosensitivity, and low adhesion ability of the photosensitive resin composition in the prior art.

[0005] To achieve the above object, according to the first aspect of the present invention, a sensitizer is provided, and the structure of the sensitizer is shown in formula (I):

[0006]

[0007] (I)

[0008] Wherein, M1 is selected from -O- or -NR4-, and R4 is selected from H or methyl;

[0009] Q is a single bond or -(CHCH) n -, and n is an integer from 1 to 3;

[0010] R1 is selected from aryl, heteroaryl, or R1 is selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester group, C1-C8 alkyl, C1-C4 alkoxy, aryl or heteroaryl substituted with at least one substituent; R5 is selected from carboxyl, C1-C4 ester group, vinyl, aryl, heteroaryl, benzoyl, or R5 is selected from aryl, heteroaryl or benzoyl substituted with at least one substituent selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester group, C1-C8 alkyl, C1-C4 alkoxy; M2 is selected from -O- or -NR6-, and R6 is selected from H or methyl;

[0011] R2 is selected from carboxyl, C1-C4 ester group, vinyl, aryl, heteroaryl, benzoyl, or R2 is selected from aryl, heteroaryl or benzoyl substituted with at least one substituent selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester group, C1-C8 alkyl, C1-C4 alkoxy;

[0012] R3 is selected from H, halogen, C1-C8 alkyl or C1-C4 alkoxy.

[0013] Further, M1 is located at the para position of the pyrazoline ring.

[0014] Preferably, R1 is selected from phenyl, naphthyl, anthryl, phenanthryl, biphenyl, 9H-fluorenyl, or R1 is phenyl, naphthyl, anthryl, phenanthryl, biphenyl or 9H-fluorenyl substituted with at least one substituent selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester group, C1-C8 alkyl, C1-C4 alkoxy, in the phenyl, naphthyl, anthryl, phenanthryl, biphenyl or 9H-fluorenyl.

[0015] Further, the sensitizer is selected from one or more of the following structures:

[0016]

[0017]

[0018] .

[0019] According to the second aspect of the present invention, a photosensitive resin composition is provided, comprising: an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, and a sensitizer as described above.

[0020] Preferably, the photosensitive resin composition comprises 45 to 65 parts by weight of an alkali-soluble resin, 35 to 50 parts by weight of a photopolymerizable monomer, 2.0 to 5.0 parts by weight of a photoinitiator, and 0.01 to 1.0 part by weight of a sensitizer.

[0021] More preferably, by weight, the photosensitive resin composition further comprises 0.5 to 5 parts of an additive, and the additive is selected from a combination of one or more of a color former, a dye, a plasticizer, a photo-thermal stabilizer, an adhesion promoter, a leveling agent, an antifoaming agent, a polymerization inhibitor in any proportion.

[0022] Furthermore, the photoinitiator includes at least one of the hexaarylbiimidazole derivatives represented by formula (II) and the acridine derivatives represented by formula (III):

[0023]

[0024] (II)

[0025]

[0026] (III)

[0027] In formula (II), each A is independently selected from one of methoxy and halogen atoms, and each n4 is independently selected from an integer of 0 to 5;

[0028] In formula (III), R c is selected from H, C1-C6 alkyl, C1-C6 alkoxy, aryl, or aryl substituted by at least one substituent of halogen atom, C1-C6 alkyl, C1-C6 alkoxy, or pyridylalkyl.

[0029] Preferably, the hexaarylbiimidazole derivatives represented by formula (II) are selected from one or more of 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,2’,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4’,5’-diphenyl-1,1’-diimidazole, and 2,2’-bis(2-chlorophenyl)-4,4’,5,5’-tetraphenylbiimidazole.

[0030] Preferably, the acridine derivatives represented by formula (III) are selected from one or more of 9-methylacridine, 9-ethylacridine, 9-phenylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 1,7-bis(9,9’-acridinyl)heptane, 9-(4-n-propylphenyl)acridine, 9-(4-n-butylphenyl)acridine, 9-(4-tert-butylphenyl)acridine, 9-(4-methoxyphenyl)acridine, 9-(4-ethoxyphenyl)acridine, 9-m-tolylacridine, 9-o-tolylacridine, 9-p-tolylacridine, and 9-p-chlorophenylacridine.

[0031] Preferably, the photoinitiator further comprises one or more of benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, benzoin methyl ether, benzoin phenyl ether, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-ethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzil derivatives such as benzil dimethyl ketal, N-phenylglycine, triarylamine compounds, oxime ester compounds, coumarin compounds, oxazole compounds, etc.

[0032] Furthermore, the photopolymerizable monomer comprises an EO / PO-modified bisphenol A structure acrylate represented by the general formula (IV):

[0033]

[0034] (IV)

[0035] In formula (IV), two Rs a are independently selected from H or methyl; m1 and m2 are each selected from integers of 1 to 30, n1 and n2 are each selected from integers of 0 to 20, and the sum of m1 and m2 is an integer of 2 to 20, and the sum of n1 and n2 is an integer of 0 to 20; the arrangement of the EO and PO repeating units is random or block, EO is an ethylene oxide unit, and PO is a propylene oxide unit.

[0036] Preferably, the photopolymerizable monomer further comprises one or more of lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, ethoxylated nonylphenol acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, polyethylene glycol (propylene glycol) dimethacrylate, polyethylene glycol (propylene glycol) diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethoxylated (propoxylated) trimethylolpropane triacrylate, ethoxylated propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc.

[0037] Furthermore, the alkali-soluble resin comprises an alkali-soluble copolymer resin represented by the general formula (V):

[0038]

[0039] (V)

[0040] In formula (V), R8 and R9 are each independently selected from one or more of a hydrogen atom, a methyl group, a dialkylamino group, or a methyl group substituted with a dialkylamino group; R 10 is selected from a C1-C 18 linear alkyl group, a C1-C 18 branched alkyl group, a C1-C linear alkyl group substituted with at least one substituent selected from a hydroxyl group and an amino group, 18 a C1-C linear alkyl group substituted with at least one substituent selected from a hydroxyl group and an amino group, 18 a C1-C linear alkyl group, a benzyl group, and a phenoxyethyl group; each R7 is independently selected from one of H, a C1-C3 alkyl group, a C1-C3 alkoxy group, an amino group, and a halogen atom, and n3 is an integer from 0 to 5; x, y, and z respectively represent the weight percentages of the respective structural units in the alkali-soluble copolymer resin, wherein x is 15% to 35%, y is 20% to 65%, and z is 0 to 55%.

[0041] Preferably, R 10 is selected from a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, an isooctyl group, a lauryl group, an octadecyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a glycidyl group, a benzyl group, or a phenoxyethyl group.

[0042] Preferably, n3 is 1, R7 is selected from H or a methyl group, and z is 5% to 55%.

[0043] Preferably, the weight-average molecular weight of the alkali-soluble copolymer resin is 30,000 to 80,000, and the acid value of the alkali-soluble resin is represented by the weight of potassium hydroxide consumed to neutralize each gram of the alkali-soluble copolymer resin. The acid value of the alkali-soluble copolymer resin is 120 to 250 mg KOH / g.

[0044] Preferably, the molecular weight distribution of the alkali-soluble copolymer resin is 1.3 to 2.5, and the polymerization conversion rate ≥ 97%.

[0045] According to the third aspect of the present invention, a photosensitive dry film is provided, which includes a support layer, a dry film resist layer, and a protective layer stacked in sequence, and the dry film resist layer includes the photosensitive resin composition as described above.

[0046] Preferably, the material of the support layer is selected from PET, and the thickness of the support layer is 10 um to 20 um.

[0047] Preferably, the thickness of the dry film resist layer is 10 um to 100 um.

[0048] Preferably, the material of the protective layer is selected from polyethylene, and the thickness of the protective layer is 10um to 30um.

[0049] According to a fourth aspect of the present invention, there is provided a method for preparing the above photosensitive dry film, comprising the following steps:

[0050] Step S1, mixing an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, a sensitizer and a solvent to obtain a resin composition solution;

[0051] Step S2, after the resin composition solution is allowed to stand for 25 minutes to 35 minutes, it is coated on the surface of the support layer and dried to form a dry film resist layer;

[0052] Step S3, laminating a protective layer on the surface of the dry film resist layer to obtain a photosensitive dry film.

[0053] Furthermore, the content of the resin composition in the resin composition solution is 30% to 50% by weight.

[0054] Furthermore, the solvent is selected from one or more of acetone, butanone, methanol, ethanol, isopropanol and toluene.

[0055] Furthermore, the drying is carried out at 80° C. to 100° C. for 5 min to 15 min.

[0056] The technical scheme of the present invention is applied to a pyrazoline structure with a specific substituent. On the one hand, the structure of the sensitizer retains the structure of pyrazoline, and the pyrazoline compound has a certain photosensitivity to a 405nm laser light source, and has good resolution when used to prepare a photosensitive dry film. On the other hand, the structure of the sensitizer contains heteroatoms of nitrogen or oxygen, and the lone pair of electrons on the nitrogen or oxygen atom forms a p-π conjugation with the benzene ring, so that the ultraviolet absorption is red-shifted, which can increase the photosensitivity of the photosensitive resist resin composition to the H-ray (405nm) exposure light source. In addition, the structure contains heteroatoms of nitrogen or oxygen, and the α-position carbon of the heteroatom is connected to a benzene ring, an aromatic group, a carbonyl group, an allyl group, etc. having an electron-withdrawing π bond, so that the H on the α-position carbon of the heteroatom is weakly acidic and has high activity. The initiator free radical is more likely to capture the H atom from the more active α-position carbon to generate an amine alkyl free radical or an oxyalkyl free radical with a higher reaction activity, thereby initiating the polymerization reaction of the photopolymerization monomer, which is conducive to the photopolymerization reaction to be carried out more quickly, efficiently, and thoroughly. The sensitizer based on the present invention has excellent photosensitivity and activity, can improve the photocuring rate and bottom curing degree of the dry film resist layer, so that the dry film resist layer has excellent exposure efficiency and photosensitivity, excellent resolution and adhesion, and the side wall morphology of the dry film resist layer has high rectangularity. DETAILED DESCRIPTION

[0057] It should be noted that, without conflict, the embodiments in the present application and the features in the embodiments can be combined with each other. The present invention will be described in detail below with reference to the embodiments.

[0058] As described in the background art, there are problems in the prior art such as low resolution, high photosensitivity, and low adhesion ability of the photosensitive resin composition. To solve the above problems, according to the first aspect of the present invention, a sensitizer is provided, and the structure of the sensitizer is shown in formula (I):

[0059]

[0060] (I)

[0061] Wherein, M1 is selected from -O- or -NR4-, and R4 is selected from H or methyl;

[0062] Q is a single bond or -(CHCH) n -, and n is an integer from 1 to 3;

[0063] R1 is selected from aryl, heteroaryl, or R1 is an aryl or heteroaryl substituted with at least one substituent selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester, C1-C8 alkyl, C1-C4 alkoxy, R5 is selected from carboxyl, C1-C4 ester, vinyl, aryl, heteroaryl, benzoyl, or R5 is an aryl, heteroaryl, or benzoyl substituted with at least one substituent selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester, C1-C8 alkyl, C1-C4 alkoxy; M2 is selected from -O- or -NR6-, and R6 is selected from H or methyl;

[0064] R2 is selected from carboxyl, C1-C4 ester, vinyl, aryl, heteroaryl, benzoyl, or R2 is an aryl, heteroaryl, or benzoyl substituted with at least one substituent selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester, C1-C8 alkyl, C1-C4 alkoxy;

[0065] R3 is selected from H, halogen, C1-C8 alkyl, or C1-C4 alkoxy.

[0066] Based on the sensitizer of the present invention, the pyrazoline structure with a specific substituent, on the one hand, the structure of the pyrazoline is retained in the structure of the sensitizer, and the pyrazoline compound has a certain photosensitivity to a 405nm laser light source, and has good resolution when used to prepare a photosensitive dry film. On the other hand, the structure of the sensitizer contains heteroatoms nitrogen or oxygen (M1 is selected from -O- or -NR4-), and the lone pair of electrons on the nitrogen or oxygen atom forms a p-π conjugation with the benzene ring, so that the ultraviolet absorption is red-shifted, which can increase the photosensitivity of the photosensitive resist resin composition to the H-ray (405nm) exposure light source. In addition, the structure contains heteroatom nitrogen or oxygen, and the α-position carbon of the heteroatom is connected to a benzene ring, an aromatic group, a carbonyl group, an allyl group, etc. having an electron-withdrawing π bond, so that the H on the α-position carbon of the heteroatom is weakly acidic and has high activity, and the initiator free radical is more likely to capture the H atom from the α-position carbon with higher activity, generating an amine alkyl free radical or an oxyalkyl free radical with higher reaction activity, thereby initiating the polymerization reaction of the photopolymerization monomer, which is conducive to the photopolymerization reaction being carried out more quickly, efficiently, and thoroughly. Based on the sensitizer of the present invention, it has excellent photosensitivity and activity, can improve the rate of photocuring and the bottom curing degree of the dry film resist layer, so that the dry film resist layer has excellent exposure efficiency and photosensitivity, has excellent resolution and adhesion, and the sidewall morphology of the dry film resist layer has high rectangularity.

[0067] In some embodiments, M1 is located in the para position of the pyrazoline ring. Based on the technical solution of the embodiments of the present invention, when M1 is arranged in the para position to the pyrazoline ring, the sensitizer has higher photosensitivity, and the H on the α-position carbon of the heteroatom has higher reactivity.

[0068] Preferably, R1 is selected from phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, 9H-fluorenyl, or R1 is halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester, C1-C8 alkyl, C1-C4 alkoxy, The phenyl group is substituted with at least one substituent, such as phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl or 9H-fluorenyl.

[0069] More preferably, R1 is selected from phenyl, naphthyl, anthracenyl, phenanthrenyl, biphenyl, 9H-fluorenyl, or R1 is selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester, C1-C8 alkyl, C1-C4 alkoxy, The phenyl group is substituted with at least one substituent, and the substituent is located at the para position of Q. The phenyl group having the above substituent structure has a good electron-withdrawing effect, is adjacent to and conjugated with the pyrazoline ring, can effectively reduce the charge density of the pyrazoline ring, increase the stability of the pyrazoline ring, and thus make the photosensitive resin composition have a relatively stable photosensitivity.

[0070] In some embodiments, in order to obtain high photosensitivity and resolution, and at the same time obtain a dry film resist layer head topography close to a rectangle, the sensitizer is selected from one or more of the following structures:

[0071]

[0072]

[0073] 。

[0074] According to a second aspect of the present invention, a photosensitive resin composition is provided, comprising: an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, and a sensitizer as described above.

[0075] Based on the photosensitive resin composition of the present invention, the sensitizer molecule structure inherently has a very active hydrogen donor structural unit. In the corresponding photosensitive resin composition system, there is no need to additionally add a hydrogen donor. The initiator radical can undergo an intermolecular reaction with the hydrogen donor structural unit in the sensitizer molecule structure, improving the efficiency of generating active radicals in the reaction, which is beneficial to improving the photocuring rate and bottom curing degree of the dry film resist layer, enabling the dry film resist layer to have excellent exposure efficiency and photosensitivity, with excellent sensitivity, resolution, and adhesion, and can be used for manufacturing high-precision HDI inner layer boards.

[0076] In one embodiment, the photosensitive resin composition comprises 45 - 65 parts of an alkali-soluble resin, 35 - 50 parts of a photopolymerizable monomer, 2.0 - 5.0 parts of a photoinitiator, and 0.01 - 1.0 part of a sensitizer. The alkali-soluble resin provides the necessary developing performance and film-forming property, ensuring that the dry film resist layer can be effectively dissolved by an alkaline developer after exposure, while maintaining good mechanical strength and chemical stability. The photopolymerizable monomer is the photoactive component in the photosensitive film, and can undergo a photopolymerization reaction under the synergistic action of the photoinitiator and the sensitizer to form a cured layer insoluble in the alkaline developer, which can affect the resolution and photosensitivity of the photosensitive film. The photoinitiator initiates the polymerization reaction of the photopolymerizable monomer under light illumination, and the addition amount thereof affects the speed and depth of the photocuring reaction. By combining the alkali-soluble resin, the photopolymerizable monomer, the photoinitiator, and the sensitizer and with the above-mentioned ratios, it is beneficial to improve the photocuring rate and bottom curing degree of the dry film resist layer, obtain a dry film resist layer with high photosensitivity, high resolution, excellent adhesion, and filling performance, which is beneficial to manufacturing high-precision HDI inner layer boards, significantly improving the fineness of the circuit and the yield of the board manufacturing, while reducing the exposure time and improving the production efficiency.

[0077] In one embodiment, the photosensitive resin composition further comprises 0.5 to 5 parts by weight of an additive, and the additive is selected from one or more of a color former, a dye, a plasticizer, a photo-thermal stabilizer, an adhesion promoter, a leveling agent, an antifoaming agent, and a polymerization inhibitor in any proportion combination.

[0078] In some embodiments, the photoinitiator comprises at least one of a hexaarylbiimidazole derivative represented by formula (II) and an acridine derivative represented by formula (III):

[0079]

[0080] (II)

[0081]

[0082] (III)

[0083] In formula (II), each A is independently selected from one of a methoxy group and a halogen atom, and each n4 is independently selected from an integer of 0 to 5;

[0084] In formula (III), R c is selected from H, a C1-C6 alkyl group, a C1-C6 alkoxy group, an aryl group, or an aryl group substituted by at least one of a halogen atom, a C1-C6 alkyl group, and a C1-C6 alkoxy group, or a pyridylalkyl group.

[0085] Based on the technical solution of the embodiments of the present invention, the biimidazole moiety in the molecular structure of the hexaarylbiimidazole derivative can absorb light of a specific wavelength (such as UV light) and decompose to generate free radicals or cations under light irradiation. The free radicals or cations will then initiate the polymerization reaction of the photopolymerizable monomer, resulting in the curing of the photosensitive resin composition. Using the hexaarylbiimidazole derivative represented by formula (II) as a photoinitiator can significantly improve the photosensitivity of the dry film resist layer, especially under a 405 nm laser light source, which helps to shorten the exposure time and improve production efficiency. At the same time, the use of such compounds helps to improve the resolution of the photosensitive material, enabling the dry film resist layer to form finer patterns, which is helpful for fabricating high-density and high-precision HDI circuit boards. The acridine derivative also has light absorption ability. Selecting the acridine derivative as a photoinitiator can enhance the photosensitivity of the photosensitive resin composition to a light source with a wavelength of 350 to 420 nm, improve the exposure efficiency, reduce the exposure time, and at the same time maintain or improve the resolution and adhesion. Using the hexaarylbiimidazole derivative represented by formula (II) and the acridine derivative represented by formula (III) as photoinitiators can improve the photosensitivity, resolution, and adhesion of the dry photosensitive resin composition.

[0086] In one embodiment, in order to improve the photosensitivity, resolution, and adhesion of the dry photosensitive resin composition, the hexaarylbiimidazole derivative represented by formula (II) is selected from one or more of 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole. Specifically, the above-mentioned hexaarylbiimidazole derivative can be purchased as a commercially available product or prepared by oneself.

[0087] In one embodiment, in order to improve the photosensitivity, resolution, and adhesion of the dry photosensitive resin composition, the acridine derivative represented by formula (III) is selected from one or more of 9-methylacridine, 9-ethylacridine, 9-phenylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 1,7-bis(9,9'-acridinyl)heptane, 9-(4-n-propylphenyl)acridine, 9-(4-n-butylphenyl)acridine, 9-(4-tert-butylphenyl)acridine, 9-(4-methoxyphenyl)acridine, 9-(4-ethoxyphenyl)acridine, 9-m-tolylacridine, 9-o-tolylacridine, 9-p-tolylacridine, and 9-p-chlorophenylacridine.

[0088] In one embodiment, the photoinitiator further includes one or more of benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, benzoin methyl ether, benzoin phenyl ether, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-ethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzil derivatives such as benzil dimethyl ketal, N-phenylglycine, triarylamine compounds, oxime ester compounds, coumarin-based compounds, oxazole-based compounds, etc. In addition to the above-mentioned hexaarylbiimidazole derivative and acridine derivative photoinitiators, the above-mentioned other types of photoinitiators can also be used in combination. By mixing different types of photoinitiators, the light response range of the photosensitive resin composition can be broadened, making the material sensitive to light of multiple wavelengths, so that it can exhibit good performance under different exposure equipment and conditions. In addition, the combined use of the above-mentioned photoinitiators also helps to balance the curing speed, curing depth, and physical and chemical properties of the material, such as adhesion, flexibility, and corrosion resistance, to meet the high requirements for the production of HDI inner layer boards.

[0089] In one embodiment, the photopolymerizable monomer comprises an EO / PO-modified bisphenol A structure acrylate represented by the general formula (IV):

[0090]

[0091] (IV)

[0092] In formula (IV), two Rs a are each independently selected from H or methyl; m1 and m2 are each selected from integers of 1 to 30, n1 and n2 are each selected from integers of 0 to 20, and the sum of m1 and m2 is an integer of 2 to 20, and the sum of n1 and n2 is an integer of 0 to 20; the arrangement of the EO and PO repeating units is random or block, EO is an ethylene oxide unit, and PO is a propylene oxide unit.

[0093] Based on the technical solution of the embodiments of the present invention, the EO / PO (ethylene oxide / propylene oxide) monomer can form a polymer with flexible segments by polymerizing with the acrylate of the bisphenol A structure. The presence of these flexible segments improves the fluidity of the resin and the adhesion to the substrate, and at the same time reduces the glass transition temperature (Tg) of the polymer, enabling it to maintain good flexibility at lower temperatures. Using the EO / PO-modified bisphenol A structure (meth)acrylate as the photopolymerizable monomer can significantly improve the filling property, resolution and adhesion in the dry and wet laminating of the photosensitive resin composition, while maintaining good photosensitivity. The introduction of this monomer enables the dry film resist layer to form clear and high-density patterns after exposure and is not easily detached from the copper surface, which is beneficial for the preparation of high-precision HDI inner layer boards.

[0094] In one embodiment, the photopolymerizable monomer further comprises one or more of lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, ethoxylated nonylphenol acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, polyethylene glycol (propylene glycol) dimethacrylate, polyethylene glycol (propylene glycol) diacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethoxylated (propoxylated) trimethylolpropane trimethacrylate, ethoxylated propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate.

[0095] Based on the technical solution of the embodiment of the present invention, acrylate monomers with two or more functional groups, such as bisphenol A dimethacrylate, trimethylolpropane trimethacrylate, etc., can form a network structure with a high degree of crosslinking due to the presence of multiple polymerizable double bonds. This highly crosslinked structure helps to improve the mechanical strength and chemical stability of the photosensitive dry film, and optimize the photocuring efficiency and physical properties of the material.

[0096] In some embodiments, the alkali-soluble resin comprises an alkali-soluble copolymer resin represented by the general formula (V):

[0097]

[0098] (V)

[0099] In formula (V), R8 and R9 are each independently selected from one or more of a hydrogen atom, a methyl group, a dialkylamino group, or a methyl group substituted with a dialkylamino group; R 10 is selected from a C1-C 18 linear alkyl group, a C1-C 18 branched alkyl group, a C1-C linear alkyl group substituted with at least one substituent selected from a hydroxyl group and an amino group, a C1-C 18 linear alkyl group substituted with at least one substituent selected from a hydroxyl group and an amino group, a C1-C 18One of a linear alkyl group, a benzyl group, and a phenoxyethyl group; each R7 is independently selected from one of H, a C1-C3 alkyl group, a C1-C3 alkoxy group, an amino group, and a halogen atom, and n3 is an integer from 0 to 5; x, y, and z respectively represent the weight percentages of the respective structural units in the alkali-soluble copolymer resin, wherein x is 15% to 35%, y is 20% to 65%, and z is 0 to 55%.

[0100] Based on the technical solution of the embodiment of the present invention, R8 and R9, as the α-position substituents of the α,β-unsaturated carboxylic acid, can be a hydrogen atom, a methyl group, or a methyl group with a dialkylamino group, which helps to adjust the glass transition temperature and polymerization reaction activity of the resin, and improve the developability of the dry film resist layer and the adhesion to the substrate; R 10 Adopting the above substituent structure is beneficial to increasing the flexibility of the alkali-soluble resin and improving its filling performance on the substrate, reducing phenomena such as open circuits and notches in the dry film resist layer on the substrate with scratches and pits; R7 is a substituent on the benzene ring, and selecting the above structure can improve the solubility and thermal stability of the alkali-soluble resin. By adopting the above substituent structure and through the ratio of x, y, and z, the above alkali-soluble copolymer resin has good film-forming properties, can form a uniform and dense dry film resist layer, and after exposure and development, can effectively protect the substrate from etching or electroplating, ensuring the accurate transfer of the circuit pattern; in addition, the above alkali-soluble copolymer resin has good adhesion, can form a stable adhesion layer on the substrate surface, and prevent peeling or displacement in subsequent processing steps. Using the above alkali-soluble copolymer resin is beneficial to obtaining a dry film resist layer with high photosensitivity, high resolution, and good adhesion, and the photosensitive resin composition can exhibit excellent performance in dry and wet laminating processes, which is beneficial to the preparation of high-precision HDI inner layer boards.

[0101] The above alkali-soluble copolymer resin can be formed by free radical copolymerization of acrylic acid (or methacrylic acid), one or several acrylate esters (for example, methacrylate ester, N,N-dimethyl ethyl methacrylate) and styrene (or its derivatives). Specifically, the alkali-soluble copolymer resin for preparation can be obtained commercially, and the alkali-soluble copolymer resin can be prepared through the following steps: mixing the monomers evenly according to the ratio to obtain a mixture, mixing 100 g of the monomer mixture, 1.0 g of AIBN photoinitiator, 90 g of methyl ethyl ketone, and 15 g of ethanol, and stirring and dissolving to obtain a mixed solution; adding 35% of the mixed solution into a three-necked flask with nitrogen protection and a condensing reflux device through a peristaltic pump, heating the oil bath to 80 °C, stirring and reacting for 1 h, then dropping the remaining mixed solution, and adding it within 3 h; continuing to keep the temperature and react for 4 h, then raising the temperature to 90 °C, adding 5 g of methyl ethyl ketone solution dissolved with 0.2 g of AIBN photoinitiator in two portions, with an interval of 1 h between the two portions, after dropping, keeping the temperature and stirring for 2 h to end the reaction, and obtaining the above alkali-soluble copolymer resin.

[0102] In one embodiment, R 10 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, isooctyl, lauryl, octadecyl, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, glycidyl, benzyl or phenoxyethyl. For example, the acrylate copolymer monomer of the above alkali-soluble copolymer resin may contain methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isooctyl methacrylate, lauryl methacrylate, octadecyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, glycidyl methacrylate, N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-diethylaminopropyl methacrylate, N,N-dimethylaminobutyl methacrylate, N,N-diethylaminobutyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, isooctyl acrylate, lauryl acrylate, octadecyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, glycidyl acrylate, N,N-dimethylaminoethyl acrylate, N,N-diethylaminoethyl acrylate, N,N-diethylaminopropyl acrylate, N,N-dimethylaminobutyl acrylate, N,N-diethylaminobutyl acrylate, benzyl acrylate, phenoxyethyl acrylate, etc. Using the above copolymer monomers can improve the flexibility of the resin and its filling performance on the substrate.

[0103] In one embodiment, n3 is 1, R7 is selected from H or methyl, and z is 5% to 55%. The copolymer monomer of the above alkali-soluble copolymer resin contains styrene or methylstyrene, preferably styrene or α-methylstyrene. Since polystyrene and poly-α-methylstyrene have relatively high glass transition temperatures and good rigidity, using styrene or methylstyrene monomers in the above amounts to prepare the alkali-soluble copolymer resin can improve the rectangularity of the head topography, etching resistance, etc., and adhesion of the dry film resist layer, while ensuring good filling performance, which helps to fabricate high-density and high-precision HDI circuit boards.

[0104] In one embodiment, the weight-average molecular weight of the alkali-soluble copolymer resin is 30,000 to 80,000, and the acid value of the alkali-soluble resin is expressed by the weight of potassium hydroxide consumed per gram of the alkali-soluble copolymer resin. The acid value of the alkali-soluble copolymer resin is 120 to 250 mg KOH / g. When the molecular weight and acid value of the above alkali-soluble copolymer resin are within the above ranges, it can exhibit a faster reaction rate and more stable performance in processes such as development and film stripping, while maintaining good film-forming properties, thereby improving the resolution and adhesion of the dry film resist layer.

[0105] In one embodiment, the molecular weight distribution of the alkali-soluble copolymer resin is 1.3 to 2.5, and the polymerization conversion rate is ≥97%. This is conducive to obtaining a high-purity and high-quality alkali-soluble copolymer resin, improving the uniformity of the resin during the curing process, reducing the stress inside the polymer, and thus improving the resolution and adhesion of the dry film.

[0106] According to the third aspect of the present invention, a photosensitive dry film is provided, which includes a support layer, a dry film resist layer, and a protective layer stacked. The dry film resist layer includes the photosensitive resin composition as described above.

[0107] In some embodiments, the material of the support layer is selected from PET, and the thickness of the support layer is 10 μm to 20 μm. This is conducive to obtaining a photosensitive dry film with high mechanical strength, dimensional stability, good transparency, and light penetration, which helps with precise exposure and imaging.

[0108] In some embodiments, the thickness of the dry film resist layer is 10 μm to 100 μm, which is conducive to obtaining a photosensitive dry film with high exposure efficiency and good resolution.

[0109] In some embodiments, the material of the protective layer is selected from polyethylene, and the thickness of the protective layer is 10 μm to 30 μm. The thickness of the protective layer being 10 μm to 30 μm helps to improve the stability of the photosensitive dry film in subsequent processing steps.

[0110] According to the fourth aspect of the present invention, a method for preparing a photosensitive dry film as described above is provided, including the following steps:

[0111] Step S1: Mix an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, a sensitizer, and a solvent to obtain a resin composition solution;

[0112] Step S2: After standing the resin composition solution for 25 min to 35 min, coat it on the surface of the support layer, and dry it to form a dry film resist layer;

[0113] Step S3: Bond a protective layer to the surface of the dry film resist layer to obtain a photosensitive dry film.

[0114] Based on the technical solution of the embodiment of the present invention, first dissolve the resin composition in a solvent to form a resin composition solution, then let the resin composition solution stand to reduce bubbles and ensure the uniformity of components, and then prepare a dry film resist layer by coating and drying, which is beneficial to forming a uniform and stable dry film resist layer inside the photosensitive dry film, reducing the defective phenomena in the subsequent exposure, development and etching processes, and improving the production yield.

[0115] In some embodiments, based on weight percentage, the content of the resin composition in the resin composition solution is 30% - 50%, which is beneficial to the coating of the resin composition solution and the formation of a uniform and stable dry film resist layer.

[0116] In some embodiments, the solvent is selected from one or more of acetone, methyl ethyl ketone, methanol, ethanol, isopropanol, and toluene. The above organic solvents can effectively dissolve the photosensitive resin composition and volatilize rapidly during the coating and drying processes to form a uniform and dense dry film resist layer.

[0117] In some embodiments, the drying is carried out at 80°C - 100°C for 5 min - 15 min to effectively remove the solvent and cure the dry film resist layer.

[0118] According to the fifth aspect of the present invention, a method for preparing a sensitizer is further provided. Specifically, the following structures D-1 to D-15 are taken as examples for description.

[0119]

[0120] Wherein, R3 is selected from H, halogen, C1-C8 alkyl or C1-C4 alkoxy;

[0121] X and Y are each independently selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester, C1-C8 alkyl or C1-C4 alkoxy;

[0122] R 11 、R 12 are selected from C1-C4 alkyl;

[0123] R4 represents a hydrogen atom or a methyl group;

[0124] R6 represents a hydrogen atom or a methyl group.

[0125] Specifically, when R4 is H and R6 is H, the preparations of the above structures D-1 to D-7, D-10 to D-12 and the above structures D-8, D-9, D-13 to D-15 are as follows respectively:

[0126] (1) For the sensitizer D-1, its synthetic route is as shown in (A):

[0127] (A)

[0128] Specifically, the synthesis steps are as follows:

[0129] Step 1: In a 500 mL three-necked flask, add the raw materials 4-aminobenzaldehyde (12.1 g), sodium bicarbonate (8.4 g), and tetrahydrofuran (100 mL). After stirring evenly, slowly add N-ethoxycarbonylphthalimide (21.9 g) under the condition of cooling in an ice-water bath. After the raw materials are added, stir and react at room temperature for 7 h. Then monitor the reaction by spotting a TLC plate. When the raw material 4-aminobenzaldehyde is completely consumed, stop the reaction. After the reaction is completed, pour the reaction mixture into water (100 g) to obtain a mixed solution. Extract the mixed solution with ethyl acetate, 500 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (200 mL × 2), dry with anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. After purification by column chromatography, the intermediate compound D-1-1 of 4-aminobenzaldehyde protected by phthalimide is obtained.

[0130] Step 2: In a 500 mL three-necked flask, add the raw material acetophenone (12.0 g) shown in formula a-1, the intermediate compound D-1-1 (25.8 g), and ethanol (200 mL). Place the flask in a water bath at room temperature and stir for 15 min to dissolve the raw materials. Then add dropwise 40% NaOH aqueous solution (by weight percentage) (8 g) to the three-necked flask over 1 h. After the addition is completed, continue to stir and react at room temperature for 8 h. Then monitor the reaction by spotting a TLC plate. When the raw material compound D-1-1 is completely consumed, stop the reaction. Filter the resulting suspension under reduced pressure. Disperse the obtained solid crude product in a small amount of ethanol (150 mL), stir at room temperature for 30 min, then filter, collect the solid, and dry it using a rotary evaporator to remove the small amount of solvent wrapped in the solid, obtaining the intermediate product compound D-1-2.

[0131] Step 3: In a 500 mL three-necked flask, add the intermediate compound D-1-2 (32.5 g) and glacial acetic acid (60 g). Place it in an oil bath and stir to heat up to 50 °C. At 50 °C, slowly add dropwise phenylhydrazine (21.6 g) shown in formula b-1 over 1 h. After the addition is completed, heat up to 80 °C and react for 8 h. Then monitor the reaction by spotting a TLC plate. After the raw materials are completely consumed, stop the reaction. Cool to room temperature and dilute with ethanol (300 ml). Stir the resulting suspension at room temperature for 30 min, then filter under reduced pressure. Disperse the obtained solid crude product in a small amount of methanol (150 mL), stir at room temperature for 30 min, then filter, collect the solid, and dry it using a rotary evaporator to remove the small amount of solvent wrapped in the solid, obtaining the intermediate product compound D-1-3.

[0132] Step 4: In a 500 mL three-necked flask, add intermediate compound D-1-3 (28.0 g) and methanol (150 mL). After stirring and dissolving, add hydrazine hydrate (10.2 g). After the reaction solution is refluxed and stirred for 16 h, it is cooled to room temperature, diluted with 0.5 M NaOH solution (150 ml). The resulting mixture is extracted with dichloromethane for this aqueous solution, 200 mL each time, for 2 times. The combined organic phases are extracted with saturated brine 2 times (100 mL × 2), dried over anhydrous sodium sulfate, filtered, and the filtrate is distilled under reduced pressure using a rotary evaporator to obtain a crude product. The obtained solid crude product is dispersed in a mixed solution (100 mL) of petroleum ether: ethyl acetate = 6:1 (volume ratio). After stirring at room temperature for 30 min, it is suction filtered, the solid is collected, and dried using a rotary evaporator. After removing the small amount of solvent encapsulated in the solid, intermediate product compound D-1-4 is obtained.

[0133] Step 5: In a 250 mL three-necked flask, add intermediate compound D-1-4 (3.0 g), benzaldehyde shown in formula c-1 (1.0 g), and methanol (100 mL). Stir at room temperature for 15 min, add 3 drops of glacial acetic acid, stir at room temperature for 4 h, and then slowly add sodium cyanoborohydride (2.3 g) under the condition of cooling in an ice-water bath. After adding, react in an ice-water bath for 30 min and stir at room temperature for 2 h. TLC plate monitoring shows that raw material D-1-4 is completely consumed. After the reaction is completed, the reaction mixture is poured into water (200 g). The resulting mixture is extracted with ethyl acetate for this aqueous solution, 200 mL each time, for 2 times. The combined organic phases are extracted with saturated brine 2 times (100 mL × 2), dried over anhydrous sodium sulfate, filtered, and the filtrate is distilled under reduced pressure using a rotary evaporator to obtain a crude product. The obtained solid crude product is dispersed in a mixed solution (100 mL) of petroleum ether: ethyl acetate = 5:1 (volume ratio). After stirring at room temperature for 30 min, it is suction filtered, the solid is collected, and dried using a rotary evaporator. After removing the small amount of solvent encapsulated in the solid, sensitizer D-1 is obtained.

[0134] (2) For sensitizer D-2, its synthesis steps refer to those of D-1, with the only difference being that acetophenone shown in formula a-1 in Step 2 is replaced by benzophenone shown in formula a-2.

[0135]

[0136] (3) For sensitizer D-3, its synthesis steps refer to D-1 in Example 1, with the only difference being that acetophenone shown in formula a-1 in Step 2 is replaced by 2-naphthylacetone shown in formula a-3, and after D-3-4 is formed in Step 4, the following Step 5 is carried out:

[0137] Step 5: In a 250 mL three-necked flask, add intermediate compound D-3-4 (5.0 g), tetrahydrofuran (50 mL), potassium carbonate (13.2 g, 0.24 mol), stir at room temperature for 15 min, cool in an ice-water bath, and slowly add 2-bromoacetophenone (11.6 g) shown in c-1 under nitrogen protection. After addition, react in an ice-water bath for 30 min and reflux for 8 h. Monitor by TLC plate that the raw material intermediate compound D-3-4 is completely consumed. After the reaction is completed, pour the reaction mixture into water (60 g) to obtain a mixed solution, extract the mixed solution with ethyl acetate, 100 mL each time, extract 2 times, combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution (100 mL) of petroleum ether:ethyl acetate = 5:1 (volume ratio), stir at room temperature for 30 min, then filter by suction, collect the solid, and dry it using a rotary evaporator. After removing a small amount of solvent wrapped in the solid, sensitizer D-3 is obtained.

[0138]

[0139] (4) For sensitizer D-4, the synthesis steps refer to D-1 in Example 1, with the only difference being that the benzaldehyde shown in formula c-1 in Step 5 is replaced by the alkyl glyoxylate shown in formula c-4.

[0140]

[0141] (5) For sensitizer D-5, the synthesis steps are as follows: In a 100 mL three-necked flask, add compound D-4 (1.5 g), methanol (30 mL), water (3 mL), stir to dissolve, then add lithium hydroxide hydrate (0.3 g), and stir at room temperature for 2 h. Monitor by TLC plate that the raw material intermediate compound D-4 is completely consumed. After the reaction is completed, pour the reaction mixture into water (30 g), extract the obtained mixture with ethyl acetate for this aqueous solution, and after extraction, adjust the aqueous phase to pH = 5 - 6 with 1 M dilute hydrochloric acid, then extract this aqueous phase with ethyl acetate, 100 mL each time, extract 2 times, combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution (100 mL) of petroleum ether:ethyl acetate = 5:1 (volume ratio), stir at room temperature for 30 min, then filter by suction, collect the solid, and dry it using a rotary evaporator. After removing a small amount of solvent wrapped in the solid, sensitizer D-5 is obtained.

[0142] (6) For sensitizer D-6, the synthesis steps refer to D-1 in Example 1, with the only difference being that: in Step 2, the acetophenone shown in Formula a-1 is changed to 2-acetylanthracene shown in Formula a-6, and in Step 4, after the reaction to generate D 6-4, the following Synthesis Step 5 is carried out:

[0143] Step 5: In a 250 mL three-necked flask, add intermediate compound D-6-4 (3.5 g), tetrahydrofuran (50 mL), potassium carbonate (3.2 g), stir at room temperature for 15 min, cool in an ice-water bath, and slowly add Br-CH2COR 12 (2.3 g). After adding, react in an ice-water bath for 30 min and reflux for 8 h. Monitor by TLC plate to ensure that the raw material compound D-6-4 is completely consumed. After the reaction is completed, pour the reaction mixture into water (100 g) to obtain a mixed solution, extract the mixed solution with ethyl acetate, 200 mL each time, extract 2 times, combine the obtained organic phases, extract with saturated brine 2 times (100 mL×2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution of petroleum ether:ethyl acetate = 5:1 (100 mL), stir at room temperature for 30 min, then filter by suction, collect the solid, and dry using a rotary evaporator. After removing the small amount of solvent wrapped in the solid, sensitizer D-6 is obtained.

[0144]

[0145] (7) For sensitizer D-7, the synthesis steps refer to D-1 in Example 1, with the only difference being that: in Step 2, the acetophenone shown in Formula a-1 is changed to 2-acetylfluorene, and in Step 4, after the reaction to generate D 7-4, the following Synthesis Step 5 is carried out:

[0146] Step 5: In a 250 mL three-necked flask, add intermediate compound D-7-4 (2.6 g), tetrahydrofuran (50 mL), potassium carbonate (3.0 g), stir at room temperature for 15 min, cool in an ice-water bath, and slowly add allyl bromide (1.9 g) under nitrogen protection. After addition, react in an ice-water bath for 30 min and then reflux for 8 h. Monitor by TLC plate to ensure complete consumption of the starting compound D-6-4. After the reaction is completed, pour the reaction mixture into water (100 g) to obtain a mixed solution, extract the mixed solution with ethyl acetate, 200 mL each time, for 2 times, combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution of petroleum ether:ethyl acetate = 5:1 (100 mL), stir at room temperature for 30 min, then filter by suction, collect the solid, dry it using a rotary evaporator, and remove a small amount of solvent encapsulated in the solid to obtain sensitizer D-7. (8) For sensitizer D-8, its synthetic route is as shown in (B). Specifically, the synthesis steps are as follows:

[0147] Step 1: In a 500 mL three-necked flask, add starting p-hydroxybenzaldehyde (24.4 g), 3,4-dihydro-2H-pyran (18.5 g), and acetonitrile (200 mL), stir evenly, and then slowly add copper sulfate pentahydrate (10.0 g) under ice-water bath cooling conditions. After the raw materials are added, the reaction is stirred at room temperature for 3 h. Monitor the reaction by TLC plate and stop the reaction when the starting p-hydroxybenzaldehyde is completely consumed. After the reaction is completed, pour the reaction mixture into water (200 g), and extract the aqueous solution with ethyl acetate, 500 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (200 mL × 2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. After purification by column chromatography, the THP-protected p-hydroxybenzaldehyde intermediate compound D-8-1 is obtained.

[0148] Step 2: In a 500 mL three-necked flask, add acetophenone (12.0 g) shown in Formula a-1, intermediate compound D-8-1 (23.3 g), and ethanol (200 mL). Place the flask in a water bath at room temperature and stir for 15 min to dissolve the raw materials. Then, add 40% NaOH aqueous solution (by weight percentage) (8.4 g) dropwise to the flask over 1 h. After the addition is complete, continue stirring the reaction at room temperature for 8 h. Then, monitor the reaction by spotting a TLC plate. When the raw material compound D-8-1 is completely consumed, stop the reaction. Filter the resulting suspension under reduced pressure. Disperse the obtained solid crude product in a small amount of ethanol (150 mL), stir at room temperature for 30 min, then filter. Collect the solid, dry it using a rotary evaporator, and remove the small amount of solvent encapsulated in the solid to obtain intermediate product compound D-8-2.

[0149] Step 3: In a 500 mL three-necked flask, add intermediate compound D-8-2 (30.1 g) and glacial acetic acid (60 g). Place it in an oil bath and stir to heat up to 50 °C. At 50 °C, slowly add phenylhydrazine (21.0 g) shown in Formula b-1 dropwise over 1 h. After the addition is complete, heat up to 80 °C and react for 8 h. Then, monitor the reaction by spotting a TLC plate. When the raw materials are completely consumed, stop the reaction. Cool to room temperature and dilute with ethanol (300 mL). Stir the resulting suspension at room temperature for 30 min, then filter under reduced pressure. Disperse the obtained solid crude product in a small amount of methanol (150 mL), stir at room temperature for 30 min, then filter. Collect the solid, dry it using a rotary evaporator, and remove the small amount of solvent encapsulated in the solid to obtain intermediate product compound D-8-3.

[0150] Step 4: In a 500 mL three-necked flask, add raw material intermediate product compound D-8-3 (27.0 g) and methanol (200 mL). Stir evenly, and then slowly add copper sulfate pentahydrate (8.9 g) under cooling in an ice-water bath. After the raw materials are added, stir the reaction at room temperature for 6 h. Monitor the reaction by spotting a TLC plate. When the raw materials are completely consumed, stop the reaction. Pour the reaction mixture into water (200 g) to obtain a mixed solution. Extract the mixed solution with ethyl acetate, 200 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution of petroleum ether:ethyl acetate = 5:1 (by volume) (100 mL), stir at room temperature for 30 min, then filter. Collect the solid, dry it using a rotary evaporator, and remove the small amount of solvent encapsulated in the solid to obtain intermediate product compound D-8-4.

[0151] Step 5: In a 250 mL three-necked flask, add intermediate product Compound D-8-4 (4.2 g), acetonitrile (50 mL), and potassium carbonate (3.8 g). Stir at room temperature for 15 min, cool in an ice-water bath, and slowly add benzyl bromide shown in c-8 (2.8 g) under nitrogen protection. After addition, react at room temperature for 30 min and then reflux for 8 h. Monitor by TLC plate until the raw material Compound D-8-4 is completely consumed. After the reaction is completed, cool the reaction solution to room temperature, pour the reaction mixture into water (200 g), extract the aqueous solution with ethyl acetate, 200 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (100 mL×3), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain the crude product. Purify the obtained solid crude product by column chromatography to obtain sensitizer D-8.

[0152] (B)

[0154] (9)For sensitizer D-9, the synthesis steps refer to those of sensitizer D-8 in Example 8, with the only difference being that the benzyl bromide shown in c-8 in Step 5 is replaced by alkyl bromoacetate shown in c-9.

[0155]

[0156] (10)For sensitizer D-10, its synthesis route is as shown in (D). Specifically, the synthesis steps are as follows:

[0157] Step 1: In a 500 mL three-necked flask, add raw material intermediate Compound D-1-1 (29.6 g), acetone (6.2 g), and ethanol (200 mL). Place the flask in a water bath at room temperature and stir for 15 min to dissolve the raw materials. Then, add 10% NaOH aqueous solution (by weight percentage) (80 g) dropwise to the flask over 1 h. After the addition is complete, continue to stir and react at room temperature for 8 h. Then, monitor the reaction by TLC plate. Stop the reaction when the reaction no longer changes. Filter the obtained suspension under reduced pressure. Disperse the obtained solid crude product in a small amount of ethanol (150 mL), stir at room temperature for 30 min, filter, collect the solid, and dry it using a rotary evaporator to remove the small amount of solvent wrapped in the solid, obtaining intermediate product Compound D-10-2.

[0158] Step 2: In a 500 mL three-necked flask, add intermediate compound D-10-2 (25 g) and glacial acetic acid (66 g). Place it in an oil bath and stir to heat up to 50 °C. At 50 °C, slowly add phenylhydrazine (11 g) dropwise over 1 h. After the addition is complete, heat up to 80 °C and react for 8 h. Then monitor the reaction by TLC plate. After the raw materials are completely consumed, stop the reaction. Cool to room temperature and dilute with ethanol (200 ml). Stir the resulting suspension at room temperature for 30 min, then filter under reduced pressure. Disperse the obtained solid crude product in a small amount of methanol (150 mL), stir at room temperature for 30 min, then filter. Collect the solid, dry it with a rotary evaporator, and remove the small amount of solvent encapsulated in the solid to obtain the sensitizer compound D-10-3.

[0159] Step 3: In a 500 mL three-necked flask, add intermediate compound D-10-3 (19.0 g) and methanol (150 mL). After stirring and dissolving, add hydrazine hydrate (7.2 g). After the reaction solution is refluxed and stirred for 16 h, cool to room temperature, dilute with 0.5 M NaOH solution (150 ml). Extract the resulting mixture with dichloromethane, 200 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure with a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution of petroleum ether:ethyl acetate = 5:1 (volume ratio) (100 mL), stir at room temperature for 30 min, then filter. Collect the solid, dry it with a rotary evaporator, and remove the small amount of solvent encapsulated in the solid to obtain the sensitizer intermediate product compound D-10-4.

[0160] Step 4: In a 250 mL three-necked flask, add intermediate compound D-10-4 (3.0 g), benzaldehyde shown in formula c-1 (2.0 g), and methanol (100 mL). Stir at room temperature for 15 min, add 3 drops of glacial acetic acid, stir at room temperature for 4 h, then cool under an ice-water bath and slowly add sodium cyanoborohydride (2.3 g). After adding, react in an ice-water bath for 30 min and stir at room temperature for 2 h. Monitor by TLC plate until the raw material D-10-4 is completely consumed. After the reaction is completed, pour the reaction mixture into water (200 g). Extract the resulting mixture with ethyl acetate, 200 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure with a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution of petroleum ether:ethyl acetate = 5:1 (volume ratio) (100 mL), stir at room temperature for 30 min, then filter. Collect the solid, dry it with a rotary evaporator, and remove the small amount of solvent encapsulated in the solid to obtain the sensitizer D-10.

[0161] (C)

[0163] (11) For sensitizer D-11, the synthesis steps refer to Step 5 of sensitizer D-3, with the only difference being that the intermediate compound D-3-4 in Step 5 is replaced by D-10-4.

[0164] (12) For sensitizer D-12, the synthesis steps refer to sensitizer D-10, with the only difference being that the benzaldehyde shown in formula c-1 in Step 4 is replaced by the alkyl glyoxylate shown in formula c-4.

[0165] (13) For sensitizer D-13, its synthesis route is as shown in (D). Specifically, the synthesis steps are as follows:

[0166] Step 1: In a 500 mL three-necked flask, add the raw material intermediate compound D-8-1 (27.5 g), acetone (6.0 g), and ethanol (200 mL). Place the flask in a water bath at room temperature and stir for 15 min to dissolve the raw materials. Then, add a 10% NaOH aqueous solution (by weight percentage) (80 g) dropwise to the flask over 1 h. After the addition is complete, continue stirring the reaction at room temperature for 8 h. Then, monitor the reaction by spotting a TLC plate. After the reaction no longer changes, stop the reaction. Filter the resulting suspension under reduced pressure. Disperse the obtained solid crude product in a small amount of ethanol (150 mL), stir at room temperature for 30 min, then filter, collect the solid, and dry it using a rotary evaporator to remove the small amount of solvent trapped in the solid, obtaining the intermediate product compound D-13-2.

[0167] Step 2: In a 500 mL three-necked flask, add the intermediate compound D-13-2 (24.1 g) and glacial acetic acid (66 g). Place it in an oil bath and stir to heat up to 50 °C. At 50 °C, slowly add phenylhydrazine (11 g) dropwise over 1 h. After the addition is complete, raise the temperature to 80 °C and react for 8 h. Then, monitor the reaction by spotting a TLC plate. After the raw materials are completely consumed, stop the reaction. Cool to room temperature and dilute with ethanol (200 ml). Stir the resulting suspension at room temperature for 30 min, then filter under reduced pressure. Disperse the obtained solid crude product in a small amount of methanol (150 mL), stir at room temperature for 30 min, then filter, collect the solid, and dry it using a rotary evaporator to remove the small amount of solvent trapped in the solid, obtaining the sensitizer compound D-13-3.

[0168] Step 3: In a 500 mL three-necked flask, add the raw material intermediate product Compound D-13-3 (18.0 g) and methanol (200 mL). After stirring evenly, slowly add copper sulfate pentahydrate (8.2 g) under the condition of cooling in an ice-water bath. After the raw materials are added, the reaction is stirred at room temperature for 6 h. Monitor the reaction by TLC plate. When the raw material p-hydroxybenzaldehyde is completely consumed, stop the reaction. Pour the reaction mixture into water (200 g). The obtained mixture is extracted with ethyl acetate, 200 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and the filtrate is distilled under reduced pressure using a rotary evaporator to obtain the crude product. Disperse the obtained solid crude product in a mixed solution (100 mL) of petroleum ether:ethyl acetate = 5:1 (volume ratio), stir at room temperature for 30 min, then filter by suction, collect the solid, and dry it using a rotary evaporator. After removing the small amount of solvent wrapped in the solid, the intermediate product Compound D-13-4 is obtained.

[0169] Step 4: In a 250 mL three-necked flask, add the intermediate product Compound D-13-4 (4.0 g), acetonitrile (50 mL), and potassium carbonate (3.6 g). Stir at room temperature for 15 min, cool in an ice-water bath, and slowly add the benzyl bromide shown in c-8 (2.7 g) under the condition of nitrogen protection. After adding, react at room temperature for 30 min and reflux for 8 h. Monitor by TLC plate until the raw material Compound D-13-4 is completely consumed. After the reaction is completed, cool the reaction solution to room temperature, pour the reaction mixture into water (200 g). The obtained mixture is extracted with ethyl acetate, 200 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 3), dry over anhydrous sodium sulfate, filter, and the filtrate is distilled under reduced pressure using a rotary evaporator to obtain the crude product. Purify the obtained solid crude product by column chromatography to obtain the sensitizer D-13.

[0170] (D)

[0172] (14) For the sensitizer D-14, its synthesis steps refer to those of the sensitizer D-13, with the only difference being that: the benzyl bromide shown in c-8 in Step 4 is replaced by ethyl bromoacetate, and an ester compound is obtained, which is further hydrolyzed with lithium hydroxide to obtain the sensitizer.

[0173] (15) For the sensitizer D-15, the synthesis steps refer to those of the sensitizer D-13, with the only difference being that: the benzyl bromide shown in c-8 in Step 4 is replaced by 2-bromoacetophenone shown in c-15.

[0174]

[0175] When R4 and R6 are methyl groups, taking Structure D-1 as an example, the preparation steps refer to the synthesis of the above Synthetic Route A. The difference is only that after the reductive amination reaction of aniline and benzaldehyde is completed in Step Five, it is necessary to further carry out a secondary reductive amination reaction of the reductive amination product with paraformaldehyde to obtain a nitrogen-methylated product.

[0176] The structures of other sensitizers shown in Formula (I) can be prepared with reference to the synthesis steps of D-1 to D-15 above, and their specific preparation steps will not be elaborated in detail here.

[0177] The following further describes the present application in detail with specific examples, and these examples should not be construed as limiting the scope claimed by the present application.

[0178] Example 1

[0179] A photosensitive resin composition includes 53 parts of alkali-soluble resin A-1, 3 parts of photopolymerizable monomer B-1, 24 parts of B-2, 5 parts of B-3, 5 parts of B-4, 3.5 parts of photoinitiator C-1, 0.3 parts of sensitizer d-1, 0.1 part of additive E-1, 1 part of additive E-2, and 2.2 parts of additive.

[0180] Among them, the synthesis route of sensitizer d-1 is as shown in (a). Specifically, the synthesis steps are as follows:

[0181] Step One, in a 500 mL three-necked flask, add raw material 4-aminobenzaldehyde (12.1 g), sodium bicarbonate (8.4 g), and tetrahydrofuran (100 mL). After stirring evenly, under the condition of cooling in an ice-water bath, slowly add N-ethoxycarbonylphthalimide (21.9 g). After the raw materials are added, stir and react at room temperature for 7 h. Then monitor the reaction by TLC plate. When the raw material 4-aminobenzaldehyde is completely consumed, stop the reaction. After the reaction is completed, pour the reaction mixture into water (100 g) to obtain a mixed solution, extract the mixed solution with ethyl acetate, 500 mL each time, extract 2 times, combine the obtained organic phases, extract with saturated brine 2 times (200 mL × 2), dry with anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure with a rotary evaporator to obtain a crude product. The crude product is purified by column chromatography to obtain the phthalimide-protected 4-aminobenzaldehyde intermediate compound d-1-1 (26.2 g, purity 95%).

[0182] Step 2: In a 500 mL three-necked flask, add the raw material acetophenone (12.0 g), intermediate compound d-1-1 (25.8 g) and ethanol (200 mL). Place the flask in a water bath at room temperature and stir for 15 min to dissolve the raw materials. Then, add dropwise 40% NaOH aqueous solution (by weight percentage) (8 g) to the three-necked flask over 1 h. After the addition is complete, continue stirring the reaction at room temperature for 8 h. Then, monitor the reaction by spotting a TLC plate. When the raw material compound d-1-1 is completely consumed, stop the reaction. Filter the resulting suspension under reduced pressure. Disperse the obtained solid crude product in a small amount of ethanol (150 mL), stir at room temperature for 30 min, then filter. Collect the solid, dry it using a rotary evaporator, and remove the small amount of solvent entrapped in the solid to obtain the intermediate product compound d-1-2 (32.5 g, purity 93%).

[0183] Step 3: In a 500 mL three-necked flask, add the intermediate compound d-1-2 (32.5 g) and glacial acetic acid (60 g). Place it in an oil bath and stir to heat up to 50 °C. At 50 °C, slowly add dropwise phenylhydrazine (21.6 g) over 1 h. After the addition is complete, heat up to 80 °C and react for 8 h. Then, monitor the reaction by spotting a TLC plate. When the raw materials are completely consumed, stop the reaction. Cool to room temperature, then dilute with ethanol (300 ml). Stir the resulting suspension at room temperature for 30 min, then filter under reduced pressure. Disperse the obtained solid crude product in a small amount of methanol (150 mL), stir at room temperature for 30 min, then filter. Collect the solid, dry it using a rotary evaporator, and remove the small amount of solvent entrapped in the solid to obtain the intermediate product compound d-1-3 (28.7 g, purity 94%).

[0184] Step 4: In a 500 mL three-necked flask, add the intermediate compound d-1-3 (28.0 g) and methanol (150 mL). After stirring to dissolve, add hydrazine hydrate (10.2 g). After refluxing and stirring the reaction solution for 16 h, cool to room temperature, then dilute with 0.5 M NaOH solution (150 ml). Extract the resulting mixture with dichloromethane for this aqueous solution, 200 mL each time, for 2 extractions. Combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution of petroleum ether:ethyl acetate = 6:1 (by volume) (100 mL), stir at room temperature for 30 min, then filter. Collect the solid, dry it using a rotary evaporator, and remove the small amount of solvent entrapped in the solid to obtain the intermediate product compound d-1-4 (14.1 g, purity 93%).

[0185] Step 5: In a 250 mL three-necked flask, add intermediate compound d-1-4 (3.0 g), benzaldehyde (1.0 g), methanol (100 mL), stir at room temperature for 15 min, add 3 drops of glacial acetic acid, stir at room temperature for 4 h, then under the condition of cooling in an ice-water bath, slowly add sodium cyanoborohydride (2.3 g). After adding, react in an ice-water bath for 30 min and stir at room temperature for 2 h. Monitor by TLC plate to ensure that the raw material d-1-4 is completely consumed. After the reaction is completed, pour the reaction mixture into water (200 g), extract the aqueous solution with ethyl acetate, 200 mL each time, extract 2 times, combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain the crude product. Disperse the obtained solid crude product in a mixed solution (100 mL) of petroleum ether:ethyl acetate = 5:1 (volume ratio), stir at room temperature for 30 min, then filter by suction, collect the solid, dry it using a rotary evaporator, and remove the small amount of solvent wrapped in the solid to obtain sensitizer d-1 (3.4 g, purity 97%). Structure characterization data of sensitizer d-1: 1 1H-NMR (CDCl3, 400 MHz): 7.48 - 7.20 (m, 15 H), 7.14 - 6.60 (m, 5 H), 5.46 - 5.36 (m, 1H), 4.32 (d, 2H), 3.66 - 3.54 (m, 1 H), 3.04 - 2.96 (m, 1H).

[0186]

[0187] (a)

[0188] Example 2

[0189] A photosensitive resin composition, which is different from that in Example 1 in that the composition of the photosensitive resin composition is different, as shown in Table 1 specifically.

[0190] Among them, the synthesis steps of sensitizer d-2 refer to those of d-1 in Example 1, with the only difference being that acetophenone in Step 2 is changed to benzilacetone, and after completing the reductive amination reaction of aniline and benzaldehyde to generate d-2-4 in Step 5, it is necessary to further perform a secondary reductive amination reaction of the reductive amination product d-2-4 with paraformaldehyde. Specifically, a nitrogen-methylated product is obtained by performing a secondary reductive amination reaction of the reductive amination product with paraformaldehyde.

[0191]

[0192] Example 3

[0193] A photosensitive resin composition, which is different from that in Example 1 in that the composition of the photosensitive resin composition is different, as shown in Table 1 specifically.

[0194] Among them, the synthesis steps of the sensitizer d-3 refer to d-1 in Example 1, with the only difference being that acetophenone in Step 2 is changed to 2-naphthylacetone, and after the reaction in Step 4 to generate d-3-4, the following Synthesis Step 5 is carried out:

[0195] Step 5: In a 250 mL three-necked flask, add the intermediate compound d-3-4 (5.0 g), tetrahydrofuran (50 mL), potassium carbonate (13.2 g, 0.24 mol), stir at room temperature for 15 min, cool in an ice-water bath, and slowly add 2-bromoacetophenone (11.6 g) under nitrogen protection. After adding, react in an ice-water bath for 30 min and reflux for 8 h. Monitor by TLC plate to ensure that the raw material intermediate compound d-3-4 is completely consumed. After the reaction is completed, pour the reaction mixture into water (60 g) to obtain a mixed solution, extract the mixed solution with ethyl acetate, 100 mL each time, extract 2 times, combine the obtained organic phases, extract with saturated brine 2 times (100 mL×2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution (100 mL) of petroleum ether:ethyl acetate = 5:1 (volume ratio), stir at room temperature for 30 min, then filter by suction, collect the solid, and dry it using a rotary evaporator. After removing a small amount of solvent encapsulated in the solid, the sensitizer d-3 (3.9 g, purity 96%) is obtained.

[0196]

[0197] Example 4

[0198] A photosensitive resin composition, which is different from that in Example 1 in that the composition of the photosensitive resin composition is different, as shown in Table 1 specifically.

[0199] Among them, the synthesis steps of the sensitizer d-4 refer to d-1 in Example 1, with the only difference being that benzaldehyde in Step 5 is replaced by ethyl glyoxylate.

[0200]

[0201] Example 5

[0202] A photosensitive resin composition, which is different from that in Example 1 in that the composition of the photosensitive resin composition is different, as shown in Table 1 specifically.

[0203] Among them, the synthesis steps of the sensitizer d-5 are as follows: In a 100 mL three-necked flask, add compound d-4 (1.5 g), methanol (30 mL), and water (3 mL). After stirring and dissolving, add lithium hydroxide hydrate (0.3 g), and stir at room temperature for 2 h. Monitor by TLC plate that the raw material intermediate compound d-4 is completely consumed. After the reaction is completed, pour the reaction mixture into water (30 g). The obtained mixture is used to extract the aqueous solution with ethyl acetate. After extraction, the aqueous phase is adjusted to pH = 5-6 with 1 M dilute hydrochloric acid, and then the aqueous phase is extracted with ethyl acetate, 100 mL each time, for 2 times. The combined organic phases are extracted with saturated brine 2 times (100 mL × 2), dried over anhydrous sodium sulfate, filtered, and the filtrate is distilled under reduced pressure using a rotary evaporator to obtain the crude product. The obtained solid crude product is dispersed in a mixed solution (100 mL) of petroleum ether:ethyl acetate = 5:1 (volume ratio), stirred at room temperature for 30 min, then filtered by suction, the solid is collected, dried using a rotary evaporator, and after removing a small amount of solvent encapsulated in the solid, the sensitizer d-5 (1.2 g, purity 96%) is obtained.

[0204]

[0205] Example 6

[0206] A photosensitive resin composition, which is different from that in Example 1 in that the composition of the photosensitive resin composition is different, as shown in Table 1 specifically.

[0207] Among them, the synthesis steps of the sensitizer d-6 refer to d-1 in Example 1, and the only difference is that: acetophenone in Step 2 is changed to 2-acetylanthracene, and after the reaction to generate d-6-4 in Step 4, the following synthesis Step 5 is carried out:

[0208] Step 5, in a 250 mL three-necked flask, add intermediate compound d-6-4 (3.5 g), tetrahydrofuran (50 mL), potassium carbonate (3.2 g-), stir at room temperature for 15 min, cool in an ice-water bath, and slowly add bromobutanone (2.3 g) under nitrogen protection. After adding, react in an ice-water bath for 30 min and reflux for 8 h. Monitor by TLC plate that the raw material compound d-6-4 is completely consumed. After the reaction is completed, pour the reaction mixture into water (100 g) to obtain a mixed solution, and extract the mixed solution with ethyl acetate, 200 mL each time, for 2 times. The combined organic phases are extracted with saturated brine 2 times (100 mL × 2), dried over anhydrous sodium sulfate, filtered, and the filtrate is distilled under reduced pressure using a rotary evaporator to obtain the crude product. The obtained solid crude product is dispersed in a mixed solution (100 mL) of petroleum ether:ethyl acetate = 5:1, stirred at room temperature for 30 min, then filtered by suction, the solid is collected, dried using a rotary evaporator, and after removing a small amount of solvent encapsulated in the solid, the sensitizer d-6 (2.7 g, purity 94%) is obtained.

[0209]

[0210] Example 7

[0211] A photosensitive resin composition, which is different from that of Example 1 in that the composition of the photosensitive resin composition is different, as specifically shown in Table 1.

[0212] Among them, the synthesis steps of the sensitizer d-7 refer to d-1 in Example 1, with the difference being only that: acetophenone in Step 2 is changed to 2-acetylfluorene, and after the reaction to generate d-7-4 in Step 4, the following synthesis Step 5 is carried out:

[0213] Step 5, in a 250 mL three-necked flask, add intermediate compound d-7-4 (2.6 g), tetrahydrofuran (50 mL), potassium carbonate (3.0 g), stir at room temperature for 15 min, cool in an ice-water bath, and slowly add allyl bromide (1.9 g) under nitrogen protection. After adding, react in an ice-water bath for 30 min and reflux for 8 h. Monitor by TLC plate to ensure that the raw material compound d-6-4 is completely consumed. After the reaction is completed, pour the reaction mixture into water (100 g) to obtain a mixed solution, extract the mixed solution with ethyl acetate, 200 mL each time, extract 2 times, combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution of petroleum ether:ethyl acetate = 5:1 (100 mL), stir at room temperature for 30 min, then filter by suction, collect the solid, and dry it using a rotary evaporator to remove a small amount of solvent wrapped in the solid, thereby obtaining the sensitizer d-7 (1.9 g, purity 95%).

[0214]

[0215] Example 8

[0216] A photosensitive resin composition, which is different from that of Example 1 in that the composition of the photosensitive resin composition is different, as specifically shown in Table 1.

[0217] Among them, the synthesis route of the sensitizer d-8 is as shown in (b). Specifically, the synthesis steps are as follows:

[0218] Step 1: In a 500 mL three-necked flask, add the raw material p-hydroxybenzaldehyde (24.4 g), 3,4-dihydro-2H-pyran (18.5 g) and acetonitrile (200 mL). After stirring evenly, slowly add copper sulfate pentahydrate (10.0 g) under the condition of cooling in an ice-water bath. After the addition of the raw materials is completed, the reaction is stirred at room temperature for 3 h. Monitor the reaction by spotting a TLC plate. When the raw material p-hydroxybenzaldehyde is completely consumed, stop the reaction. After the reaction is completed, pour the reaction mixture into water (200 g). The resulting mixture is used to extract the aqueous solution with ethyl acetate, 500 mL each time, for 2 extractions. The combined organic phases are extracted with saturated brine 2 times (200 mL × 2), dried over anhydrous sodium sulfate, filtered, and the filtrate is distilled under reduced pressure using a rotary evaporator to obtain the crude product. After purification by column chromatography, the THP-protected p-hydroxybenzaldehyde intermediate compound d-8-1 (28.2 g, purity 95%) is obtained.

[0219] Step 2: In a 500 mL three-necked flask, add the raw material acetophenone (12.0 g), intermediate compound d-8-1 (23.3 g) and ethanol (200 mL). Place the flask in a water bath at room temperature and stir for 15 min to dissolve the raw materials. Then, add 40% NaOH aqueous solution (by weight percentage) (8.4 g) dropwise to the flask over 1 h. After the addition is completed, continue to stir the reaction at room temperature for 8 h. Then, monitor the reaction by spotting a TLC plate. When the raw material compound d-8-1 is completely consumed, stop the reaction. Filter the resulting suspension under reduced pressure. The obtained solid crude product is dispersed in a small amount of ethanol (150 mL), stirred at room temperature for 30 min, then filtered. The solid is collected, dried using a rotary evaporator, and after removing the small amount of solvent trapped in the solid, the intermediate product compound d-8-2 (30.4 g, purity 94%) is obtained.

[0220] Step 3: In a 500 mL three-necked flask, add intermediate compound d-8-2 (30.1 g) and glacial acetic acid (60 g). Place it in an oil bath and stir to heat up to 50 °C. At 50 °C, slowly add phenylhydrazine (21.0 g) dropwise over 1 h. After the addition is completed, heat up to 80 °C and react for 8 h. Then, monitor the reaction by spotting a TLC plate. After the raw materials are completely consumed, stop the reaction. Cool to room temperature and dilute with ethanol (300 ml). The resulting suspension is stirred at room temperature for 30 min, then filtered under reduced pressure. The obtained solid crude product is dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 min, then filtered. The solid is collected, dried using a rotary evaporator, and after removing the small amount of solvent trapped in the solid, the intermediate product compound d-8-3 (27.7 g, purity 93%) is obtained.

[0221] Step 4: In a 500 mL three-necked flask, add the raw material intermediate product compound d-8-3 (27.0 g) and methanol (200 mL). After stirring evenly, slowly add copper sulfate pentahydrate (8.9 g) under the condition of cooling in an ice-water bath. After the raw materials are added, the reaction is stirred at room temperature for 6 h. Monitor the reaction by TLC plate. When the raw materials are completely consumed, stop the reaction. Pour the reaction mixture into water (200 g) to obtain a mixed solution. Extract the mixed solution with ethyl acetate, 200 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and concentrate the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution of petroleum ether:ethyl acetate = 5:1 (volume ratio) (100 mL), stir at room temperature for 30 min, then filter by suction, collect the solid, and dry it using a rotary evaporator. After removing a small amount of solvent wrapped in the solid, obtain the intermediate product compound d-8-4 (16.9 g, purity 95%).

[0222] Step 5: In a 250 mL three-necked flask, add the intermediate product compound d-8-4 (4.2 g), acetonitrile (50 mL), and potassium carbonate (3.8 g). Stir at room temperature for 15 min, cool in an ice-water bath, and slowly add benzyl bromide (2.8 g) under the condition of nitrogen protection. After adding, react at room temperature for 30 min and reflux for 8 h. Monitor by TLC plate until the raw material compound intermediate product compound d-8-4 is completely consumed. After the reaction is completed, cool the reaction solution to room temperature, pour the reaction mixture into water (200 g), and extract the obtained mixture with ethyl acetate, 200 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 3), dry over anhydrous sodium sulfate, filter, and concentrate the filtrate under reduced pressure using a rotary evaporator to obtain a crude product. Purify the obtained solid crude product by column chromatography to obtain the sensitizer d-8 (2.0 g, purity 95%).

[0223] Structure characterization data of the sensitizer d-8: 1 H-NMR (CDCl3, 400 MHz): 7.46 - 7.22 (m, 15 H), 7.14 - 6.82 (m, 4 H), 5.27 - 5.15 (m, 1H), 5.04 (s, 2H), 3.67 - 3.54 (m, 1H), 3.08 - 2.98 (m, 1 H).

[0224]

[0225] (b)

[0226] Example 9

[0227] A photosensitive resin composition, which is different from that of Example 1 in that the composition of the photosensitive resin composition is different, as shown in Table 1 specifically.

[0228] Among them, the synthesis steps of sensitizer d-9 refer to those of sensitizer d-8 in Example 8, with the only difference being that ethyl bromoacetate is used instead of benzyl bromide in Step 5.

[0229]

[0230] Example 10

[0231] A photosensitive resin composition, which is different from that of Example 1 in that the composition of the photosensitive resin composition is different, as shown in Table 1 specifically.

[0232] Among them, the synthesis route of sensitizer d-10 is as shown in (c). Specifically, the synthesis steps are as follows:

[0233] Step 1: In a 500 mL three-necked flask, add raw material intermediate compound d-1-1 (29.6 g), acetone (6.2 g), and ethanol (200 mL). Place the flask in a water bath at room temperature and stir for 15 min to dissolve the raw materials. Then, add 10% NaOH aqueous solution (by weight percentage) (80 g) dropwise to the flask over 1 h. After the addition is complete, continue to stir and react at room temperature for 8 h. Then, monitor the reaction by TLC plate. After the reaction no longer changes, stop the reaction. Filter the resulting suspension under reduced pressure. Disperse the obtained solid crude product in a small amount of ethanol (150 mL), stir at room temperature for 30 min, then filter, collect the solid, and dry it with a rotary evaporator to remove the small amount of solvent wrapped in the solid, obtaining intermediate product compound d-10-2 (27.1 g, purity 91%).

[0234] Step 2: In a 500 mL three-necked flask, add intermediate compound d-10-2 (25 g) and glacial acetic acid (66 g). Place it in an oil bath and stir to heat up to 50 °C. At 50 °C, slowly add phenylhydrazine (11 g) dropwise over 1 h. After the addition is complete, heat up to 80 °C and react for 8 h. Then, monitor the reaction by TLC plate. After the raw materials are completely consumed, stop the reaction. Cool to room temperature and dilute with ethanol (200 ml). Stir the resulting suspension at room temperature for 30 min, then filter under reduced pressure. Disperse the obtained solid crude product in a small amount of methanol (150 mL), stir at room temperature for 30 min, then filter, collect the solid, and dry it with a rotary evaporator to remove the small amount of solvent wrapped in the solid, obtaining sensitizer compound d-10-3 (20.3 g, purity 95%).

[0235] Step 3: In a 500 mL three-necked flask, add intermediate compound d-10-3 (19.0 g) and methanol (150 mL). After stirring and dissolving, add hydrazine hydrate (7.2 g). After refluxing and stirring the reaction solution for 16 h, cool it to room temperature, dilute it with 0.5 M NaOH solution (150 ml). The obtained mixture is extracted with dichloromethane, 200 mL each time, for 2 times. The combined organic phases are extracted with saturated brine 2 times (100 mL × 2), dried over anhydrous sodium sulfate, filtered, and the filtrate is distilled under reduced pressure using a rotary evaporator to obtain a crude product. The obtained solid crude product is dispersed in a mixed solution (100 mL) of petroleum ether: ethyl acetate = 5:1 (volume ratio). After stirring at room temperature for 30 min, filter by suction, collect the solid, and dry it using a rotary evaporator. After removing a small amount of solvent wrapped in the solid, the sensitizer intermediate product compound d-10-4 (12.1 g, purity 93%) is obtained.

[0236] Step 4: In a 250 mL three-necked flask, add intermediate compound d-10-4 (3.0 g), benzaldehyde (2.0 g), and methanol (100 mL). Stir at room temperature for 15 min, add 3 drops of glacial acetic acid, stir at room temperature for 4 h, and then slowly add sodium cyanoborohydride (2.3 g) under the condition of cooling in an ice-water bath. After adding, react in an ice-water bath for 30 min and stir at room temperature for 2 h. Monitor by TLC plate to ensure that the raw material d-10-4 is completely consumed. After the reaction is completed, pour the reaction mixture into water (200 g). The obtained mixture is extracted with ethyl acetate, 200 mL each time, for 2 times. The combined organic phases are extracted with saturated brine 2 times (100 mL × 2), dried over anhydrous sodium sulfate, filtered, and the filtrate is distilled under reduced pressure using a rotary evaporator to obtain a crude product. The obtained solid crude product is dispersed in a mixed solution (100 mL) of petroleum ether: ethyl acetate = 5:1 (volume ratio). After stirring at room temperature for 30 min, filter by suction, collect the solid, and dry it using a rotary evaporator. After removing a small amount of solvent wrapped in the solid, the sensitizer d-10 (3.1 g, purity 97%) is obtained.

[0237] Structure characterization data of sensitizer d-10: 1 H-NMR (CDCl3, 400 MHz): 7.40 - 6.86 (m, 25 H), 7.16 (d, 1H), 6.52 (d, 1H), 5.44 - 5.20 (m, 1H), 4.32 (d, 4H), 3.64 - 5.58 (m, 1 H), 3.24 - 3.02 (m, 1H).

[0238] (c)

[0239] Example 11

[0240] A photosensitive resin composition, which is different from that of Example 1 in that the composition of the photosensitive resin composition is different, as shown in Table 1 specifically.

[0241] Among them, the synthesis steps of sensitizer d-11 refer to Step 6 of sensitizer d-3, and the difference is only that: the intermediate compound d-3-4 in Step 6 is replaced by d-10-4.

[0242]

[0243] Example 12

[0244] A photosensitive resin composition, which is different from that of Example 1 in that the composition of the photosensitive resin composition is different, as shown in Table 1 specifically.

[0245] Among them, the synthesis steps of sensitizer d-12 refer to sensitizer d-10, and the difference is only that: benzaldehyde in Step 4 is replaced by ethyl glyoxylate.

[0246]

[0247] Example 13

[0248] A photosensitive resin composition, which is different from that of Example 1 in that the composition of the photosensitive resin composition is different, as shown in Table 1 specifically.

[0249] Among them, the synthesis route of sensitizer d-13 is as shown in (d). Specifically, the synthesis steps are as follows:

[0250] Step 1, in a 500 mL three-necked flask, add the raw material intermediate compound d-8-1 (27.5 g), acetone (6.0 g), and ethanol (200 mL). After placing the flask in a water bath at room temperature and stirring for 15 min to dissolve the raw materials, add 10% NaOH aqueous solution (by weight percentage) (80 g) dropwise to the flask. The dropping time is 1 h. After the dropping is completed, continue stirring and reacting at room temperature for 8 h. Then monitor the reaction by TLC plate. After the reaction no longer changes, stop the reaction. Filter the obtained suspension under reduced pressure. Disperse the obtained solid crude product in a small amount of ethanol (150 mL), stir at room temperature for 30 min, then filter, collect the solid, and dry it with a rotary evaporator to remove a small amount of solvent wrapped in the solid to obtain the intermediate product compound d-13-2 (25.1 g, purity 92%).

[0251] Step 2: In a 500 mL three-necked flask, add intermediate compound d-13-2 (24.1 g) and glacial acetic acid (66 g), place it in an oil bath and stir to heat up to 50 °C. At 50 °C, slowly add phenylhydrazine (11 g) dropwise over 1 h. After the addition is complete, heat up to 80 °C and react for 8 h. Then monitor the reaction by TLC plate. After the raw materials are completely consumed, stop the reaction. Cool to room temperature and dilute with ethanol (200 ml). Stir the resulting suspension at room temperature for 30 min, then filter under reduced pressure. Disperse the obtained solid crude product in a small amount of methanol (150 mL), stir at room temperature for 30 min, then filter. Collect the solid, dry it with a rotary evaporator, and remove the small amount of solvent encapsulated in the solid to obtain sensitizer compound d-13-3 (19.1 g, purity 94%).

[0252] Step 3: In a 500 mL three-necked flask, add raw material intermediate product compound d-13-3 (18.0 g) and methanol (200 mL), stir evenly, and slowly add copper sulfate pentahydrate (8.2 g) under cooling in an ice-water bath. After the raw materials are added, stir the reaction at room temperature for 6 h. Monitor the reaction by TLC plate. When the raw materials are completely consumed, stop the reaction. Pour the reaction mixture into water (200 g), extract the resulting mixture with ethyl acetate, 200 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 2), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure with a rotary evaporator to obtain a crude product. Disperse the obtained solid crude product in a mixed solution (100 mL) of petroleum ether:ethyl acetate = 5:1 (volume ratio), stir at room temperature for 30 min, then filter. Collect the solid, dry it with a rotary evaporator, and remove the small amount of solvent encapsulated in the solid to obtain intermediate product compound d-13-4 (14.7 g, purity 95%).

[0253] Step 4: In a 250 mL three-necked flask, add intermediate product compound d-13-4 (4.0 g), acetonitrile (50 mL), and potassium carbonate (3.6 g), stir at room temperature for 15 min, cool in an ice-water bath, and slowly add benzyl bromide (2.7 g) under nitrogen protection. After adding, react at room temperature for 30 min and reflux for 8 h. Monitor by TLC plate until the raw material compound intermediate product compound d-13-4 is completely consumed. After the reaction is completed, cool the reaction solution to room temperature, pour the reaction mixture into water (200 g), extract the resulting mixture with ethyl acetate, 200 mL each time, for 2 times. Combine the obtained organic phases, extract with saturated brine 2 times (100 mL × 3), dry over anhydrous sodium sulfate, filter, and distill the filtrate under reduced pressure with a rotary evaporator to obtain a crude product. Purify the obtained solid crude product by column chromatography to obtain sensitizer d-13 (1.9 g, purity 95%).

[0254] Structural characterization data of sensitizer d-13: 1 1H-NMR (CDCl3, 400 MHz): 7.44 - 6.84 (m, 23 H), 7.18 (d, 1H), 6.54 (d, 1H), 5.46 - 5.24 (m, 1H), 5.04 (s, 4H), 3.60 - 5.54 (m, 1 H), 3.12 - 2.98 (m, 1H).

[0255]

[0256] (d)

[0257] Example 14

[0258] A photosensitive resin composition, which is different from that of Example 1 in that the composition of the photosensitive resin composition is different, as specifically shown in Table 1.

[0259] Among them, the synthesis steps of sensitizer d-14 refer to those of sensitizer d-13, and the only difference is that: benzyl bromide in Step 4 is replaced with ethyl bromoacetate, and the obtained ethyl ester compound needs to be further hydrolyzed with lithium hydroxide.

[0260]

[0261] Example 15

[0262] A photosensitive resin composition, which is different from that of Example 1 in that the composition of the photosensitive resin composition is different, as specifically shown in Table 1.

[0263] Among them, the synthesis steps of sensitizer d-15 refer to those of sensitizer d-13, and the only difference is that: benzyl bromide in Step 4 is replaced with 2-bromoacetophenone.

[0264]

[0265] Example 16

[0266] A photosensitive resin composition comprising 53 parts of alkali-soluble resin A-1, 3 parts of photopolymerizable monomer B-1, 25 parts of B-2, 6 parts of B-3, 6 parts of B-4, 6 parts of B-6, 0.6 part of photoinitiator C-2, 0.2 part of sensitizer d-1, 0.1 part of additive E-1, 1 part of additive E-2, and 2.1 parts of additive. See Table 2 for details.

[0267] Examples 17 to 30

[0268] The difference from Example 16 is only that sensitizer d-1 is replaced with d-2 to d-15 respectively. See Table 2 for details.

[0269] Example 31

[0270] The only difference from Example 16 is that the sensitizer d-1 is replaced by the sensitizer d-16, and the structure of the sensitizer d-16 is as shown in D-1 (where X is H, Y is a chlorine atom, and R3 and R4 are H). See Table 2 for details.

[0271] Example 32

[0272] The only difference from Example 16 is that the sensitizer d-1 is replaced by the sensitizer d-17, and the structure of the sensitizer d-17 is as shown in D-1 (where X is H, Y is a trifluoromethyl group, and R3 and R4 are H). See Table 2 for details.

[0273] Example 33

[0274] The only difference from Example 16 is that the sensitizer d-1 is replaced by the sensitizer d-18, and the structure of the sensitizer d-18 is as shown in D-1 (where X is H, Y is an acetyl group, and R3 and R4 are H). See Table 2 for details.

[0275] Example 34

[0276] The only difference from Example 16 is that the sensitizer d-1 is replaced by the sensitizer d-19, and the structure of the sensitizer d-19 is as shown in D-1 (where X is H, Y is an ethyl ester group, and R3 and R4 are H). See Table 2 for details.

[0277] Example 35

[0278] The only difference from Example 16 is that the sensitizer d-1 is replaced by the sensitizer d-20, and the structure of the sensitizer d-20 is as shown in D-2 (where Y is H, X is a methoxy group, and R3 and R4 are H). See Table 2 for details.

[0279] Example 36

[0280] The only difference from Example 16 is that the sensitizer d-1 is replaced by the sensitizer d-21, and the structure of the sensitizer d-21 is as shown in D-2 (where Y is H, X is a nitro group, and R3 and R4 are H. See Table 2 for details.

[0281] Comparative Example 1

[0282] The only difference from Example 1 is that the sensitizer D-1 in the photosensitive resin composition is replaced by the sensitizer D1. See Table 3 for details.

[0283] Comparative Example 2

[0284] The only difference from Example 1 is that the sensitizer D-1 in the photosensitive resin composition is replaced by the sensitizer D2. See Table 3 for details.

[0285] Comparative Example 3

[0286] The difference from Example 3 is only that the sensitizer D-1 in the photosensitive resin composition is replaced by sensitizer D1. See Table 3 for details.

[0287] Comparative Example 4

[0288] The difference from Example 3 is only that the sensitizer D-1 in the photosensitive resin composition is replaced by sensitizer D2. See Table 3 for details.

[0289] Comparative Example 5

[0290] The difference from Example 3 is only that the photosensitive resin composition further includes 0.1 part of photoinitiator C-3, and the sensitizer D-1 is replaced by sensitizer D1. See Table 3 for details.

[0291] Photosensitive films were prepared from the photosensitive resin compositions of the examples and comparative examples, and their properties were evaluated as follows:

[0292] Preparation of photosensitive dry film: According to the composition of the photosensitive resin composition, an alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, a sensitizer, and an additive were mixed, and then the solvent methyl ethyl ketone was added and stirred thoroughly until all components were dissolved to obtain a resin composition solution; wherein, by weight percentage, the content of the resin composition in the resin composition solution was 40%. The resin composition solution was allowed to stand for 30 min to fully defoam, and then the resin composition solution was coated on the surface of a 16-μm-thick PET film support layer using a coater, and then placed in an oven at 90°C for 10 min to form a 25-μm-thick dry film resist layer. A 20-μm-thick polyethylene film protective layer was laminated on the surface of the dry film resist layer to obtain a photosensitive dry film.

[0293] Performance evaluation

[0294] 1) Sensitivity evaluation: The samples after dry lamination were successively exposed and developed, and a cured film formed by the cured product of the photosensitive resin composition was formed on the copper surface of the substrate. The cured film was exposed using a Stouffer 41-step exposure scale. When the cured film was first fully cured on the exposure scale and reached 17 remaining segments, the exposure amount (mJ / cm 2 2) was recorded, and the sensitivity of the photosensitive resin composition was evaluated by this exposure amount. The sensitivity results are shown in Tables 4 and 5 (where, ◎: 9 - 12 mJ / cm 2 2; ○: 13 - 16 mJ / cm 2 2; △: 17 - 30 mJ / cm 2 2; ×: > 30 mJ / cm 2 2), and the smaller the exposure amount value, the better the sensitivity.

[0295] 2) Evaluation of dry pressing resolution: After the samples with dry film lamination are exposed and developed in sequence, the dry pressing resolution is evaluated. Specifically, with the exposure dose at 17 grids (mJ / cm 2 ), exposure is carried out using a mask with a wiring pattern where the widths of the exposed part and the unexposed part are 1:1. After developing with twice the minimum developing time, the minimum mask width at which the cured resist lines are normally formed is taken as the value of the resolution, and the minimum mask width value is obtained by observing with a scanning electron microscope (SEM). The dry pressing resolution is shown in Tables 4 and 5. The smaller the value, the better the resolution.

[0296] 3) Evaluation of wet pressing resolution: After the samples with wet film lamination are exposed and developed in sequence, the wet pressing resolution is evaluated. Specifically, with the exposure dose at 17 grids (mJ / cm 2 ), exposure is carried out using a mask with a wiring pattern where the widths of the exposed part and the unexposed part are 1:1. After developing with twice the minimum developing time, the minimum mask width at which the cured resist lines are normally formed is taken as the value of the resolution, and the minimum mask width value is obtained by observing with a scanning electron microscope (SEM). The wet pressing resolution is shown in Tables 4 and 5. The smaller the value, the better the resolution.

[0297] 4) Evaluation of dry pressing adhesion: After the samples with dry film lamination are exposed and developed in sequence, the dry pressing adhesion is evaluated. Specifically, with the exposure dose at 17 grids (mJ / cm 2 ), exposure is carried out using a mask with a wiring pattern where the widths of the exposed part and the unexposed part are n:400. After developing with twice the minimum developing time, observation is carried out using a magnifying glass, and the minimum mask width at which the complete cured resist lines are formed is taken as the value of the adhesion. The dry pressing adhesion is shown in Tables 4 and 5. The smaller the value, the better the adhesion.

[0298] 5) Evaluation of wet pressing adhesion: After the samples with wet film lamination are exposed and developed in sequence, the wet pressing adhesion is evaluated. Specifically, with the exposure dose at 17 grids (mJ / cm 2 ), exposure is carried out using a mask with a wiring pattern where the widths of the exposed part and the unexposed part are n:400. After developing with twice the minimum developing time, observation is carried out using a magnifying glass, and the minimum mask width at which the complete cured resist lines are formed is taken as the value of the adhesion. The wet pressing adhesion is shown in Tables 4 and 5. The smaller the value, the better the adhesion.

[0299] 6) Side shape evaluation: After exposing and developing the sample after dry film lamination, side shape evaluation is carried out. Specifically, it is exposed using a mask with a wiring pattern having a width ratio of n:400 between the exposed part and the unexposed part. After developing with 2.0 times the minimum developing time, the head shape of the dry film with a line width of 25 μm is photographed with a scanning electron microscope (SEM) at a magnification of 800 times. The results of side shape evaluation are shown in Table 4 and Table 5 (where ○: the cross-section of the dry film head is rectangular; △: the cross-section of the dry film head somewhat presents an inverted trapezoid; ×: the inverted trapezoid of the dry film head cross-section is serious or the bottom is hollowed out).

[0300] 7) Evaluation of dry pressing filling property:

[0301] The copper surface of the copper clad laminate is polished by a grinding machine, washed with water, micro-etched, and dried by hot air blowing to obtain a bright and fresh copper surface. After laminating and thermally bonding a commercially available photosensitive dry film (DuPont DI9325), a film with strip (75 μm) and circular patterns is masked. After completing exposure and development, through multiple micro-etchings and stripping, a filling substrate with a certain groove depth is obtained;

[0302] The prepared photosensitive dry film is laminated on the above-mentioned filling substrate by dry film lamination. A film with a strip (75 μm) pattern is masked. The placement direction of the film is perpendicular to the grooves on the filling substrate. Exposure is carried out with an exposure amount of 17 grids (mJ / cm 2 ), and it is developed with 2.0 times the minimum developing time. After completing the exposure and development processes, a dry film image is obtained;

[0303] The dry film morphology is photographed with a scanning electron microscope (SEM) at a magnification of 400 times to observe whether the dry film lines can completely fit and fill the grooves and round pits without any gaps. The maximum dimension (μm) of the groove depth that can be completely filled, that is, the filling ability of the photosensitive dry film under dry pressing conditions, and the results are shown in Table 4 and Table 5.

[0304] 8) Evaluation of wet pressing filling property:

[0305] The copper surface of the copper clad laminate is polished by a grinding machine, washed with water, micro-etched, and dried by hot air blowing to obtain a bright and fresh copper surface. After laminating and thermally bonding a mass-produced photosensitive dry film, a film with strip (75 μm) and circular patterns is masked. After completing exposure and development, through multiple micro-etchings and stripping, a filling substrate with a certain groove depth is obtained;

[0306] The prepared photosensitive dry film is laminated on the above-mentioned filling substrate by wet film lamination. A film with a strip (75 μm) pattern is masked. The placement direction of the film is perpendicular to the grooves on the filling substrate. Exposure is carried out with an exposure amount of 17 grids (mJ / cm 2 ), and it is developed with 2.0 times the minimum developing time. After completing the exposure and development processes, a dry film image is obtained;

[0307] The dry film morphology was photographed with a scanning electron microscope (SEM) at a magnification of 400 times to observe whether the dry film lines could completely fit and fill the grooves and pits without any gaps. The maximum dimension (μm) of the groove depth that could be completely filled was the filling ability of the photosensitive dry film under wet pressing conditions. The results are shown in Tables 4 and 5.

[0308] Among them, the specific processes involved in the above performance evaluation are as follows:

[0309] Dry film lamination: The copper clad laminate was polished on its copper surface by a grinding machine, washed with water, micro-etched, and dried with hot air to obtain a bright and fresh copper surface. The temperature of the pressure roller of the laminating machine was set at 110 °C, the conveying speed was 1.0 m / min. After removing the polyethylene film protective layer of the prepared photosensitive film, it was thermally laminated with the copper clad laminate under standard pressure.

[0310] Wet film lamination: The copper clad laminate was polished on its copper surface by a grinding machine, washed with water, and dried to obtain a bright and fresh copper surface. Deionized water was added to the sponge roller, and then the flexible substrate was passed through the sponge roller to uniformly coat a water film on the copper surface. The lamination temperature of the laminating machine was set at 100 °C, the pressure was 4.0 Kg / cm 2 , the speed was 1.0 m / min. After removing the polyethylene film protective layer of the prepared photosensitive film, it was thermally laminated with the copper clad laminate under standard pressure.

[0311] Exposure: The laminated sample was left standing for 15 min, and then exposed using a Japanese Adtec exposure machine, model: IP-6, a laser direct imaging (LDI) exposure machine with a wavelength of 405 nm, and a stouffer 41-step exposure ruler was used for photosensitivity testing.

[0312] Development: The exposed sample was left standing for 15 min, and then developed. The development temperature was 30 °C, the pressure was 1.2 Kg / cm 2 , the developer was a 1% (weight percentage) aqueous sodium carbonate solution, the development time was 2.0 times the minimum development time, and after development, it was washed with water and dried. Among them, the minimum time required to completely dissolve the dry film resist layer in the unexposed part was taken as the minimum development time.

[0313] Stripping: The stripping solution was an aqueous NaOH solution, the concentration of NaOH was 3.0% (weight percentage), the temperature was 50 °C, the pressure was 1.2 Kg / cm 2 , the stripping time was 1.5 - 2.0 times the minimum stripping time, and after stripping, it was washed with water and dried.

[0314] Table 1

[0315]

[0316] Table 2

[0317]

[0318] Table 3

[0319]

[0320] In Tables 1 - 3, the alkali - soluble copolymer resin A - 1 is obtained by copolymerizing monomers methacrylic acid, methyl methacrylate, butyl acrylate, and styrene. The weight ratio of methacrylic acid, methyl methacrylate, butyl acrylate, and styrene is 25:30:18:27. The specific preparation steps of A - 1 are as follows: Mix the monomers evenly according to the ratio to obtain a mixture. Mix 100 g of the monomer mixture, 1.0 g of AIBN photoinitiator, 90 g of methyl ethyl ketone, and 15 g of ethanol, and stir to dissolve to obtain a mixed solution; Add 35% of the mixed solution into a three - necked flask with nitrogen protection and a condensation reflux device through a peristaltic pump, heat it to 80 °C in an oil bath, stir and react for 1 h, then drop - wise add the remaining mixed solution within 3 h; After continuing to keep the temperature for reaction for 4 h, raise the temperature to 90 °C, add 5 g of methyl ethyl ketone solution dissolved with 0.2 g of AIBN photoinitiator in two portions, with an interval of 1 h between the two additions. After dropping, keep the temperature and stir for 2 h to end the reaction, obtaining the alkali - soluble copolymer resin A - 1; Based on the weight of potassium hydroxide consumed per gram of the alkali - soluble copolymer resin for neutralization, the acid value of the alkali - soluble copolymer resin is 131 mg KOH / g, the weight - average molecular weight measured by GPC is 57000 g / mol, the polymerization conversion rate is 97.0%, and the molecular weight distribution is 1.8;

[0321] The photopolymerizable monomer B - 1 is 4 - ethoxybisphenol A dimethacrylate (Miyakoshi Specialty Chemicals, BPA(EO)4DMA);

[0322] The photopolymerizable monomer B - 2 is 10 - ethoxybisphenol A dimethacrylate (Miyakoshi Specialty Chemicals, BPA(EO) 10 DMA);

[0323] The photopolymerizable monomer B - 3 is polyethylene glycol (propylene glycol) dimethacrylate (Miyakoshi Specialty Chemicals);

[0324] The photopolymerizable monomer B - 4 is 4 - ethoxylated nonylphenol acrylate (Miyakoshi Specialty Chemicals);

[0325] The photopolymerizable monomer B - 5 is 8 - ethoxylated nonylphenol acrylate (Miyakoshi Specialty Chemicals);

[0326] The photopolymerizable monomer B - 6 is 3 - ethoxylated trimethylolpropane trimethacrylate (Miyakoshi Specialty Chemicals);

[0327] Photoinitiator C-1 is 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole BCIM (Changzhou Qiangli Electronic Materials);

[0328] Photoinitiator C-2 is 9-phenylacridine (Changzhou Qiangli Electronic Materials);

[0329] Photoinitiator C-3 was N-phenylglycine (Xia Chemical);

[0330] D1 is 1-phenyl-3-(4-methoxyphenylvinyl)-5-(4-methoxyphenyl)pyrazoline, and its structure is shown in formula (1) (wherein R1 and R2 are methoxy groups, and R3 is H);

[0331] (1)

[0333] D2 is 1-phenyl-3-(4-biphenyl)-5-(4-tert-butylphenyl)pyrazoline, and its structure is shown in formula (2) (wherein R is tert-butyl);

[0334] (2)

[0336] Additive E-1 is brilliant green pigment (Shanghai Bailingwei Chemical Technology Co., Ltd.);

[0337] Additive E-2 was leuco crystal violet (Shanghai Bailingwei Chemical Technology Co., Ltd.);

[0338] Additive E-3 is p-toluenesulfonamide (Shanghai TCI Chemical).

[0339] Table 4

[0340]

[0341] Table 5

[0342]

[0343] It can be seen from Table 4 and Table 5 that the photosensitive resin composition in Examples 1-36 has high photosensitivity, dry pressing resolution, wet pressing resolution, dry pressing adhesion, wet pressing adhesion and filling capacity, can take into account both dry film lamination and wet film lamination processes, and the dry film sidewall morphology is rectangular without obvious inclination or depression. The formed dry film resist layer has high resolution, line stability and adhesion, which is conducive to the formation of high-precision circuits, meets the requirements of high-precision HDI inner layer boards, improves production yield, significantly improves the production efficiency of PCB manufacturing, lead frame manufacturing, semiconductor packaging, ITO and other components in the field of flat panel displays, and reduces production costs.

[0344] Compared with the use of sensitizer d-1 in Example 1, hexaarylbisimidazole derivative D1 was used in Comparative Example 1, and hexaarylbisimidazole derivative D2 was used in Comparative Example 2. Their photosensitivity was significantly insufficient, making it difficult to meet the requirements for the efficient production of HDI inner layer boards. Moreover, the resolution, especially the wet press resolution, was significantly reduced, making it difficult to meet the accuracy requirements of HDI inner layer boards.

[0345] Compared with the use of sensitizer d-3 in Example 3, hexaarylbisimidazole derivative D1 was used in Comparative Example 3, and hexaarylbisimidazole derivative D1 was used in Comparative Example 4. Their photosensitivity was significantly insufficient, the resolution, especially the wet press resolution, was significantly reduced, and the dry film side shape was poor, making it difficult to meet the accuracy requirements of HDI inner layer boards.

[0346] Compared with the use of sensitizer d-3 in Example 3, hexaarylbisimidazole derivative D1 was used in Comparative Example 5, and a small amount of conventional hydrogen donor photoinitiator C-3 was added. Although the photosensitivity was improved to some extent, the dry resolution, wet press resolution, and dry film side shape still could not meet the accuracy requirements of HDI inner layer boards.

[0347] The above are only the preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, various modifications and changes can be made to the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A sensitizer, characterized in that, The structure of the sensitizer is shown in formula (I): （I） Wherein, M1 is selected from -O- or -NR4-, and R4 is selected from H or methyl; Q is a single bond or -(CHCH) n -, and n is an integer from 1 to 3; R1 is selected from aryl, heteroaryl, or R1 is selected from aryl or heteroaryl substituted by at least one substituent selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester, C1-C8 alkyl, C1-C4 alkoxy, aryl or heteroaryl; R5 is selected from carboxyl, C1-C4 ester, vinyl, aryl, heteroaryl, benzoyl, or R5 is selected from aryl, heteroaryl or benzoyl substituted by at least one substituent selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester, C1-C8 alkyl, C1-C4 alkoxy; M2 is selected from -O- or -NR6-, and R6 is selected from H or methyl; R2 is selected from a carboxyl group, a C1-C4 ester group, a vinyl group, an aryl group, a heteroaryl group, a benzoyl group, or R2 is an aryl group, a heteroaryl group or a benzoyl group substituted with at least one substituent selected from a halogen, a nitro group, a trifluoromethyl group, a cyano group, a C1-C4 alkanoyl group, a C1-C4 ester group, a C1-C8 alkyl group, a C1-C4 alkoxy group; R3 is selected from H, a halogen, a C1-C8 alkyl group or a C1-C4 alkoxy group.

2. The sensitizer according to claim 1, wherein The M1 is located at the para position of the pyrazoline ring.

3. The sensitizer according to claim 1 or 2, characterized in that, The R1 is selected from phenyl, naphthyl, anthryl, phenanthryl, biphenyl, 9H-fluorenyl, or the phenyl, naphthyl, anthryl, phenanthryl, biphenyl or 9H-fluorenyl substituted by at least one substituent selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester group, C1-C8 alkyl, C1-C4 alkoxy, wherein the substituent is selected from halogen, nitro, trifluoromethyl, cyano, C1-C4 alkanoyl, C1-C4 ester group, C1-C8 alkyl, C1-C4 alkoxy.

4. The sensitizer according to claim 1 or 2, characterized in that, The sensitizer is selected from one or more of the following structures: 。 5. A photosensitive resin composition, characterized in that, Including: An alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, and the sensitizer according to any one of claims 1 to 4.

6. The photosensitive resin composition according to claim 5, wherein The photosensitive resin composition includes 45 to 65 parts of the alkali-soluble resin, 35 to 50 parts of the photopolymerizable monomer, 2.0 to 5.0 parts of the photoinitiator, and 0.01 to 1.0 part of the sensitizer.

7. The photosensitive resin composition according to claim 6, wherein By weight, the photosensitive resin composition further includes 0.5 to 5 parts of an additive, and the additive is selected from one or more of a color former, a dye, a plasticizer, a photo-thermal stabilizer, an adhesion promoter, a leveling agent, an antifoaming agent, a polymerization inhibitor in any proportion combination.

8. The photosensitive resin composition according to claim 5, wherein The photoinitiator includes at least one of a hexaarylbiimidazole derivative represented by formula (II) and an acridine derivative represented by formula (III): (II) (III) In the formula (II), each A is independently selected from one of a methoxy group and a halogen atom, and each n4 is independently selected from an integer of 0 to 5; In the formula (III), R c is selected from one of H, C1-C6 alkyl, C1-C6 alkoxy, aryl, or aryl, pyridylalkyl substituted by at least one substituent of a halogen atom, C1-C6 alkyl, and C1-C6 alkoxy.

9. The photosensitive resin composition according to claim 8, wherein The hexaarylbiimidazole derivative represented by the formula (II) is selected from one or more of 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole; and / or, The acridine derivative represented by the formula (III) is selected from one or more of 9-methylacridine, 9-ethylacridine, 9-phenylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9-(4-methylphenyl)acridine, 9-(4-ethylphenyl)acridine, 1,7-bis(9,9'-acridinyl)heptane, 9-(4-n-propylphenyl)acridine, 9-(4-n-butylphenyl)acridine, 9-(4-tert-butylphenyl)acridine, 9-(4-methoxyphenyl)acridine, 9-(4-ethoxyphenyl)acridine, 9-m-tolylacridine, 9-o-tolylacridine, 9-p-tolylacridine, 9-p-chlorophenylacridine; and / or, The photoinitiator further comprises one or more of benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, benzoin methyl ether, benzoin phenyl ether, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2-ethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzil derivatives such as benzil dimethyl ketal, N-phenylglycine, triarylamine compounds, oxime ester compounds, coumarin compounds, oxazole compounds, etc.

10. The photosensitive resin composition according to any one of claims 5 to 9, characterized in that The photopolymerizable monomer comprises an EO / PO-modified bisphenol A structure acrylate represented by the general formula (IV): (IV) In the formula (IV), the two Rs a are each independently selected from H or methyl; m1 and m2 are each selected from integers of 1 to 30, n1 and n2 are each selected from integers of 0 to 20, and the sum of m1 and m2 is an integer of 2 to 20, and the sum of n1 and n2 is an integer of 0 to 20; the arrangement of the EO and PO repeating units is random or block, where EO is an ethylene oxide unit and PO is a propylene oxide unit.

11. The photosensitive resin composition according to claim 10, wherein The photopolymerizable monomer further comprises one or more of lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, ethoxylated nonylphenol acrylate, isobornyl acrylate, tetrahydrofurfuryl acrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol dimethacrylate, polypropylene glycol diacrylate, ethoxylated neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, ethoxylated and propoxylated trimethylolpropane triacrylate, ethoxylated trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc.

12. The photosensitive resin composition according to any one of claims 5 to 9, characterized in that, The alkali-soluble resin comprises an alkali-soluble copolymer resin represented by the general formula (V): （V） In the formula (V), R8 and R9 are each independently selected from one or more of a hydrogen atom, a methyl group, a dialkylamino group, or a methyl group substituted with a dialkylamino group; R 10 is selected from a C1-C 18 linear alkyl group, a C1-C 18 branched alkyl group, a C1-C linear alkyl group substituted with at least one substituent selected from a hydroxyl group and an amino group, 18 a C1-C linear alkyl group substituted with at least one substituent selected from a hydroxyl group and an amino group, 18 a C1-C linear alkyl group, a benzyl group, and a phenoxyethyl group; each R7 is independently selected from one of H, a C1-C3 alkyl group, a C1-C3 alkoxy group, an amino group, and a halogen atom, and n3 is an integer from 0 to 5; x, y, and z respectively represent the weight percentages of the respective structural units in the alkali-soluble copolymer resin, wherein x is 15% to 35%, y is 20% to 65%, and z is 0 to 55%.

13. The photosensitive resin composition according to claim 12, wherein The R 10 is selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, isooctyl, lauryl, octadecyl, 2-hydroxyethyl, 2-hydroxypropyl, 4-hydroxybutyl, glycidyl, benzyl or phenoxyethyl; and / or, n3 is 1, R7 is selected from H or methyl, and z is 5% - 55%; and / or, The weight-average molecular weight of the alkali-soluble copolymer resin is 30,000 - 80,000. The acid value of the alkali-soluble resin is expressed by the weight of potassium hydroxide consumed to neutralize each gram of the alkali-soluble copolymer resin, and the acid value of the alkali-soluble copolymer resin is 120 - 250 mg KOH / g; and / or, The molecular weight distribution of the alkali-soluble copolymer resin is 1.3 - 2.5, and the polymerization conversion rate ≥ 97%.

14. A photosensitive dry film, characterized in that, It includes a support layer, a dry film resist layer, and a protective layer stacked. The dry film resist layer comprises the photosensitive resin composition according to any one of claims 5 to 13.

15. The photosensitive dry film according to claim 14, wherein The material of the support layer is selected from PET, and the thickness of the support layer is 10 um - 20 um; and / or, The thickness of the dry film resist layer is 10 um - 100 um; and / or, The material of the protective layer is selected from polyethylene, and the thickness of the protective layer is 10 um - 30 um.

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