Photosensitive resin composition, photosensitive dry film and application thereof

Abstract

The invention provides a photosensitive resin composition, a photosensitive dry film and application thereof, the photosensitive resin composition comprises 50-65 parts by weight of alkali soluble resin, 30-45 parts by weight of a photopolymerization monomer, 0.49-6.0 parts by weight of a photoinitiator, 0.01-0.7 part by weight of a photosensitizer and 0.001-5.0 parts by weight of an additive, the additive comprises a polymerization inhibitor, and the weight ratio of the polymerization inhibitor to the photosensitizer is 0.1-10; the photosensitizer is an aryl modified anthracene compound. According to the invention, the specific aryl modified anthracene compound is adopted as the photosensitizer and is matched with the polymerization inhibitor with a specific mass dosage, so that the formed photosensitive resist layer with the thickness of more than or equal to 35 microns has excellent resolution ratio, photosensitivity, adhesive force and depth-to-width ratio performance.

Description

Technical Field

[0001] The present invention relates to the technical field of photosensitive resins, and in particular, to a photosensitive resin composition, a photosensitive dry film and their applications. Background Art

[0002] In the manufacturing processes of printed circuit boards and semiconductor package substrates, photosensitive resin compositions are widely used as resist materials for etching or electroplating. The photosensitive resin composition is usually coated on the surface of a PET (polybutylene terephthalate) support film, and after drying, a protective layer such as a polyethylene (PE) protective film is closely attached to its surface, which is also called a photosensitive dry film, etc. For example, in the manufacturing of substrates, first, the photosensitive resin composition is laminated onto a copper plate (film lamination); then, specific regions of the photosensitive resin composition layer are exposed; then, the PET support film is peeled off, and the unexposed regions are removed with a chemical solution (development); then, electroplating treatment is performed on the substrate with the resist pattern formed thereon, and then the resist layer is peeled off and the metal surface covered by the resist layer is etched, thereby obtaining a circuit board with a wire pattern formed thereon.

[0003] In the manufacturing of electronic devices such as power inductors and logic processors, the method of thickening copper wires is widely used to ensure reliability and heat dissipation performance. This requires the photosensitive resist to form wire patterns with a higher aspect ratio to meet the requirements of advanced packaging, and requires a faster stripping time of the resist pattern to improve production efficiency. However, in the conventional photosensitive resist for thick films (thickness ≥ 35 μm), the use of acrylate-based photopolymerizable monomers can improve the stripping time to a certain extent, but the adhesion and resolution are still not satisfactory enough. In other photosensitive resist for thick films, light is difficult to reach the bottom of the photosensitive layer sufficiently, and sometimes the insufficient photopolymerization reaction will also result in the adhesion and resolution of the resist lines being not satisfactory enough. Therefore, photosensitive resists with excellent adhesion and resolution, and excellent stripping performance and high aspect ratio have received extensive attention.

[0004] In the photosensitive resin composition for a carrier board at present, 2,4,5-triaryl imidazole dimer (HABI) is widely used as a photoinitiator, and anthracene compounds, pyrazoline compounds, and coumarin compounds are used as sensitizers, which has a high resolution. Patent CN114585974A discloses a photosensitive resin composition containing an alkali-soluble resin with a styrene copolymer unit and a specific pyrazoline compound, obtaining good flexibility and aspect ratio, but the resolution and aspect ratio are still not sufficient. Patent CN117099044A discloses a photosensitive resin composition containing a diacrylate photo-polymerizable monomer with a bisphenol skeleton or an alicyclic skeleton, obtaining good adhesion and stripping properties, but its resolution and aspect ratio still cannot meet the requirements of advanced packaging. CN114667487A discloses a photosensitive resin composition containing an alkali-soluble resin with a benzyl methacrylate copolymer unit and a specific compound with an acrylate group having three or more functional groups, and limits the ultraviolet absorbance value and thickness of the photosensitive layer within a certain range, obtaining a dry film resist line with a small residual foot size at the bottom of the line and good electroplating performance. However, the ultraviolet absorbance value is too low and the photosensitivity is not sufficient.

[0005] In view of this, the present invention is particularly proposed. Summary of the Invention

[0006] The main object of the present invention is to provide a photosensitive resin composition, a photosensitive dry film and their applications, so as to solve the problems in the prior art that the photosensitive resin composition has poor photosensitivity, low resolution, low aspect ratio, poor adhesion, poor stripping performance, etc.

[0007] To achieve the above object, according to one aspect of the present invention, there is provided a photosensitive resin composition, which includes: 50-65 parts by weight of an alkali-soluble resin, 30-45 parts by weight of a photo-polymerizable monomer, 0.49-6.0 parts by weight of a photoinitiator, 0.01-0.7 parts by weight of a photosensitizer, 0.001-5.0 parts by weight of an additive, the additive includes a polymerization inhibitor, wherein the weight ratio of the polymerization inhibitor to the photosensitizer is 0.1-10; and the photosensitizer is an aryl-modified anthracene compound.

[0008] Further, the aryl-modified anthracene compounds include at least one of 9-phenylanthracene, 9,10-diphenylanthracene, 9,10-diphenoxyanthracene, 9,10-bis(2-methylphenoxy)anthracene, 9,10-bis(2-methoxyphenoxy)anthracene, 9,10-bis(3-methylphenoxy)anthracene, 9,10-bis(4-ethylphenoxy)anthracene, 9,10-bis(4-propylphenoxy)anthracene, 9,10-bis(4-butylphenoxy)anthracene, 9,10-bis(4-tert-butylphenoxy)anthracene, 9,10-bis(4-pentylphenoxy)anthracene, 9,10-bis(4-hexylphenoxy)anthracene, 9,10-bis(4-nonylphenoxy)anthracene, 9,10-bis(benzyloxy)anthracene, 9,10-bis(2-methylbenzyloxy)anthracene, 9,10-bis(3-methylbenzyloxy)anthracene, 9,10-bis(2,3-dimethylbenzyloxy)anthracene, 9,10-bis(2,4-dimethylbenzyloxy)anthracene, 9,10-bis(2,3,4,5,6-pentamethylbenzyloxy)anthracene, 9,10-bis(benzoyloxy)anthracene, 9,10-bis(2-methylbenzoyloxy)anthracene, 9,10-bis(3-methylbenzoyloxy)anthracene, 9,10-bis(4-methylbenzoyloxy)anthracene, 9,10-bis(3,5-dimethylbenzoyloxy)anthracene, 9,10-bis(4-butylbenzoyloxy)anthracene, 9,10-bis(4-hexylbenzoyloxy)anthracene.

[0009] Further, the aryl-modified anthracene compounds include at least one of 9,10-bis(4-tert-butylphenoxy)anthracene and 9,10-diphenoxyanthracene.

[0010] Further, the polymerization inhibitor includes piperidine oxide and / or an alkyl-substituted phenol compound. More specifically, the polymerization inhibitor is an alkyl-substituted phenol compound.

[0011] Further, the alkyl-substituted phenol compounds include at least one of 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butylphenol, 3,5-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,5-di-tert-octylhydroquinone, 4-n-butylresorcinol, 4-ethylresorcinol, 3-ethylcatechol, 1,3-di-tert-butyl-4,6-benzenediol, p-tert-butylcatechol, 3,5-di-tert-butylcatechol, 3-tert-butylcatechol.

[0012] Further, the piperidine oxide includes 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl and / or 2,2,6,6-tetramethylpiperidine-1-oxyl.

[0013] Further, the amount of the polymerization inhibitor is 0.01-0.1 part by weight.

[0014] Further, the photo-polymerizable monomer includes methacrylate monomers and non-methacrylate monomers, wherein the weight percentage of the non-methacrylate monomers in the photo-polymerizable monomer is 0%-10%.

[0015] Further, the methacrylate monomers include at least one of ethoxylated (propoxylated) bisphenol A dimethacrylate, polyethylene glycol dimethacrylate, ethoxylated (propoxylated) trimethylolpropane trimethacrylate, ethoxylated (propoxylated) pentaerythritol trimethacrylate, ethoxylated (propoxylated) pentaerythritol tetramethacrylate, and ethoxylated (propoxylated) dimethacrylate.

[0016] Further, the methacrylate monomers include at least one of ethoxylated bisphenol A dimethacrylate, propoxylated bisphenol A dimethacrylate, and ethoxylated propoxylated bisphenol A dimethacrylate.

[0017] Further, the non-methacrylate monomers include at least one of ethoxylated (propoxylated) nonylphenoxy acrylate, ethoxylated (propoxylated) bisphenol A diacrylate, polyethylene glycol diacrylate, ethoxylated (propoxylated) trimethylolpropane triacrylate, ethoxylated (propoxylated) pentaerythritol triacrylate, ethoxylated (propoxylated) pentaerythritol tetraacrylate, and ethoxylated (propoxylated) diacrylate; more preferably, the non-methacrylate monomers include at least one of ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, and ethoxylated propoxylated bisphenol A diacrylate.

[0018] Further, the photo-polymerizable monomer includes ethoxylated (propoxylated) nonylphenoxy acrylate, and the total number of ethoxy groups and propoxy groups in the ethoxylated (propoxylated) nonylphenoxy acrylate is 2-9.

[0019] Further, the ethoxylated (propoxylated) nonylphenoxy acrylate includes at least one of 4-(ethoxy) nonylphenoxy acrylate, 8-(ethoxy) nonylphenoxy acrylate, 2-(propoxy) nonylphenoxy acrylate, 4-(propoxy) nonylphenoxy acrylate, 8-(propoxy) nonylphenoxy acrylate, and 2-(propoxy)-7-(ethoxy) nonylphenoxy acrylate.

[0020] Further, the amount of the ethoxylated (propoxylated) nonylphenoxy acrylate is 1-6 parts by weight.

[0021] Further, the alkali-soluble resin is obtained by copolymerizing (meth)acrylic monomers, optional (meth)acrylic alkyl ester monomers, and a comonomer having an aromatic group.

[0022] Furthermore, the comonomer having an aromatic group accounts for ≥ 50% of the total weight of the alkali-soluble resin.

[0023] Furthermore, the comonomer having an aromatic group includes at least one of styrene, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and o-phenylphenoxyethyl acrylate.

[0024] Furthermore, the alkyl (meth)acrylate monomer includes at least one of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl methacrylate.

[0025] Furthermore, the weight-average molecular weight of the alkali-soluble resin is 25,000 to 65,000, the acid value of the alkali-soluble resin is 130 to 210 mg KOH / g, and the molecular weight distribution of the alkali-soluble resin is 1.0 to 3.0.

[0026] Furthermore, the photoinitiator is a triarylimidazole dimer and its derivatives.

[0027] Furthermore, the photoinitiator 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, and 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, preferably one or more of 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.

[0028] Furthermore, the photoinitiator is 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.

[0029] Furthermore, the additive further includes at least one of a dye, a color former, a plasticizer, an antifoaming agent, and a leveling agent.

[0030] According to the second aspect of the present invention, a photosensitive dry film is provided. The photosensitive dry film includes a support layer, a photosensitive resist layer, and a protective layer stacked in sequence; wherein, the material of the photosensitive resist layer is the photosensitive resin composition provided in the first aspect, and the thickness of the photosensitive resist layer is 35 to 300 μm.

[0031] According to the third aspect of the present invention, an application of the photosensitive dry film provided in the second aspect in the manufacturing process of a printed circuit board, a lead frame, or a semiconductor packaging substrate is provided.

[0032] Applying the technical solution of the present invention, the present invention provides a photosensitive resin composition. By using a specific aryl-modified anthracene compound as a photosensitizer and cooperating with a specific mass dosage of an inhibitor, the formed photosensitive resist layer with a thickness ≥ 35 μm has excellent resolution, photosensitivity, adhesion and aspect ratio performance. The photosensitive resin composition of the present application can be widely used in the manufacturing processes of printed circuit boards (PCBs), lead frames (LFs), and semiconductor package (IC) substrates, improving production efficiency and yield. Detailed Embodiments

[0033] 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.

[0034] As analyzed in the background art of the present application, in the prior art, the photosensitive resist layer with a thickness ≥ 35 μm has problems such as poor photosensitivity, low resolution, low aspect ratio, poor adhesion, or poor stripping performance. To solve the above problems, the present application provides a photosensitive resin composition, a photosensitive dry film and their applications.

[0035] In a typical embodiment of the present application, a photosensitive resin composition is provided. The photosensitive resin composition includes: 50 - 65 parts by weight of an alkali-soluble resin, 30 - 45 parts by weight of a photopolymerizable monomer, 0.49 - 6.0 parts by weight of a photoinitiator, 0.01 - 0.7 parts by weight of a photosensitizer, 0.001 - 5.0 parts by weight of an additive, wherein the additive includes an inhibitor, and the weight ratio of the photosensitizer to the inhibitor is 0.1 - 10; the photosensitizer is an aryl-modified anthracene compound.

[0036] The present invention provides a photosensitive resin composition, in which a specific aryl-modified anthracene compound is used as a photosensitizer. The addition of the aryl-modified anthracene compound enables the photosensitive resin composition to form a photosensitive resist layer with a thickness ≥ 35 μm, having excellent resolution and photosensitivity. A polymerization inhibitor is added to the photosensitive resin composition, which further improves the resolution and aspect ratio performance of the product. However, if the content of the polymerization inhibitor is too high, the photosensitivity of the product will decrease. Based on this, the present application defines the weight ratio of the polymerization inhibitor to the photosensitizer as 0.1 - 10. When the weight ratio is less than 0.1, problems such as insufficient bottom curing and insufficient resolution are likely to occur in the formed photosensitive resist layer; when the weight ratio is greater than 10, the photosensitivity of the photosensitive resist layer is insufficient. By adding a polymerization inhibitor and a photosensitizer with a weight ratio of 0.1 - 10 to the photosensitive resin composition, the formed photosensitive resist layer simultaneously has excellent resolution, photosensitivity, adhesion, and aspect ratio performance. The photosensitive resin composition of the present application can be widely used in the manufacturing processes of printed circuit boards (PCBs), lead frames (LFs), and semiconductor package (IC) substrates, improving production efficiency and the yield rate.

[0037] Typical but non-limiting, in the photosensitive resin composition provided by the present application, the weight ratio of the polymerization inhibitor to the photosensitizer is, for example, 0.1, 0.14, 0.25, 0.3, 0.4, 0.5, 0.7, 1.0, 2.0, 4.0, 6.0, 8.0, 10.0, or a range value composed of any two numerical values.

[0038] Typical but non-limiting, in the photosensitive resin composition provided by the present application, the dosage of the alkali-soluble resin is 50 parts by weight, 52 parts by weight, 54 parts by weight, 56 parts by weight, 60 parts by weight, 62 parts by weight, 65 parts by weight, or an end value composed of any two numerical values; the dosage of the photopolymerizable monomer is 30 parts by weight, 32 parts by weight, 34 parts by weight, 36 parts by weight, 40 parts by weight, 42 parts by weight, 45 parts by weight, or an end value composed of any two numerical values; the dosage of the photoinitiator is 0.49 parts by weight, 1.0 part by weight, 2.0 parts by weight, 3.0 parts by weight, 4.0 parts by weight, 5.0 parts by weight, 6.0 parts by weight, or an end value composed of any two numerical values; the dosage of the photosensitizer is 0.01 parts by weight, 0.03 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, or an end value composed of any two numerical values; the dosage of the additive is 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1.0 parts by weight, 2.0 parts by weight, 3.0 parts by weight, 4.0 parts by weight, 5.0 parts by weight, or an end value composed of any two numerical values.

[0039] The photosensitive resin composition provided by the present invention is based on the above-mentioned alkali-soluble resin, photopolymerizable monomer, photoinitiator, photosensitizer and additive, and has a better synergistic effect. The photosensitive resist layer with a thickness ≥ 35 μm formed by it has more excellent resolution, photosensitivity, adhesion and aspect ratio performance. When the dosage of the alkali-soluble resin is less than 50 parts by weight, the photosensitive resist layer formed by the photosensitive resin composition is prone to bleeding of glue and is not easy to store. When the dosage of the alkali-soluble resin is higher than 65 parts by weight, there is a risk that the resolution of the formed photosensitive dry film becomes poor; when the dosage of the photopolymerizable monomer is less than 30 parts by weight, there is a problem that the resolution of the formed photosensitive dry film decreases. When the dosage of the photopolymerizable monomer is higher than 45 parts by weight, the formed photosensitive resist layer is prone to bleeding of glue; when the dosage of the photoinitiator is less than 0.49 parts by weight or higher than 6.0 parts by weight, the photosensitivity and resolution of the formed photosensitive dry film decrease; when the dosage of the photosensitizer is less than 0.01 parts by weight, the photosensitivity of the formed photosensitive resist layer is insufficient. When the dosage of the photosensitizer is higher than 0.7 parts by weight, there is a risk that the formed photosensitive resist layer has insufficient curing at the bottom due to too fast curing on the surface layer, resulting in poor resolution of the inverted trapezoid of the resist line.

[0040] [Photosensitizer]

[0041] In order to further improve the photosensitivity and resolution of the photosensitive resist layer, the above-mentioned aryl-modified anthracene compounds preferably used as photosensitizers are anthracene compounds having substituents at the 9-position and / or 10-position of anthracene, aryloxy groups with substituents, and arylcarbonyloxy groups with substituents. Specifically, the aryl-modified anthracene compounds include 9-phenylanthracene, 9,10-diphenylanthracene, 9,10-diphenoxyanthracene, 9,10-bis(2-methylphenoxy)anthracene, 9,10-bis(2-methoxyphenoxy)anthracene, 9,10-bis(3-methylphenoxy)anthracene, 9,10-bis(4-ethylphenoxy)anthracene, 9,10-bis(4-propylphenoxy)anthracene, 9,10-bis(4-butylphenoxy)anthracene, 9,10-bis(4-tert-butylphenoxy)anthracene, 9,10-bis(4-pentylphenoxy)anthracene, 9,10-bis(4-hexylphenoxy)anthracene, 9,10-bis(4-nonylphenoxy)anthracene, 9,10-bis(benzyloxy)anthracene, 9,10-bis(2-methylbenzyloxy)anthracene, 9,10-bis(3-methylbenzyloxy)anthracene, 9,10-bis(2,3-dimethylbenzyloxy)anthracene, 9,10-bis(2,4-dimethylbenzyloxy)anthracene, 9,10-bis(2,3,4,5,6-pentamethylbenzyloxy)anthracene, 9,10-bis(benzoyloxy)anthracene, 9,10-bis(2-methylbenzoyloxy)anthracene, 9,10-bis(3-methylbenzoyloxy)anthracene, 9,10-bis(4-methylbenzoyloxy)anthracene, 9,10-bis(3,5-dimethylbenzoyloxy)anthracene, 9,10-bis(4-butylbenzoyloxy)anthracene, 9,10-bis(4-hexylbenzoyloxy)anthracene, or one or more of them.

[0042] In order to further improve the photosensitivity and resolution of the photosensitive dry film, it is further preferred that the aryl-modified anthracene compounds are one or more of 9,10-bis(4-tert-butylphenoxy)anthracene and 9,10-diphenoxyanthracene.

[0043] [Inhibitor]

[0044] In order to improve the photosensitivity, resolution and aspect ratio of the photosensitive dry film, it is preferred that the inhibitor includes piperidine oxide or an alkyl-substituted phenol compound. Especially when the inhibitor is an alkyl-substituted phenol compound, it is more beneficial to improve the resolution and aspect ratio of the photosensitive dry film.

[0045] In some embodiments, the alkyl-substituted phenol compounds include one or more of 2-tert-butylphenol, 3-tert-butylphenol, 4-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butylphenol, 3,5-di-tert-butylphenol, 2,4,6-tri-tert-butylphenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,5-di-tert-octylhydroquinone, 4-n-butylresorcinol, 4-ethylresorcinol, 3-ethylcatechol, 1,3-di-tert-butyl-4,6-benzenediol, p-tert-butylcatechol, 3,5-di-tert-butylcatechol, and 3-tert-butylcatechol.

[0046] In some embodiments, the piperidine oxides include 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl radical and / or 2,2,6,6-tetramethylpiperidine-1-oxyl radical.

[0047] In the photosensitive resin composition provided in the present application, from the perspective of further improving the resolution and photosensitivity of the photosensitive dry film, the dosage of the polymerization inhibitor is preferably 0.01-0.1 parts by weight (such as 0.01 parts by weight, 0.02 parts by weight, 0.05 parts by weight, 0.08 parts by weight, 0.10 parts by weight, or a range value composed of any two numerical values).

[0048] [Photopolymerizable monomer]

[0049] In the present application, the photopolymerizable monomer is a commonly used acrylate monomer in the art. Specifically, the photopolymerizable monomer includes methacrylate monomers and non-methacrylate monomers.

[0050] In the present application, the methacrylate monomer refers to a monomer in which a hydrogen atom on a carbon atom of acrylic acid in the acrylate monomer is replaced by a methyl group. On the contrary, if a hydrogen atom on a carbon atom of acrylic acid is not replaced, it is called a non-methacrylate monomer.

[0051] In order to further improve the resolution and aspect ratio of the photosensitive dry film, it is preferred that the weight ratio of the non-methacrylate monomer in the photopolymerizable monomer is 0%-10% (such as 0%, 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1%, 2%, 5%, 8%, 10%, or a range value composed of any two numerical values). If the weight ratio of the non-methacrylate monomer is too high, it is not conducive to improving the resolution and aspect ratio performance of the photosensitive dry film.

[0052] In the photosensitive resin composition provided by the present application, by adding polyfunctional acrylate photopolymerizable monomers, the crosslinking density and hydrophobicity of the photosensitive layer can be improved to a certain extent. However, since the unsaturated double bond of the non-methyl substituted acrylate monomer has a smaller steric hindrance than that of the methyl substituted acrylate monomer, the photoreaction activity of the non-methyl substituted acrylate monomer is higher than that of the methyl substituted acrylate monomer. If the addition amount of the non-methyl substituted acrylate monomer is too much, the curing rate of the surface layer of the photosensitive resist layer is faster than that of the bottom layer, which will cause a tendency of decreasing resolution and aspect ratio, and is also likely to cause a decrease in flexibility, unable to fully meet the development requirements of advanced packaging.

[0053] Exemplarily, the methyl substituted acrylate monomers include at least one of ethoxylated (propoxylated) bisphenol A dimethacrylate, polyethylene glycol dimethacrylate, ethoxylated (propoxylated) trimethylolpropane trimethacrylate, ethoxylated (propoxylated) pentaerythritol trimethacrylate, ethoxylated (propoxylated) pentaerythritol tetramethacrylate, and ethoxylated (propoxylated) dimethacrylate; Further preferably, the methyl substituted acrylate monomers include at least one of ethoxylated bisphenol A dimethacrylate, propoxylated bisphenol A dimethacrylate, and ethoxylated propoxylated bisphenol A dimethacrylate.

[0054] Exemplarily, the non-methyl substituted acrylate monomers include at least one of ethoxylated (propoxylated) nonylphenoxy acrylate, ethoxylated (propoxylated) bisphenol A diacrylate, polyethylene glycol diacrylate, ethoxylated (propoxylated) trimethylolpropane triacrylate, ethoxylated (propoxylated) pentaerythritol triacrylate, ethoxylated (propoxylated) pentaerythritol tetraacrylate, and ethoxylated (propoxylated) diacrylate; Further preferably, the non-methyl substituted acrylate monomers include at least one of ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, and ethoxylated propoxylated bisphenol A diacrylate.

[0055] In this application, ethoxylated (propoxylated) bisphenol A dimethacrylate refers to any one of ethoxylated bisphenol A dimethacrylate, propoxylated bisphenol A dimethacrylate, and ethoxylated-propoxylated bisphenol A dimethacrylate; ethoxylated (propoxylated) trimethylolpropane trimethacrylate refers to any one of ethoxylated trimethylolpropane trimethacrylate, propoxylated trimethylolpropane trimethacrylate, and ethoxylated-propoxylated trimethylolpropane trimethacrylate; ethoxylated (propoxylated) pentaerythritol trimethacrylate refers to any one of ethoxylated pentaerythritol trimethacrylate, propoxylated pentaerythritol trimethacrylate, and ethoxylated-propoxylated pentaerythritol trimethacrylate; ethoxylated (propoxylated) pentaerythritol tetramethacrylate refers to any one of ethoxylated pentaerythritol tetramethacrylate, propoxylated pentaerythritol tetramethacrylate, and ethoxylated-propoxylated pentaerythritol tetramethacrylate; ethoxylated (propoxylated) dimethacrylate refers to any one of ethoxylated dimethacrylate, propoxylated dimethacrylate, and ethoxylated-propoxylated dimethacrylate.

[0056] In this application, ethoxylated (propoxylated) nonylphenoxy acrylate refers to any one of ethoxylated nonylphenoxy acrylate, propoxylated nonylphenoxy acrylate, and ethoxylated-propoxylated nonylphenoxy acrylate; ethoxylated (propoxylated) bisphenol A diacrylate refers to any one of ethoxylated bisphenol A diacrylate, propoxylated bisphenol A diacrylate, and ethoxylated-propoxylated bisphenol A diacrylate; ethoxylated (propoxylated) trimethylolpropane triacrylate refers to any one of ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, and ethoxylated-propoxylated trimethylolpropane triacrylate; ethoxylated (propoxylated) pentaerythritol triacrylate refers to any one of ethoxylated pentaerythritol triacrylate, propoxylated pentaerythritol triacrylate, and ethoxylated-propoxylated pentaerythritol triacrylate; ethoxylated (propoxylated) pentaerythritol tetraacrylate refers to any one of ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, and ethoxylated-propoxylated pentaerythritol tetraacrylate; ethoxylated (propoxylated) diacrylate refers to any one of ethoxylated diacrylate, propoxylated diacrylate, and ethoxylated-propoxylated diacrylate.

[0057] To further shorten the film stripping time, the preferred photopolymerizable monomer includes ethoxylated (propoxylated) nonylphenoxy acrylate, and the total number of ethoxy groups and propoxy groups in ethoxylated (propoxylated) nonylphenoxy acrylate is 2 - 9.

[0058] In order to further shorten the film stripping time, preferably, the ethoxylated (propoxylated) nonylphenoxy acrylate includes one or more of 4-(ethoxy)nonylphenoxy acrylate, 8-(ethoxy)nonylphenoxy acrylate, 2-(propoxy)nonylphenoxy acrylate, 4-(propoxy)nonylphenoxy acrylate, 8-(propoxy)nonylphenoxy acrylate, 2-(propoxy)-7-(ethoxy)nonylphenoxy acrylate.

[0059] In this application, the ethoxylated (propoxylated) nonylphenoxy acrylate refers to any one of ethoxylated nonylphenoxy acrylate, propoxylated nonylphenoxy acrylate, and ethoxylated-propoxylated nonylphenoxy acrylate. 4-(Ethoxy)nonylphenoxy acrylate means that the nonylphenoxy acrylate contains 4 ethoxy groups; 8-(ethoxy)nonylphenoxy acrylate means that the nonylphenoxy acrylate contains 8 ethoxy groups; 2-(propoxy)nonylphenoxy acrylate means that the nonylphenoxy acrylate contains 2 propoxy groups; 4-(propoxy)nonylphenoxy acrylate means that the nonylphenoxy acrylate contains 4 propoxy groups; 8-(propoxy)nonylphenoxy acrylate means that the nonylphenoxy acrylate contains 8 propoxy groups; 2-(propoxy)-7-(ethoxy)nonylphenoxy acrylate means that the nonylphenoxy acrylate contains 2 propoxy groups and 7 ethoxy groups.

[0060] In order to further improve the resolution and film stripping speed of the photosensitive dry film, preferably, the amount of the ethoxylated (propoxylated) nonylphenoxy acrylate is 1-6 parts by weight (such as 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight or a range value composed of any two numerical values).

[0061] [Alkali-soluble resin]

[0062] In order to further improve the resolution of the photosensitive dry film, the alkali-soluble resin is obtained by copolymerization of (meth)acrylic acid monomers, optional (meth)acrylic acid alkyl ester monomers and a comonomer having an aromatic group. Preferably, the comonomer having an aromatic group includes at least one of styrene, (meth)acrylic acid phenyl ester, (meth)acrylic acid benzyl ester, (meth)acrylic acid phenoxyethyl ester, and o-phenylphenoxyethyl acrylate; preferably, the (meth)acrylic acid alkyl ester monomers include at least one of (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid butyl ester, and methyl methacrylate cyclohexyl ester.

[0063] In this application, the (meth)acrylic acid monomer refers to acrylic acid monomer and / or methacrylic acid monomer; the (meth)acrylic acid alkyl ester monomer refers to acrylic acid alkyl ester monomer and / or methacrylic acid alkyl ester monomer.

[0064] In the comonomer of aromatic group provided by this application, phenyl (meth)acrylate refers to phenyl acrylate and / or phenyl methacrylate; benzyl (meth)acrylate refers to benzyl acrylate and / or benzyl methacrylate; phenoxyethyl (meth)acrylate refers to phenoxyethyl acrylate and / or phenoxyethyl methacrylate.

[0065] In the (meth)acrylic acid alkyl ester monomers provided by this application, methyl (meth)acrylate refers to methyl acrylate and / or methyl methacrylate; ethyl (meth)acrylate refers to ethyl acrylate and / or ethyl methacrylate; butyl (meth)acrylate refers to butyl acrylate and / or butyl methacrylate.

[0066] In order to further improve the resolution and adhesion of the anti-corrosion layer, it is preferred that the comonomer with an aromatic group accounts for more than 50% of the total weight of the alkali-soluble resin.

[0067] The photosensitive dry film formed by using the photosensitive resin composition of the above alkali-soluble resin can simultaneously have excellent adhesion and resolution, can effectively reduce the poor plating penetration, and improve the yield.

[0068] In some embodiments of this application, the weight average molecular weight of the alkali-soluble resin is 25,000 - 65,000, the acid value of the alkali-soluble resin is 130 - 210 mg KOH / g, and the molecular weight distribution of the alkali-soluble resin is 1.0 - 3.0. Further preferably, the molecular weight distribution is 1.8 - 2.0. The alkali-soluble resin within the above index range has more excellent developability and resolution, as well as the effects of suppressing bottom residue and easy overflow of the photosensitive anti-corrosion layer. When the weight average molecular weight of the alkali-soluble resin is less than 25,000, there is a tendency for the resistance to the developer solution to decrease and for the photosensitive anti-corrosion layer to easily overflow; when the weight average molecular weight exceeds 65,000, there is a tendency for the resolution to decrease; when the molecular weight distribution exceeds 3.0, there is a risk of decreased resolution and longer bottom residue of the anti-corrosion circuit.

[0069] [Photoinitiator]

[0070] To improve the resolution and photosensitivity of the photosensitive dry film, the photoinitiator is preferably a triarylimidazole dimer and its derivatives, and more preferably the photoinitiator 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, and 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole, preferably one or more of 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer; more preferably, the photoinitiator is 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer.

[0071] [Additive]

[0072] To further improve the comprehensive performance of the photosensitive dry film, the additive preferably further includes one or more of a dye, a color former, a plasticizer, an antifoaming agent, and a leveling agent.

[0073] Exemplarily, the dye is selected from one or more of malachite green, diamond green, crystal violet, victoria blue, basic blue 7, or basic blue 20; the color former is selected from one or more of tribromomethylphenyl sulfone, tris(2,3-dibromopropyl) phosphate, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, and leuco crystal violet; the plasticizer is selected from one or more of o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, and triethyl citrate; the antifoaming agent is selected from one or more of polypropylene glycol, polypropylene glycol alkyl ether, octamethylcyclotetrasiloxane, or tributyl phosphate; the leveling agent is selected from one or more of BYK-L9565, BYK-333, BYK-348, and BYK-306.

[0074] In the second typical embodiment of the present application, a photosensitive dry film is further provided. The photosensitive dry film includes a support layer, a photosensitive resist layer, and a protective layer stacked in sequence; wherein, the material of the photosensitive resist layer is the aforementioned photosensitive resin composition, and the thickness of the photosensitive resist layer in the present application is 35-300 μm.

[0075] The photosensitive dry film provided by the present application is a thick film with a photosensitive resist layer thickness of 35-300 μm. It not only has excellent photosensitivity, resolution, and aspect ratio, but also has excellent adhesion and stripping performance, and has broad application prospects in the fields of printed circuit boards, lead frames, or semiconductor packaging substrates.

[0076] In the third typical embodiment of the present application, an application of the photosensitive dry film provided in the second typical embodiment in the manufacturing process of printed circuit boards, lead frames or semiconductor packaging substrates is also provided. It can be widely used in the manufacturing processes of printed circuit boards (PCBs), lead frames (LFs), and semiconductor packaging (IC) substrates, improving production efficiency and the yield rate of qualified products.

[0077] The following further describes the present application in detail with specific embodiments, and these embodiments should not be construed as limiting the scope claimed in the present application.

[0078] Preparation method of alkali-soluble resin A-5:

[0079] Using the copolymerization monomers used in A-5 shown in Table 1 as the main raw materials, alkali-soluble resin A-5 is prepared by a solution polymerization method. Mix the monomers corresponding to A-5 evenly according to the weight ratio (a total of 100 g) and set aside. Mix it with 2.0 g of photoinitiator AIBN, 70 g of methyl ethyl ketone, and 5 g of ethanol to obtain a mixed solution (the mass fraction of the solute is 35%), and stir to dissolve. Add part of the mixed solution into a three-necked flask with a nitrogen protection and condensation reflux device through a peristaltic pump, heat it to 80 °C in an oil bath, stir and react for 1 h, then dropwise add the remaining mixed solution, and add all the mixed solution within 3 h. Continue to keep the temperature and react for 4 h, then raise the temperature to 90 °C, add 5 g of ethanol solution dissolved with 0.2 g of initiator in two portions with an interval of 1 h between the two additions. After the dropping is completed, keep the temperature and stir for 3 h to end the reaction, and obtain alkali-soluble resin A-5.

[0080] The preparation methods of the remaining alkali-soluble resins are similar to that of A-5. Those skilled in the art can select suitable initiators, solvents, and reaction parameters with reference to the preparation process of A-5 to make the product indexes of the obtained alkali-soluble resins meet the records in Table 1. Table 1 records the components and indexes of the alkali-soluble resins.

[0081] Table 1

[0082]

[0083] Mix each component according to the formulations in Table 2-1, Table 2-2, and Table 2-3 (Examples and Comparative Examples) below in proportion, add 150 parts by weight of acetone, and then stir thoroughly until completely dissolved to prepare a photosensitive resin composition solution with a solid content of 40%. Use a coater to evenly coat it on the surface of a 15-μm-thick PET support film, and place it in an oven at 95 °C for 12 min to form a 100-μm-thick photosensitive resist layer, which shows blue-green under a yellow light lamp. Then, attach a 20-μm-thick polyethylene protective film (PE) protective layer on its surface to obtain a photosensitive dry film with a three-layer structure.

[0084] Alkali-soluble resin:

[0085] A-1: The main components are methacrylic acid / styrene / butyl methacrylate = 20 / 50 / 30 (weight average molecular weight 60,000, acid value 130.5 mg KOH / g, molecular weight distribution 2.0);

[0086] A-2: The main components are methacrylic acid / styrene / phenoxyethyl methacrylate / butyl methacrylate = 26 / 40 / 26 / 8 (weight average molecular weight 50,000, acid value 169.6 mg KOH / g, molecular weight distribution 1.9);

[0087] A-3: The main components are methacrylic acid / styrene / phenoxyethyl methacrylate / butyl methacrylate = 30 / 50 / 18 / 2 (weight average molecular weight 25,000, acid value 195.7 mg KOH / g, molecular weight distribution 2.1);

[0088] A-4: The main components are methacrylic acid / styrene / butyl methacrylate = 26 / 40 / 34 (weight average molecular weight 50,000, acid value 169.6 mg KOH / g, molecular weight distribution 1.9);

[0089] A-5: The main components are methacrylic acid / styrene / phenoxyethyl methacrylate / butyl methacrylate = 26 / 46 / 20 / 8 (weight average molecular weight 50,000, acid value 169.6 mg KOH / g, molecular weight distribution 1.9);

[0090] A-6: The main components are acrylic acid / methacrylic acid / styrene / butyl methacrylate = 5 / 15 / 50 / 30 (weight average molecular weight 65,000, acid value 136.7 mg KOH / g, molecular weight distribution 2.0);

[0091] A-7: The main components are acrylic acid / methacrylic acid / styrene / phenoxyethyl methacrylate / butyl methacrylate = 10 / 20 / 55 / 13 / 2 (weight average molecular weight 25,000, acid value 208.4 mg KOH / g, molecular weight distribution 1.8);

[0092] Photopolymerizable monomer:

[0093] B-1: 10 Ethoxylated bisphenol A dimethacrylate (Sartomer)

[0094] B-2: 30 Ethoxylated bisphenol A dimethacrylate (Sartomer)

[0095] B-3: 30 Ethoxylated 4 propoxylated bisphenol A dimethacrylate (Sartomer)

[0096] B-4: 6 Ethoxylated 12 propoxylated dimethacrylate (Sartomer)

[0097] B-5: 8-ethoxylated nonylphenoxy acrylate (Sartomer)

[0098] B-6:10 Ethoxylated Bisphenol A Diacrylate (Sartomer)

[0099] B-7:3 Ethoxylated trimethylolpropane triacrylate (Sartomer)

[0100] B-8: 10 ethoxylated 4 propoxylated bisphenol A dimethacrylate (Sartomer)

[0101] B-9:21 Ethoxylated trimethylolpropane trimethacrylate (Sartomer)

[0102] B-10: 2-Propoxy Nonylphenoxy Acrylate (Sartomer)

[0103] B-11:4-ethoxylated nonylphenoxy acrylate (Sartomer)

[0104] B-12: 2 (propyloxy) 7 (ethoxy) nonylphenoxy acrylate (Sartomer)

[0105] Photoinitiator:

[0106] C-1: 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer (Changzhou Qiangli Electronic Materials)

[0107] C-2: 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole (Changzhou Qiangli Electronic Materials)

[0108] Photosensitizer:

[0109] D-1: 9,10-diphenoxyanthracene (McLean)

[0110] D-2: 1-phenyl-3-(4-methoxyphenylvinyl)-5-(4-methoxyphenyl)pyrazoline (McLean)

[0111] D-3: N,N'-tetraethyl-4,4'-diaminobenzophenone (McLean)

[0112] D-4: 9,10-di(4-tert-butylphenoxy)anthracene (McLean)

[0113] D-5: 9,10-dibutoxyanthracene (McLean)

[0114] additive:

[0115] E-1 (dye): Malachite green (Shanghai Bailingwei Chemical Technology Co., Ltd.)

[0116] E-2 (Color former): Leuco Crystal Violet (Shanghai TCI Chemical Technology Co., Ltd.)

[0117] E-3 (Plasticizer): p-Toluenesulfonamide (Shanghai TCI Chemical Industry Co., Ltd.)

[0118] E-4 (Phenolic inhibitor): 4-tert-Butylphenol (Shanghai TCI Chemical Technology Co., Ltd.)

[0119] E-5 (Phenolic inhibitor): 2,2'-Methylenebis(4-ethyl-6-tert-butylphenol) (Macklin)

[0120] E-6 (Piperidine inhibitor): 4-Hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl (Macklin)

[0121] Table 2-1

[0122]

[0123] Table 2-2

[0124]

[0125] Table 2-3

[0126]

[0127] The following describes the sample preparation methods (including film laminating, exposure, and development), sample evaluation methods, and evaluation results for the examples and comparative examples (see Tables 3-1 and 3-2).

[0128]

Film Laminating

[0129] The copper clad laminate is polished on its copper surface by a grinding machine, washed with water, and dried to obtain a bright and fresh copper surface. The temperature of the pressure roller of the film laminating machine is set at 110°C, the conveying speed is 1.5 m / min, and hot lamination is carried out under standard pressure.

[0130]

Exposure

[0131] After film laminating, the sample is left standing for more than 15 min and exposed using an Adtec IP-6 exposure machine with 17 exposure grids.

[0132]

Development

[0133] After exposure, the sample is left standing for more than 15 min. The development temperature is 30°C, the pressure is 1.2 Kg / cm 2 , the developer is a 1%wt aqueous sodium carbonate solution, the development time is 2.0 times the minimum development time, and after development, it is washed with water and dried. The time required for the resist layer in the unexposed part to be just completely dissolved through the development tank section is taken as the minimum development time.

[0134]

Evaluation of Photosensitivity

[0135] After the film was applied, the sample was allowed to stand for more than 15 min, exposed using an Adtec IP-6 exposure machine, and the sensitivity was measured using a stouffer 41-step exposure scale. After exposure, the sample was allowed to stand for more than 15 min, and then sprayed with a 1% wt aqueous sodium carbonate solution at 30 °C. The development time was 2.0 times the minimum development time, thereby removing the unexposed part. After such an operation, a cured film formed from the cured product of the photosensitive resin composition was formed on the copper surface of the substrate. The exposure amount (mJ / cm 2 ), when the remaining number of segments of the stepwise exposure table obtained as the cured film became 17 grids, was used to evaluate the photosensitivity of the photosensitive resin composition. The smaller this value, the better the photosensitivity.

[0136]

Evaluation of Resolution

[0137] Exposure was performed using a mask having a wiring pattern with widths of the exposed part and the unexposed part of n:n (n is 5 to 50 μm). After development with 2.0 times the minimum development time, the minimum mask width at which a cured resist line was normally formed was taken as the resolution value and observed using a magnifying glass. The smaller the number read, the better the resolution.

[0138]

Evaluation of Adhesion

[0139] A photosensitive dry film resist was laminated on a copper plate by hot press lamination. Exposure was performed using a mask having a wiring pattern with widths of the exposed part and the unexposed part of n:400 (n is 5 to 50 μm). After development with 2.0 times the minimum development time, the minimum mask width at which a cured resist line was normally formed was taken as the adhesion value and observed using a magnifying glass. The smaller the number read, the better the adhesion.

[0140]

Evaluation of Aspect Ratio

[0141] The aspect ratio is the ratio of the dry film thickness to the dry film resolution. The larger the ratio, the better the aspect ratio ability.

[0142]

Evaluation of Flexibility

[0143] Take the FPC substrate after laminating, exposure, and development, cut it into strips of 5 mm * 100 mm, and measure the softness performance of the photosensitive layer using a cylindrical bending measuring instrument. Place the sample strip at the center of a cylindrical shaft with a specific diameter and bend it by about 180 degrees. Hold both ends of the strip and pull it back and forth around the cylinder 5 times, and observe whether the dry film lines on the strip are peeled off or cracked. Record the size of the cylindrical diameter corresponding to when the dry film is not peeled off or cracked. The cylindrical diameters are 2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 13, 15, 20, 25, and 30 (unit: mm). The smaller the number read, the better the softness.

[0144]

Evaluation of Stripping Rate

[0145] Take 1 substrate after laminating, exposure, and development, cut it into a square of 4 * 5 cm, put it into a beaker containing 300 mL of stripping solution (aqueous sodium hydroxide solution, concentration 3 wt%, temperature 50 °C), stir magnetically, and record the time when the dry film completely falls off. Evaluate the stripping rate by measuring the stripping time. The shorter the stripping time, the faster the stripping rate.

[0146] Table 3-1

[0147]

[0148] Table 3-2

[0149]

[0150] Through the comparison between Examples 1-7 and Comparative Examples 1-4, it can be found that: Photosensitive resin compositions with excellent photosensitivity, resolution, adhesion, and aspect ratio performance are obtained in Examples 1-7. In Comparative Example 1 and Comparative Example 3, the weight ratio of the alkyl-substituted phenol compound (polymerization inhibitor) to the aryl-modified anthracene compound (photosensitizer) is less than 0.1, that is, the addition amount of the polymerization inhibitor is too low, resulting in a significant decrease in the resolution and aspect ratio performance; in Comparative Example 2, the weight ratio of the alkyl-substituted phenol compound (polymerization inhibitor) to the aryl-modified anthracene compound (photosensitizer) is greater than 10, that is, the addition amount of the polymerization inhibitor is too high. Although the resolution is excellent, the photosensitivity significantly decreases; in Comparative Example 4, a pyrazoline compound is used as the photosensitizer, resulting in insufficient resolution; in Comparative Example 8, an alkoxy anthracene compound is used as the photosensitizer, resulting in a decrease in both photosensitivity and resolution performance; in Comparative Example 9, a benzophenone compound is used as the photosensitizer, and the weight percentage of the non-methyl-substituted acrylate monomer in the photopolymerizable monomer exceeds 10%, resulting in a significant decrease in the resolution and aspect ratio performance.

[0151] Furthermore, if the copolymerization ratio of the comonomer having an aromatic group in the alkali-soluble resin in Example 8 is less than 50% relative to the total mass of the alkali-soluble resin, the adhesion and resolution are insufficient; if the weight proportion of the non-methyl-substituted acrylate monomer in the photopolymerizable monomer in Example 9 exceeds 10%, the resolution and aspect ratio performance will significantly decline.

[0152] By comparing Examples 10 to 15 with Comparative Examples 5 to 7, it can be found that the photosensitive resin compositions obtained in Examples 10 to 15 have excellent photosensitivity, resolution, adhesion, and aspect ratio performance. In Comparative Example 5, a pyrazoline compound was used as the photosensitizer, resulting in insufficient resolution; in Comparative Example 6, no inhibitor was added, resulting in poor adhesion, resolution, and aspect ratio; in Comparative Example 7, a benzophenone compound was used as the photosensitizer, and the weight proportion of the non-methyl-substituted acrylate monomer in the photopolymerizable monomer exceeded 10%, resulting in low photosensitivity, insufficient resolution, and aspect ratio.

[0153] Furthermore, if the copolymerization ratio of the copolymer unit having an aromatic group in the alkali-soluble resin in Example 16 is less than 50% relative to the total mass of the alkali-soluble resin, the adhesion, resolution, and aspect ratio will decrease to a certain extent; in Example 17, no nonylphenol acrylate photopolymerizable monomer was added, resulting in a significant prolongation of the film stripping time; in Example 18, too much nonylphenol acrylate photopolymerizable monomer was added, resulting in a decrease in adhesion, resolution, and aspect ratio; in Example 19, a diacrylate photopolymerizable monomer having a bisphenol A backbone was used, but its content in the photopolymerizable monomer exceeded 10% by weight, resulting in insufficient resolution and aspect ratio.

[0154] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects:

[0155] The photosensitive resin composition provided by the present invention uses a specific aryl-modified anthracene compound as a photosensitizer in combination with a specific mass dosage of an inhibitor, so that the formed photosensitive resist layer with a thickness ≥ 35 μm has excellent resolution, photosensitivity, adhesion, and aspect ratio performance. The photosensitive resin composition of the present application can be widely used in the manufacturing processes of printed circuit boards (PCBs), lead frames (LFs), and semiconductor package (IC) substrates, improving production efficiency and the yield rate.

[0156] 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, the present invention can have various modifications and changes. Any modifications, equivalent replacements, improvements, 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 photosensitive resin composition, characterized in that The photosensitive resin composition comprises: 50 to 65 parts by weight of an alkali-soluble resin, 30 to 45 parts by weight of a photopolymerizable monomer, 0.49 to 6.0 parts by weight of a photoinitiator, 0.01 to 0.7 parts by weight of a photosensitizer, and 0.001 to 5.0 parts by weight of an additive, wherein the additive comprises an inhibitor, wherein the weight ratio of the inhibitor to the photosensitizer is 0.1 to 10; and the photosensitizer is an aromatic-modified anthracene compound.

2. The photosensitive resin composition according to claim 1, characterized in that The aromatic modified anthracene compounds include 9-phenylanthracene, 9,10-diphenylanthracene, 9,10-diphenoxyanthracene, 9,10-di(2-methylphenoxy)anthracene, 9,10-di(2-methoxyphenoxy)anthracene, 9,10-di(3-methylphenoxy)anthracene, 9,10-di(4-ethylphenoxy)anthracene, 9,10-di(4-propylphenoxy)anthracene, 9,10-di(4-butylphenoxy)anthracene, 9,10-di(4-tert-butylphenoxy)anthracene, 9,10-di(4-pentylphenoxy)anthracene, 9,10-di(4-hexylphenoxy)anthracene, 9,10-di(4-nonylphenoxy)anthracene, 9,10-di(benzyloxy)anthracene, 9,10-di(2 At least one of 9,10-bis(3-methylbenzyloxy)anthracene, 9,10-bis(2,3-dimethylbenzyloxy)anthracene, 9,10-bis(2,4-dimethylbenzyloxy)anthracene, 9,10-bis(2,3,4,5,6-pentamethylbenzyloxy)anthracene, 9,10-bis(benzoyloxy)anthracene, 9,10-bis(2-methylbenzoyloxy)anthracene, 9,10-bis(3-methylbenzoyloxy)anthracene, 9,10-bis(4-methylbenzoyloxy)anthracene, 9,10-bis(3,5-dimethylbenzoyloxy)anthracene, 9,10-bis(4-butylbenzoyloxy)anthracene and 9,10-bis(4-hexylbenzoyloxy)anthracene.

3. The photosensitive resin composition according to claim 1, characterized in that The polymerization inhibitor includes piperidine oxide and / or an alkyl-substituted phenol compound.

4. The photosensitive resin composition according to claim 3, characterized in that: The polymerization inhibitor is an alkyl-substituted phenol compound.

5. The photosensitive resin composition according to claim 1, characterized in that: The photopolymerizable monomers include methyl-substituted acrylate monomers and non-methyl-substituted acrylate monomers, wherein the weight proportion of the non-methyl-substituted acrylate monomers in the photopolymerizable monomers is 0%-10%.

6. The photosensitive resin composition according to claim 5, characterized in that: The photopolymerizable monomer comprises ethoxylated (propoxylated) nonylphenoxy acrylate, wherein the total number of ethoxyl groups and propoxyl groups in the ethoxylated (propoxylated) nonylphenoxy acrylate is 2-9.

7. The photosensitive resin composition according to claim 1, characterized in that: The alkali-soluble resin is obtained by copolymerizing a (meth)acrylic acid monomer, an optional (meth)acrylic acid alkyl ester monomer and a comonomer having an aromatic group.

8. The photosensitive resin composition according to claim 7, characterized in that: The comonomer having an aromatic group accounts for ≥50% of the total weight of the alkali-soluble resin.

9. A photosensitive dry film, characterized in that: The photosensitive dry film comprises a supporting layer, a photosensitive resist layer and a protective layer which are stacked in sequence; wherein the material of the photosensitive resist layer is the photosensitive resin composition according to any one of claims 1 to 8, and the thickness of the photosensitive resist layer is 35-300 μm.

10. Use of the photosensitive dry film according to claim 9 in the manufacturing process of a printed circuit board, a lead frame or a semiconductor packaging substrate.

Images