Negative photosensitive resin composition, preparation method and photoetching product

Abstract

The invention discloses a negative photosensitive resin composition, a preparation method and a photoetching product, and the composition at least comprises the following components (a), (b) and (c): the component (a) is an alkali-soluble resin polymer; the component (b) is a photo-induced free radical polymerization reaction initiator; component (c): a compound containing one or more polymerizable functional groups; in terms of 100 parts by weight of the component (a), the use amount of the component (b) is 1-20 parts by weight, and the use amount of the component (c) is 1-60 parts by weight. The negative photosensitive resin composition has a negative characteristic, can be developed by an alkaline aqueous solution, can form a radiation-sensitive film with a thickness greater than the thickness required by deposition to form a bump and the like, has high resolution, and is low in production cost and high in yield.

Description

Technical Field

[0001] The invention belongs to the technical field of photolithography, and in particular relates to a negative photosensitive resin composition, a preparation method and a photolithography product. Background Art

[0002] Photoresist, also known as photoresist, is a medium that uses photochemical reactions to transfer patterns. It is a type of fine chemical with a wide variety of products and properties and is widely used. This article mainly introduces various types of photoresists used in the electronics industry.

[0003] The development of the electronics industry is closely related to the development of photoresist. The development of photoresist provides the basis for the industrialization of the electronics industry, while the development of the electronics industry constantly puts forward new requirements for photoresist, promoting the development of photoresist. Due to the rapid development of the electronics industry, photoresist has become a hot research field, with a large number of related papers published and new products launched every year.

[0004] Photoresist is mainly used in the micro-processing of integrated circuits and semiconductor discrete devices in the electronics industry. It uses photochemical reactions to transfer the required fine patterns from the mask to the substrate to be processed through exposure and development, and then performs etching, diffusion, ion implantation, metallization and other processes. Therefore, photoresist is a key basic chemical material in the electronics industry.

[0005] The history of photoresist can be traced back to the origin of photography. In 1826, the first human photograph was made of photoresist material - photosensitive asphalt. In the mid-19th century, it was discovered that mixing dichromate with gelatin could produce very good graphics after exposure and development, which led to the rapid development of the printing industry at that time. In 1954, Eastman-Kodak synthesized the first photosensitive polymer in the world - polyvinyl cinnamate, and created the polyvinyl cinnamate and its derivative photoresist system, which was the first photoresist used in the electronics industry. In 1958, the company developed cyclized rubber - diazide photoresist, making the industrialization of integrated circuit manufacturing a reality. Prior to this, the diazonaphthoquinone-phenolic resin photoresist was invented around 1950. It was first used in the printing industry and is currently the most used photoresist in the electronics industry. In recent years, with the rapid development of the electronics industry, the development of photoresists has been changing with each passing day, and new photoresist products have continued to emerge. Depending on the exposure light source or radiation source used, photoresist can be divided into ultraviolet photoresist, deep ultraviolet photoresist, electron beam photoresist, ion beam photoresist, X-ray photoresist, etc.

[0006] Depending on the retention or removal of the photoresist film caused by the changes in the chemical properties of the photoresist film after exposure, photoresists can be divided into positive photoresists and negative photoresists.

[0007] When positive photoresist is exposed to ultraviolet / ultraviolet light, the polymer chains in the photoresist in the exposed area undergo chemical reactions such as degradation, functional group deprotection, rearrangement, and intramolecular dehydration, which increases its solubility in the developer and obtains the same pattern as the mask on the substrate. Conversely, the polymer chains of negative photoresist are insoluble in the photoresist in the exposed area due to cross-linking, and the unexposed area is dissolved in the developer, thereby obtaining a pattern opposite to the mask pattern.

[0008] In actual production, since negative photoresist is prone to deformation and expansion during development, the resolution can usually only reach 2 microns. Therefore, positive photoresist is more widely used and is the mainstream photoresist.

[0009] However, due to the strong heat resistance of negative resist, it is mostly used in high-voltage power devices, high-energy consumption devices, etc. In addition, it is also often used in some special processes. Due to the difficulty in removing negative resist, negative resist can be used in the final packaging stage of the chip to play the role of insulation and chip protection.

[0010] Photolithography is a general term for the technology of manufacturing various precision components through the following steps:

[0011] Applying a radiation-sensitive resin composition to a surface of a workpiece;

[0012] forming a pattern on the resulting thin film by photolithography;

[0013] Chemical etching or electroforming using a patterned film as a mask, mainly electrolytic etching or electroplating, or a combination thereof. This lithography method is currently the mainstream technology for manufacturing precision and fine components.

[0014] In recent years, the miniaturization of electronic devices has accelerated the high integration and multi-layering of large-scale integrated circuits (LSI). To adapt to such miniaturization, it is required to assemble electronic devices by mounting LSI on a substrate with a high pin count. As such mounting technology, bare chip mounting technology such as TAB mounting and flip chip mounting are increasingly attracting attention. In high-density mounting, there are strict requirements for metal conductors formed by electrolytic plating. For example, one requirement is that the metal conductor forms a micro pattern. Such a metal pattern includes a protrusion (called a microelectrode) and a wiring that forms a conductive path with the electrode. These metal patterns are required to be more miniaturized to meet the trend of miniaturization, high pin count and multi-layer packaging. For example, for conventional protruding microelectrodes, metal protrusions of about 20 microns high are arranged at a pitch of about 40 microns or more, and the distance between the edges of the protrusions is 5-10 microns. However, due to the higher performance and smaller size of electronic devices, the protrusion spacing is required to be smaller, and the protrusion spacing is currently required to be 20 microns.

[0015] Requirements for the radiation-sensitive resin composition used in producing such fine metal patterns are as follows:

[0016] Forming a radiation sensitive film having a thickness greater than that required for depositing bumps and having a high resolution, for example, having such a high resolution that a film 20 microns or thicker is patterned at 25 microns pitch in making gold bumps; or having such a resolution that a film 10 microns thick is patterned at 5 microns pitch in forming wiring.

[0017] Furthermore, the patterned product obtained by curing the radiation-sensitive resin composition is used as a mask in electrolytic plating. However, the patterned product is required to have sufficient wettability to the plating solution and a certain plating resistance. Moreover, the patterned product must be easily and completely de-filmed by a de-filming solution, etc., without damaging the metal pattern obtained after electroplating.

[0018] However, it is difficult for existing radiation-sensitive resin compositions for manufacturing metal patterns to meet sufficient resolution and electroplating resistance. When the resolution of the resin composition is poor, the required tiny metal pattern is difficult to form, and semiconductor devices with such metal patterns cannot be manufactured. Moreover, when the wettability is poor, a sufficient amount of electroplating solution cannot be provided in the tiny pattern of the cured product. Therefore, a metal pattern cannot be formed. Similarly, poor electroplating resistance can lead to plating and cracking during electroplating, causing short circuits between conductive elements, and the device cannot operate normally.

[0019] Therefore, in view of the above technical problems, it is necessary to provide a negative photosensitive resin composition, a preparation method and a photolithography product.

[0020] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the invention

[0021] The object of the present invention is to provide a negative photosensitive resin composition, a preparation method and a photolithography product. The composition has negative characteristics and can be developed with an alkaline aqueous solution. The portion of the composition not exposed to ultraviolet light is easily soluble in an alkaline aqueous solution, while the portion exposed to ultraviolet light is insoluble in an alkaline aqueous solution. The unexposed portion and the exposed portion have excellent alkali solubility differentiation, can form a radiation-sensitive film with a thickness greater than the thickness required for deposition to form protrusions, etc., and has high resolution, and its production cost is low and the yield is high.

[0022] In order to achieve the above object, a technical solution provided by a specific embodiment of the present invention is as follows:

[0023] The negative photosensitive resin composition comprises at least the following components (a), (b) and (c):

[0024] Component (a) is: an alkali-soluble resin polymer;

[0025] Component (b) is: a photo-inducible free radical polymerization initiator;

[0026] Component (c) is: a compound containing one or more polymerizable functional groups, that is, a monofunctional compound or a multifunctional compound;

[0027] Wherein, based on 100 parts by weight of component (a), 1-20 parts by weight of component (b) and 1-60 parts by weight of component (c) are used.

[0028] In one or more embodiments of the present invention, component (a) is selected from:

[0029] A free radical polymerizable compound having a carboxyl structure;

[0030] A free radical polymerizable compound having a benzene ring structure;

[0031] Free radical polymerizable compounds having an ester structure;

[0032] A free radical polymerizable compound having two or more unsaturated double bonds.

[0033] In one or more embodiments of the present invention, the free radical polymerizable compound having a carboxyl structure is selected from the group consisting of acrylic acid, methacrylic acid, heptenoic acid, octenoic acid, nonenoic acid, pentenoic acid, 4-pentenoic acid, dimethylacrylic acid, cinnamic acid, maleic acid, fumaric acid, 4-vinylbenzoic acid, lauroleic acid, 3-butenoic acid, 5-hexenoic acid, etc. Preferably, the compound is at least one of acrylic acid, methacrylic acid and 4-vinylbenzoic acid.

[0034] In one or more embodiments of the present invention, the free radical polymerizable compound having a benzene ring structure is selected from the group consisting of styrene, α-methylstyrene, isopropylstyrene, 2-phenoxyethyl acrylate, 3-acetoxystyrene, 4-acetoxystyrene, phenyl methacrylate, 2-tert-butylstyrene, 4-tert-butylstyrene, 2-naphthyl methacrylate, hydroquinone monomethacrylate, 4-tert-butyloxycarbonylstyrene, 4-vinylbenzoic acid ethyl ester, cinnamyl methacrylate, etc. Preferably, the compound is at least one of styrene, α-methylstyrene, 2-phenoxyethyl acrylate, and 4-acetoxystyrene.

[0035] In one or more embodiments of the present invention, the free radical polymerizable compound having an ester structure is selected from the group consisting of methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, cyclohexyl 2-acrylate, tert-butyl (meth)acrylate, acrylic acid, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, adamantyl 1-acrylate, lauryl (meth)acrylate, 2-methoxyethyl 2-acrylate, glycidyl (meth)acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl 2-acrylate, etc. Preferably, the compound is at least one of isobornyl (meth)acrylate, adamantyl 1-acrylate, 2-methoxyethyl 2-acrylate, and glycidyl (meth)acrylate.

[0036] In one or more embodiments of the present invention, the free radical polymerizable compound having two unsaturated double bonds is selected from the group consisting of 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 1,7-octadiene, propadiene, isoprene, piperylene, allyl ether, etc. Preferably, the free radical polymerizable compound having two unsaturated double bonds is selected from the group consisting of 1,3-butadiene, 1,2-pentadiene, and isoprene.

[0037] In one or more embodiments of the present invention, in the resin polymer of component (a): the free radical polymerizable compound having a carboxyl group accounts for 1-50 weight percent of component (a), preferably 5-45 weight percent, and more preferably 10-40 weight percent; the free radical polymerizable compound having a benzene ring accounts for 1-40 weight percent of component (a), preferably 5-35 weight percent, and more preferably 10-30 weight percent; the free radical polymerizable compound having an ester structure accounts for 1-70 weight percent of component (a), preferably 10-60 weight percent, and more preferably 30-50 weight percent; the free radical polymerizable compound having two unsaturated double bonds accounts for 1-30 weight percent of component (a), preferably 5-25 weight percent, and more preferably 10-20 weight percent.

[0038] In one or more embodiments of the present invention, component (b) is selected from: benzoin ether photoinitiators, benzophenone photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, α-dialkylaminoketone photoinitiators, and carbazole-based photoinitiators.

[0039] In one or more embodiments of the present invention, the benzoin ether photoinitiator is selected from: benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and hydroxymethyl benzoin methyl ether.

[0040] In one or more embodiments of the present invention, the benzophenone photoinitiator is selected from: benzophenone (BP), 4-chlorobenzophenone (CBP), 4-phenylbenzophenone (PBZ), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 2,4,6-trimethylbenzoylphosphonic acid ethyl ester (TPO-L) and a polymerizable benzophenone derivative.

[0041] In one or more embodiments of the present invention, the thioxanthone photoinitiator is selected from: 2-hydroxythioxanthone (TX1), 2-hydroxy-3-(2-thioxanthoneoxy)propyltrimethylammonium chloride (TX2), Irageure 184D

[0042] In one or more embodiments of the present invention, the acylphosphine oxide photoinitiator is selected from: photoinitiator 819, photoinitiator 1800, photoinitiator 1700, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), 4-diethylaminobenzoyldiphenylphosphine oxide (DEAPO), (2,4,6-trimethyl-3-benzoyl)benzoyldiphenylphosphine oxide (BzTPO), bis(2,4,6-trimethylbenzoyl)diphenylphosphine oxide

[0043] In one or more embodiments of the present invention, the α-dialkylaminoketone photoinitiator is selected from: 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, and α-aminoalkylphenone.

[0044] In one or more embodiments of the present invention, the carbazole-based photoinitiator is selected from: carbazole-based oxime esters (OXEs), 3,6-bis[2-(4-pyridyl)vinyl]-9-phenylcarbazole, 3,6-bis[2-(2-pyridyl)vinyl]-9-phenylcarbazole, and carbazole-based α-diketone.

[0045] In one or more embodiments of the present invention, component (b) is preferably selected from 2-hydroxy-2-methyl-1-phenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and ethyl 2,4,6-trimethylbenzoylphosphonate (TPO-L).

[0046] In one or more embodiments of the present invention, component (c) is selected from: monofunctional compounds, multifunctional compounds.

[0047] In one or more embodiments of the present invention, the monofunctional compound is selected from the group consisting of: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, tert-octyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diacetone (meth)acrylamide, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, glycerol (meth)acrylate, acrylamide, methyl acrylate Acrylamide, (meth)acrylonitrile, methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dodecyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofuran (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, (meth)acrylate 2-Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, isobutoxymethyl (meth)acrylamide, N-vinylpyrrolidone, N-vinylcaprolactam, N,N-dimethyl (meth)acrylamide, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylate Phenoxyethyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, dicyclopentadienyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclodecyl (meth)acrylate, isobornyl (meth)acrylate, and bornyl (meth)acrylate.

[0048] In one or more embodiments of the present invention, the multifunctional compound is selected from: trimethylolpropane di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, butanediol di(meth)acrylate, propylene glycol di(meth)acrylate, bisphenol A-di(meth)acryloyloxyethyl ether, bisphenol A-di(meth)acryloyloxyethoxyethyl ether, bisphenol A-di(meth)acryloyloxymethylethyl ether, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate. acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tetramethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate, diethylene glycol dimethacrylate.

[0049] In one or more embodiments of the present invention, (d) a solvent is further included. Based on 100 parts by weight of component (a), the amount of component (d) is 80-120 parts by weight.

[0050] In one or more embodiments of the present invention, the solvent is selected from: propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, methyl 3-methoxypropionate, methanol, ethanol, diethylene glycol, propylene glycol, isopropanol, ethyl acetate, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, ethyl lactate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, 1-methoxy-2-propanol, 1-methoxy-2-acetoxypropane, propylene glycol 1-monomethyl ether 2-acetate.

[0051] In one or more embodiments of the present invention, (e) an antioxidant is further included. Based on 100 parts by weight of component (a), the amount of component (e) is 0.1-1 part by weight.

[0052] In one or more embodiments of the present invention, the antioxidant is selected from: N-phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, octylated diphenylamine, 4,4′-bis(α,α-dimethylbenzyl) diphenylamine, N-cyclohexyl-N-phenyl-p-phenylenediamine, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-p-cresol, N-phenyl-α-aniline, antioxidant BHA, antioxidant 2246, antioxidant 264, 2-mercaptobenzimidazole (MBI, MB), 2-mercaptomethylbenzimidazole (MMBI, MMB), 2-mercaptomethylbenzimidazole zinc salt (ZMBI, MBZ), 2-mercaptomethylbenzimidazole zinc salt (ZMMBI, ZMTI, MMBZ)

[0053] In one or more embodiments of the present invention, (f) a polymerization inhibitor is further included. Based on 100 parts by weight of component (a), the amount of component (f) is 0.1-5 parts by weight.

[0054] In one or more embodiments of the present invention, the inhibitor is selected from: hydroquinone (HQ), para-benzoquinone (PBQ), methylhydroquinone (THQ), tetrachlorobenzoquinone, anthraquinone, 1,4-naphthoquinone, p-hydroxyanisole (HQMME), 2-tert-butylhydroquinone (MTBHQ), 2,5-di-tert-butylhydroquinone (2,5-DTBHQ), and p-tert-butylcatechol.

[0055] In one or more embodiments of the present invention, (g) a surfactant is further included. Based on 100 parts by weight of component (a), the amount of component (g) is 0.1-5 parts by weight.

[0056] In one or more embodiments of the present invention, the surfactant is selected from: polydimethylsiloxane, organic modified polydimethylsiloxane, polyether polyester modified organic siloxane, alkyl modified organic siloxane, MONENG-1073, MONENG-1153, FCF-203 polyacrylic fluorinated ester leveling agent.

[0057] In one or more embodiments of the present invention, the method for preparing the negative photosensitive resin composition comprises: at least fully mixing and stirring raw materials including components (a), (b), and (c) at room temperature.

[0058] In one or more embodiments of the present invention, a photolithography product comprises at least a structure obtained by using the negative photosensitive resin composition according to any one of claims 1 to 8 as a raw material.

[0059] In one or more embodiments of the present invention, based on 100 parts by weight of the component (a), the content of the component (b) can be 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 5 parts by weight, 10 parts by weight, 15 parts by weight or 20 parts by weight, etc.; the content of the component (c) can be 1 part by weight, 10 parts by weight, 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight or 60 parts by weight, etc.

[0060] In one or more embodiments of the present invention, based on 100 parts by weight of the component (a), the content of the solvent (d) may be 80 parts by weight, 90 parts by weight, 100 parts by weight, 110 parts by weight or 120 parts by weight, etc.; the content of the antioxidant (e) may be 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight or 1 part by weight, etc.; the content of the inhibitor (f) may be 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight or 0.5 parts by weight.

[0061] In view of the insufficient resolution of the photosensitive resin composition, other benzene ring structures can be introduced into the resin polymer to improve the overall resolution.

[0062] In view of the poor electroplating resistance of the photosensitive resin composition, a polyunsaturated double bond structure can be introduced into the resin polymer to improve the electroplating resistance and improve the cracking and plating problems.

[0063] Compared with the prior art, the negative photosensitive resin composition, preparation method and photolithography product of the present invention have negative characteristics and can be developed with alkaline aqueous solution. The part of the negative photosensitive resin composition not exposed to ultraviolet light is easily soluble in alkaline aqueous solution, while the part exposed to ultraviolet light is insoluble in alkaline aqueous solution. The alkali solubility difference between the unexposed part and the exposed part is excellent, and a radiation-sensitive film with a thickness greater than the thickness required for deposition to form protrusions can be formed, and the film has high resolution. The production cost is low and the yield is high. DETAILED DESCRIPTION

[0064] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0065] The polymerization process of component (a) of the negative photosensitive resin composition of the present invention uses a solvent, preferably an organic solvent; such as propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, methyl 3-methoxypropionate, methanol, ethanol, diethylene glycol, propylene glycol, isopropanol, ethyl acetate, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, ethyl lactate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, 1-methoxy-2-propanol, 1-methoxy-2-acetoxypropane, propylene glycol 1-monomethyl ether 2-acetate and the like solvents.

[0066] Among these solvents, propylene glycol methyl ether acetate, diethylene glycol dimethyl ether and methanol are preferred.

[0067] The preparation of component (a) alkali-soluble resin polymer uses conventional free radical polymerization initiators, which are mainly divided into three types: azo compounds, peroxides and redox types.

[0068] Azo compound initiators, such as azobisisobutyronitrile (AIBN), azobisisoheptanenitrile (ABVN), dimethyl azobisisobutyrate (AIBME), azobisisobutylamidine hydrochloride (AIBA), azobisisobutylimidazoline hydrochloride (AIBI), azoisobutylcyanamide and other initiators.

[0069] Peroxide initiators, such as dibenzoyl peroxide (BPO), methyl ethyl ketone peroxide (MEKP), tert-butyl perbenzoate (TBPB), hydrogen peroxide (H2O2), potassium persulfate (KPS), ammonium persulfate (APS), dibenzoic acid peroxide, diisopropylbenzene peroxide, dicyclohexyl peroxide and other initiators.

[0070] Redox initiators, such as: oxidants - hydrogen peroxide, persulfate, hydroperoxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, diphenylphthalide peroxide, etc.; reducing agents - sodium sulfite, sodium bisulfite, N,N-dimethylaniline, N,N-diethylaniline, etc., oxidants and reducing agents are used in combination.

[0071] Among these conventional radical polymerization initiators, azobisisobutyronitrile (AIBN), azobisisoheptanenitrile (ABVN), dimethyl azobisisobutyrate (AIBME), dibenzoyl peroxide (BPO), methyl ethyl ketone peroxide (MEKP) and tert-butyl peroxydibenzoate (TBPB) are preferred.

[0072] The free radical polymerization reaction of the above monomers and initiators can obtain a polymer with a weight average molecular weight of preferably 1000-50000, more preferably 5000-40000, and more preferably 10000-30000. The molecular weight here is determined by gel permeation chromatography based on a polystyrene standard curve.

[0073] The negative photosensitive resin composition of the present invention may contain (a) an alkali-soluble resin polymer; (b) a photo-induced free radical polymerization initiator; and (c) a compound containing one or more polymerizable functional groups.

[0074] The alkali-soluble resin polymer of component (a) can be obtained by reacting the following compounds:

[0075] A free radical polymerizable compound having a carboxyl structure;

[0076] A free radical polymerizable compound having a benzene ring structure;

[0077] Free radical polymerizable compounds having an ester structure;

[0078] A free radical polymerizable compound having two or more ethylenically unsaturated double bonds.

[0079] Specifically:

[0080] A. The free radical polymerizable compound having a carboxyl structure is selected from the following compounds: acrylic acid, methacrylic acid, heptenoic acid, octenic acid, nonenoic acid, pentenoic acid, 4-pentenoic acid, dimethylacrylic acid, cinnamic acid, maleic acid, fumaric acid, 4-vinylbenzoic acid, lauryl acid, 3-butenoic acid, 5-hexenoic acid and the like.

[0081] Of these compounds, acrylic acid, methacrylic acid and 4-vinylbenzoic acid are preferred.

[0082] The free radical polymerizable compound having a carboxyl group accounts for 1-50 weight percent of component (a), preferably 5-45 weight percent, and more preferably 10-40 weight percent.

[0083] By changing the proportion of A, the alkali solubility of the alkali-soluble resin (a) can be controlled. When the A content in the resin (a) is too low, the alkali-soluble resin (a) cannot be dissolved in the alkaline developer; therefore, the film will not show a pattern after development, and the unexposed area will still remain and cannot be patterned. When the A content is too high, the alkali-soluble resin (a) dissolves quickly in the alkaline developer, and the exposed area will be continuously attacked by the alkaline developer, causing the pattern to fall off or shrink in size, affecting the resolution and subsequent performance.

[0084] B. Free radical polymerizable compounds having a benzene ring structure; such as styrene, α-methylstyrene, isopropylstyrene, 2-phenoxyethyl acrylate, 3-acetoxystyrene, 4-acetoxystyrene, phenyl methacrylate, 2-tert-butylstyrene, 4-tert-butylstyrene, 2-naphthyl methacrylate, hydroquinone monomethacrylate, 4-tert-butoxycarbonylstyrene, 4-vinylbenzoic acid ethyl ester, cinnamyl methacrylate and the like.

[0085] Among these compounds, styrene, α-methylstyrene, 2-phenoxyethyl acrylate and 4-acetoxystyrene are preferred.

[0086] The free radical polymerizable compound having a benzene ring accounts for 1-40 weight percent of component (a), preferably 5-35 weight percent, and more preferably 10-30 weight percent.

[0087] Changing the proportion of B has a significant effect on the resolution of the negative photosensitive resin composition. When the proportion of B is too low, the resolution of the negative photosensitive resin composition is low, the tiny graphics cannot be displayed, and the pattern morphology is poorly steep; when the proportion of B is too high, due to its high polymerization reactivity, the structure of the polymer is deviated, the polymerization conversion rate is reduced, and the resolution of the negative photosensitive resin composition is reduced.

[0088] C. Free radical polymerizable compounds having an ester structure; such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2-cyclohexyl acrylate, tert-butyl (meth)acrylate, acrylic acid, isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, lauryl (meth)acrylate, 2-methoxyethyl 2-acrylate, glycidyl (meth)acrylate, 4-hydroxybutyl acrylate, 2-hydroxypropyl 2-acrylate and the like.

[0089] Among these compounds, isobornyl (meth)acrylate, adamantyl 1-acrylate, 2-methoxyethyl 2-acrylate, and glycidyl (meth)acrylate are preferred.

[0090] The free radical polymerizable compound having an ester structure accounts for 1-70 weight percent of component (a), preferably 10-60 weight percent, and more preferably 30-50 weight percent.

[0091] Changing the proportion of C has a significant effect on the mechanical properties of the negative photosensitive resin composition. When the proportion of C is too low, the pattern morphology formed by the negative photosensitive resin composition is poor, the size of the pattern after development is small, the bonding force with the bottom substrate is poor, and the pattern is easy to fall off; when the proportion of C is too high, the size of the pattern after development is large, which affects the opening, the resolution is reduced, the bonding force with the bottom substrate is too good, and it is difficult to remove the pattern after electroplating.

[0092] D. Free radical polymerizable compounds having two unsaturated double bonds; such as 1,3-butadiene, 1,2-butadiene, 1,2-pentadiene, 1,3-pentadiene, 1,7-octadiene, propadiene, isoprene, isoprene, allyl ether and the like.

[0093] Among these compounds, 1,3-butadiene, 1,2-pentadiene and isoprene are preferred.

[0094] The free radical polymerizable compound having two unsaturated double bonds accounts for 1-30 weight percent of component (a), preferably 5-25 weight percent, and more preferably 10-20 weight percent.

[0095] Changing the proportion of D has a significant effect on the electroplating resistance of the negative photosensitive resin composition. When the proportion of D is too low, the distance between the free radical polymerizable compounds of the copolymer is small, the toughness is insufficient, the negative photosensitive resin composition is hard after film formation, and the electroplating resistance is poor; when the proportion of D is too high, the copolymer has sufficient toughness, but insufficient rigidity, and the resolution of the negative photosensitive resin composition is poor.

[0096] The photo-induced free radical polymerization initiator of component (b) mainly includes:

[0097] Benzoin ether photoinitiators: benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, hydroxymethyl benzoin methyl ether, etc.

[0098] Benzophenone photoinitiators: benzophenone (BP), 4-chlorobenzophenone (CBP), 4-phenylbenzophenone (PBZ), 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), 2,4,6-trimethylbenzoylphosphonic acid ethyl ester (TPO-L) and polymerizable benzophenone derivatives;

[0099] Thioxanthone photoinitiators: 2-hydroxythioxanthone (TX1), 2-hydroxy-3-(2-thioxanthoneoxy)propyltrimethylammonium chloride (TX2), Irageure184D, etc.

[0100] Acylphosphine oxide photoinitiators: photoinitiator 819, photoinitiator 1800, photoinitiator 1700, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), 4-diethylaminobenzoyldiphenylphosphine oxide (DEAPO), (2,4,6-trimethyl-3-benzoyl)benzoyldiphenylphosphine oxide (BzTPO), bis(2,4,6-trimethylbenzoyl)diphenylphosphine oxide, etc.

[0101] α-Dialkylaminoketone photoinitiators: 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenylketone, 2-dimethylamino-2-benzyl-1-[4-(4-morpholinyl)phenyl]-1-butanone, α-aminoalkylphenone, etc.

[0102] Carbazole-based photoinitiators: carbazole-based oxime esters (OXEs), 3,6-bis[2-(4-pyridyl)vinyl]-9-phenylcarbazole, 3,6-bis[2-(2-pyridyl)vinyl]-9-phenylcarbazole, carbazole-based α-diketone, etc.

[0103] Among these photoinitiators, 2-hydroxy-2-methyl-1-phenylpropanone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (TPO), and ethyl 2,4,6-trimethylbenzoylphosphonate (TPO-L) are preferred.

[0104] These photoinduced free radical polymerization initiators can be used alone or in combination of two or more. Based on 100 parts by weight of the alkali-soluble resin polymer (a), the amount of the initiator used is preferably 5-20 parts by weight.

[0105] The compound containing one or more polymerizable functional groups as component (c) mainly includes:

[0106] Monofunctional compounds: methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, tert-octyl (meth)acrylamide, dimethylaminoethyl (meth)acrylate, diacetone (meth)acrylamide, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, glycerol (meth)acrylate, acrylamide, methacrylamide, (meth)acrylonitrile, ( Methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate and 2-ethylhexyl (meth)acrylate, diethylaminoethyl (meth)acrylate, 7-amino-3,7-dimethyloctyl (meth)acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, dodecyl (meth)acrylate, lauryl (meth)acrylate, octadecyl (meth)acrylate, stearyl (meth)acrylate, tetrahydrofuran (meth)acrylate, butoxyethyl (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (meth)acrylate 2-Hydroxypropyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, isobutoxymethyl (meth)acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, N,N-dimethyl (meth)acrylamide, 2-hydroxybutyl (meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, phenoxypolypropylene glycol (meth)acrylate, ethoxyethyl (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, dicyclopentadienyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, tricyclodecyl (meth)acrylate, isobornyl (meth)acrylate, and bornyl (meth)acrylate.trimethylolpropane di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, 1,4-butanediol di(meth)acrylate, butanediol di(meth)acrylate, propylene glycol di(meth)acrylate, bisphenol A-di(meth)acryloyloxyethyl ether, bisphenol A-di(meth)acryloyloxyethoxyethyl ether, bisphenol A-di(meth)acryloyloxymethylethyl ether, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, ethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, tetramethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0107] Multifunctional compounds:

[0108] These compounds containing one or more polymerizable functional groups can be used alone or in combination of two or more. The amount of the multifunctional compound is preferably 30-60 parts by weight based on 100 parts by weight of the alkali-soluble resin polymer (a).

[0109] The negative photosensitive resin composition of the present invention contains not only (a) an alkali-soluble resin polymer, (b) a photo-induced free radical polymerization initiator, and (c) a compound containing one or more polymerizable functional groups, but also other organic solvents and various auxiliary agents.

[0110] Organic solvents such as propylene glycol methyl ether acetate, diethylene glycol dimethyl ether, methyl 3-methoxypropionate, methanol, ethanol, diethylene glycol, propylene glycol, isopropanol, ethyl acetate, acetone, diethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, ethyl lactate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ethyl ether, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, 1-methoxy-2-propanol, 1-methoxy-2-acetoxypropane, propylene glycol 1-monomethyl ether 2-acetate and other solvents. The organic solvent may be added alone or in combination of two or more. The selected solvent can uniformly dissolve (a) alkali-soluble resin polymers; (b) photo-induced free radical polymerization initiators; (c) compounds containing one or more polymerizable functional groups and other components, and will not react with them.

[0111] Various additives such as:

[0112] Antioxidants, which delay the aging of the composition, such as: N-phenyl-α-naphthylamine, N-phenyl-β-naphthylamine, octylated diphenylamine, 4,4′-bis(α,α-dimethylbenzyl) diphenylamine, N-cyclohexyl-N-phenyl-p-phenylenediamine, 2,2′-methylenebis(4-methyl-6-tert-butylphenol), 2,6-di-tert-butyl-p-cresol, N-phenyl-α-aniline, antioxidant BHA, antioxidant 2246, antioxidant 264, 2-mercaptobenzimidazole (MBI, MB), 2-mercaptomethylbenzimidazole (MMBI, MMB), 2-mercaptomethylbenzimidazole zinc salt (ZMBI, MBZ), 2-mercaptomethylbenzimidazole zinc salt (ZMMBI, ZMTI, MMBZ), etc. The amount of the antioxidant added is preferably 0.1-1 part by weight relative to 100 parts by weight of component (a).

[0113] Inhibitors, which prevent the thermal reaction of double bonds, such as hydroquinone (HQ), p-benzoquinone (PBQ), methyl hydroquinone (THQ), tetrachlorobenzoquinone, anthraquinone, 1,4-naphthoquinone, p-hydroxyanisole (HQMME), 2-tert-butylhydroquinone (MTBHQ), 2,5-di-tert-butylhydroquinone (2,5-DTBHQ), and p-tert-butylcatechol. The amount of the inhibitor added is preferably 0.1-5 parts by weight relative to 100 parts by weight of component (a).

[0114] Surfactants improve the fluidity and smoothness of the coating, such as polydimethylsiloxane, organic modified polydimethylsiloxane, polyether polyester modified organic siloxane, alkyl modified organic siloxane, MONENG-1073, MONENG-1153, FCF-203 polyacrylic acid fluorinated ester leveling agent, etc. The amount of the polymerization inhibitor added is preferably 0.1-5 parts by weight relative to 100 parts by weight of component (a).

[0115] The preparation method of the negative photosensitive resin composition is as follows: at room temperature, components (a), (b), (c) and other solvents and additives are fully mixed and stirred.

[0116] Use a coating machine to coat, bake and then expose the pattern. After exposure, place it in a developer to develop it, and then observe the resolution and line retention. The developed substrate is then electroplated, and the film is removed after electroplating to observe the metal pattern.

[0117] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

[0118] Preparation Example of Alkali-Soluble Resin of Component (a)

[0119] Example 1

[0120] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 5 g of acrylic acid (monomer A), 5 g of methacrylic acid (monomer A), 10 g of styrene (monomer B), 10 g of 4-acetoxystyrene (monomer B), 25 g of hydroxyethyl methacrylate (monomer C), 25 g of isobornyl acrylate (monomer C), 20 g of isoprene (monomer D), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0121] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0122] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0123] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0124] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0125] Example 2

[0126] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 5 g of acrylic acid (monomer A), 5 g of methacrylic acid (monomer A), 10 g of styrene (monomer B), 20 g of 4-acetoxystyrene (monomer B), 25 g of hydroxyethyl methacrylate (monomer C), 25 g of isobornyl acrylate (monomer C), 10 g of isoprene (monomer D), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0127] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0128] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0129] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0130] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0131] Example 3

[0132] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 5 g of acrylic acid (monomer A), 5 g of methacrylic acid (monomer A), 10 g of styrene (monomer B), 10 g of 4-acetoxystyrene (monomer B), 20 g of hydroxyethyl methacrylate (monomer C), 20 g of isobornyl acrylate (monomer C), 20 g of isoprene (monomer D), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0133] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0134] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0135] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0136] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0137] Example 4

[0138] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 10 g of acrylic acid (monomer A), 10 g of methacrylic acid (monomer A), 10 g of styrene (monomer B), 10 g of 4-acetoxystyrene (monomer B), 25 g of hydroxyethyl methacrylate (monomer C), 25 g of isobornyl acrylate (monomer C), 10 g of isoprene (monomer D), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0139] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0140] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0141] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0142] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0143] Example 5

[0144] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 10 g of acrylic acid (monomer A), 10 g of methacrylic acid (monomer A), 10 g of styrene (monomer B), 10 g of 4-acetoxystyrene (monomer B), 20 g of hydroxyethyl methacrylate (monomer C), 20 g of isobornyl acrylate (monomer C), 20 g of isoprene (monomer D), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0145] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0146] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0147] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0148] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0149] Example 6

[0150] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 10 g of acrylic acid (monomer A), 20 g of methacrylic acid (monomer A), 5 g of styrene (monomer B), 5 g of 4-acetoxystyrene (monomer B), 20 g of hydroxyethyl methacrylate (monomer C), 20 g of isobornyl acrylate (monomer C), 20 g of isoprene (monomer D), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0151] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0152] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0153] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0154] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0155] Example 7

[0156] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 10 g of acrylic acid (monomer A), 20 g of methacrylic acid (monomer A), 10 g of styrene (monomer B), 10 g of 4-acetoxystyrene (monomer B), 10 g of hydroxyethyl methacrylate (monomer C), 20 g of isobornyl acrylate (monomer C), 20 g of isoprene (monomer D), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0157] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0158] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0159] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0160] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0161] Example 8

[0162] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 20 g of acrylic acid (monomer A), 20 g of methacrylic acid (monomer A), 5 g of styrene (monomer B), 5 g of 4-acetoxystyrene (monomer B), 20 g of hydroxyethyl methacrylate (monomer C), 20 g of isobornyl acrylate (monomer C), 10 g of isoprene (monomer D), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0163] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0164] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0165] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0166] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0167] Example 9

[0168] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 20 g of acrylic acid (monomer A), 20 g of methacrylic acid (monomer A), 10 g of styrene (monomer B), 10 g of 4-acetoxystyrene (monomer B), 15 g of hydroxyethyl methacrylate (monomer C), 15 g of isobornyl acrylate (monomer C), 10 g of isoprene (monomer D), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0169] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0170] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0171] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0172] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0173] Example 10

[0174] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 20 g of acrylic acid (monomer A), 20 g of methacrylic acid (monomer A), 10 g of styrene (monomer B), 10 g of 4-acetoxystyrene (monomer B), 15 g of hydroxyethyl methacrylate (monomer C), 10 g of isobornyl acrylate (monomer C), 10 g of isoprene (monomer D), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0175] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0176] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0177] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0178] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0179] Comparative Example 1

[0180] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 10 g of acrylic acid (monomer A), 10 g of methacrylic acid (monomer A), 15 g of styrene (monomer B), 15 g of 4-acetoxystyrene (monomer B), 25 g of hydroxyethyl methacrylate (monomer C), 25 g of isobornyl acrylate (monomer C), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0181] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0182] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0183] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0184] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0185] That is, the monomers of the first component of this comparative example only contain the acrylic acid ester monomer A, and do not contain the acrylic acid ester monomer B and the monomer C.

[0186] Comparative Example 2

[0187] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 10 g of acrylic acid (monomer A), 10 g of methacrylic acid (monomer A), 20 g of styrene (monomer B), 20 g of 4-acetoxystyrene (monomer B), 20 g of hydroxyethyl methacrylate (monomer C), 20 g of isobornyl acrylate (monomer C), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0188] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0189] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0190] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0191] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0192] That is, the monomers of the first component of this comparative example only contain the acrylic acid ester monomer B, and do not contain the acrylic acid ester monomer A and the monomer C.

[0193] Comparative Example 3

[0194] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 5 g of acrylic acid (monomer A), 5 g of methacrylic acid (monomer A), 20 g of styrene (monomer B), 20 g of 4-acetoxystyrene (monomer B), 25 g of hydroxyethyl methacrylate (monomer C), 25 g of isobornyl acrylate (monomer C), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0195] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0196] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0197] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0198] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0199] That is, the monomers of the first component of this comparative example only contain the monomer C, and do not contain the acrylic acid ester monomer A and the acrylic acid ester monomer B.

[0200] Comparative Example 4

[0201] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 10 g of acrylic acid (monomer A), 10 g of methacrylic acid (monomer A), 10 g of styrene (monomer B), 25 g of 4-acetoxystyrene (monomer B), 20 g of hydroxyethyl methacrylate (monomer C), 25 g of isobornyl acrylate (monomer C), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0202] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0203] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0204] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0205] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0206] That is, the monomers of the first component of this comparative example only contain the acrylic ester monomer B and the monomer C, but do not contain the acrylic ester monomer A.

[0207] Comparative Example 5

[0208] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 15 g of acrylic acid (monomer A), 15 g of methacrylic acid (monomer A), 15 g of styrene (monomer B), 15 g of 4-acetoxystyrene (monomer B), 20 g of hydroxyethyl methacrylate (monomer C), 20 g of isobornyl acrylate (monomer C), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0209] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0210] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0211] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0212] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0213] That is, the monomers of the first component of this comparative example only contain the acrylic acid ester monomer A and the monomer C, but do not contain the acrylic acid ester monomer B.

[0214] Comparative Example 6

[0215] (1) Into a four-necked flask equipped with a condenser, a thermometer and a stirrer, a mixture of 5 g of acrylic acid (monomer A), 5 g of methacrylic acid (monomer A), 10 g of styrene (monomer B), 10 g of 4-acetoxystyrene (monomer B), 30 g of hydroxyethyl methacrylate (monomer C), 4 g of isobornyl acrylate (monomer C), 0.2 g of n-dodecyl mercaptan, 4 g of azobisisobutyronitrile and 150 g of methanol was added.

[0216] (2) Heat the mixed solution in a constant temperature oil bath at 80°C until the internal temperature reaches boiling point.

[0217] (3) Heat the reaction for 4 h, add a solution consisting of 1 g of azobisisobutyronitrile and 35 g of methanol to the reaction solution, and continue heating the reaction for 8 h.

[0218] (4) Terminate the reaction and start to cool down to ≤40°C before discharging the material.

[0219] (5) The resin was dissolved in tetrahydrofuran, and then added dropwise into pure water and stirred thoroughly to disperse. After standing for stratification, the upper clear liquid was removed. This process was repeated three times, and then the mixture was dried in a vacuum drying oven at 45°C for 48 hours to obtain a white powdery polymer. The molecular weight of the polymer was measured.

[0220] The polymerizable monomers of the alkali-soluble resin component (a) of the above comparative example only contain monomer A, monomer B and monomer C, and do not contain monomer D.

[0221] The copolymer resins synthesized above are listed in Table 1. The weight average molecular weight (Mw) of the alkali-soluble resin (a) obtained by each polymerization reaction is also listed in Table 1.

[0222] Table 1

[0223]

[0224] (II) Composition Examples

[0225] Part (1)

[0226] 100 parts of the alkali-soluble resin (a) prepared above were mixed with 100 parts of propylene glycol methyl ether acetate solvent to obtain a mixed solution (the amount of other components used subsequently was based on 100 parts by weight of the alkali-soluble resin (a)), and the following components were added to the mixed solution: 10 parts of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide and 10 parts of methyl benzoylformate as a photoinducible free radical polymerization initiator (b); 20 parts of pentaerythritol tetraacrylate and 20 parts of diethylene glycol dimethacrylate as components (c); 0.25 parts of 2,2-methylenebis(4-methyl-6-tert-butylphenol) as an antioxidant; 0.25 parts of p-hydroxyanisole as an inhibitor, and these components were fully stirred until they were completely dissolved and mixed to obtain the desired negative photosensitive resin composition, and their properties were measured. The results are shown in Table 2.

[0227] Table 2

[0228] Film thickness μm <![CDATA[Exposure energy mj / cm 2 > Development time Resolution μm plating Embodiment b1 21 300-500 50 6 No abnormality Embodiment b2 20 300-500 50 6 No abnormality Embodiment b3 22 300-500 50 6 No abnormality Embodiment b4 23 300-500 45 6 No abnormality Embodiment b5 21 300-500 50 6 No abnormality Embodiment b6 22 300-500 45 6 No abnormality Embodiment b7 24 300-500 50 6 No abnormality Embodiment b8 22 300-500 40 6 No abnormality Embodiment b9 22 300-500 40 6 No abnormality Embodiment b10 23 300-500 40 6 No abnormality Comparative Example b1 21 300-500 45 8 Plating Comparative Example b2 22 300-500 45 8 Plating Comparative Example b3 22 300-500 80 8 Plating Comparative Example b4 23 300-500 60 6 Cracking Comparative Example b5 21 300-500 30 6 Plating Comparative Example b6 20 300-500 90 6 Cracking

[0229] It can be seen from Table 2 that the photosensitive resin compositions provided in Examples b1-b10 all have relatively excellent development windows, indicating that the alkali solubility difference contrast between the unexposed area and the exposed area is relatively excellent.

[0230] Compared with the embodiments, comparative examples b1 and b2 exhibit relatively excellent alkali solubility, but perform poorly in terms of adhesion to the substrate and resolution. In comparative examples b1 and b5, the 6μm lines cannot be retained, and seepage occurs during electroplating; comparative examples b2, b4 and b6 have very poor alkali solubility, and cracking and seepage occur during electroplating; comparative example b3 exhibits faster alkali solubility and sufficient resolution, but seepage still occurs during electroplating, indicating that the electroplating resistance is insufficient.

[0231] Part (2)

[0232] 100 parts of the alkali-soluble resin (a) prepared above were mixed with 80 parts of propylene glycol methyl ether acetate solvent to obtain a mixed solution (the amount of other components used subsequently was based on 100 parts by weight of the alkali-soluble resin (a)), and the following components were added to the mixed solution: 1 part of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide and 10 parts of methyl benzoylformate as a photoinducible free radical polymerization initiator (b); 1 part of pentaerythritol tetraacrylate as component (c); 0.1 part of 2,2-methylenebis(4-methyl-6-tert-butylphenol) as an antioxidant; 0.1 part of p-hydroxyanisole as an inhibitor, and these components were fully stirred until they were completely dissolved and mixed to obtain the desired negative photosensitive resin composition, and their properties were measured. The results are shown in Table 3.

[0233] Table 3

[0234] Film thickness μm <![CDATA[Exposure energy mj / cm 2 > Development time Resolution μm plating Example c1 30 300-500 90 4 No abnormality Example c2 31 300-500 90 4 No abnormality Example c3 32 300-500 90 4 No abnormality Example c4 33 300-500 85 4 No abnormality Example c5 31 300-500 90 4 No abnormality Example c6 32 300-500 85 4 No abnormality Example c7 34 300-500 90 4 No abnormality Example c8 32 300-500 80 4 No abnormality Example c9 32 300-500 80 4 No abnormality Example c10 33 300-500 80 4 No abnormality Comparative Example c1 31 300-500 85 4 Plating Comparative Example c2 32 300-500 85 4 Plating Comparative Example c3 32 300-500 120 4 Plating Comparative Example c4 33 300-500 100 4 Cracking Comparative Example c5 31 300-500 70 4 Plating Comparative Example c6 30 300-500 130 4 Cracking

[0235] Part (3)

[0236] 100 parts of the alkali-soluble resin (a) prepared above were mixed with 120 parts of propylene glycol methyl ether acetate solvent to obtain a mixed solution (the amount of other components used subsequently was based on 100 parts by weight of the alkali-soluble resin (a)), and the following components were added to the mixed solution: 20 parts of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide and 10 parts of methyl benzoylformate as a photoinducible free radical polymerization initiator (b); 20 parts of pentaerythritol tetraacrylate and 40 parts of diethylene glycol dimethacrylate as components (c); 1 part of 2,2-methylenebis(4-methyl-6-tert-butylphenol) as an antioxidant; 5 parts of p-hydroxyanisole as an inhibitor, and these components were fully stirred until they were completely dissolved and mixed to obtain the desired negative photosensitive resin composition, and their properties were measured. The results are shown in Table 4.

[0237] Table 4

[0238]

[0239]

[0240] Part (4)

[0241] 100 parts of the alkali-soluble resin (a) prepared above were mixed with 100 parts of propylene glycol methyl ether acetate solvent to obtain a mixed solution (the amount of other components used subsequently was based on 100 parts by weight of the alkali-soluble resin (a)), and the following components were added to the mixed solution: 10 parts of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide and 10 parts of methyl benzoylformate as photoinducible free radical polymerization initiator (b); 20 parts of pentaerythritol tetraacrylate and 20 parts of diethylene glycol dimethacrylate as component (c); 0.25 parts of 2,2-methylenebis(4-methyl-6-tert-butylphenol) as an antioxidant; 0.25 parts of p-hydroxyanisole as an inhibitor; 1 part of polydimethylsiloxane as a surfactant. These components were fully stirred until they were completely dissolved and mixed to obtain the desired negative photosensitive resin composition, and their properties were measured. The results are shown in Table 5.

[0242] Table 5

[0243] Film thickness μm <![CDATA[Exposure energy mj / cm 2 > Development time Resolution μm plating Embodiment e1 20 300-500 50 5 No abnormality Embodiment e2 19 300-500 50 5 No abnormality Embodiment e3 21 300-500 50 5 No abnormality Embodiment e4 22 300-500 45 5 No abnormality Embodiment e5 20 300-500 50 5 No abnormality Embodiment e6 21 300-500 45 5 No abnormality Embodiment e7 23 300-500 50 5 No abnormality Embodiment e8 21 300-500 40 5 No abnormality Embodiment e9 21 300-500 40 5 No abnormality Embodiment e10 22 300-500 40 5 No abnormality Comparative Example e1 20 300-500 45 7 Plating Comparative Example e2 21 300-500 45 7 Plating Comparative Example e3 21 300-500 80 7 Plating Comparative Example e4 22 300-500 60 5 Cracking Comparative Example e5 20 300-500 30 5 Plating Comparative Example e6 19 300-500 90 5 Cracking

[0244] Part (5)

[0245] 100 parts of the alkali-soluble resin (a) prepared above were mixed with 100 parts of propylene glycol methyl ether acetate solvent to obtain a mixed solution (the amount of other components used subsequently was based on 100 parts by weight of the alkali-soluble resin (a)), and the following components were added to the mixed solution: 10 parts of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide and 10 parts of methyl benzoylformate as photoinducible free radical polymerization initiator (b); 20 parts of pentaerythritol tetraacrylate and 20 parts of diethylene glycol dimethacrylate as component (c); 0.25 parts of 2,2-methylenebis(4-methyl-6-tert-butylphenol) as an antioxidant; 0.25 parts of p-hydroxyanisole as an inhibitor; 0.1 parts of polydimethylsiloxane as a surfactant. These components were fully stirred until they were completely dissolved and mixed to obtain the desired negative photosensitive resin composition, and their properties were measured. The results are shown in Table 6.

[0246] Table 6

[0247] Film thickness μm <![CDATA[Exposure energy mj / cm 2 > Development time Resolution μm plating Embodiment f1 21 300-500 50 6 No abnormality Embodiment f2 20 300-500 50 6 No abnormality Embodiment f3 22 300-500 50 6 No abnormality Embodiment f4 23 300-500 45 6 No abnormality Embodiment f5 21 300-500 50 6 No abnormality Embodiment f6 22 300-500 45 6 No abnormality Embodiment f7 24 300-500 50 6 No abnormality Embodiment f8 22 300-500 40 6 No abnormality Embodiment f9 22 300-500 40 6 No abnormality Embodiment f10 23 300-500 40 6 No abnormality Comparative Example f1 21 300-500 45 8 Plating Comparative Example f2 22 300-500 45 8 Plating Comparative Example f3 22 300-500 80 8 Plating Comparative Example f4 23 300-500 60 6 Cracking Comparative Example f5 21 300-500 30 6 Plating Comparative Example f6 20 300-500 90 6 Cracking

[0248] Part (6)

[0249] 100 parts of the alkali-soluble resin (a) prepared above were mixed with 100 parts of propylene glycol methyl ether acetate solvent to obtain a mixed solution (the amount of other components used subsequently was based on 100 parts by weight of the alkali-soluble resin (a)), and the following components were added to the mixed solution: 10 parts of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide and 10 parts of methyl benzoylformate as photoinducible free radical polymerization initiator (b); 20 parts of pentaerythritol tetraacrylate and 20 parts of diethylene glycol dimethacrylate as component (c); 0.25 parts of 2,2-methylenebis(4-methyl-6-tert-butylphenol) as an antioxidant; 0.25 parts of p-hydroxyanisole as an inhibitor; 5 parts of polydimethylsiloxane as a surfactant. These components were fully stirred until they were completely dissolved and mixed to obtain the desired negative photosensitive resin composition, and their properties were measured. The results are shown in Table 7.

[0250] Table 7

[0251]

[0252]

[0253] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0254] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A negative photosensitive resin composition comprising at least the following components (a), (b) and (c): Component (a) is: an alkali-soluble resin polymer; Component (b) is: a photo-inducible free radical polymerization initiator; Component (c) is: a compound containing one or more polymerizable functional groups; Wherein, based on 100 parts by weight of component (a), 1-20 parts by weight of component (b) and 1-60 parts by weight of component (c) are used.

2. The negative photosensitive resin composition according to claim 1, characterized in that: The component (a) is selected from: A free radical polymerizable compound having a carboxyl structure; A free radical polymerizable compound having a benzene ring structure; Free radical polymerizable compounds having an ester structure; A free radical polymerizable compound having two or more unsaturated double bonds.

3. The negative photosensitive resin composition according to claim 1, characterized in that: The component (b) is selected from: benzoin ether photoinitiators, benzophenone photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators, α-dialkylaminoketone photoinitiators, and carbazole photoinitiators.

4. The negative photosensitive resin composition according to claim 1, characterized in that: The component (c) is selected from: monofunctional compounds and multifunctional compounds.

5. The negative photosensitive resin composition according to claim 1, characterized in that: The composition further comprises (d) a solvent. Based on 100 parts by weight of component (a), the amount of component (d) is 80-120 parts by weight.

6. The negative photosensitive resin composition according to claim 5, characterized in that: The composition further comprises (e) an antioxidant, wherein the amount of the component (e) is 0.1-1 part by weight based on 100 parts by weight of the component (a).

7. The negative photosensitive resin composition according to claim 6, characterized in that: It also includes (f) [3IN negative photosensitive resin composition negative photosensitive resin composition DD1F] inhibitor, based on 100 parts by weight of component (a), the amount of component (f) is 0.1-5 parts by weight.

8. The negative photosensitive resin composition according to claim 7, characterized in that: The composition further comprises (g) a surfactant. Based on 100 parts by weight of component (a), the amount of component (g) is 0.1-5 parts by weight.

9. The method for preparing the negative photosensitive resin composition according to any one of claims 1 to 8, comprising: At least the raw materials including components (a), (b) and (c) are thoroughly mixed and stirred at room temperature.

10. A photolithography product, comprising at least a structure obtained by using the negative photosensitive resin composition according to any one of claims 1 to 8 as a raw material.

Images