Dry film resist, photosensitive dry film, and copper-clad laminate

Abstract

A dry film resist, a photosensitive dry film and a copper-clad laminate, the dry film resist comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator and (D) a sensitizer, the sensitizer comprising a compound containing a pyrazoline structure. The dry film resist has good overall performance due to the use of a specific type of sensitizer, and is particularly outstanding in photosensitivity, resolution, alignment recognition adaptability and electroplating resistance.

Description

[Technical Field]

[0001] This invention relates to the field of optoelectronic materials, and more specifically to dry film resists, photosensitive dry films, and copper-clad laminates. [Background technology]

[0002] Since their introduction, photosensitive resin compositions have become important materials in the field of modern electronics, particularly in the field of printed circuit boards (PCBs).

[0003] As electronic devices become smaller, lighter, and more compact, there is a corresponding demand for higher resolution, higher density, and multilayering of PCBs. Conventional photomask exposure methods consume a large amount of film, have high manufacturing costs, and have limitations in the precision of circuit patterns obtained through exposure using this method. Therefore, they are being replaced by laser direct imaging (LDI), which does not require film and uses digital data to directly irradiate active light images. This direct lithography exposure method allows for the formation of resist patterns with high productivity and high resolution. i-line (355 nm) or h-line (405 nm) light sources are used. Generally, a 405 nm laser is used, which offers superior exposure accuracy and can form high-density photosensitive resist patterns that are difficult to produce with conventional techniques.

[0004] Integrated circuits (ICs) are the core of electronic devices. IC package substrates, also known as IC carrier boards, are high-end PCBs with higher wiring density and are used directly to mount chips, providing electrical connections between the chips and the PCB motherboard.

[0005] Over the past decade, the annual production volume of smartphones has continued to increase, and constant iterative updates are necessary. Meanwhile, as high-precision PCB manufacturing processes such as SAP (semi-additive process), mSAP (modified semi-additive process), and SLP (substance-like PCB) become increasingly mature, the global market size for high-end PCBs such as carrier boards and substrate-like PCBs is experiencing rapid growth. In recent years, the development and production of high-end PCBs such as carrier boards and substrate-like PCBs have been mainly centered on Japanese and Korean companies, but in recent years, some domestic companies have also grasped IC carrier board production technology and are experiencing very rapid development.

[0006] IC carrier boards are an evolution of HDI boards, but because the package substrate size is smaller and the electrical structure is more complex, the difficulty of manufacturing technology exceeds that of HDI and regular PCBs. Similar to the PCB manufacturing process, the package substrate manufacturing process is broadly divided into three different manufacturing processes: subtractive, additive, and semi-additive. Currently, the semi-additive method (mSAP) is the mainstream manufacturing process. The manufacturing process includes multiple steps such as drilling, through-hole plating, electroplating, pattern transfer, etching, solder mask application, and coating. Using the mSAP method, it is possible to produce fine circuits with line widths and line pitches of less than 25 μm, effectively overcoming the side etching problem of circuit fabrication using the subtractive method. The mSAP method mainly utilizes electroplating and flash etching. First, chemical copper is applied to a thin copper substrate and a resist pattern is formed on it. The pattern on the substrate is thickened by the electroplating process and the resist pattern is removed. Next, the excess chemical copper layer is removed by flash etching, and the remaining part forms the circuit. Compared to the subtractive method, the circuit width is not affected by the thickness of the electroplated copper, it has a higher resolution, and the line width and line pitch of the fabricated fine circuits are nearly identical.

[0007] As the integration density of chips increases, the fineness and integration density of carrier boards also increase accordingly. Therefore, higher requirements are also being placed on the performance of the dry film photoresist used in carrier boards. For dry film resist for manufacturing package substrates, the requirements regarding analysis precision, resist shape, etc. are extremely high, and it is required that a resist pattern with a line width / line pitch (L / S) of 10 / 10 μm or less can be formed.

[0008] In order to form a resist pattern with high precision, it is generally necessary to add a photosensitizer to the photosensitive resin composition. For dry film resist used in the production of IC carrier boards, substrates like PCBs, generally, for example, 9,10-dibutoxyanthracene (DBA) is added as a photosensitizer.

[0009] As described in the patent application with publication number CN102272676A submitted by Hitachi Chemical Co., Ltd., for dry film resist for manufacturing package substrates, the requirements regarding analysis precision, resist shape, etc. are extremely high, and it is required that a resist pattern with a line width / line pitch (L / S) of 10 / 10 μm or less can be formed. For such high-end dry film resist, in the initiator system, generally a combination of a hexaaryl bisimidazole derivative and pyrazoline, anthracene-based, or triarylamine, etc. is used as a sensitizer. As shown by the results of the examples of this patent, when such a dry film resist combines an appropriate alkali-soluble resin and a photopolymerizable monomer, excellent performance can be obtained in terms of resolution, adhesion, and resist shape, etc., but its sensitivity is extremely low. Even when the exposure energy reaches 70 mJ / cm 2 , the sensitivity of the dry film resist is only 11 grades. Using a dry film resist with such low sensitivity will have a great impact on the production efficiency of PCB production clients.

[0010] In addition, the dry film resist is generally coated on the surface of a PET support film, dried in an oven, and then, for example, a single-layer polyethylene thin film protective layer is adhered to its surface. For example, as described in the patent application with the publication number CN113557474A, when the dry film resist contains 9,10-dibutoxyanthracene (DBA), the phenomenon of DBA penetrating into the polyethylene thin film cannot be avoided, and problems such as the sensitivity of the dry film resist continuing to decline and the inability to form a desired pattern shape may occur. Such penetration problems are particularly prominent when the protective layer is a polyethylene film.

[0011] Due to the negative impact of light scattering on the analysis performance of the dry film resist, the analysis ability of the dry film resist clearly decreases with the increase in thickness. The analysis ability of conventional dry film resists is generally 0.8 to 1.0 times the thickness of the dry film resist. For carrier boards and substrates like PCBs, due to the requirements of the process and accuracy, the analysis ability of the dry film resist used is required to be less than 0.5 times the film thickness. Since the film thickness of the dry film resist used in the production of conventional carrier boards and substrates like PCBs is generally 20 to 29 μm, the analysis ability is required to be 15 μm or less. Moreover, the 10 μm / 10 μm circuit process is already on the schedule, and in the near future, the circuit accuracy of IC carrier boards will reach 5 μm / 5 μm.

[0012] While several types of initiator systems for dry film resists for PCB pattern transfer suitable for LDI 405nm exposure light sources, as reported in the prior art, all have clear advantages, they also have clear disadvantages. Currently, acridine and its derivatives are generally used as initiator systems for highly analytical and highly sensitive dry film resists for fabricating high-precision HDI inner layer plates. Acridine-based initiators are highly photosensitive under 405nm wavelength exposure light sources, but they cannot promote the oxidative development of leuco-developers after exposure, resulting in poor pattern contrast before and after exposure. Furthermore, alignment recognition is not possible with domestically produced LDI exposure machines. Therefore, they cannot meet the usage needs of PCB clients, such as high photosensitivity, high precision, and high adaptability to alignment recognition on different types of LDI exposure machines.

[0013] Furthermore, as electronic devices become smaller, lighter, and more compact, there is a corresponding demand for higher resolution, higher density, and multilayering of PCBs. Conventional photomask exposure methods consume a large amount of film, have high manufacturing costs, and have limitations in the precision of circuit patterns obtained through exposure using this method. Therefore, they are being replaced by laser direct imaging (LDI), which does not require film and uses digital data to directly irradiate active light images. This direct lithography exposure method allows for the formation of resist patterns with high productivity and high resolution. A laser with a wavelength of 405 nm is generally used as the exposure light source, resulting in superior exposure accuracy and the formation of high-density photosensitive resist patterns that are difficult to produce with conventional techniques.

[0014] Automotive PCB panels account for a very large portion of the total PCB demand, and the volume continues to increase. In the manufacturing of PCB panels that require thick copper plates, such as automotive PCB panels and industrial control boards, plating processes are generally used. Until now, the exposure method for such PCB panel manufacturing processes has been the conventional photomask exposure method, with UV mercury lamp irradiation or LED light sources. However, in recent years, laser direct imaging (LDI) has been replacing the conventional photomask exposure method in order to improve the level of automation in production by PCB manufacturing clients and to increase efficiency and accuracy.

[0015] To meet the process optimization requirements of PCB manufacturing clients as described above, the dry film resist needs to simultaneously possess high photosensitivity to a laser light source of laser direct imaging (LDI) with a wavelength of 405 nm, and excellent resistance to electroplating.

[0016] As reported in the patent with publication number CN101802710, the resulting dry film resist exhibited excellent electroplating resistance, but its photosensitivity to exposure using laser direct imaging (LDI) at a laser wavelength of 405 nm was extremely poor. The initiator system used in this patent, like those commonly used in dry film resists, uses 4,4'-bis(diethylamino)benzophenone as the initiator. Such initiators have severely insufficient photosensitivity to a 405 nm laser light source and therefore cannot be used to directly image dry film resists by LDI.

[0017] In short, there is still a need for improvement in dry film resist resin compositions containing DBA in order to obtain dry film resists with relatively more stable sensitivity and to obtain more accurate resist patterns. Therefore, in order to obtain more stable and more precise overall performance, further optimization of the initiator system for dry film resists used in the fabrication of high-precision carrier boards is an urgent issue that needs to be addressed. [Overview of the project] [Problems that the invention aims to solve]

[0018] The main objective of the present invention is to provide a dry film resist, a photosensitive dry film, and a copper-clad laminate, thereby solving the problem that conventional dry film resists need improved performance. [Means for solving the problem]

[0019] To achieve the above objective, one aspect of the present invention provides a dry film resist comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a sensitizer, wherein (D) the sensitizer comprises a compound containing a pyrazoline structure.

[0020] Furthermore, (D) the sensitizer includes a compound containing an anthracene-substituted and / or triarylamine-substituted pyrazoline structure, Preferably, (D) the sensitizer comprises one or more compounds represented by structural formulas D1, D2, D3, D4, and D5. [ka] [ka] [ka] [ka] [Chemical formula] In the formula, R 01 , R 02 , R 03 , R 04 , R 05 are each independently one or more of hydrogen, halogen, nitro group, C1-C8 alkyl group, and C1-C4 alkoxy group, a represents any integer from 0 to 5, b represents any integer from 0 to 4, c represents any integer from 0 to 5, d represents any integer from 0 to 4, and when a is greater than or equal to 2, multiple R 01 may be the same or different from each other, and when b is greater than or equal to 2, multiple R 02 may be the same or different from each other, and when c is greater than or equal to 2, multiple R 04 may be the same or different from each other, and when d is greater than or equal to 2, multiple R 05 may be the same or different from each other, M are each independently a benzene ring, a biphenyl group, a condensed ring functional group, or an electron-rich heterocyclic or condensed heterocyclic functional group, Preferably, M is a phenyl group, a biphenyl group, or a condensed ring functional group having one or more of a C1-C4 alkoxy group, an amino group, and an alkyl group, or a heterocyclic or condensed heterocyclic functional group having furan, thiophene, indole, thiazole, benzofuran, benzothiazole, or fluorene, More preferably, the sensitizer contains a compound having the following structure, [Chemical formula]

[0021] Optionally, the benzene ring, biphenyl ring, fused ring, and heterocycle in the above structures contain substituents, and the substituents are one or more of the following: halogen, C1-C8 alkyl group, and C1-C4 alkoxy group, preferably the substituents are located at the para position.

[0022] Furthermore, (D) the sensitizer comprises one or more compounds represented by the following structural formulas I or II: [ka] [ka] In each of the formulas, R0 is independently hydrogen, halogen, C1-C8 alkyl group, or C1-C4 alkoxy group; the modified functional group M1 in structural formula I is independently a biphenyl functional group, a fused ring functional group, or a substituted benzene ring having one or more of the following: an electron-rich heterocycle, a fused heterocycle, or a C1-C4 alkoxy group or an amino group; the modified functional group M2 in structural formula II is selected from biphenyl, a fused ring functional group, or a substituted benzene ring having one or more of the following: an electron-rich heterocycle, a fused heterocycle, or a C1-C4 alkoxy group, a C1-C3 alkyl group, or an amino group; the modified functional group W is either a benzene ring or a fluorene ring, or a benzene ring, biphenyl ring, or fluorene ring having one or more substituents from the following: halogen, C1-C8 alkyl group, or C1-C4 alkoxy group; Preferably, the modified functional group M1 is a condensed ring functional group comprising one or more C1-C4 alkoxy groups, amino groups, or alkyl groups independently, or one of furan, thiophene, indole, thiazole, benzofuran, benzothiazole, indene, anthracene, acridine, or aromatic amine. Preferably, the specific structural formulas of the modified functional groups M1 and / or M2 are: [ka] [ka] is the bonding position of the functional group, and optionally, the benzene ring, biphenyl ring, fused ring, or heterocycle in the specific structural formula of the modified functional group M1 and / or M2 contains one or more substituents from among halogens, C1-C8 alkyl groups, and C1-C4 alkoxy groups, preferably the substituent is located at the para position.

[0023] Furthermore, the dry film resist comprises 45 to 65 parts by weight of (A) an alkali-soluble resin, 30 to 50 parts by weight of (B) a photopolymerizable monomer, 1.0 to 5.0 parts by weight of (C) a photopolymerization initiator, and 0.01 to 0.5 parts by weight of (D) a sensitizer. Preferably, the dry film resist comprises 45 to 65 parts by weight of (A) an alkali-soluble resin, 30 to 50 parts by weight of (B) a photopolymerizable monomer, 2.0 to 5.0 parts by weight of (C) a photopolymerization initiator, and 0.01 to 0.5 parts by weight of (D) a sensitizer. Preferably, the sensitizer content is 0.01 wt% to 0.5 wt% of the total weight of the dry film resist.

[0024] Furthermore, (C) the photopolymerization initiator contains the compound shown in the following structural formula C1, [ka] In the formula, substituent A in the benzene ring is independently one or more of the following: hydrogen, a methoxy group, and a halogen atom.

[0025] Preferably, (C) the photopolymerization initiator comprises one or more selected from 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

[0026] Furthermore, the dry film resist further comprises (E) a copper complex, the compound that forms a complex with copper in (E) the copper complex comprises a nitrogen-containing heterocyclic compound, and (B) the photopolymerizable monomer comprises an EO segment and a PO segment, the EO segment representing an oxyethylene group and the PO segment representing an oxypropylene group, preferably the weight of (E) the copper complex is 0.01 to 0.5, preferably the compound that forms a complex with copper in (E) the copper complex simultaneously contains a nitrogen-containing heterocyclic compound and a mercapto group, and more preferably the compound that forms a complex with copper in (E) the copper complex has one or more of the structures represented by structural formula III or IV. [ka] [ka]

[0027] In structural formula III or IV, X is 1 to 3 carbon atoms, or 1 to 2 nitrogen atoms, or 1 carbon atom and 1 nitrogen atom, the carbon atoms and / or nitrogen atoms are connected by single or double bonds, Y is one or more selected from oxygen atoms, sulfur atoms, carbon atoms, and nitrogen atoms, and the hydrogen atoms of the ring formed by X, Y and -C=NH- are carboxyl groups, amino groups, C1-C 12 Alkyl alkyl groups, C1-C 12 Alkoxy group, C6~C 12 It may be substituted with one or more of aryl groups and hydrazino groups, and M is a single bond, C1-C 12 Alkyl alkyl groups, C1-C 12 Ester group or C2~C 12 Selected from the ether group,

[0028] In structural formula IV, the ring composed of X, Y, and Z is a benzene ring or a heterocycle, and the benzene ring and heterocycle may comprise one or more of the following: C1-C6 alkyl groups, C1-C6 alkoxy groups, amino groups, carboxylic acids, nitro groups, and halogens.More preferably, the compound that forms a complex with copper in (E) the copper complex is mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, mercaptoimidazole, mercaptobenzimidazole, 2-mercapto-5-carboxybenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-mercaptobenzimidazole-4-carboxylic acid, mercaptobenzothiazole, 3-mercaptonidole, 1,3,5-tris(mercaptoethyl) -1,3,5-triazine-2,4,6-trione, mercaptopurine, 6-thioguanine, trithiocyanuric acid, 2,6-dimercaptopurine, 4-thiouracil, 2-mercaptobenzoxazole, 4,6-diamino-2,6-mercaptopyrimidine, 4-thioureauracil, 2-mercapto-4-hydroxy-5,6-diaminopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, dithiourea, 2-mercaptopyrazine, 3,6-dimercaptopyridazine, 2-mercaptoimidazole, 2-mercapto Thiazole, 8-mercaptoadenine, 4-thiouracil, mercaptotriazole, 3-mercapto-1,2,4-triazole dimercaptolate, 3-amino-5-mercapto-1,2,4-triazole, 4-methyl-4H-3-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 6,7-dihydro-6-mercapto-5H-pyrazolo[1,2-α][1,2,4]triazole chloride, 4-amino-3-hydradi No-5-mercapto-1,2,4-triazole, 1-methyl-5-mercapto-1H-tetrazol, 1-hydroxyethyl-5-mercapto-1H-tetrazol, 1-(2-dimethylaminoethyl)-1H-5-mercapto-tetrazol, 1-phenyl-5-mercaptotetrazol, 1,2-dihydro-1-(4-methoxyphenyl)-5H-tetraaza-5-thione, 1-ethyl-5-mercapto-1,2,3,4-tetrazol, 5-mercapto-H-tetrazol-1-acetic acid, 5-mercapto-1,2,3,It is one or more of the following selected compounds: 4-tetrazole-1-methylsulfonic acid, 1-(3-acetamido)phenyl-5-mercaptotetrazole, 1-(4-hydroxyphenyl)-5-mercaptotetrazole, 1-(4-ethoxyphenyl)-1,2-dihydro-5H-tetrazole-5-thion, 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, and 4-amino-2-mercaptopyrimidine.

[0029] Furthermore, (B) the photopolymerizable monomer includes one or more of the compounds represented by structural formulas B1, B2, and B3. [ka] [ka] [ka] In the formula, R1 is independently either H or CH3, EO represents an oxyethylene group, PO represents an oxypropylene group, the arrangement of the repeating units of EO and PO is random or blocky, m1 and m2 are each any integer between 1 and 20, n1 and n2 are each any integer between 0 and 20, and m1+m2 is any integer between 2 and 20, n1+n2 is any integer between 0 and 20, a1 is any integer between 4 and 20, b1 is any integer between 0 and 20, a2 is any integer between 3 and 20, b2 is any integer between 0 and 20, and c2 is any integer between 3 and 20.

[0030] Preferably, the photopolymerizable monomer having the structure represented by structural formula B1 accounts for 40% to 90% of the total amount of (B) photopolymerizable monomer, more preferably 50% to 80%, and also accounts for 20% to 40% of the total weight of (B) photopolymerizable monomer and (A) alkali-soluble resin.

[0031] More preferably, (B) the photopolymerizable monomer further comprises one or more of the structures represented by structural formula B4, [ka] In the formula, R1 is independently either H or CH3, and a3 is independently any integer between 1 and 10.

[0032] More preferably, (B) the photopolymerizable monomer is one or more selected from among lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, isobornyl ester, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) pentaerythritol triacrylate, ethoxylated (propoxylated) pentaerythritol tetraacrylate, ethoxylated (propoxylated) dipentaerythritol pentaacrylate, and ethoxylated (propoxylated) dipentaerythritol hexaacrylate.

[0033] Furthermore, (B) the photopolymerizable monomer includes one or more of the compounds represented by structural formula B1, [ka] In the formula, R1 is independently H or CH3, m1 and m2 are any integer between 1 and 20, n1 and n2 are any integer between 0 and 20, m1+m2 is any integer between 2 and 20, n1+n2 is any integer between 0 and 20, EO represents an oxyethylene group, PO represents an oxypropylene group, and the arrangement of the repeating units of EO and PO is random or blocky. Preferably, the photopolymerizable monomer having the structure shown in structural formula B1 accounts for 20% to 80% of the total amount of photopolymerizable monomers, more preferably 40% to 80%, and 10% to 35% of the total weight of (B) photopolymerizable monomers and (A) alkali-soluble resin, and more preferably, the (B) photopolymerizable monomer is further lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, isobornyl ester, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate It contains one or more selected from polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0034] Furthermore, (B) the photopolymerizable monomer includes one or more of the compounds represented by structural formulas B1, B5, B6, and B7. [ka] [ka] [ka] [ka] In the formulas, R1 is independently either H or CH3, the arrangement of the repeating units of the EO and PO segments is random or blocky, in structural formula IV, m1 and m2 are each any integer between 0 and 30, n1 and n2 are each any integer between 0 and 20, and m1+m2 is any integer between 0 and 30, and n1+n2 is any integer between 0 and 20, in structural formula B5, a5 is any integer between 0 and 30, and b5 is any integer between 0 and 20, in structural formula B6, a6 is any integer between 0 and 30, and b6 is any integer between 0 and 20, in structural formula B7, a7 is any integer between 0 and 20, and b7 is any integer between 0 and 20. Preferably, the molar amount of the PO segment is 15% to 60% of the total molar amount of the EO segment and PO segment in the photopolymerizable monomer. More preferably, the photopolymerizable monomer further comprises one or more selected from lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, isobornyl ester, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polyurethane acrylate.

[0035] Furthermore, (A) the alkali-soluble resin is obtained by copolymerizing (meth)acrylic acid, (meth)acrylate, and styrene or a derivative of styrene, and (A) the alkali-soluble resin contains any one or more of the compounds represented by structural formula A1. [ka] In the formula, R2, R3, R5, and R7 are each independently hydrogen or a methyl group; R4 and R6 are each independently one or more of the following: an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom; p and q are each independently any integer from 0 to 5; R8 is one of the following: a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms; and x, y, z, and u represent the ratio of each copolymer component in the alkali-soluble resin, where x is 15 to 40 wt%, z is 0 to 50 wt%, u is 0 to 80 wt%, and y is 0 to 40 wt%. Preferably, (A) the acid value of the alkali-soluble resin is 120 to 250 mg KOH / g, more preferably the weight-average molecular weight is 30,000 to 120,000, the molecular weight distribution is 1.3 to 2.5, and even more preferably the polymerization conversion rate is ≥ 97%.

[0036] Furthermore, in structural formula A1, x is 15-35 wt%, z is 0-50 wt%, u is 0-80 wt%, y is 0-25 wt%, and the value of z+u is 40 wt%-80 wt%. Preferably, the copolymerization unit of (A) the alkali-soluble resin is one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, N,N-dimethyl(meth)acrylate, N,N-diethyl(meth)acrylate, N,N-diethyl(meth)acrylate, propyl (meth)acrylate, and N,N-dimethyl(meth)acrylate, N,N-diethyl(meth)acrylate, and butyl (meth)acrylate, N,N-diethyl(meth)acrylate. Preferably, (A) the weight-average molecular weight of the alkali-soluble resin is 30,000 to 80,000, and the molecular weight distribution is 1.3 to 2.5.

[0037] Furthermore, in structural formula A1, R3 is hydrogen, x is 15-40 wt%, z is 0-40 wt%, u is 0, and y is 20-60 wt%. Preferably, the copolymerization unit of (A) the alkali-soluble resin is selected from alkyl (meth)acrylate and styrene and / or its derivatives, and the alkyl (meth)acrylate is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate The styrene derivative is one or more selected from 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, ethyl N,N-dimethyl(meth)acrylate, ethyl N,N-diethyl(meth)acrylate, propyl N,N-diethyl(meth)acrylate, butyl N,N-dimethyl(meth)acrylate, and butyl N,N-diethyl(meth)acrylate, and the styrene derivative is one or more selected from α-methylstyrene and benzyl (meth)acrylate. More preferably, (A) the styrene content in the copolymer units of the alkali-soluble resin is 0 to 40 wt% of the total weight of the copolymer units. Preferably, (A) the weight-average molecular weight of the alkali-soluble resin is 30,000 to 80,000, and the molecular weight distribution is 1.3 to 2.5.

[0038] Furthermore, in structural formula A1, R3 is hydrogen, x is 15-40 wt%, z is 0-40 wt%, u is 0, and y is 20-70 wt%. Preferably, the (meth)acrylate is one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, ethyl N,N-dimethyl(meth)acrylate, ethyl N,N-diethyl(meth)acrylate, propyl N,N-diethyl(meth)acrylate, butyl N,N-dimethyl(meth)acrylate, and butyl N,N-diethyl(meth)acrylate. Preferably, (A) the weight-average molecular weight of the alkali-soluble resin is 50,000 to 120,000, and the molecular weight distribution is 1.3 to 2.5.

[0039] Furthermore, the dry film resist further contains additives, the additives comprising one or more of the following: free radical polymerization inhibitors, colorants, dyes, plasticizers, photothermal stabilizers, adhesion promoters, leveling agents, and defoamers, preferably in an additive content of 0.5 to 5.0 parts by weight. More preferably, the content of the free radical polymerization inhibitor is 0.001 wt% to 0.005 wt% of the total weight of the dry film resist. More preferably, the free radical polymerization inhibitors are p-methoxyphenol, 4-ethyl-6-tert-butylphenol, nitrosophenylhydroxyamine aluminum salt, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, catechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5- It is one or more selected from methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, 1,4-hydroquinone, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, pyrogallol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxy, and 2,2-methylenebis(4-methyl-6-tert-butylphenol).

[0040] To achieve the above objective, another aspect of the present application provides a photosensitive dry film comprising a dry film resist layer and support and protective layers located on both sides of the dry film resist layer, wherein the dry film resist layer comprises any of the above-mentioned dry film resists.

[0041] Another aspect of the present application provides a dry film resist comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (E) a copper complex, wherein the compound forming a complex with copper in (E) the copper complex comprises a nitrogen-containing heterocyclic compound, and (B) the photopolymerizable monomer comprises an EO segment and a PO segment, where the EO segment represents an oxyethylene group and the PO segment represents an oxypropylene group.

[0042] Furthermore, in the (E) copper complex, the compound that forms a complex with copper contains both a nitrogen-containing heterocycle and a mercapto group, and preferably, the compound that forms a complex with copper in the (E) copper complex has one or more of the structures represented by structural formula III or IV. [ka] [ka] In structural formula III or IV, X is 1 to 3 carbon atoms, or 1 to 2 nitrogen atoms, or 1 carbon atom and 1 nitrogen atom, the carbon atoms and / or nitrogen atoms are connected by single or double bonds, Y is one or more selected from oxygen atoms, sulfur atoms, carbon atoms, and nitrogen atoms, and the hydrogen atoms of the ring formed by X, Y and -C=NH- are carboxyl groups, amino groups, C1-C 12 Alkyl alkyl groups, C1-C 12 Alkoxy group, C6~C 12 It may be substituted with one or more of aryl groups and hydrazino groups, and M is a single bond, C1-C 12 Alkyl alkyl groups, C1-C 12 Ester group or C2~C 12 Selected from the ether group, In structural formula IV, the ring composed of X, Y, and Z is a benzene ring or a heterocycle, and the benzene ring and heterocycle may comprise one or more of the following: C1-C6 alkyl groups, C1-C6 alkoxy groups, amino groups, carboxylic acids, nitro groups, and halogens. More preferably, the compound that forms a complex with copper in (E) the copper complex is mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, mercaptoimidazole, mercaptobenzimidazole, 2-mercapto-5-carboxybenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-mercaptobenzimidazole-4-carboxylic acid, mercaptobenzothiazole, 3-mercaptonidole, 1,3,5-tris(mercaptoethyl) -1,3,5-triazine-2,4,6-trione, mercaptopurine, 6-thioguanine, trithiocyanuric acid, 2,6-dimercaptopurine, 4-thiouracil, 2-mercaptobenzoxazole, 4,6-diamino-2,6-mercaptopyrimidine, 4-thioureauracil, 2-mercapto-4-hydroxy-5,6-diaminopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, dithiourea, 2-mercaptopyrazine, 3,6-dimercaptopyridazine, 2-mercaptoimidazole, 2-mercapto Thiazole, 8-mercaptoadenine, 4-thiouracil, mercaptotriazole, 3-mercapto-1,2,4-triazole dimercaptolate, 3-amino-5-mercapto-1,2,4-triazole, 4-methyl-4H-3-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 6,7-dihydro-6-mercapto-5H-pyrazolo[1,2-α][1,2,4]triazole chloride, 4-amino-3-hydradi No-5-mercapto-1,2,4-triazole, 1-methyl-5-mercapto-1H-tetrazol, 1-hydroxyethyl-5-mercapto-1H-tetrazol, 1-(2-dimethylaminoethyl)-1H-5-mercapto-tetrazol, 1-phenyl-5-mercaptotetrazol, 1,2-dihydro-1-(4-methoxyphenyl)-5H-tetraaza-5-thione, 1-ethyl-5-mercapto-1,2,3,4-tetrazol, 5-mercapto-H-tetrazol-1-acetic acid, 5-mercapto-1,2,3,It is one or more of the following selected compounds: 4-tetrazole-1-methylsulfonic acid, 1-(3-acetamido)phenyl-5-mercaptotetrazole, 1-(4-hydroxyphenyl)-5-mercaptotetrazole, 1-(4-ethoxyphenyl)-1,2-dihydro-5H-tetrazole-5-thion, 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, and 4-amino-2-mercaptopyrimidine.

[0043] Furthermore, on a weight basis, the dry film resist contains (A) 40 to 65 parts by weight of alkali-soluble resin, (B) 35 to 60 parts by weight of photopolymerizable monomer, (C) 2.0 to 4.5 parts by weight of photopolymerization initiator, and (E) 0.01 to 0.5 parts by weight of copper complex.

[0044] Furthermore, the dry film resist further comprises 0.01 to 0.5 parts by weight of (D) sensitizer, preferably (D) comprising one or more compounds represented by structural formula I or II. [ka] [ka] In each of the formulas, R0 is independently hydrogen, halogen, C1-C8 alkyl group, or C1-C4 alkoxy group; the modified functional group M1 in structural formula I is independently biphenyl, fused ring functional group, or electron-rich heterocycle, fused heterocycle, or C1-C4 alkoxy group, or a benzene ring having an amino group; the modified functional group M2 in structural formula II is one selected from biphenyl, fused ring functional group, or electron-rich heterocycle, fused heterocycle, or a benzene ring having a C1-C4 alkoxy group, or an amino group, or a substituted phenyl group having a C1-C4 alkoxy group; the modified functional group W is either a benzene ring or a fluorene ring, or a benzene ring, biphenyl ring, or fluorene ring having one or more substituents from halogen, C1-C8 alkyl group, or C1-C4 alkoxy group.

[0045] More preferably, each modified functional group M1 is a condensed ring functional group comprising one or more C1-C4 alkoxy groups, amino groups, and alkyl groups independently, or one of furan, thiophene, indole, thiazole, benzofuran, benzothiazole, indene, anthracene, acridine, and aromatic amine. Even more preferably, the specific structural formulas of the modified functional groups M1 and / or M2 are: [ka] Includes, During the ceremony, [ka] is the bonding position of the functional group, and optionally, the benzene ring, biphenyl ring, fused ring, or heterocycle in the specific structural formula of the modified functional group M1 and / or M2 contains one or more substituents from among halogens, C1-C8 alkyl groups, and C1-C4 alkoxy groups, preferably the substituent is located at the para position.

[0046] Furthermore, (C) the photopolymerization initiator contains the compound shown in the following structural formula C1, [ka] In the formula, substituent A in the benzene ring is independently a hydrogen atom, a methoxy group, and a halogen atom. Preferably, (C) the photopolymerization initiator comprises one or more selected from 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole. Optionally, (C) the photopolymerization initiator may also be thioxanthone, benzoin phenyl ether, benzophenone, benzoin methyl ether, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzo It contains one or more compounds selected from anthraquinone, 2,3-benzoanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzyldimethyl ketal, 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane, N-phenylglycine, coumarin compounds, and oxazole compounds.

[0047] Furthermore, the photopolymerizable monomer includes one or more compounds represented by structural formulas B1, B2, B3, and B4. [ka] [ka] [ka] [ka] In the formulas, R1 is independently either H or CH3, the arrangement of the EO segment and PO segment repeating units is random or blocky, in structural formula B1, m1 and m2 are each any integer between 0 and 30, n1 and n2 are each any integer between 0 and 20, and m1+m2 is any integer between 0 and 30, and n1+n2 is any integer between 0 and 20, in structural formula B5, a5 is any integer between 0 and 30, and b5 is any integer between 0 and 20, in structural formula B6, a6 is any integer between 0 and 30, and b6 is any integer between 0 and 20, in structural formula B7, a7 is any integer between 0 and 20, and b7 is any integer between 0 and 20. Preferably, the molar amount of the PO segment is 15% to 60% of the total molar amount of the EO segment and PO segment in the photopolymerizable monomer. More preferably, (B) the photopolymerizable monomer further comprises one or more selected from lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, isobornyl ester, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polyurethane acrylate.

[0048] Furthermore, (A) the alkali-soluble resin is obtained by copolymerizing (meth)acrylic acid, (meth)acrylate, and styrene or a derivative of styrene, and the alkali-soluble resin contains one or more of the structures shown in structural formula A2. [ka] In the formula, R2 and R7 are independently hydrogen or a methyl group, and R8 is C1-C18 Linear alkyl groups and C3~C 18 Substitutive C1-C2 groups containing a branched alkyl group, a benzyl group, a hydroxyl group, and / or an amino group. 18 Linear alkyl groups or C3-C 18 It is one of the branched alkyl groups, and R4 is one of the C1-C3 alkyl groups, C1-C3 alkoxy groups, amino groups, and halogen atoms, and the structural formula A2 The number of substituents on the benzene ring is 0 to 5, and x, y, and z represent the ratio of each copolymer component in the alkali-soluble resin, where x is 15 to 40 wt%, y is 20 to 70 wt%, and z is 0 to 40 wt%. Preferably, the (meth)acrylate is one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, ethyl N,N-dimethyl(meth)acrylate, ethyl N,N-diethyl(meth)acrylate, propyl N,N-diethyl(meth)acrylate, butyl N,N-dimethyl(meth)acrylate, and butyl N,N-diethyl(meth)acrylate. More preferably, the alkali-soluble resin has an acid value of 120 to 250 mg KOH / g, more preferably a weight-average molecular weight of 50,000 to 120,000, a molecular weight distribution of 1.3 to 2.5, and even more preferably a polymerization conversion rate of ≥ 97%.

[0049] Furthermore, the dry film resist further contains additives, one or more of which are colorants, dyes, plasticizers, photothermal stabilizers, adhesion promoters, leveling agents, polymerization inhibitors, and defoamers, and preferably the content of the additives is 0.5 to 5.0 parts by weight.

[0050] Another aspect of the present application provides a photosensitive dry film comprising a dry film resist layer and support and protective layers located on both sides of the dry film resist layer, wherein the dry film resist layer comprises any of the above-mentioned dry film resists.

[0051] Another aspect of the present invention provides a copper-clad laminate on which any of the above dry film resists are provided. [Effects of the Invention]

[0052] The dry film resist of this invention, due to the use of a specific type of sensitizer, exhibits excellent overall performance, particularly in terms of photosensitivity, resolution, alignment recognition adaptability, and electroplating resistance. [Modes for carrying out the invention]

[0053] Furthermore, the embodiments and features of the embodiments of this application can be combined with each other, as long as there is no contradiction. The present invention will be described in detail below with reference to the embodiments.

[0054] As described in the background art of this application, conventional dry film resists have problems such as poor photosensitivity and resolution, and insufficient sensitivity and stability of the resist pattern. To solve these problems, this application provides a dry film resist, a photosensitive dry film, and a copper-clad laminate.

[0055] In one typical embodiment of the present application, a dry film resist is provided, which comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a sensitizer, wherein the (D) sensitizer comprises a compound containing a pyrazoline structure.

[0056] This dry film resist contains a sensitizer with a pyrazoline structure, and when used in combination with an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator, it can effectively improve the overall performance of the dry film resist.

[0057] In some typical embodiments of the present application, the (D) sensitizer described above includes compounds containing anthracene-substituted and / or triarylamine-substituted pyrazoline structures. By introducing the pyrazoline structure to anthracene and / or triarylamine, the present application optimizes the structure for anthracene-based and triarylamine-based sensitizers commonly used in dry film resists for high-end PCBs such as carrier boards and substrate-like PCBs. Because the imidazoline compound has good photosensitivity, its photosensitivity to an LDI 405nm laser light source is higher than that of anthracene-based and triarylamine-based sensitizers. The sensitizer compounds of the above structure generally have a large π-conjugated structure, and due to such a large π-conjugated electron effect, the maximum absorption wavelength of the modified sensitizer compound shifts towards the red, getting closer to the wavelength of the 405nm laser light source. Therefore, by introducing the pyrazoline structure to specific anthracene and triarylamine molecules, the present application can clearly improve the photosensitivity of the resulting dry film resist to an LDI 405nm laser light source.

[0058] Because the above-described sensitizer structure simultaneously contains a pyrazoline ring structure and an anthracene or triarylamine structure, the optimized and modified sensitizer compound has a dual active functional group. The photosensitivity of the pyrazoline structure and the high-precision analytical capability of the anthracene or triarylamine structure are effectively combined, thereby ensuring high-precision analytical capability for dry film resists containing it, and improving the production efficiency of clients manufacturing high-end PCBs such as carrier boards and substrate-like PCBs.

[0059] Analysis of the causes of the adverse effect of migration and penetration of the sensitizer 9,10-dibutoxyanthracene (DBA) revealed that, on the one hand, DBA has very low sensitivity, and a large amount of DBA is required to reach a certain degree of curing and form a good resist pattern. On the other hand, DBA is a small molecule and contains a long alkyl chain in its molecular structure. Due to molecular motion and the theory that similar molecules dissolve together, DBA molecules are prone to migrating to polyethylene protective films that also have an alkyl structure. Based on the mechanism of molecular motion and the theory that similar substances dissolve together, this invention modifies the structure of the anthracene-based sensitizer DBA by introducing a pyrazoline structure into an anthracene-based compound. Since the introduced pyrazoline functional group generally also possesses other aromatic ring structures, the molecular weight of the anthracene-based sensitizer increases, and a large aromatic ring structure is introduced into the DBA molecular structure. In both cases, the adverse effect of the pyrazoline structure sensitizer of this invention migrating to and penetrating the polyethylene protective film can be significantly suppressed, thereby obtaining a dry film resist in which properties such as sensitivity and resist pattern are more stable.

[0060] The compounds containing the above-mentioned anthracene-substituted and / or triarylamine-substituted pyrazoline structures only need to have the corresponding chemical structure; therefore, compounds having the corresponding structure can be selected from conventional compounds. In some preferred embodiments of the present application, (D) the sensitizer has one or more of the structures represented by structural formulas D1, D2, D3, D4, and D5. [ka] [ka] [ka] [ka] [ka] In the formula, R 01 , R 02 , R 03 , R 04 , R 05 Each of these is independently one or more of the following: hydrogen, halogen, nitro group, C1-C8 alkyl group, or C1-C4 alkoxy group. If a is any integer between 0 and 5, b is any integer between 0 and 4, c is any integer between 0 and 5, and d is any integer between 0 and 4, and a is greater than or equal to 2, then there are multiple R 01 These can be the same or different, and if b is greater than or equal to 2, there are multiple R 02 These can be the same or different, and if c is greater than or equal to 2, there are multiple R 04 These can be the same or different, and if d is greater than or equal to 2, there are multiple R 05 Each of these may be the same or different, and each M is independently a benzene ring, a biphenyl group, a fused ring functional group, or an electron-rich heterocycle or fused heterocycle functional group, where a benzene ring represents a phenyl group or a derivative functional group of a phenyl group, a biphenyl group represents a biphenyl group or a derivative functional group of a biphenyl group, a fused ring functional group represents a fused ring or a derivative functional group of a fused ring, and an electron-rich heterocycle or fused heterocycle functional group represents an electron-rich heterocycle or a derivative functional group of a fused heterocycle. Exemplarily, the above derivative functional groups may be functional groups containing substituents such as C1-C4 alkoxy groups, amino groups, C1-C8 alkyl groups, halogens, etc., and the number of substituents may be one or more.

[0061] However, M in the above structural formulas D3, D4, and D5 may be selected from conventional benzene rings, biphenyl groups, fused ring functional groups, or benzene rings, biphenyl groups, fused ring functional groups having electron-donating substituents, or electron-rich heterocyclic or fused heterocyclic functional groups. In some examples of this application, M is a phenyl group, biphenyl group, or fused ring functional group having one or more of the C1-C4 alkoxy groups, amino groups, or alkyl groups, or furan, thiophene, indole, thiazole, benzofuran, benzothiazole, fluorene, and derivatives of the above heterocyclic or fused heterocyclic groups. Preferably, the sensitizer comprises a compound having the following structure: [ka]

[0062] The above-mentioned benzene ring, biphenyl ring, fused ring, and heterocycle may further contain substituents, one or more of which are halogens, C1-C8 alkyl groups, and C1-C4 alkoxy groups, and there is no limit to the number of substituents. Preferably, the substituents are located at the para position, which provides superior effects.

[0063] In some typical embodiments of this application, the (D) sensitizer described above comprises one or more compounds represented by the following structural formulas I or II: [ka] [ka] In each of the formulas, R0 is independently hydrogen, halogen, C1-C8 alkyl group, or C1-C4 alkoxy group; the modified functional group M1 in structural formula I is independently a biphenyl functional group, a fused ring functional group, or a substituted benzene ring having one or more of the following: an electron-rich heterocycle, a fused heterocycle, a C1-C4 alkoxy group, or an amino group; the modified functional group M2 in structural formula II is selected from biphenyl, a fused ring functional group, or a substituted benzene ring having one or more of the following: an electron-rich heterocycle, a fused heterocycle, or a C1-C4 alkoxy group, a C1-C3 alkyl group, or an amino group; the modified functional group W is either a benzene ring or a fluorene ring, or a benzene ring, biphenyl ring, or fluorene ring having one or more substituents from the following: halogen, C1-C8 alkyl group, or C1-C4 alkoxy group.

[0064] This invention introduces several modifying functional groups, such as biphenyl, fused ring functional groups, and electron-rich heterocycles or benzene rings comprising fused heterocycles and amino groups, to pyrazoline compounds. As a result, the sensitizer compounds represented by formulas I and II, after modification, have an electron-rich conjugated molecular structure. This electron-rich conjugation effect helps to promote the redshift of the sensitizer's absorption spectrum, extending its absorption spectrum to the visible light region. After modification, the maximum absorption wavelength of the sensitizer is closer to a 405 nm exposure light source, making it more sensitive to this light source, thereby improving the photosensitivity of the dry film resist to a 405 nm LDI exposure light source. Furthermore, by selecting a sensitizer with the above specific structure, the dry film resist not only exhibits high photosensitivity and resolution, but such sensitizers can also effectively promote the oxidative development of leuco-developers after exposure, further enhancing the contrast of patterns before and after exposure. This further aids in alignment recognition in domestic LDI exposure machines, ensuring alignment accuracy in domestic LDI exposure machines. Furthermore, the dry film resist containing the above-mentioned sensitizer of this application has a rich variety of components, and in particular, the sensitizer not only gives the dry film resist both high photosensitivity and high alignment recognition adaptability, but is also inexpensive and has a rich variety of components, so it can effectively reduce the manufacturing cost of high-end dry film sensitizers and has very good market application value.

[0065] The modified functional group M of the above structural formula I or II may be selected from one or more of biphenyl, fused ring functional groups, or electron-rich heterocycles, fused heterocycles, or benzene rings having amino groups. For example, each modified functional group M is independently a fused ring functional group having one or more of C1-C4 alkoxy groups, amino groups, or alkyl groups, or a heterocycle or fused heterocycle functional group of one of furan, thiophene, indole, thiazole, benzofuran, benzothiazole, indene, anthracene, acridine, or aromatic amine, and also includes derivatives of the above functional groups.

[0066] In some preferred embodiments, the specific structural formulas of the above-mentioned modified functional groups M1 and / or M2 are as follows: [ka] It includes one of the following, and in the formula, [ka] is the bonding position of the functional group, and optionally, the benzene ring, biphenyl ring, fused ring, or heterocycle in the specific structural formula of the modified functional group M1 and / or M2 contains one or more substituents from among halogens, C1-C8 alkyl groups, and C1-C4 alkoxy groups, and there is no limit to the number of substituents, preferably the substituents are located at the para position.

[0067] In the dry film resist of this application, the content of (A) alkali-soluble resin, (B) photopolymerizable monomer, (C) photopolymerization initiator, and (D) sensitizer may be determined based on prior art and are not limited in this application. In some embodiments of the present application, in order to better exhibit the synergistic effect of each component, the dry film resist contains 45 to 65 parts by weight of (A) alkali-soluble resin, 30 to 50 parts by weight of (B) photopolymerizable monomer, 1.0 to 5.0 parts by weight of (C) photopolymerization initiator, and 0.01 to 0.5 parts by weight of (D) sensitizer. If the amount of sensitizer added is too low, the resulting dry film resist will not be very photosensitive. If the amount added is too high, the surface layer of the dry film resist will harden too quickly, affecting the depth of hardening and increasing the risk of reduced adhesion of the dry film resist to the copper surface. To further improve sensitivity, resolution, and adhesion in a balanced manner, the sensitizer content is preferably 0.01 wt% to 0.5 wt% of the total weight of the dry film resist.

[0068] In some embodiments of the present application, in order to further improve the photosensitivity, resolution, sensitivity and stability of the resist pattern of the dry film resist, the dry film resist comprises 45 to 65 parts by weight of (A) alkali-soluble resin, 30 to 50 parts by weight of (B) photopolymerizable monomer, 2.0 to 5.0 parts by weight of (C) photopolymerization initiator, and 0.01 to 0.5 parts by weight of (D) sensitizer.

[0069] The above (C) photopolymerization initiator may be selected from the prior art, for example, a hexaarylbisimidazole derivative-based photopolymerization initiator. In order to further improve the photosensitivity, resolution, and adhesion of the dry film resist, in some embodiments of this application, the (C) photopolymerization initiator has a compound represented by the following structural formula C1, [ka] In the formula, each substituent A in the benzene ring is independently one or more of the following: hydrogen, a methoxy group, and a halogen atom.

[0070] Preferably, the photopolymerization initiator is 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2,2',4-tris(2-chlorophenyl)-5 -(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole is selected from one or more of the above photopolymerization initiators, and at the same time as adding the above photopolymerization initiator, a small amount of other types of photopolymerization initiators, such as thioxanthone, benzoinphenyl ether, benzophenone, benzoin methyl ether, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminoben Zophenone, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthrenequinone, 2,3-dimethylanthraquinone, benzyl derivatives such as benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzyl dimethyl ketal, and benzoyl dimethyl ether, acridine derivatives such as 9-phenylacridine and 1,7-bis(9,9'-acridinyl)heptane, N-phenylglycine, coumarin compounds, and oxazole compounds may be used in combination, and the specific amount used may be determined based on prior art and is not limited herein.

[0071] In some typical embodiments of the present application, in order to improve the electroplating resistance of the dry film resist, any of the above dry film resists further comprises (E) a copper complex, wherein the compound forming the complex with copper in (E) the copper complex comprises a nitrogen-containing heterocyclic compound, and (B) a photopolymerizable monomer comprising an EO segment and a PO segment, wherein the EO segment represents an oxyethylene group and the PO segment represents an oxypropylene group. The above EO segment and PO segment may be derived from one or more specific photopolymerizable monomers that simultaneously contain the EO segment and the PO segment, or a photopolymerizable monomer containing the EO segment and the PO segment may be blended, or a photopolymerizable monomer containing the EO segment and the PO segment in different ratios may be blended.

[0072] The dry film resist containing the complex formed by the above-mentioned nitrogen-containing heterocyclic compound and copper has two advantages: on the one hand, the nitrogen-containing heterocyclic structure is highly polar, which allows the copper complex to enhance its interaction with metallic copper; on the other hand, the lone pair of electrons of the nitrogen atom can form a coordinate bond with the copper atom, and the formation of such a coordinate chemical bond further improves the bonding strength between the compound and the copper atom. Due to these two effects, adding the above-mentioned copper coordination compound significantly strengthens the bonding strength of the dry film resist to the copper surface, mitigating the phenomenon of slight warping of the bottom sidewall during the electroplating process of the dry film, thereby improving the electroplating resistance of the dry film resist.

[0073] Furthermore, the above-mentioned photopolymerizable monomer simultaneously contains both a hydrophilic functional group ethylene oxide (EO) and a hydrophobic functional group propylene oxide (PO). On the one hand, when the photopolymerizable monomer contains a hydrophilic functional group ethylene oxide (EO) segment, the water solubility of the dry film resist can be improved, thereby improving the developability and resolution of the dry film resist. On the other hand, when the photopolymerizable monomer contains only an ethylene oxide segment, the water solubility of the dry film resist is improved, but in the dry film resist, swelling can easily cause warping of the sidewalls of the dry film, leading to the harmful issue of cementation. However, by adding a hydrophobic functional group propylene oxide (PO) segment to the photopolymerizable monomer, the hydrophobicity of the dry film resist can be improved to some extent, thereby improving the electroplating resistance of the dry film resist. Moreover, the photopolymerizable monomer has a good balance of hydrophilicity and hydrophobicity in the dry film resist due to its chemical structure, thereby making it possible to obtain a dry film resist photosensitive material with balanced developability, analytical ability, and electroplating resistance.

[0074] To further improve the electroplating resistance of the dry film resist, in some embodiments of this application, the amount of (E) copper complex by weight is 0.01 to 0.5. There are no special requirements for the nitrogen-containing heterocyclic compound that forms a complex with the copper; it may be a saturated nitrogen-containing heterocyclic compound or an unsaturated nitrogen-containing heterocyclic compound, and the heterocyclic compound may contain one nitrogen atom or multiple nitrogen atoms. In some preferred embodiments of this application, the compound that forms a complex with copper in the copper complex contains both a nitrogen-containing heterocyclic compound and a mercapto group, and the number of mercapto groups may be one or more.

[0075] In some preferred embodiments, (E) the compound that forms a complex with copper in the copper complex has one or more of the structures represented by structural formula III or IV, [ka] [ka]

[0076] In structural formula III or IV, X is 1 to 3 carbon atoms, or 1 to 2 nitrogen atoms, or 1 carbon atom and 1 nitrogen atom, the carbon atoms and / or nitrogen atoms are connected by single or double bonds, Y is one or more selected from oxygen atoms, sulfur atoms, carbon atoms, and nitrogen atoms, and the hydrogen atoms of the ring formed by X, Y and -C=NH- are carboxyl groups, amino groups, C1-C 12 Alkyl alkyl groups, C1-C 12 Alkoxy group, C6~C 12 It may be substituted with one or more of aryl groups and hydrazino groups, and M is a single bond, C1-C 12 Alkyl alkyl groups, C1-C 12 Ester group or C2~C 12 Selected from ether groups, the ring composed of X, Y, and Z in structural formula IV is a benzene ring or a heterocycle, and the benzene ring and heterocycle may comprise one or more of the following: C1-C6 alkyl groups, C1-C6 alkoxy groups, amino groups, carboxylic acids, nitro groups, and halogens.

[0077] In structural formula IV, Z is not limited to a single atom or functional group, and the ring formed by it and X and Y is a benzene ring or a heterocycle, provided that the heterocycle is saturated or unsaturated, and the benzene ring and heterocycle may contain one or more of the following: C1-C6 alkyl groups, C1-C6 alkoxy groups, amino groups, carboxylic acids, nitro groups, and halogens. In other words, structural formula IV represents a heterocyclic compound formed by the condensation of a benzene ring or heterocycle with a nitrogen-containing heterocycle. In structural formula III or IV above, the number of mercapto groups may be 1 to 6.

[0078] Examples of compounds that form complexes with the above copper include mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, mercaptoimidazole, mercaptobenzimidazole, 2-mercapto-5-carboxybenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-mercapto-5-aminobenzimidazole, 2-mercaptobenzimidazole-4-carboxylic acid, mercaptobenzothiazole, 3-mercaptonidole, and 1,3,5-tris(mercaptoethyl)-1,3,5-t Liazin-2,4,6-trione, mercaptopurine, 6-thioguanine, trithiocyanuric acid, 2,6-dimercaptopurine, 4-thiouracil, 2-mercaptobenzoxazole, 4,6-diamino-2,6-mercaptopyrimidine, 4-thioureauracil, 2-mercapto-4-hydroxy-5,6-diaminopyrimidine, 4,6-dimethyl-2-mercaptopyrimidine, dithiourea, 2-mercaptopyrazine, 3,6-dimercaptopyridazine, 2-mercaptoimidazole, 2-mercaptothiazole, 8-mercaptoadenine, 4-thiouracil, mercaptotriazole, 3-mercapto-1,2,4-triazole dimercaptolate, 3-amino-5-mercapto-1,2,4-triazole, 4-methyl-4H-3-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 6,7-dihydro-6-mercapto-5H-pyrazolo[1,2-α][1,2,4]triazole chloride, 4-amino-3-hydrazino-5 -Mercapto-1,2,4-triazole, 1-methyl-5-mercapto-1H-tetrazol, 1-hydroxyethyl-5-mercapto-1H-tetrazol, 1-(2-dimethylaminoethyl)-1H-5-mercapto-tetrazol, 1-phenyl-5-mercaptotetrazol, 1,2-dihydro-1-(4-methoxyphenyl)-5H-tetraaza-5-thione, 1-ethyl-5-mercapto-1,2,3,4-tetrazol, 5-mercapto-H-tetrazol-1-acetic acid, 5-mercapto-1,2,3,One or more compounds may be selected from 4-tetrazole-1-methylsulfonic acid, 1-(3-acetamido)phenyl-5-mercaptotetrazole, 1-(4-hydroxyphenyl)-5-mercaptotetrazole, 1-(4-ethoxyphenyl)-1,2-dihydro-5H-tetrazole-5-thion, 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, and 4-amino-2-mercaptopyrimidine. The structural formulas of some of these compounds are shown below. Note that, due to electron rearrangement, the chemical structural formulas may show that the sulfur atom and the heterocycle are connected to the nitrogen-containing heterocycle by single or double bonds. [ka]

[0079] The above photopolymerizable monomers may be selected from the prior art, and in some embodiments of the present application, when the sensitizer in the dry film resist contains a compound containing the above anthracene-substituted and / or triarylamine-substituted pyrazoline structure, in order to further improve the resolution and adhesion of the dry film resist, (B) the photopolymerizable monomer includes one or more of the compounds represented by the following structural formulas B1, B2, and B3, [ka] [ka] [ka] In the formula, R1 is independently either H or CH3, EO represents an oxyethylene group, PO represents an oxypropylene group, the arrangement of the repeating units of EO and PO is random or blocky, m1 and m2 are each any integer between 1 and 20, n1 and n2 are each any integer between 0 and 20, and m1+m2 is any integer between 2 and 20, n1+n2 is any integer between 0 and 20, a1 is any integer between 4 and 20, b1 is any integer between 0 and 20, a2 is any integer between 3 and 20, b2 is any integer between 0 and 20, and c2 is any integer between 3 and 20.

[0080] In the above dry film resist system, in order to further improve the balance between resolution and adhesion, the photopolymerizable monomer having the structure shown by structural formula B1 accounts for 40% to 90% of the total amount of the photopolymerizable monomer, more preferably 50% to 80%, and is 20% to 40% of the total weight of the photopolymerizable monomer and the alkali-soluble resin.

[0081] To further improve the adhesion of the dry film resist, in some embodiments of the present application, the above (B) photopolymerizable monomer may further include a polyfunctional photopolymerizable monomer represented by the following formula B4, where R1 is independently H or CH3, and a3 is independently any integer from 1 to 10. [ka]

[0082] Preferably, in addition to the above-mentioned photopolymerizable monomer, the photopolymerizable monomer further includes several other commonly used monofunctional, difunctional, or polyfunctional (meth)acrylate-based ethylenically unsaturated double bond monomers. The above-mentioned polyfunctional photopolymerizable monomer may be a trifunctional photopolymerizable monomer represented by structural formula B4, or another tetrafunctional, pentafunctional, or hexafunctional photopolymerizable monomer.

[0083] In some embodiments of the present application, the photopolymerizable monomer is one or more selected from lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, isobornyl ester, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) pentaerythritol triacrylate, ethoxylated (propoxylated) pentaerythritol tetraacrylate, ethoxylated (propoxylated) dipentaerythritol pentaacrylate, and ethoxylated (propoxylated) dipentaerythritol hexaacrylate.

[0084] The total weight of the photopolymerizable monomer is preferably 30 to 50 parts by weight. If the weight is too low, the photosensitive resin composition is likely to have problems with low sensitivity and low resolution, and if the weight is too high, the adhesive is likely to ooze out onto the photosensitive layer.

[0085] When the sensitizer in a dry film resist contains a compound represented by the above structural formula I or II, in some embodiments of the present application, in order to further improve the resolution and adhesion of the dry film resist, the (B) photopolymerizable monomer component contains at least one or more of the compounds represented by the following structural formula B1, i.e., an EO / PO modified bisphenol A structure (meth)acrylate. [ka] In the formula, R1 is independently either H or CH3, m1 and m2 are any integer between 1 and 20, n1 and n2 are any integer between 0 and 20, m1 + m2 is any integer between 2 and 20, n1 + n2 is any integer between 0 and 20, EO represents an oxyethylene group, PO represents an oxypropylene group, and the arrangement of the repeating units of EO and PO is random or blocky.

[0086] In the dry film resist system, in order to further improve the balance between resolution and adhesion, the photopolymerizable monomer having the structure shown in structural formula IV accounts for 20% to 80% of the total amount of (B) photopolymerizable monomer, more preferably 40% to 80%, and 10% to 35% of the total weight of (B) photopolymerizable monomer and (A) alkali-soluble resin. Preferably, in addition to the above photopolymerizable monomer, (B) photopolymerizable monomer may further contain several other commonly used monofunctional, difunctional, or polyfunctional (meth)acrylate-based ethylenically unsaturated double bond monomers. In some embodiments of the present application, the photopolymerizable monomer further comprises one or more selected from lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, isobornyl ester, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

[0087] In a dry film resist system in which the sensitizer described above contains a compound represented by structural formula I or II, the total weight of the photopolymerizable monomer is preferably 35 to 50 parts by weight. If the weight is too low, the photosensitive resin composition is likely to have problems with low sensitivity and low resolution, and if the weight is too high, the adhesive is likely to protrude into the photosensitive layer.

[0088] When the dry film resist of this application contains the above copper complex, in order to better exhibit the synergistic effect of each component and further improve the electroplating resistance, developability and analytical capability of the dry film resist, (B) the photopolymerizable monomer includes one or more of the compounds represented by structural formulas B1, B5, B6 and B7. [ka] [ka] [ka] [ka] In the formulas, R1 is independently either H or CH3, the arrangement of the repeating units of the EO segment and PO segment is random or blocky, in structural formula B1, m1 and m2 are each any integer between 0 and 30, n1 and n2 are each any integer between 0 and 20, and m1 + m2 is any integer between 0 and 30, and n1 + n2 is any integer between 0 and 20, in structural formula B5, a5 is any integer between 0 and 30, and b5 is any integer between 0 and 20, in structural formula B6, a6 is any integer between 0 and 30, and b6 is any integer between 0 and 20, and in structural formula B7, a7 is any integer between 0 and 20, and b7 is any integer between 0 and 20. Preferably, the molar amount of the PO segment is 15% to 60% of the total molar amount of the EO segment and PO segment in the photopolymerizable monomer. More preferably, (B) the photopolymerizable monomer further comprises one or more selected from lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, isobornyl ester, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polyurethane acrylate.

[0089] The alkali-soluble resin (A) of the present application may be selected from the prior art, and in some embodiments of the present application, in order to improve the overall performance of the dry film resist, the alkali-soluble resin (A) comprises one or more of the structures represented by structural formula A1 and is obtained by free radical copolymerization of (meth)acrylic acid, (meth)acrylate and styrene or derivatives thereof. [ka] In the formula, R2, R3, R5, and R7 are each independently hydrogen or a methyl group, R4 and R6 are each independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxyl group, or a halogen atom, p and q are each independently any integer from 0 to 5, R8 is one of a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, and x, y, z, and u each represent the ratio of each copolymer component in the alkali-soluble resin, where x is 15 to 40 wt%, z is 0 to 50 wt%, u is 0 to 80 wt%, and y is 0 to 40 wt%.

[0090] In some embodiments of the present application, (A) the acid value of the alkali-soluble resin is 120 to 250 mg KOH / g, because if the acid value of the alkali-soluble resin is too low, the solubility in alkali deteriorates, and the development and film detachment time tends to be longer, and if the acid value of the alkali-soluble resin is too high, the resolution tends to deteriorate.

[0091] Preferably, in order to further improve the overall performance of the dry film resist, the weight-average molecular weight of the alkali-soluble resin (A) described above is 30,000 to 120,000, and the molecular weight distribution is 1.3 to 2.5. The alkali-soluble resin (A) described above may be a single copolymer resin represented by structural formula A1, or it may be an alkali-soluble copolymer resin obtained by blending two or more such copolymer resins with different molecular weights, different acid values, or different styrene content, and preferably the polymerization conversion rate is 97% or greater.

[0092] In some embodiments of the present application, when the sensitizer in the dry film resist includes a compound containing the above-mentioned anthracene-substituted and / or triarylamine-substituted pyrazoline structure, in order to better exhibit a synergistic effect, in structural formula A1 representing the above-mentioned alkali-soluble resin, x is 15-35 wt%, z is 0-50 wt%, u is 0-80 wt%, y is 0-25 wt%, and the value of z+u is 40 wt%-80 wt%, which helps to further improve the photosensitivity, resolution, sensitivity and resist pattern stability of the dry film resist. When using the dry film resist system, preferably, the copolymer unit of (A) the alkali-soluble resin is one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, N,N-dimethyl(meth)acrylate, N,N-diethyl(meth)acrylate, N,N-diethyl(meth)acrylate, propyl (meth)acrylate, and N,N-dimethyl(meth)acrylate, and N,N-diethyl(meth)acrylate. Preferably, the weight-average molecular weight of the alkali-soluble resin is 30,000 to 80,000, and the molecular weight distribution is 1.3 to 2.5. A narrow molecular weight distribution helps to improve the resolution of the dry film resist.

[0093] When the sensitizer in the dry film resist contains a compound represented by the above structural formula I or II, in order to further improve the overall performance of the dry film resist, in structural formula A1 representing the alkali-soluble resin, R3 is hydrogen, x is 15-40 wt%, z is 0-40 wt%, u is 0, and y is 20-60 wt%. When using the dry film resist system, preferably, (A) the copolymerization unit of the alkali-soluble resin contains an alkyl methacrylate, for example, one selected from alkyl methacrylate and styrene and / or its derivatives, and the alkyl methacrylate is methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, isooctyl methacrylate, lauryl methacrylate, stearyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate The copolymer units of the alkali-soluble resin are one or more selected from roxypropyl, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, ethyl N,N-dimethyl(meth)acrylate, ethyl N,N-diethyl(meth)acrylate, propyl N,N-diethyl(meth)acrylate, butyl N,N-dimethyl(meth)acrylate, and butyl N,N-diethyl(meth)acrylate. The copolymer units of the alkali-soluble resin contain styrene or its derivatives, preferably one or more styrene derivatives selected from α-methylstyrene and benzyl (meth)acrylate. When benzyl (meth)acrylate is selected as the copolymer unit, styrene copolymer units may be omitted. Compared to styrene derivatives, styrene is more effective as a copolymer monomer, and in some preferred examples of this application, the styrene content in the copolymer units of the alkali-soluble resin is 0 to 40 wt% of the total weight of the copolymer units. Preferably, the weight-average molecular weight of the alkali-soluble resin is 30,000 to 80,000, and the molecular weight distribution is 1.3 to 2.5. A narrow molecular weight distribution helps to improve the resolution of the dry film resist.

[0094] When the dry film resist of this application contains a copper complex, in order to further exhibit the synergistic effect between each component, in the structural formula A1 representing the alkali-soluble resin (A) above, R3 is hydrogen, x is 15-40 wt%, z is 0-40 wt%, u is 0, and y is 20-70 wt%, that is, the alkali-soluble resin (A) is obtained by copolymerizing (meth)acrylic acid, (meth)acrylate and styrene or a derivative of styrene, preferably the above (meth)acrylate may be an alkyl (meth)acrylate ester, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, (meth)acrylic acid The material is one or more of the following: isopropyl, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, N,N-dimethyl(meth)acrylate, N,N-diethyl(meth)acrylate, N,N-diethyl(meth)acrylate, propyl (meth)acrylate, N,N-dimethyl(meth)acrylate, and N,N-diethyl(meth)acrylate. The weight-average molecular weight of the alkali-soluble resin is 50,000 to 120,000, and the molecular weight distribution is 1.3 to 2.5. A narrow molecular weight distribution is useful for improving the resolution of dry film resists.

[0095] To further improve resolution and adhesion, and to enhance properties such as the pattern shape of the dry film resist, the additive components of the dry film resist may further contain a free radical polymerization inhibitor, from the viewpoint of suppressing polymerization of unexposed areas during resist pattern formation. From the viewpoint of the manufacturing process, the additives of the present invention may further contain one or more of the following: colorants, dyes, plasticizers, photothermal stabilizers, adhesion promoters, leveling agents, and defoamers, and may be in the same proportions as in the prior art. Preferably, the content of the above additives is 0.5 to 5.0 parts by weight.

[0096] The above free radical polymerization inhibitors may be selected from the prior art, for example, p-methoxyphenol, 4-ethyl-6-tert-butylphenol, nitrosophenylhydroxyamine aluminum salt, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, catechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, resorcinol, 2-methylresorcinol, 4-methyl re It is one or more selected from sorcinol, 5-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol, 1,4-hydroquinone, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, pyrogallol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxy, and 2,2-methylenebis(4-methyl-6-tert-butylphenol). In some embodiments of this application, the content of the free radical polymerization inhibitor is 0.001 wt% to 0.005 wt% of the total weight of the dry film resist. If the amount added is too low, the resolution of the resulting dry film resist is insufficient, and if the amount added is too high, the photosensitivity of the dry film resist is not very good.

[0097] Another typical embodiment of the present application provides a photosensitive dry film comprising a dry film resist layer and support and protective layers located on both sides of the dry film resist layer, wherein the dry film resist layer comprises any of the above-described dry film resists.

[0098] The photosensitive dry film of this invention uses a dry film resist that has high photosensitivity, high resolution, and more stable characteristics in terms of sensitivity, resist pattern, and other aspects. Therefore, it has superior performance in terms of photosensitivity, resolution, and stability, making it suitable for the manufacture of high-end PCBs such as carrier boards and substrate-like PCBs. It can improve the yield rate, significantly improve the production efficiency of components such as ITO in PCB manufacturing, lead frame manufacturing, semiconductor packaging, and flat panel display fields, and reduce manufacturing costs.

[0099] The photosensitive dry film of this invention uses an imaging-type dry film resist produced by direct writing exposure, which has high photosensitivity and high resolution, and is highly adaptable to alignment recognition in different types of LDI exposure machines. Therefore, it has good photosensitivity, resolution and alignment accuracy, and can be used in different types of LDI exposure machines to achieve excellent overall performance, including superior alignment recognition adaptability. This improves the yield rate and significantly enhances the production efficiency of components such as ITO in PCB manufacturing, lead frame manufacturing, semiconductor packaging, and flat panel display fields, thereby reducing manufacturing costs.

[0100] In one typical embodiment of the present application, a dry film resist is provided, which comprises (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (E) a copper complex, wherein the compound that forms a complex with copper in the copper complex comprises a nitrogen-containing heterocyclic compound, the photopolymerizable monomer contains an EO segment and a PO segment, the EO segment represents an oxyethylene group, and the PO segment represents an oxypropylene group, and the above-mentioned EO segment and PO segment may be derived from one or more specific photopolymerizable monomers that simultaneously contain the EO segment and the PO segment, or a photopolymerizable monomer containing the EO segment and the PO segment may be blended, or a photopolymerizable monomer containing the EO segment and the PO segment in different ratios may be blended.

[0101] The dry film resist contains a complex formed between a nitrogen-containing heterocyclic compound and copper. On the one hand, because the nitrogen-containing heterocyclic structure is highly polar, the copper complex can enhance the interaction with metallic copper. On the other hand, the lone pair of electrons of the nitrogen atom can form a coordinate bond with the copper atom, and the formation of such a coordinate chemical bond can further improve the bonding strength between the compound and the copper atom. Due to these two effects, the addition of the above copper complex significantly strengthens the bonding strength of the dry film resist to the copper surface, improving the phenomenon of slight warping of the bottom sidewall during the electroplating process of the dry film, thereby improving the electroplating resistance of the dry film resist.

[0102] Furthermore, the photopolymerizable monomer in the above-mentioned dry film resist contains both a hydrophilic functional group ethylene oxide (EO) and a hydrophobic functional group propylene oxide (PO). On the one hand, if the photopolymerizable monomer contains a hydrophilic functional group ethylene oxide (EO) segment, the water solubility of the dry film resist can be improved, thereby improving the developability and resolution of the dry film resist. On the other hand, if the photopolymerizable monomer contains only an ethylene oxide segment, the water solubility of the dry film resist is improved, but in the dry film resist, swelling can easily cause warping of the sidewalls of the dry film, leading to the harmful issue of cementation. However, by adding a hydrophobic functional group propylene oxide (PO) segment to the photopolymerizable monomer, the hydrophobicity of the dry film resist can be improved to some extent, thereby improving the electroplating resistance of the dry film resist. Moreover, the photopolymerizable monomer has a good balance of hydrophilicity and hydrophobicity in the dry film resist due to its chemical structure, thereby making it possible to obtain a dry film resist photosensitive material with balanced developability, analytical ability and electroplating resistance.

[0103] For specific selections of (A) alkali-soluble resin, (B) photopolymerizable monomer, (C) photopolymerization initiator, and (E) copper complex in the dry film resist described above, refer to the content described above in this application. In some preferred embodiments of this application, the overall performance of the dry film resist is good when the dry film resist contains, on a weight basis, 40 to 65 parts by weight of (A) alkali-soluble resin, 35 to 60 parts by weight of (B) photopolymerizable monomer, 2.0 to 4.5 parts by weight of (C) photopolymerization initiator, and 0.01 to 0.5 parts by weight of (E) copper complex. Preferably, the dry film resist may further contain 0.01 to 0.5 parts by weight of (D) sensitizer, and preferably, (D) sensitizer has one or more of the structures represented by structural formula I or II. [ka] [ka] In each of the formulas, R0 is independently hydrogen, halogen, C1-C8 alkyl group, or C1-C4 alkoxy group; the modified functional group M1 in structural formula I is independently biphenyl, fused ring functional group, or electron-rich heterocycle, fused heterocycle, or C1-C4 alkoxy group, or a benzene ring having an amino group; the modified functional group M2 in structural formula II is selected from biphenyl, fused ring functional group, or electron-rich heterocycle, fused heterocycle, or a benzene ring having a C1-C4 alkoxy group, or an amino group, or a substituted phenyl group having a C1-C4 alkoxy group; the modified functional group W is either a benzene ring or a fluorene ring, or a benzene ring, biphenyl ring, or fluorene ring having one or more substituents from halogen, C1-C8 alkyl group, or C1-C4 alkoxy group. In the above modified functional groups M1 and M2, the biphenyl functional group represents biphenyl or a derivative thereof, and the corresponding fused ring functional group and electron-rich heterocycle, fused heterocycle functional group represents the corresponding functional group or a derivative thereof. The type of derivative of the above functional group may be any type that is common in the art, for example, containing substituents such as halogens, C1-C8 alkyl groups, or C1-C4 alkoxy groups.

[0104] The above-mentioned sensitizer is a pyrazoline-based compound into which several modified functional groups, such as electron-donating substituents like benzene rings, fused ring functional groups, or electron-rich heterocycles or fused heterocycle compounds, are introduced. As a result, the overall molecular structure is an electron-rich conjugated system. This electron-rich conjugation effect helps to promote the redshift of the sensitizer's absorption spectrum, extending its absorption spectrum to the visible light region. Since the absorption wavelength is closer to the wavelength of the 405 nm exposure light source, it is more sensitive to this exposure light source, thereby improving the photosensitivity of the dry film resist to the LDI 405 nm exposure light source.

[0105] Preferably, the modified functional group M1 is a condensed ring functional group comprising one or more C1-C4 alkoxy groups, amino groups, or alkyl groups independently, or one of furan, thiophene, indole, thiazole, benzofuran, benzothiazole, indene, anthracene, acridine, or aromatic amine. More preferably, the specific structural formulas of the modified functional groups M1 and / or M2 are: [ka] Includes, During the ceremony, [ka] is the bonding position of the functional group, and optionally, the benzene ring, biphenyl ring, fused ring, or heterocycle in the specific structural formula of the modified functional group M1 and / or M2 contains one or more substituents from among halogens, C1-C8 alkyl groups, and C1-C4 alkoxy groups, preferably the substituent is located at the para position.

[0106] Furthermore, the applicant conducted numerous studies and tests and found the following: When using the above-mentioned sensitizer, the overall performance of the dry film resist, particularly its resistance to electroplating, is good when the weight ratio of the sensitizer to the copper complex is in the range of 30:1 to 1:50. For example, the weight ratios of the sensitizer to the copper complex are 20:1, 10:1, 5:1, 2:1, 1:1, 1:5, 1:10, and 1:20.

[0107] In another typical embodiment of the present application, a photosensitive dry film is provided, the photosensitive dry film comprising a dry film resist layer and support and protective layers located on both sides of the dry film resist layer, wherein the dry film resist layer contains one of the dry film resists described above. Since the dry film resist contains a complex formed by a nitrogen-containing heterocyclic compound and copper, on the one hand, because the nitrogen-containing heterocyclic structure is highly polar, the copper complex can increase the interaction force with metallic copper, and on the other hand, the lone pair of electrons of the nitrogen atom can form a coordinate bond with the copper atom, and the formation of such a coordinate chemical bond can further improve the bonding force between such a compound and the copper atom. Due to both of these effects, the addition of the copper complex can significantly strengthen the bonding force of the dry film resist to the copper surface, improving the phenomenon of slight warping of the bottom sidewall during the electroplating process of the dry film, thereby improving the electroplating resistance of the dry film resist.

[0108] In yet another typical embodiment of the present invention, a copper-clad laminate is provided, wherein one of the above-described dry film resists is provided on the copper-clad laminate. Because the copper-clad laminate of the present invention is provided with the above-described dry film resist having good electroplating resistance, it has good electroplating resistance and can improve the yield rate of the product manufacturing process.

[0109] The beneficial effects that can be achieved with this application will be further explained below with reference to examples and comparative examples.

[0110] The synthesis method for the sensitizer compound is as follows:

[0111] Synthesis of sensitizer compound D-1: In a 500 mL three-necked flask, the starting materials 9-anthracene carboxyaldehyde (62 g), acetone (7 g), and ethanol (150 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 120 g of 10% NaOH aqueous solution was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was allowed to react for 8 hours while continuing to stir at room temperature. The reaction was monitored by placing a drop on a TLC plate, and stopped when there was no further change in the reaction. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (100 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 1 (49 g, purity 91%) shown in the following reaction structural formula.

[0112] In a 500 mL three-necked flask, intermediate compound 1 (49 g) and glacial acetic acid (150 g) were added, and the mixture was stirred in an oil bath and raised to 50°C. At 50°C, phenylhydrazine (22 g) was slowly added dropwise, and the addition was continued for 1 hour. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (200 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected, dried in a rotary evaporator to remove the small amount of solvent contained in the solid, and sensitizer compound D-1 (44 g, purity 95%), shown in the following reaction structural formula, was obtained.

[0113] The specific reaction structure I is shown below. [ka]

[0114] The structure of the sensitizer compound shown above is merely illustrative; however, the anthracene ring may have substituents such as halogens, alkyl groups with carbon chain lengths of C1 to C8, or alkoxy groups with carbon chain lengths of C1 to C4, and the number of substituents may be one or one to five.

[0115] Synthesis of sensitizer compound D-2: In a 250 mL three-necked flask, the starting materials 2-acetylfluorene (21.8 g), 9-anthracene carboxaldehyde (20.6 g), and ethanol (100 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 3 mol / L aqueous NaOH solution (66 mL) was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was continued to stir at room temperature for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and the reaction was stopped when the starting material p-anisaldehyde was completely consumed. The suspended substance obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (100 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 2 (36 g, purity 90%), shown by the following reaction structural formula.

[0116] In a 250 mL three-necked flask, intermediate compound 2 (36 g) and glacial acetic acid (100 g) were added, and the mixture was stirred in an oil bath and raised to 50°C. At 50°C, phenylhydrazine (19 g) was slowly added dropwise, and the addition was continued for 30 minutes. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (150 mL), and the resulting suspension was stirred at room temperature for 30 minutes. After that, it was filtered by suction under reduced pressure, and the resulting crude solid product needed further purification. It was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, filtered by suction, and the solid was collected. After drying in a rotary evaporator to remove the small amount of solvent contained in the solid, sensitizer compound D-2 (28 g, purity 96%), shown in the following reaction structural formula, was obtained.

[0117] The specific reaction structure II is shown below. [ka]

[0118] The structure of the sensitizer compound shown above is merely illustrative; however, the anthracene ring and fluorene ring may have substituents such as halogens, alkyl groups with carbon chain lengths of C1 to C8, or alkoxy groups with carbon chain lengths of C1 to C4, and the number of substituents may be one or one to five.

[0119] Synthesis of sensitizer compound D-3: In a 250 mL three-necked flask, the starting materials acetophenone (12.6 g), 9-anthracene carboxaldehyde (20.6 g), and ethanol (100 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 3 mol / L aqueous NaOH solution (66 mL) was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was continued to stir at room temperature for 8 hours. The reaction was monitored by adding one drop at a time to a TLC plate, and the reaction was stopped when the starting material p-anisaldehyde was completely consumed. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (100 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 3 (24 g, purity 91%), shown by the following reaction structural formula.

[0120] In a 250 mL three-necked flask, intermediate compound 3 (24 g) and glacial acetic acid (100 g) were added, and the mixture was stirred in an oil bath and raised to 50°C. At 50°C, phenylhydrazine (15 g) was slowly added dropwise, and the addition was continued for 20 minutes. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (150 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected, dried in a rotary evaporator to remove the small amount of solvent contained in the solid, and sensitizer compound D-3 (19 g, purity 97%), shown in the following reaction structural formula, was obtained.

[0121] The specific reaction structure III is shown below. [ka]

[0122] The structure of the sensitizer compound shown in the above formula is merely illustrative; however, the benzene ring and anthracene ring may have substituents such as halogens, alkyl groups with carbon chain lengths of C1 to C8, or alkoxy groups with carbon chain lengths of C1 to C4, and the number of substituents may be one or one to five.

[0123] Synthesis of sensitizer compound D-4: In a 250 mL three-necked flask, the starting materials 4-acetylbiphenyl (20.5 g), 9-anthracene carboxaldehyde (20.6 g), and ethanol (100 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 3 mol / L aqueous NaOH solution (66 mL) was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was stirred at room temperature and allowed to react for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and the reaction was stopped when the starting material p-anisaldehyde was completely consumed. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (100 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 4 (32 g, purity 92%), shown by the following reaction structural formula.

[0124] In a 250 mL three-necked flask, intermediate compound 4 (32 g) and glacial acetic acid (100 g) were added, and the mixture was stirred in an oil bath and raised to 50°C. At 50°C, phenylhydrazine (17 g) was slowly added dropwise, and the addition was continued for 20 minutes. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (150 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected, dried in a rotary evaporator to remove the small amount of solvent contained in the solid, and sensitizer compound D-4 (26 g, purity 96%), shown in the following reaction structural formula, was obtained.

[0125] The specific reaction structure IV is shown below. [ka]

[0126] The structure of the sensitizer compound shown in the above formula is merely illustrative; however, the biphenyl ring and anthracene ring may have substituents such as halogens, alkyl groups with carbon chain lengths of C1 to C8, or alkoxy groups with carbon chain lengths of C1 to C4, and the number of substituents may be one or one to five.

[0127] Synthesis of sensitizer compound D-5: In a 250 mL three-necked flask, the starting materials 2'-acetonaphthone (17.8 g), 4-(N,N-diphenylamino)benzaldehyde (27.3 g), and ethanol (100 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 3 mol / L aqueous NaOH solution (66 mL) was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was continued to stir at room temperature for 8 hours. The reaction was monitored by adding one drop at a time to a TLC plate, and the reaction was stopped when the starting material p-anisaldehyde was completely consumed. The suspension obtained from the reaction was filtered by suction under reduced pressure, and the resulting crude solid product was dispersed in a small amount of ethanol (100 mL). After stirring at room temperature for 30 minutes, intermediate product compound 5 (30 g, purity 91%), shown in the reaction structural formula, was obtained.

[0128] In a 250 mL three-necked flask, intermediate compound 5 (30 g) and glacial acetic acid (100 g) were added, and the mixture was stirred in an oil bath and raised to 50°C. At 50°C, phenylhydrazine (14.7 g) was slowly added dropwise, and the addition was continued for 20 minutes. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (150 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected, dried in a rotary evaporator to remove the small amount of solvent contained in the solid, and sensitizer compound D-5 (33 g, purity 95%), shown in the following reaction structural formula, was obtained.

[0129] The specific reaction structure V is shown below. [ka]

[0130] The structure of the sensitizer compound shown in the above formula is merely illustrative; however, the naphthalene ring and benzene ring may have substituents such as halogens, alkyl groups with carbon chain lengths of C1 to C8, or alkoxy groups with carbon chain lengths of C1 to C4, and the number of substituents may be one or one to five.

[0131] Synthesis of sensitizer compound D-6: In a 250 mL three-necked flask, the starting materials 3-acetylthiophene (13.2 g), 4-(N,N-diphenylamino)benzaldehyde (27.3 g), and ethanol (100 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 3 mol / L aqueous NaOH solution (66 mL) was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was continued to stir at room temperature for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and the reaction was stopped when the starting material p-anisaldehyde was completely consumed. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (100 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 6 (26 g, purity 90%), shown by the following reaction structural formula.

[0132] In a 250 mL three-necked flask, intermediate compound 6 (26 g) and glacial acetic acid (100 g) were added, and the mixture was stirred in an oil bath and raised to 50°C. At 50°C, phenylhydrazine (14 g) was slowly added dropwise, and the addition was continued for 20 minutes. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (150 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected, dried in a rotary evaporator to remove the small amount of solvent contained in the solid, and sensitizer compound D-6 (21 g, purity 96%), shown in the following reaction structural formula, was obtained.

[0133] The specific reaction structure VI is shown below. [ka]

[0134] The structure of the sensitizer compound shown in the above formula is merely illustrative; however, the benzene ring and heterocycle may have substituents such as halogens, alkyl groups with carbon chain lengths of C1 to C8, or alkoxy groups with carbon chain lengths of C1 to C4, and the number of substituents may be one or one to five.

[0135] Synthesis of sensitizer compound D-7: In a 500 mL three-necked flask, the starting materials 4-(N,N-diphenylamino)benzaldehyde (49.6 g), acetone (5.8 g), and ethanol (150 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 160 g of 10% NaOH aqueous solution was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was stirred at room temperature and allowed to react for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and stopped when there was no further change in the reaction. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 7 (41 g, purity 91%), shown by the following reaction structural formula.

[0136] In a 500 mL three-necked flask, intermediate compound 7 (41 g) and glacial acetic acid (150 g) were added and stirred in an oil bath, raising the temperature to 50°C. At 50°C, phenylhydrazine (16 g) was slowly added dropwise, continuing for 1 hour. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (200 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected and dried in a rotary evaporator to remove the small amount of solvent contained in the solid, yielding sensitizer compound D-7 (34 g, purity 95%), shown in the following reaction structural formula.

[0137] The specific reaction structure VII is shown below. [ka]

[0138] The structure of the sensitizer compound shown in the above formula is merely illustrative; however, the benzene ring may have substituents such as halogens, alkyl groups with carbon chain lengths of C1 to C8, or alkoxy groups with carbon chain lengths of C1 to C4, and the number of substituents may be one or one to five.

[0139] The components were mixed in the predetermined ratios according to the formulations in Tables 1 and 2 below, and 60 parts by weight of solvent were added. However, suitable solvents for preparing the coating adhesive solution may be acetone, butanone, methanol, ethanol, isopropyl alcohol, toluene, etc. The mixture was then stirred thoroughly to completely dissolve the components and a resin composition solution with a solid content of 40% was prepared. After standing for 30 minutes to allow for thorough degassing, the solution was uniformly coated onto the surface of a 16 μm thick PET support film using a coating apparatus and dried in a 90°C oven for 10 minutes to form a 25 μm thick dry film resist layer, which showed a blue-green color under a yellow lamp. Next, a 20 μm thick polyethylene thin film protective layer was applied to the surface to obtain a three-layer photosensitive dry film. [Table 1] [Table 2]

[0140] Here, the alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, sensitizer, and additive are as follows: A-1: Methacrylic acid:Methyl methacrylate:Styrene:Benzyl methacrylate = 25:15:40:20, the acid value was 163 mgKOH / g, the weight-average molecular weight measured by GPC was 50000 g / mol, the molecular weight distribution (PID) was 1.8, and the conversion rate was 97.0%. A-2: Methacrylic acid:Methyl methacrylate:Styrene:Benzyl methacrylate = 25:15:40:20, the acid value was 163 mgKOH / g, the weight-average molecular weight measured by GPC was 100,000 g / mol, the molecular weight distribution (PID) was 2.0, and the conversion rate was 97.0%. A-3: Methacrylic acid:Methyl methacrylate:Styrene = 25:50:25, the acid value was (120~250) mgKOH / g, the weight-average molecular weight measured by GPC was 50000 g / mol, the molecular weight distribution (PID) was 2.0, and the conversion rate was 95%. B-1:(4) Ethoxybisphenol A diacrylate (Miwon Chemicals), and in the corresponding photopolymerizable monomer structural formula B1, n1+n2=0, m1+m2=4, and R1 is CH3. B-2: (10) Ethoxybisphenol A diacrylate (Miwon Chemicals), and in the corresponding photopolymerizable monomer structural formula B1, n1+n2=0, m1+m2=10, and R1 is CH3. B-3:(6) Ethoxypolypropylene glycol (700) dimethacrylate (Miwon Chemicals), and in the corresponding photopolymerizable monomer structural formula B3, b2=12, a2+c2=6, and R1 is CH3. B-4:(3) Ethoxylated trimethylolpropane trimethacrylate (Miwon Chemicals), and in the corresponding photopolymerizable monomer structural formula B4, a3=1 and R1=CH3. B-5: (4) Ethoxylated nonylphenol methacrylate (Miwon Chemicals). C-1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (BCIM, Changzhou Strong Electronic Materials). C-2: Benzoyldimethyl ether (also known as α,α-dimethoxy-α-phenylacetophenone, Shanghai McLin Biochemical Materials Co., Ltd.). D-1 is 1-phenyl-3-(9-anthracenylvinyl)-5-(9-anthracenyl)pyrazoline; see synthesis example D-1. D-2 is 1-phenyl-3-(2-fluorenyl)-5-(9-anthracenyl)pyrazoline; see synthesis example D-2. D-3 is 1-phenyl-3-phenyl-5-(9-anthracenyl)pyrazoline; see synthesis example D-3. D-4 is 1-phenyl-3-biphenyl-5-(9-anthracenyl)pyrazoline; see synthesis example D-4. D-5 is 1-phenyl-3-(2-naphthyl)-5-(4-dianilinophenyl)pyrazoline; see synthesis example D-5. D-6 is 1-phenyl-3-(3-thienyl)-5-(4-dianilinophenyl)pyrazoline; see synthesis example D-6. D-7 is 1-phenyl-3-(4-dianilinophenylvinyl)-5-(4-dianilinophenyl)pyrazoline; see Synthesis Example D-7. D-8: 9,10-Dibutoxyanthracene (DBA). D-9: 1-phenyl-3-(4-methoxy-styryl)-5-(4-methoxy-phenyl)pyrazoline (sensitizer represented by formula (1) reported in patent CN104111583, R = methoxy group). F-1: 4-tert-butylcatechol. F-2: Dye Brilliant Green (Shanghai Bailingwei Chemical Technology Co., Ltd.). F-3: Leucocrystal violet (Shanghai Bailingwei Chemical Technology Co., Ltd.). F-4: p-toluenesulfonamide (Shanghai Tixiai Chemical).

[0141] The following describes the methods for preparing the samples for Examples 1-14 and Comparative Examples 1-3 (including film application, exposure, development, and electrolytic copper plating), the methods for evaluating the samples, and the evaluation results.

[0142] (1) Method for preparing samples (Film application) The copper surface of the copper-clad laminate was polished using a grinder, washed with water, wiped clean, and a bright and novel copper surface was obtained. The press roller temperature of the film laminator was set at 110 °C and the conveying speed was set at 1.5 meters per minute. After removing the surface PE protective film from the photosensitive dry film obtained from the above examples and comparative examples, it was thermally attached to the copper-clad laminate under standard pressure to obtain a sample with the film attached.

[0143] (Exposure) The sample with the film attached was allowed to stand for 15 minutes or more. For resolution and adhesion performance, it was exposed using a laser direct imaging (LDI) exposure machine with a wavelength of 405 nm of model IP-6 manufactured by Adtec Japan, and a photosensitivity test was conducted using a stouffer 41-step exposure scale, and the exposure grid count was set to 13 - 17 grids.

[0144] (Development) The exposed sample was allowed to stand for 15 minutes or more. The development temperature was 30 °C, the pressure was 1.2 Kg / cm 2 and the developer was a 1%wt aqueous sodium carbonate solution. The development time was 1.5 - 2.0 times the minimum development time. After development, it was washed with water and dried. The minimum time required for the resist layer in the unexposed part to completely dissolve was defined as the minimum development time.

[0145] (Etching) An etching process was performed on the copper plate after development. The etching solution was copper chloride, the etching speed was 1.0 meter per minute, the etching temperature was 48 °C, the spray pressure was 1.5 bar, the specific gravity was 1.3 g / mL, the acidity was 2 mol / L, the copper ion was 140 g / L, and the etching machine was model GL181946 manufactured by Dongguan Cosmos.

[0146] (Film stripping) The film stripping solution was NaOH, the concentration was 3.0 wt%, the temperature was 50 °C, the pressure was 1.2 Kg / cm 2 and the film stripping time was 1.5 - 2.0 times the minimum film stripping time. After film stripping, it was washed with water and dried.

[0147] (2) Evaluation method (Sensitivity evaluation) The film-attached sample was left to stand for at least 15 minutes, then exposed using an Adtec IP-6 405nm LDI exposure machine. Sensitivity testing was performed using a Stuffer 41-step exposure scale. After exposure, a 1wt% sodium carbonate aqueous solution was sprayed at 30°C, and the development time was 2.0 times the minimum development time. In this way, the unexposed areas were removed. Through this process, a cured film consisting of cured products of each component of the dry film resist was formed on the copper surface of the substrate. The exposure amount (mJ / cm²) when the remaining number of steps on the step exposure tablet for the obtained cured film reached 15 was measured. 2 The sensitivity of the photosensitive resin composition was evaluated using the following method. A smaller value indicates better sensitivity.

[0148] Criteria: ○: 20-30 mJ / cm² 2 Δ: 30~50 mJ / cm 2 ×:>50mJ / cm 2 .

[0149] (Resolution evaluation) The mask has a wiring pattern with a 1:1 width ratio between exposed and unexposed areas. After exposure and development for twice the minimum development time, the minimum mask width for which the cured resist line was formed normally is defined as the resolution value. The mask is then observed with a 2D imager or scanning electron microscope (SEM), and a smaller reading indicates better resolution.

[0150] (Evaluation of adhesion strength) A photosensitive dry film resist is laminated onto a copper plate by hot pressing. The plate is then exposed to a mask with a wiring pattern where the width of the exposed and unexposed areas is n:400, with a corresponding sensitivity of 15. After development for twice the minimum development time, the plate is observed with a magnifying glass. The minimum mask width at which a completely cured resist line is formed is defined as the adhesion strength value, and a smaller reading indicates better adhesion.

[0151] (Evaluation of the side profile) After removing the PE film from the fabricated photosensitive dry film resist, the dry film was laminated onto a copper plate using a heated press roller. The resist was then exposed using a mask with a wiring pattern where the width of the exposed and unexposed areas was n:400. The exposure energy was the corresponding sensitivity of 15, and the resist was developed for 2.0 times the minimum development time. After developing, a dry film image was obtained, and a side view of the dry film with a line width of 15 μm was captured using a scanning electron microscope (SEM) at 1000x magnification.

[0152] Criteria: ○: The cross-section of the leading edge of the dry film is rectangular. Δ: The cross-section of the leading edge of the dry film is slightly inverted trapezoidal. ×: The cross-section of the leading edge of the dry film is severely inverted, or the bottom is gouged out, or there are obvious cracks on the side walls.

[0153] (Initiator transfer evaluation) A dry film resist with a polyethylene thin film protective layer attached to its surface was left to stand at 30°C for 48 hours. After removing the polyethylene thin film protective layer from the surface of the resist, the ultraviolet absorption spectrum of the polyethylene thin film protective layer was detected using an ultraviolet-visible spectrophotometer, and the detected wavelength was 380-450 nm.

[0154] Criteria: ○: In the corresponding ultraviolet absorption spectrum, no clear absorption peak is observed at wavelengths of 380-450 nm. Δ: In the corresponding ultraviolet absorption spectrum, there is a weak absorption peak at wavelengths of 380-450 nm, and the molar extinction coefficient of the maximum absorption peak is less than 0.01. ×: In the corresponding ultraviolet absorption spectrum, there is a clear absorption peak at wavelengths of 380-450 nm, and the molar extinction coefficient of the maximum absorption peak is greater than 0.01.

[0155] (3) Refer to Tables 3 and 4 for the results of the characterization evaluation, including sensitivity, resolution, adhesion, lateral shape, and initiator migration.

Table 3

Table 4

[0156] As can be seen from the comparison between Examples 1 to 14 and Comparative Examples 1 to 3, in the case of the examples, in each case, dry film resists suitable for manufacturing high-end PCBs such as carrier boards and substrates like PCBs were obtained, with excellent comprehensive performance in terms of sensitivity, resolution, adhesion performance, side surface morphology, migration of initiators, etc.

[0157] In Comparative Example 1, the initiator system is a combination of a hexaaryl bisimidazole derivative and an anthracene-based (DBA), and this initiator system is a commonly used initiator system in the production of dry film resists for high-end PCBs such as carrier boards and substrates like PCBs. When the addition amount of DBA is equivalent to the sensitizer in the examples, the sensitivity of the corresponding dry film resist is very low, and there are harmful matters such as the migration of DBA to the polyethylene protective film.

[0158] In Comparative Example 2, based on Comparative Example 1, the addition amount of DBA was further increased, and the sensitivity was improved, but the migration of DBA to the polyethylene protective film became more prominent.

[0159] In Comparative Example 3, a normal pyrazoline compound reported in the patent was used. Although the sensitivity is good, when using this initiator system, even when a high-resolution alkali-soluble resin and a photopolymerizable monomer are combined, the resolution ability and adhesion ability of the corresponding dry film resist are still not very good, and the performance requirements of the dry film resist are not met in the production of high-end PCBs such as carrier boards and substrates like PCBs.

[0160] As can be seen from the above description, the above embodiments of the present invention achieve the following technical effects. By introducing a pyrazoline structure to anthracene and triarylamine, the structure is optimized for anthracene-based and triarylamine-based sensitizers commonly used in dry film resists for high-end PCBs such as carrier boards and substrate-like PCBs. Because the imidazoline compound has good photosensitivity, its photosensitivity to an LDI 405nm laser light source is higher than that of anthracene-based and triarylamine-based sensitizers. The modified sensitizer compounds of the present invention generally have a large π-conjugated structure, and due to this large π-conjugated electron effect, the maximum absorption wavelength of the modified sensitizer compound shifts towards the red, getting closer to the wavelength of the 405nm laser light source. Therefore, by introducing a pyrazoline structure to specific anthracene and triarylamine molecules, the present invention can clearly improve the photosensitivity of the obtained dry film resist to an LDI 405nm laser light source.

[0161] In this invention, the sensitizer compound obtained through optimization modification contains both a pyrazoline ring structure and an anthracene or triarylamine structure in its structure. Therefore, the sensitizer compound after optimization modification has a dual active functional group, and the photosensitivity of the pyrazoline structure and the high-precision resolving ability of the anthracene or triarylamine structure are effectively combined. As a result, the obtained dry film resist has high-precision resolving ability, and the production efficiency of clients who manufacture high-end PCBs such as carrier boards and substrate-like PCBs can be improved.

[0162] Synthesis of sensitizer compound D-21: In a 500 mL three-necked flask, the starting materials 4-acetylbiphenyl (117 g), p-anisaldehyde (68 g), and ethanol (200 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 40 g of 40% aqueous NaOH solution was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was continued to stir at room temperature for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and the reaction was stopped when the starting material p-anisaldehyde was completely consumed. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 21 (145 g, purity 92%) shown in the following reaction structural formula.

[0163] In a 500 mL three-necked flask, intermediate compound 21 (145 g) and glacial acetic acid (300 g) were added, and the mixture was stirred in an oil bath and raised to 50°C. At 50°C, phenylhydrazine (95 g) was slowly added dropwise, and the addition was continued for 1 hour. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (300 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected, dried in a rotary evaporator to remove the small amount of solvent contained in the solid, and sensitizer compound D-21 (122 g, purity 95.5%), shown in the following reaction structural formula, was obtained.

[0164] The specific reaction structure is shown below. [ka]

[0165] The sensitizer compound structure shown in the above formula is merely illustrative; however, the benzene ring and biphenyl ring may have substituents such as halogens, C1-C8 alkyl groups, or C1-C4 alkoxy groups, and the number of substituents may be one or one to five.

[0166] Synthesis of sensitizer compound D-22: In a 1000 mL three-necked flask, the starting materials p-anisaldehyde (182 g), acetone (29 g), and ethanol (300 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 10% NaOH aqueous solution (480 g) was added dropwise to the flask for 2 hours. After the addition was complete, the mixture was stirred at room temperature and allowed to react for 8 hours. The reaction was monitored by placing a drop on a TLC plate, and stopped when there was no further change in the reaction. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 22 (180 g, purity 90%), shown by the following reaction structural formula.

[0167] In a 500 mL three-necked flask, intermediate compound 22 (120 g) and glacial acetic acid (300 g) were added, and the mixture was stirred in an oil bath and raised to 50°C. At 50°C, phenylhydrazine (55 g) was slowly added dropwise, and the addition was continued for 1 hour. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (300 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected, dried in a rotary evaporator to remove the small amount of solvent contained in the solid, and the sensitizer compound D-22 (101 g, purity 96%) shown in the following reaction structural formula was obtained.

[0168] The specific reaction structure is shown below. [ka]

[0169] The sensitizer compound structure shown in the above formula is merely illustrative; however, the benzene ring and biphenyl ring may have substituents such as halogens, C1-C8 alkyl groups, or C1-C4 alkoxy groups, and the number of substituents may be one or one to five.

[0170] Synthesis of sensitizer compound D-23: In a 500 mL three-necked flask, the starting materials acridine-9-carbaldehyde (124 g), acetone (14 g), and ethanol (200 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 10% NaOH aqueous solution (240 g) was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was stirred at room temperature and allowed to react for 8 hours. The reaction was monitored by placing a drop on a TLC plate, and stopped when there was no further change in the reaction. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 23 (94 g, purity 91%), shown by the following reaction structural formula.

[0171] In a 500 mL three-necked flask, intermediate compound 23 (80 g) and glacial acetic acid (200 g) were added, and the mixture was stirred in an oil bath and raised to 50°C. At 50°C, phenylhydrazine (34 g) was slowly added dropwise, and the addition was continued for 1 hour. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting materials were completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (200 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected, dried in a rotary evaporator to remove the small amount of solvent contained in the solid, and sensitizer compound D-23 (57 g, purity 95%), shown in the following reaction structural formula, was obtained.

[0172] The specific reaction structure is shown below. [ka]

[0173] The sensitizer compound structure shown in the above formula is merely illustrative; however, the benzene ring and acridine ring may have substituents such as halogens, C1-C8 alkyl groups, or C1-C4 alkoxy groups, and the number of substituents may be one or one to five.

[0174] Synthesis of sensitizer compound D-24: In a 500 mL three-necked flask, the starting materials 2-acetylfluorene (62 g), p-anisaldehyde (34 g), and ethanol (200 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 40% NaOH aqueous solution (20 g) was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was continued to stir at room temperature for 8 hours. The reaction was monitored by adding one drop at a time to a TLC plate, and the reaction was stopped when the starting material p-anisaldehyde was completely consumed. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 24 (78 g, purity 90%), shown by the following reaction structural formula.

[0175] In a 500 mL three-necked flask, intermediate compound 24 (78 g) and glacial acetic acid (150 g) were added and stirred in an oil bath, raising the temperature to 50°C. At 50°C, phenylhydrazine (40 g) was slowly added dropwise, continuing for 1 hour. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (150 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected and dried in a rotary evaporator to remove the small amount of solvent contained in the solid, yielding sensitizer compound D-24 (65 g, purity 96%) shown in the following reaction structural formula.

[0176] The specific reaction structure is shown below. [ka]

[0177] The sensitizer compound structure shown in the above formula is merely illustrative; however, the benzene ring and fluorene ring may have substituents such as halogens, C1-C8 alkyl groups, or C1-C4 alkoxy groups, and the number of substituents may be one or one to five.

[0178] Synthesis of sensitizer compound D-25: In a 500 mL three-necked flask, the starting materials 4-acetylbiphenyl (58 g), benzothiophene-2-carbaldehyde (40 g), and ethanol (150 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 40% aqueous NaOH solution (20 g) was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was continued to stir at room temperature for 8 hours. The reaction was monitored by adding one drop at a time to a TLC plate. The reaction was stopped when the benzothiophene-2-carbaldehyde was completely consumed. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (150 mL) and stirred at room temperature for 30 minutes. After suction filtration, the solid was collected and dried using a rotary evaporator to remove any small amount of solvent contained within the solid. This yielded intermediate product compound 25 (83 g, purity 93%), shown by the following reaction structural formula.

[0179] In a 500 mL three-necked flask, intermediate compound 25 (83 g) and glacial acetic acid (200 g) were added, and the mixture was stirred in an oil bath and raised to 50°C. At 50°C, phenylhydrazine (42 g) was slowly added dropwise, and the addition was continued for 1 hour. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (200 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected and dried in a rotary evaporator to remove the small amount of solvent contained in the solid, yielding sensitizer compound D-25 (67 g, purity 95%), shown in the following reaction structural formula.

[0180] The specific reaction structure is shown below. [ka]

[0181] The sensitizer compound structure shown in the above formula is merely illustrative; however, the benzene ring and biphenyl ring may have substituents such as halogens, C1-C8 alkyl groups, or C1-C4 alkoxy groups, and the number of substituents may be one or one to five. Furthermore, the benzothiophene heterocycle may be replaced with a heterocyclic functional group having extra electrons, such as furan, thiophene, indole, thiazole, benzofuran, benzothiazole, indene, anthracene, acridine, or aromatic amine.

[0182] Synthesis of the sensitizer compound D-26 shown in the following formula: In a 1000 mL three-necked flask, the starting materials 6-methoxy-2-naphthaldehyde (112 g), acetone (14 g), and ethanol (300 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 10% NaOH aqueous solution (240 g) was added dropwise to the flask for 2 hours. After the addition was complete, the mixture was stirred at room temperature and allowed to react for 8 hours. The reaction was monitored by placing a drop on a TLC plate, and stopped when there was no further change in the reaction. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 26 (82 g, purity 91%), shown by the following reaction structural formula.

[0183] In a 500 mL three-necked flask, intermediate compound 26 (82 g) and glacial acetic acid (200 g) were added, and the mixture was stirred in an oil bath and raised to 50°C. At 50°C, phenylhydrazine (34 g) was slowly added dropwise, and the addition was continued for 1 hour. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (200 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected, dried in a rotary evaporator to remove the small amount of solvent contained in the solid, and the sensitizer compound D-26 (74 g, purity 96%) shown in the following reaction structural formula was obtained.

[0184] The specific reaction structure is shown below. [ka]

[0185] The sensitizer compound structure shown in the above formula is merely illustrative; however, the benzene ring and naphthalene ring may have substituents such as halogens, C1-C8 alkyl groups, or C1-C4 alkoxy groups, and the number of substituents may be one or one to five. Furthermore, the naphthalene ring may be replaced with a functional group of a condensed aromatic ring structure, etc.

[0186] According to the formulations in Tables 5 and 6 below, alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, and additives were mixed in predetermined ratios, and 60 parts by weight of solvent were added. However, solvents suitable for preparing the coating adhesive solution may also be acetone, butanone, methanol, ethanol, isopropyl alcohol, toluene, etc. The mixture was then stirred thoroughly to completely dissolve it, and a resin composition solution with a solid content of 40% was prepared. After standing for 30 minutes to allow for thorough degassing, the solution was uniformly coated onto the surface of a 16 μm thick PET support film using a coating apparatus, and dried in a 90°C oven for 10 minutes to form a 25 μm thick dry film resist layer, which showed a blue-green color under a yellow lamp. Next, a 20 μm thick polyethylene thin film protective layer was applied to the surface to obtain a three-layer photosensitive dry film. [Table 5] [Table 6]

[0187] Here, the alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, sensitizer, and additive are as follows: A-21 had a ratio of 25:40:7:28 for methacrylic acid, methyl methacrylate, butyl acrylate, and styrene. The acid value was 131 mgKOH / g, the weight-average molecular weight measured by GPC was 55000 g / mol, the molecular weight distribution (PID) was 1.8, and the conversion rate was 97.0%. B-21: (4) Ethoxybisphenol A diacrylate (Miwon Chemicals). B-22: (10) Ethoxybisphenol A diacrylate (Miwon Chemicals). B-23: (6) Ethoxypolypropylene glycol (700) dimethacrylate (Miwon Chemicals). B-24: (4) Ethoxylated nonylphenol acrylate (Miwon Chemicals). B-25: (3) Ethoxylated trimethylolpropane trimethacrylate (Miwon Chemicals). C-21:2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (BCIM, Changzhou Strong Electronic Materials). C-22:9-phenylacridine (Changzhou Strong Electronic Materials). C-23: N-phenylglycine (Nishi-A Chemical). D-21 is 1-phenyl-3-biphenyl-5-(4-methoxyphenyl)pyrazoline; see synthesis example D-21. D-22 is 1-phenyl-3-(biphenylvinyl)-5-biphenylpyrazoline; see synthesis example D-22. D-23 is 1-phenyl-3-(9-acridinyl vinyl)-5-(9-acridinyl group)pyrazoline; see synthesis example D-23. D-24 is 1-phenyl-3-(2-fluorenyl)-5-(4-methoxyphenyl)pyrazoline; see synthesis example D-24. D-25 is 1-phenyl-3-(biphenyl)-5-(2-benzothienyl)pyrazoline; see synthesis example D-25. D-26 is 1-phenyl-3-(6-methoxy-2-naphthylvinyl)-5-(6-methoxy-2-naphthyl)pyrazoline; see synthesis example D-26. D-10: 1-phenyl-3-(4-methoxyvinyl)-5-(4-methoxyphenyl)pyrazoline (a sensitizer reported in Hitachi Chemical's patent CN104111583, R = methoxy group). D-11: 1-phenyl-3-(biphenyl)-5-(4-tert-butylphenyl)pyrazoline (a sensitizer reported in Asahi Kasei's patent CN101652715, R=tert-butyl group). F-21: Dye Brilliant Green (Shanghai Bailingwei Chemical Technology Co., Ltd.). F-22: Leucocrystal violet (Shanghai Bailingwei Chemical Technology Co., Ltd.). F-23: Tribromomethylphenylsulfone (Shanghai Tixiai Chemical). F-24: p-toluenesulfonamide (Shanghai Tixiai Chemical).

[0188] The following describes the methods for preparing the samples (including film application, exposure, development, and electrolytic copper plating), the methods for evaluating the samples, and the evaluation results for Examples 15-27 and Comparative Examples 4-8.

[0189] (1) Method for preparing samples (Film application) The copper surface of the copper-clad laminate was polished using a grinder, washed with water, and wiped clean to obtain a bright and novel copper surface. The press roller temperature of the film application machine was set to 110°C and the conveying speed to 1.5 meters / minute. After removing the PE protective film from the surface of the photosensitive dry film obtained from the above examples and comparative examples, the film was heat-applied to the copper-clad laminate under standard pressure to obtain a sample with the film applied.

[0190] (exposure) Samples with the film attached were left to stand for at least 15 minutes. Resolution and adhesion performance were assessed by exposure using a 405nm wavelength laser direct imaging (LDI) exposure machine, Model IP-6, manufactured by Adtec Japan. Photosensitivity tests were performed using a Stuffer 41-step exposure scale, with the exposure count set to 14-20.

[0191] The alignment recognition characteristics of the samples were tested using a domestically produced exposure machine. Exposure was performed using a laser direct imaging (LDI) exposure machine manufactured by Wuxi Yingsu Semiconductor Co., Ltd. The exposure machine was model IC2000, with a wavelength of 405 nm, and the exposure count was controlled to 14-20.

[0192] (developing) The exposed sample was allowed to stand for at least 15 minutes, at a development temperature of 30°C and a pressure of 1.2 kg / cm². 2 The developer was a 1% wt aqueous sodium carbonate solution, and the development time was 1.5 to 2.0 times the minimum development time. After development, the material was washed with water and dried. The minimum development time was defined as the minimum time required for the resist layer in the unexposed areas to completely dissolve.

[0193] (etching) An etching process was performed on the developed copper plate. The etching solution was copper chloride, the etching rate was 1.0 m / min, the etching temperature was 48°C, the spray pressure was 1.5 bar, the specific gravity was 1.3 g / mL, the acidity was 2 mol / L, the copper ion concentration was 140 g / L, and the etching machine was a Dongguan Space Model GL181946.

[0194] (Leaving the film studio) The film removal solution was NaOH, with a concentration of 3.0 wt%, at a temperature of 50°C, and a pressure of 1.2 kg / cm². 2 The film removal time was 1.5 to 2.0 times the minimum film removal time, and after film removal, the film was washed with water and dried.

[0195] (2) Evaluation method (Sensitivity evaluation) The film-attached sample was left to stand for at least 15 minutes, then exposed using an Adtec IP-6 405nm LDI exposure machine. Sensitivity testing was performed using a Stuffer 41-step exposure scale. After exposure, a 1% wt sodium carbonate aqueous solution was sprayed at 30°C, and the development time was 2.0 times the minimum development time. In this way, the unexposed areas were removed. Through this process, a cured film consisting of a cured photosensitive resin composition was formed on the copper surface of the substrate. The exposure amount (mJ / cm²) when the remaining number of steps on the step exposure tablet for the obtained cured film reached 17 was measured. 2 The sensitivity of the photosensitive resin composition was evaluated using the following method. A smaller value indicates better sensitivity.

[0196] Criteria: ○: 10~20 mJ / cm 2 Δ: 20~50 mJ / cm 2 ×:>50mJ / cm 2 .

[0197] (Resolution evaluation) The mask has a wiring pattern with a 1:1 width ratio between exposed and unexposed areas. After exposure and development for twice the minimum development time, the minimum mask width for which the cured resist line was formed normally is defined as the resolution value. The mask is then observed with a 2D imager or scanning electron microscope (SEM), and a smaller reading indicates better resolution.

[0198] (Evaluation of adhesion strength) A photosensitive dry film resist is laminated onto a copper plate by hot pressing. The plate is then exposed to a mask with a wiring pattern where the width of the exposed and unexposed areas is n:400, and the corresponding sensitivity is 17. After development for twice the minimum development time, the plate is observed with a magnifying glass. The minimum mask width at which a completely cured resist line is formed is defined as the adhesion strength value, and a smaller reading indicates better adhesion.

[0199] (Alignment recognition in domestically produced LDI exposure machines) Exposure was performed using a Yingsu Technology H-9300D LDI exposure machine, and the exposure energy was measured using a 41-grid stouffer exposure scale, with 17 grid points being exposed. Simultaneously with the exposure of side A, side B was completed with color burning by irradiation using a UV LED lamp, and then the exposure machine automatically performed point capture and identification using red or yellow light. The shorter the color burning time by irradiation, the greater the contrast of the image after irradiation, and the clearer the boundaries of the irradiated points. Furthermore, if point capture and identification is possible with either red or yellow light after color burning, it indicates that the alignment recognition characteristics of domestically produced LDI exposure machines are superior.

[0200] Criteria: ○: The color imprinting time by irradiation is 0.5 to 2.0 seconds, and after color imprinting, spot detection and identification are possible with both red and yellow light. Δ: The color imprinting time due to irradiation is 2.0 to 3.0 seconds. After color imprinting, spot detection is not possible with red light, and detection is only possible with yellow light. ×: The color imprinting time due to irradiation is longer than 3.0 seconds, and after color imprinting, spot detection and identification are not possible with either red or yellow light.

[0201] (Evaluation of the side profile) After removing the PE film from the fabricated photosensitive dry film resist, the dry film was laminated onto a copper plate using a heated press roller. The plate was then exposed using a mask with a wiring pattern where the width of the exposed and unexposed areas was n:400. After development for 2.0 times the minimum development time, a dry film image was obtained, and a side view of the dry film with a line width of 25 μm was captured using a scanning electron microscope (SEM) at 1000x magnification.

[0202] Criteria: ○: The cross-section of the leading edge of the dry film is rectangular. Δ: The cross-section of the leading edge of the dry film is slightly inverted trapezoidal. ×: The cross-section of the leading edge of the dry film is severely inverted, or the bottom is gouged out, or there are obvious cracks on the side walls.

[0203] (Evaluation of film detachment speed) The film detachment speed is evaluated by testing the film detachment time; the shorter the film detachment time, the faster the film detachment speed.

[0204] (3) For the results of the characteristic evaluations, such as sensitivity, resolution, adhesion, lateral shape, and alignment recognition using a domestically produced LDI exposure machine, please refer to Tables 7 and 8. [Table 7] [Table 8]

[0205] As can be seen from the comparison between the examples and comparative examples, the examples all yielded dry film resists suitable for use with LDI exposure machines, exhibiting superior overall performance in key areas such as sensitivity, resolution, adhesion, side profile, and alignment recognition characteristics on domestically produced LDI exposure machines.

[0206] In Comparative Examples 4 and 5, a conventional pyrazoline compound was used as a sensitizer. The test results showed that the test data was almost identical to the data provided in the patent. The alignment recognition characteristics on the domestically produced LDI exposure machine were good, but the sensitivity was clearly insufficient, and further improvements in resolution and adhesion are needed.

[0207] In Comparative Example 6, the amount of sensitizer added was increased based on Comparative Example 4 in order to further improve sensitivity. However, the test results showed that although sensitivity improved after such a large increase in the amount of sensitizer used, adhesion decreased drastically, the dry film line could not adhere to the copper surface at all, and the color of the dry film after exposure and development became abnormally dark. The reason for this is presumed to be that the hardening of the resist was limited to the surface, and as the surface color became darker, the hardening depth became insufficient, and the dry film pattern could not adhere to the copper surface at all after exposure.

[0208] In Comparative Example 7, the initiator was hexaarylimidazole, and no sensitizer was used. The results of the examples showed that the corresponding dry film resist had very poor photosensitivity, and its properties such as analysis, adhesion, and lateral appearance were all poor.

[0209] Comparative Example 8 is a conventional solution for producing a high-sensitivity, high-resolution dry film resist used in the fabrication of HDI inner layer plates. The test results are consistent with those of PCB clients, showing high sensitivity at 405 nm and excellent resolution accuracy. However, even with the addition of a certain amount of tribromomethylphenyl sulfone to enhance the contrast of the image before and after exposure, alignment recognition is not possible with domestically produced LDI exposure machines. Dry film resists using this formulation cannot be used with domestically produced LDI exposure machines that are currently widely used by PCB clients. The reason for this is presumed to be that an acridine-based initiator is used in this formulation, and when such an initiator initiates photopolymerization, development after exposure becomes too slow, and the contrast of the pattern before and after exposure becomes too weak, preventing alignment recognition with domestically produced LDI exposure machines.

[0210] As can be seen from the above description, the above-mentioned embodiments of the present application achieve the following technical effects. By introducing several modifying functional groups such as biphenyl, fused ring functional groups, electron-rich heterocycles, or benzene rings comprising fused heterocycles and amino groups to pyrazoline compounds, the sensitizer compounds shown in structural formulas I and II after modification have an electron-rich conjugated system as a whole molecular structure. Such electron-rich conjugation effect helps to promote the redshift of the sensitizer absorption spectrum, and its absorption spectrum is extended to the visible light region. Since the maximum absorption wavelength of the sensitizer after modification is closer to the exposure light source with a wavelength of 405 nm, it is more sensitive to the exposure light source, thereby improving the photosensitivity of the dry film resist to the LDI 405 nm exposure light source and significantly improving the resolution. Furthermore, because the present application selects a specific sensitizer, the dry film resist not only has high photosensitivity and resolution, but the contrast of the pattern before and after exposure can be further enhanced, which is useful for alignment recognition in domestic LDI exposure machines and ensures the alignment accuracy of domestic LDI exposure machines.

[0211] Synthesis of sensitizer compound D-27: In a 1000 mL three-necked flask, the starting materials p-anisaldehyde (68 g), acetone (14 g), and ethanol (150 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 10% NaOH aqueous solution (240 g) was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was stirred at room temperature and allowed to react for 8 hours. The reaction was monitored by placing a drop on a TLC plate, and stopped when there was no further change in the reaction. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (100 mL) and stirred at room temperature for 30 minutes. After suction filtration, the solid was collected and dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 27 (56 g, purity 90%), shown in the following reaction structural formula (2).

[0212] In a 500 mL three-necked flask, intermediate compound 27 (56 g) and glacial acetic acid (150 g) were added and stirred in an oil bath, raising the temperature to 50°C. At 50°C, phenylhydrazine (29 g) was slowly added dropwise, continuing for 30 minutes. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (150 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected and dried in a rotary evaporator to remove the small amount of solvent contained in the solid, yielding sensitizer compound D-27 (52 g, purity 97%) shown in the following reaction structural formula.

[0213] The specific reaction structure is shown below. [ka]

[0214] The sensitizer compound structure shown in the above formula is merely illustrative; however, the benzene ring may have substituents such as halogens, alkyl groups with carbon chain lengths of C1 to C8, or alkoxy groups with carbon chain lengths of C1 to C4, and the number of substituents may be one or one to five.

[0215] Synthesis of sensitizer compound D-28: In a 500 mL three-necked flask, the starting materials indole-3-carbaldehyde (72 g), acetone (14 g), and ethanol (100 mL) were added. The flask was placed in a water bath at room temperature and stirred for 15 minutes. Once the starting materials were dissolved, 10% NaOH aqueous solution (240 g) was added dropwise to the flask for 1 hour. After the addition was complete, the mixture was stirred at room temperature and allowed to react for 8 hours. The reaction was monitored by placing a drop on a TLC plate, and stopped when there was no further change in the reaction. The suspension obtained from the reaction was filtered by suction under reduced pressure. The resulting crude solid product was dispersed in a small amount of ethanol (200 mL), stirred at room temperature for 30 minutes, and then filtered by suction to collect the solid. The solid was dried using a rotary evaporator to remove the small amount of solvent contained within the solid, yielding intermediate product compound 28 (63 g, purity 89%), shown by the following reaction structural formula.

[0216] In a 500 mL three-necked flask, intermediate compound 28 (63 g) and glacial acetic acid (200 g) were added, and the mixture was placed in an oil bath and stirred to raise the temperature to 50°C. At 50°C, phenylhydrazine (33 g) was slowly added dropwise, and the addition was continued for 1 hour. After the addition was complete, the temperature was raised to 80°C and the reaction was allowed to proceed for 8 hours. The reaction was monitored by adding a drop to a TLC plate, and when the starting material was completely consumed, the reaction was stopped, cooled to room temperature, diluted with ethanol (200 mL), and the resulting suspension was stirred at room temperature for 30 minutes. The resulting crude solid product needed further purification, so it was dispersed in a small amount of methanol (150 mL), stirred at room temperature for 30 minutes, and then filtered by suction. The solid was collected, dried in a rotary evaporator to remove the small amount of solvent contained in the solid, and the sensitizer compound D-28 (55 g, purity 95%) shown in the following reaction structural formula was obtained.

[0217] The specific reaction structure is shown below. [ka]

[0218] The sensitizer compound structure shown in the above formula is merely illustrative; however, the benzene ring and indole ring may have substituents such as halogens, alkyl groups with carbon chain lengths of C1 to C8, or alkoxy groups with carbon chain lengths of C1 to C4, and the number of substituents may be one or one to five.

[0219] The components were mixed in the predetermined ratios according to the formulations in Tables 9 and 10 below, and 60 parts by weight of solvent were added. However, suitable solvents for preparing the coating adhesive solution may be acetone, butanone, methanol, ethanol, isopropyl alcohol, toluene, etc. The mixture was then stirred thoroughly to completely dissolve the components and a solution with a solid content of 40% was prepared. After standing for 30 minutes to allow for thorough degassing, the solution was uniformly coated onto the surface of a 16 μm thick PET support film using a coating apparatus and dried in a 90°C oven for 10 minutes to form a 38 μm thick dry film resist layer, which showed a blue-green color under a yellow lamp. Next, a 20 μm thick polyethylene thin film protective layer was applied to the surface to obtain a three-layer photosensitive dry film. [Table 9] [Table 10]

[0220] Here, the alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, sensitizer, compound that forms a complex with copper, and additive are as follows: A-31 had a composition of methacrylic acid, methyl methacrylate, butyl acrylate, butyl acrylate, and styrene in a ratio of 22:40:20:11:7. The acid value was 127 mgKOH / g, the weight-average molecular weight measured by GPC was 91000 g / mol, the molecular weight distribution (PID) was 2.0, and the conversion rate was 97.0%. B-31:(10) Ethoxybisphenol A dimethacrylate (Miwon Chemicals), and in the corresponding photopolymerizable monomer structural formula VI, m1+m2=10, n1+n2=0, and R1=methyl group. B-32 is (10)ethoxy(4)propoxybisphenol A dimethacrylate (Miwon Chemicals), and in the corresponding photopolymerizable monomer structural formula VI, m1+m2=10, n1+n2=4, and R1=methyl group. B-33 is (6) Ethoxypolypropylene glycol (700) dimethacrylate (Miwon Chemicals), and in the corresponding photopolymerizable monomer structural formula VIII, a2=6, b2=12, and R1=methyl group. B-34 is (8)ethoxy(4)propoxynonylphenol acrylate (Miwon Chemicals), and in the corresponding photopolymerizable monomer structural formula VII, a1=8, b1=4, and R1=H. B-35:(3) Ethoxylated trimethylolpropane trimethacrylate (Miwon Chemicals), in the corresponding photopolymerizable monomer structural formula X, a4=1, b4=0, and R1=H. B-36: Polyethylene glycol (400) dimethacrylate (Miwon Chemicals). B-37: (20) Ethoxybisphenol A dimethacrylate (Miwon Chemicals). B-38: Polypropylene glycol (400) dimethacrylate (Miwon Chemicals). C-31:2,2'-Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (BCIM, Changzhou Strong Electronic Materials). C-32: 4,4'-Bis(diethylamino)benzophenone. C-33:9-phenylacridine (Changzhou Strong Electronic Materials). C-34: N-phenylglycine (Nishi-A Chemical). D-21 is 1-phenyl-3-biphenyl-5-(4-methoxyphenyl)pyrazoline, refer to synthesis example D-21, with a purity of 95%. D-27 is 1-phenyl-3-(4-methoxyvinyl)-5-(4-methoxyphenyl)pyrazoline; see synthesis example D-27. D-22 is 1-phenyl-3-(biphenylvinyl)-5-biphenylpyrazoline, refer to synthesis example D-22, and has a purity of 95.5%. D-23 is 1-phenyl-3-(9-acridinyl vinyl)-5-(9-acridinyl group)pyrazoline, refer to synthesis example D-23, and has a purity of 94%. D-28 is 1-phenyl-3-(3-indolylvinyl)-5-(3-indolyl)pyrazoline; see synthesis example D-28. D-26 is 1-phenyl-3-(6-methoxy-2-naphthylvinyl)-5-(6-methoxy-2-naphthyl)pyrazoline, refer to synthesis example D-26, with a purity of 96%. D-12 is 1-phenyl-3-(4-methoxyvinyl)-5-(4-methoxyphenyl)pyrazoline, which is a sensitizer reported in Hitachi Chemical's patent CN104111583. E-1 is 2-mercaptobenzimidazole-4-carboxylic acid and belongs to structural formula IV. E-2: This is a mercaptobenzothiazole, belonging to structural formula IV. E-3 is 6-thioguanine and belongs to structural formula IV. E-4: This is a mercaptotriazole and belongs to structural formula III. E-5 is 1-hydroxyethyl-5-mercapto-1H-tetrazole, and belongs to structural formula III. F-31: The pigment is Brilliant Green (Shanghai Bailingwei Chemical Technology Co., Ltd.). F-32: Leucocrystal violet (Shanghai Bailingwei Chemical Technology Co., Ltd.). F-33 ​​is p-toluenesulfonamide (Shanghai Tixiai Chemical).

[0221] The following describes the methods for preparing the samples for Examples 28-46 and Comparative Examples 9-11 (including film application, exposure, development, electrolytic copper plating, and electrolytic tin plating), as well as the methods and results for evaluating the samples.

[0222] (1) Method for preparing samples (Film application) The copper surface of the copper-clad laminate was polished using a grinder, washed with water, and wiped clean to obtain a bright and novel copper surface. The press roller temperature of the film application machine was set to 110°C and the conveying speed to 1.5 meters / minute. After removing the PE protective film from the surface of the photosensitive dry film obtained from the above examples and comparative examples, the film was heat-applied to the copper-clad laminate under standard pressure to obtain a sample with the film applied.

[0223] (exposure) The film-attached samples were left to stand for at least 15 minutes, then exposed using a 405nm wavelength laser direct imaging (LDI) exposure machine, Model IP-6, manufactured by Adtec Japan. Photosensitivity tests were performed using a Stuffer 41-step exposure scale, with the number of exposures controlled to 17-20.

[0224] (developing) The exposed sample was allowed to stand for at least 15 minutes, at a development temperature of 30°C and a pressure of 1.2 kg / cm². 2 The developer was a 1% wt aqueous sodium carbonate solution, and the development time was 1.5 to 2.0 times the minimum development time. After development, the material was washed with water and dried. The minimum development time was defined as the minimum time required for the resist layer in the unexposed areas to completely dissolve.

[0225] (Pattern electroplating) The electroplating solution used was a copper sulfate and stannous sulfate system manufactured by Zheng Tian Wei Co., Ltd., and copper plating was performed first, followed by tin plating, as follows: Acid degreasing (10% concentration, 10 minutes, 40°C) → rinse with water for 2 minutes → micro-etching for 1 minute (60 g / L sodium persulfate + 20 mL / L concentrated sulfuric acid) → rinse with water for 1 minute → acid immersion for 1 minute (10% sulfuric acid solution) → electrolytic copper plating (current density 2ASD, temperature 22-27°C, 60 minutes) → rinse with water for 1 minute → acid immersion for 1 minute (10% sulfuric acid solution) → electrolytic tin plating (current density 1ASD, temperature 20-25°C, 10 minutes).

[0226] (etching) An etching process was performed on the developed copper plate. The etching solution was copper chloride, the etching rate was 1.0 m / min, the etching temperature was 48°C, the spray pressure was 1.5 bar, the specific gravity was 1.3 g / mL, the acidity was 2 mol / L, the copper ion concentration was 140 g / L, and the etching machine was a Dongguan Space Model GL181946.

[0227] (Leaving the film studio) The film removal solution was NaOH, with a concentration of 3.0 wt%, at a temperature of 50°C, and a pressure of 1.2 kg / cm². 2 The film removal time was 1.5 to 2.0 times the minimum film removal time, and after film removal, the film was washed with water and dried.

[0228] (2) Evaluation method (Sensitivity evaluation) The film-attached sample was left to stand for at least 15 minutes, then exposed using an Adtec IP-6 405nm LDI exposure machine. Sensitivity testing was performed using a Stuffer 41-step exposure scale. After exposure, a 1% wt sodium carbonate aqueous solution was sprayed at 30°C, and the development time was 2.0 times the minimum development time to remove the unexposed areas. Through this process, a cured film consisting of a cured photosensitive resin composition was formed on the copper surface of the substrate. The exposure amount (mJ / cm²) when the remaining number of steps on the step-type exposure tablet for the obtained cured film reached 18 was measured. 2The sensitivity of the photosensitive resin composition was evaluated using the following method. A smaller value indicates better sensitivity.

[0229] Judgment criteria:○:10~30mJ / cm 2 Δ: 30~50 mJ / cm 2 ×:>50mJ / cm 2 .

[0230] (Resolution evaluation) The mask has a wiring pattern with a 1:1 width ratio between exposed and unexposed areas. After exposure and development for twice the minimum development time, the minimum mask width for which the cured resist line was formed normally is defined as the resolution value. The mask is then observed with a 2D imager or scanning electron microscope (SEM), and a smaller reading indicates better resolution.

[0231] (Evaluation of adhesion strength) A photosensitive dry film resist is laminated onto a copper plate by hot pressing. The plate is then exposed to a mask with a wiring pattern where the width of the exposed and unexposed areas is n:400. The corresponding sensitivity is 18. After development for twice the minimum development time, the plate is observed with a magnifying glass. The minimum mask width at which a completely cured resist line is formed is defined as the adhesion strength value. A smaller reading indicates better adhesion.

[0232] (Evaluation of electroplating resistance) After film mounting, exposure, development, pattern electroplating, and film removal, the presence or absence of cementation phenomena was observed using a scanning electron microscope (SEM).

[0233] Criteria: ○: No cementation phenomenon Δ: Minor cementation phenomenon ×: Severe cementation phenomenon.

[0234] (Evaluation of electroplating contamination) A dry film resist sample after exposure (20 exposure squares) is 0.8 m². 2It was dissolved in a copper sulfate electroplating solution at a ratio of / L, immersed at room temperature for 24 hours, and then the dry film resist was filtered off to obtain a test sample. By the high-temperature catalytic combustion oxidation method, the organic carbon content (TOC) of the test electroplating solution sample was measured, and the electroplating solution sample without the resist sample added was used as a blank sample. The larger the measured value of the organic carbon content (TOC), the more serious the contamination of the electroplating solution.

[0235] Judgment criteria: ○: When subtracting the blank, the TOC value < 500 ppm Δ: When subtracting the blank, 500 ppm < TOC value < 1000 ppm ×: When subtracting the blank, the TOC value > 1000 ppm.

[0236] (Side morphology evaluation) After removing the PE film from the prepared photosensitive dry film resist, the dry film was laminated on a copper plate using a heated press roller. Here, it was exposed with a mask having a wiring pattern where the widths of the exposed part and the unexposed part are n:400, developed for 2.0 times the minimum development time, and then a dry film image was obtained. A side view of the dry film with a line width of 25 μm was photographed with a scanning electron microscope (SEM) while magnifying 1000 times.

[0237] Judgment criteria: ○: The cross-section of the tip of the dry film is rectangular Δ: The cross-section of the tip of the dry film is slightly trapezoidal in reverse ×: The cross-section of the tip of the dry film is extremely trapezoidal in reverse or the bottom is pinched, or there is an obvious crack phenomenon on the side wall.

[0238] (3) Refer to Table 11 and Table 12 for the results of the characteristic evaluations such as sensitivity, resolution, adhesion, electroplating resistance, and electroplating contamination.

Table 11

Table 12

[0239] As can be seen from the comparison between the example and the comparative example, the example obtained a dry film resist with good key properties such as sensitivity, resolution, adhesion performance, side profile, electroplating resistance, and electroplating contamination resistance.

[0240] In Example 40, the ratio of sensitizer to complex exceeded the preferred ratio range, and the resulting dry film resist had high photosensitivity but poor corresponding analytical, adhesion, and electroplating resistance performance. In Example 43, the ratio of PO segments in the photocurable monomer exceeded the preferred ratio range, and the resulting dry film resist had poor analytical, adhesion, and lateral appearance. In Example 44, the pyrazoline sensitizer reported in Hitachi Chemical's patent CN104111583 was used, and the resulting dry film resist had poor sensitivity, analytical, adhesion, and lateral appearance. In Example 45, the initiator system used is an initiator system currently commonly used for high-sensitivity LDI laser direct imaging resists, but its electroplating resistance and electroplating contamination properties were poor, making it unsuitable for the electroplating process. The reasons for this include, on the one hand, that acridine-based initiators have a small molecular weight and are used in large quantities, making it easy for initiator fragments in the dry film resist after exposure to penetrate the electroplating solution and contaminate it; on the other hand, with such initiators, the sides of the bottom of the dry film may not be very orderly after exposure, and a minor cementation phenomenon may occur. In Example 46, the initiator system used is one that is currently commonly used for electroplated dry films. Although its photosensitivity to the LDI 405nm laser light source is very poor, the addition of a complexing agent results in a dry film resist with excellent electroplating resistance.

[0241] On the other hand, in Comparative Examples 9 and 10, since no complex was added, the electroplating resistance properties of the resulting dry film resists were poor in both cases. In Comparative Example 11, the photocurable monomer did not contain hydrophobic PO segments, but only hydrophilic EO segments. The resulting dry film resist had excellent properties such as sensitivity, resolution, and adhesion, but poor electroplating resistance and minor cementation.

[0242] The foregoing describes only preferred embodiments of the present invention and does not limit it. Those skilled in the art can make various modifications and changes to the present invention. Any modifications, equivalent substitutions, improvements, etc., made without departing from the spirit and principles of the present invention shall be within the scope of protection of the present invention.

Claims

1. A dry film resist comprising (A) an alkali-soluble resin, (B) a photopolymerizable monomer, (C) a photopolymerization initiator, and (D) a sensitizer, wherein the (D) sensitizer contains a compound containing an anthracene-substituted and / or triarylamine-substituted pyrazoline structure.

2. The (D) sensitizer comprises one or more compounds represented by structural formulas D1, D2, D3, D4, and D5, 【Chemistry 1】 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 【Transformation 5】 wherein, R ０１ , R ０２ , R ０３ , R ０４ , R ０５ are each independently hydrogen, a halogen, a nitro group, C １ to C ８ alkyl group, C １ to C ４ alkoxy group, and are any one or more thereof, a represents any integer between 0 and 5, b represents any integer between 0 and 4, c represents any integer between 0 and 5, d represents any integer between 0 and 4, and if a is greater than or equal to 2, there are multiple R ０１ These can be the same or different, and if b is greater than or equal to 2, there are multiple R ０２ These can be the same or different, and if c is greater than or equal to 2, there are multiple R ０４ These can be the same or different, and if d is greater than or equal to 2, there are multiple R ０５ They can be the same or different. The dry film resist according to claim 1, characterized in that M is independently a benzene ring, a biphenyl group, a fused ring functional group, or an electron-rich heterocycle or fused heterocycle functional group.

3. The M is C １ ~C ４ The dry film resist according to claim 2, characterized in that it is a phenyl group, biphenyl group, or fused ring functional group comprising one or more of an alkoxy group, an amino group, or an alkyl group, or a heterocyclic or fused heterocyclic functional group comprising furan, thiophene, indole, thiazole, benzofuran, benzothiazole, or fluorene.

4. The sensitizer comprises a compound having the following structure, which may contain substituents: 【Transformation 6】 When the substituent is present, the benzene ring, biphenyl ring, fused ring, and heterocycle in the above structure contain the substituent, and the substituent is a halogen, C １ ~C ８ Alkyl alkyl group, C １ ~C ４ The dry film resist according to claim 3, characterized in that it is one or more of the alkoxy groups.

5. The dry film resist according to claim 4, characterized in that the substituent is located in the para position.

6. The (D) sensitizer comprises one or more compounds represented by the following structural formulas I or II: 【Transformation 7】 【Transformation 8】 In the formula, R ０ These are hydrogen, halogen, and C, respectively, independently. １ ~C ８ Alkyl alkyl group or C １ ~C ４ The alkoxy group, and the modified functional group W is either a benzene ring or a fluorene ring, or a halogen, C １ ~C ８ Alkyl alkyl group, C １ ~C ４ A benzene ring, biphenyl ring, or fluorene ring having one or more substituents of any alkoxy group, The specific structural formulas of the modified functional groups M1 and / or M2 may include substituents. 【Chemistry 9】 It includes any one of the following, and in the formula, 【Chemistry 10】 is the bonding position of the modified functional group, and when the substituent is present, the fused ring and heterocycle of the above functional groups are halogen, C １ ~C ８ Alkyl alkyl group, C １ ~C ４ The dry film resist according to claim 1, characterized by containing one or more substituents among alkoxy groups.

7. The dry film resist according to claim 6, characterized in that the substituent is located in the para position.

8. The dry film resist comprises 45 to 65 parts by weight of (A) alkali-soluble resin, 30 to 50 parts by weight of (B) photopolymerizable monomer, 1.0 to 5.0 parts by weight of (C) photopolymerization initiator, and 0.01 to 0.5 parts by weight of (D) sensitizer, or The dry film resist according to any one of claims 1 to 7, characterized in that the content of the sensitizer is 0.01 wt% to 0.5 wt% of the total weight of the dry film resist.

9. The (C) photopolymerization initiator comprises a compound represented by the following structural formula C1, 【Chemistry 11】 The dry film resist according to any one of claims 1 to 7, characterized in that the substituent A in the benzene ring is independently one or more of hydrogen, a methoxy group, and a halogen atom.

10. The dry film resist according to claim 9, characterized in that the (C) photopolymerization initiator comprises one or more selected from 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole.

11. The dry film resist according to any one of claims 1 to 7, wherein the dry film resist further comprises (E) a copper complex, the compound forming a complex with copper in the (E) copper complex comprises a nitrogen-containing heterocyclic compound, and the (B) photopolymerizable monomer comprises an EO segment and a PO segment, the EO segment representing an oxyethylene group, and the PO segment representing an oxypropylene group.

12. The weight of the copper complex (E) is 0.01 to 0.5, or The dry film resist according to claim 11, characterized in that the compound forming a complex with copper in the (E) copper complex simultaneously contains a nitrogen-containing heterocycle and a mercapto group.

13. In the copper complex (E), the compound that forms a complex with copper has one or more of the structures represented by structural formula III or IV, 【Chemistry 12】 【Chemistry 13】 In the above structural formula III or IV, X is 1 to 3 carbon atoms, or 1 to 2 nitrogen atoms, or 1 carbon atom and 1 nitrogen atom, and the carbon atoms and / or nitrogen atoms are connected by single or double bonds, and Y is one or more selected from oxygen atoms, sulfur atoms, carbon atoms, and nitrogen atoms, and the hydrogen atoms of the ring formed by X, Y and -C=NH- are a carboxyl group, an amino group, C １ ~C １２ Alkyl alkyl group, C １ ~C １２ Alkoxy group, C ６ ~C １２ It may be substituted with one or more of aryl groups and hydrazino groups, where M is a single bond, C １ ~C １２ Alkyl alkyl group, C １ ~C １２ Ester group or C ２ ~C １２ Selected from the ether group, In the above structural formula IV, the ring composed of X, Y, and Z is a benzene ring or a heterocycle, and the benzene ring and the heterocycle are C １ ~C ６ Alkyl alkyl group, C １ ~C ６ The dry film resist according to claim 12, which may contain one or more of the following: an alkoxy group, an amino group, a carboxylic acid, a nitro group, and a halogen.

14. The compound that forms a complex with copper in the (E) copper complex is mercaptopyrimidine, 4,6-diamino-2-mercaptopyrimidine, mercaptoimidazole, mercaptobenzimidazole, 2-mercapto-5-carboxybenzimidazole, 2-mercapto-5-nitrobenzimidazole, 2-mercapto-5-aminobenzimidazole, 2-mercaptobenzimidazole-4-carboxylic acid, mercaptobenzothiazole, 3-mercaptonidole, 1,3,5-tris(mercaptoethyl)-1,3 5-Triadine-2,4,6-Trione, Mercaptopurine, 6-Thiogunine, Trithiocyanuric acid, 2,6-Dimercaptopurine, 4-Thiouracil, 2-Mercaptobenzoxazole, 4,6-Diamino-2,6-Mercaptopyrimidine, 4-Thioureauracil, 2-Mercapto-4-Hydroxy-5,6-Diaminopyrimidine, 4,6-Dimethyl-2-Mercaptopyrimidine, Dithiourea, 2-Mercaptopyrazine, 3,6-Dimercaptopyridazine, 2-Mercaptoimidazole, 2-Mercaptothiazo Lu, 8-mercaptoadenine, 4-thiouracil, mercaptotriazole, 3-mercapto-1,2,4-triazole dimercaptorate, 3-amino-5-mercapto-1,2,4-triazole, 4-methyl-4H-3-mercapto-1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 3-mercapto-1,2,4-triazole, 6,7-dihydro-6-mercapto-5H-pyrazolo[1,2-α][1,2,4]triazole chloride, 4-amino-3-hydrazino 5-mercapto-1,2,4-triazole, 1-methyl-5-mercapto-1H-tetrazol, 1-hydroxyethyl-5-mercapto-1H-tetrazol, 1-(2-dimethylaminoethyl)-1H-5-mercapto-tetrazol, 1-phenyl-5-mercaptotetrazol, 1,2-dihydro-1-(4-methoxyphenyl)-5H-tetraaza-5-thione, 1-ethyl-5-mercapto-1,2,3,4-tetrazol, 5-mercapto-H-tetrazol-1-acetic acid, 5-mercapto-1,2,3,The dry film resist according to claim 13, characterized in that it is one or more selected from 4-tetrazole-1-methylsulfonic acid, 1-(3-acetamide)phenyl-5-mercaptotetrazole, 1-(4-hydroxyphenyl)-5-mercaptotetrazole, 1-(4-ethoxyphenyl)-1,2-dihydro-5H-tetrazole-5-thion, 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, and 4-amino-2-mercaptopyrimidine.

15. The (B) photopolymerizable monomer comprises one or more of the compounds represented by structural formulas B1, B2, and B3. 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 In the formula, R １ Each is independently H or CH ３ Here, EO represents an oxyethylene group, PO represents an oxypropylene group, and the arrangement of the repeating EO and PO units is random or blocky. １ , m ２ Each of these is any integer between 1 and 20, n １ , n ２ Each of these is any integer between 0 and 20, and m １ +m ２ n is any integer between 2 and 20. １ +n ２ is any integer between 0 and 20, and a １ b is any integer between 4 and 20. １ is any integer between 0 and 20, and a ２ b is any integer between 3 and 20. ２ c is any integer between 0 and 20. ２ The dry film resist according to claim 2, characterized in that is any one integer from 3 to 20.

16. The photopolymerizable monomer having the structure represented by structural formula B1 accounts for 40% to 90% of the total amount of the (B) photopolymerizable monomer, and is 20% to 40% of the total weight of the (B) photopolymerizable monomer and the (A) alkali-soluble resin, or The (B) photopolymerizable monomer further comprises one or more of the structures represented by structural formula B4, 【Chemistry 17】 In the formula, R １ Each is independently H or CH ３ and a ３ The dry film resist according to claim 15, characterized in that each of these is an arbitrary integer from 1 to 10, independently of the others.

17. The dry film resist according to claim 16, characterized in that the (B) photopolymerizable monomer is one or more selected from among lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, isobornyl ester, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) pentaerythritol triacrylate, ethoxylated (propoxylated) pentaerythritol tetraacrylate, ethoxylated (propoxylated) dipentaerythritol pentaacrylate, and ethoxylated (propoxylated) dipentaerythritol hexaacrylate.

18. The (B) photopolymerizable monomer comprises one or more of the compounds represented by structural formula B1, [Chemistry 18] In the formula, R １ Each is independently H or CH ３ And, m １ , m ２ Each of these is any integer between 1 and 20, and n １ , n ２ Each of these is any integer between 0 and 20, and m １ +m ２ n is any integer between 2 and 20, and n １ +n ２ The dry film resist according to claim 6 or 7, characterized in that is any integer between 0 and 20, EO represents an oxyethylene group, PO represents an oxypropylene group, and the arrangement of the repeating units of EO and PO is random or block.

19. The photopolymerizable monomer having the structure represented by structural formula B1 accounts for 20% to 80% of the total amount of the photopolymerizable monomer, and is 10% to 35% of the total weight of the (B) photopolymerizable monomer and the (A) alkali-soluble resin, or The dry film resist according to claim 18, characterized in that the (B) photopolymerizable monomer further comprises one or more selected from lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, isobornyl ester, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate.

20. The (B) photopolymerizable monomer comprises one or more compounds represented by structural formulas B1, B5, B6, and B7. 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 wherein R １ is each independently H or CH ３ and the arrangement of the repeating units of the EO segment and the PO segment is random or block, and in Structural Formula IV, m １ , m ２ are each any integer from 0 to 30, n １ , n ２ are each any integer from 0 to 20, and m １ + m ２ is any integer from 0 to 30, n １ + n ２ is any integer from 0 to 20, and in Structural Formula B5, a ５ is any integer from 0 to 30, b ５ is any integer from 0 to 20, and in Structural Formula B6, a ６ is any integer from 0 to 30, b ６ is any integer from 0 to 20, and in Structural Formula B7, a ７ is any integer from 0 to 20, b ７ is any integer from 0 to 20, characterized in that the dry film resist according to claim 11.

21. The molar amount of the PO segment is 15% to 60% of the total molar amount of the EO segment and the PO segment in the photopolymerizable monomer, or The dry film resist according to claim 20, characterized in that the photopolymerizable monomer further comprises one or more selected from lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, isobornyl ester, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, polyethylene glycol (propylene glycol) di(meth)acrylate, ethoxylated (propoxylated) neopentyl glycol diacrylate, trimethylolpropane tri(meth)acrylate, ethoxylated (propoxylated) trimethylolpropane tri(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and polyurethane acrylate.

22. The alkali-soluble resin (A) is obtained by copolymerizing (meth)acrylic acid, (meth)acrylate, and styrene or a derivative of styrene, and the alkali-soluble resin (A) contains one or more of the compounds represented by structural formula A1. 【Chemistry 23】 wherein R ２ , R ３ , R ５ , R ７ are each independently hydrogen or a methyl group, and R ４ , R ６ are each independently any one or more of an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, or a halogen atom; p and q each independently represent any integer from 0 to 5; R ８ is any one of a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms; x, y, z and u each represent the ratio of each copolymer component in the alkali-soluble resin, provided that x is 15 wt% to 40 wt%, z is 0 wt% to 50 wt%, u is 0 wt% to 80 wt%, and y is 0 wt% to 40 wt%. The dry film resist according to any one of claims 1 to 7, characterized in that.

23. The dry film resist according to claim 22, characterized in that the acid value of the alkali-soluble resin (A) is 120 mg KOH / g to 250 mg KOH / g, or the weight-average molecular weight is 30,000 to 120,000, the molecular weight distribution is 1.3 to 2.5, or the polymerization conversion rate is ≥ 97%.

24. The structural formula A1 is, (1) The conditions are that x is between 15 wt% and 35 wt%, z is between 0 wt% and 50 wt%, u is between 0 wt% and 80 wt%, y is between 0 wt% and 25 wt%, and the value of z + u is between 40 wt% and 80 wt%, (2) The conditions are that R3 is hydrogen, x is between 15 wt% and 40 wt%, z is between 0 wt% and 40 wt%, u is 0, and y is between 20 wt% and 60 wt%, (3) The dry film resist according to 22, characterized in that it satisfies one of the following conditions: R3 is hydrogen, x is 15 wt% to 40 wt%, z is 0 wt% to 40 wt%, u is 0, and y is 20 wt% to 70 wt%.

25. When condition (1) is met, the copolymer unit of the alkali-soluble resin (A) of structural formula A1 is one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, N,N-dimethyl(meth)acrylate, N,N-diethyl(meth)acrylate, N,N-diethyl(meth)acrylate, propyl (meth)acrylate, and N,N-dimethyl(meth)acrylate, N,N-diethyl(meth)acrylate, or The weight-average molecular weight of the alkali-soluble resin (A) is 30,000 to 80,000, and the molecular weight distribution is 1.3 to 2.

5. When condition (2) is met, the copolymer unit of the alkali-soluble resin (A) in structural formula A1 is selected from alkyl (meth)acrylate and styrene and / or its derivatives, and the alkyl (meth)acrylate is methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate The styrene derivative is one or more selected from droxyethyl, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, ethyl N,N-dimethyl(meth)acrylate, ethyl N,N-diethyl(meth)acrylate, propyl N,N-diethyl(meth)acrylate, butyl N,N-dimethyl(meth)acrylate, and butyl N,N-diethyl(meth)acrylate, and the styrene derivative is one or more selected from α-methylstyrene and benzyl (meth)acrylate, or The styrene content in the copolymer units of the alkali-soluble resin (A) is 0 wt% to 40 wt% of the total weight of the copolymer units, or The weight-average molecular weight of the alkali-soluble resin (A) is 30,000 to 80,000, and the molecular weight distribution is 1.3 to 2.

5. When condition (3) is met, the (meth)acrylate in structural formula A1 is one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, isooctyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, ethyl N,N-dimethyl(meth)acrylate, ethyl N,N-diethyl(meth)acrylate, propyl N,N-diethyl(meth)acrylate, butyl N,N-dimethyl(meth)acrylate, and butyl N,N-diethyl(meth)acrylate, or The dry film resist according to claim 24, characterized in that the weight-average molecular weight of the alkali-soluble resin (A) is 50,000 to 120,000, and the molecular weight distribution is 1.3 to 2.

5.

26. The dry film resist according to any one of claims 1 to 7, wherein the dry film resist further comprises an additive, the additive comprising one or more of the following: a free radical polymerization inhibitor, a colorant, a dye, a plasticizer, a photothermal stabilizer, an adhesion promoter, a leveling agent, and an antifoaming agent.

27. ​​The content of the additive is 0.5 parts by weight to 5.0 parts by weight, The content of the free radical polymerization inhibitor is 0.001 wt% to 0.005 wt% of the total weight of the dry film resist, or The free radical polymerization inhibitors are p-methoxyphenol, 4-ethyl-6-tert-butylphenol, nitrosophenylhydroxyamine aluminum salt, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, catechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, resorcinol, 2-methylresorcinol, 4-methylresorcinol, 5-methylresorcinol, 2-ethyl The dry film resist according to claim 26, characterized in that it is one or more selected from sorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, 2-n-butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, 4-tert-butyl resorcinol, 1,4-hydroquinone, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butyl-4-methylphenol, pyrogallol, 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxy and 2,2-methylenebis(4-methyl-6-tert-butylphenol).

28. A photosensitive dry film comprising a dry film resist layer and a support layer and a protective layer located on both sides of the dry film resist layer, wherein the dry film resist layer comprises the dry film resist described in any one of claims 1 to 7.

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