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

[0002] 2. Description of the Related Art Since their introduction into the world, 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 progress toward becoming lighter, thinner, shorter, and smaller, there is a corresponding demand for PCBs with higher definition, higher density, and more layers. Conventional photomask exposure methods consume a large amount of film, have high manufacturing costs, and have limitations in the precision of the 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 actinic images. This direct writing exposure method can form resist patterns with high productivity and high resolution. I-lines (355 nm) or h-lines (405 nm) are used as the light source. A laser with a wavelength of 405 nm is generally used, which has better exposure precision and can form high-density photosensitive resist patterns that are difficult to produce using conventional technology.

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

[0005] In the past decade, the annual production volume of smartphones has been increasing, and it is always necessary to update it again and again, while high-precision PCB manufacturing processes such as SAP (Semi-Additive Processing), mSAP (Improved Semi-Additive Processing), SLP (Substrate-Like PCB) are becoming more and more mature, and the global market size of high-end PCBs such as carrier boards and substrate-like PCBs is entering a stage of rapid growth. In recent years, the development and production of high-end PCBs such as carrier boards and substrate-like PCBs has been mainly centered on Japanese and Korean companies, but in recent years, some domestic companies have also mastered the production technology of IC carrier boards and have achieved very rapid development.

[0006] IC carrier boards are an evolution of HDI boards, but the manufacturing technology is more difficult than HDI and normal PCBs because the package substrate is smaller in size and the electrical structure is more complex. Similar to the PCB manufacturing process, the manufacturing process of package substrates is also mainly divided into three different manufacturing processes, such as subtractive, additive, and semi-additive, and currently, semi-additive (mSAP) is the mainstream manufacturing process. The manufacturing process includes multiple steps such as drilling, plated through holes, electroplating, pattern transfer, etching, solder mask application, and coating. The mSAP method can produce fine circuits with line widths and line pitches of less than 25 μm, effectively overcoming the side etching problem of subtractive circuit fabrication. The mSAP method mainly uses electroplating and flash etching, which first provides chemical copper on a thin copper substrate and then forms a resist pattern on it, then thickens the pattern on the substrate through an electroplating process and removes the resist pattern, and then removes the excess chemical copper layer through flash etching, and the remaining part forms the circuit. Compared with subtractive methods, the width of the circuit is not affected by the thickness of the electroplated copper, and it has higher resolution, and the line width and line pitch of the produced fine circuits are nearly consistent.

[0007] As the integration level of chips increases, the definition and integration level of carrier boards also increase accordingly. This places higher demands on the performance of dry film photoresists used in carrier boards. Dry film resists used to manufacture package substrates have extremely high requirements for analytical precision and resist shape, and are required to form resist patterns with line width / line pitch (L / S) of 10 / 10μm or less.

[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 example, 9,10-dibutoxyanthracene (DBA) is generally added as a photosensitizer to dry film resists used in the production of IC carrier boards and substrate-like PCBs.

[0009] As described in a patent application submitted by Hitachi Chemical Co., Ltd. with publication number CN102272676A, dry film resists for producing package substrates have extremely high requirements for resolution and resist shape, and are required to be able to form resist patterns with a line width / line pitch (L / S) of 10 / 10 μm or less. In such high-end dry film resists, a combination of a hexaarylbisimidazole derivative and a pyrazoline, an anthracene, or a triarylamine is generally used as a sensitizer in the initiator system. As shown in the results of the examples of the patent, such dry film resists can achieve excellent performance in terms of resolution, adhesion, and resist shape when combined with an appropriate alkali-soluble resin and a photopolymerizable monomer, but their sensitivity is extremely low, and the exposure energy is as low as 70 mJ / cm. 2 Even if the sensitivity of dry film resist reaches 11, the sensitivity of dry film resist is only 11. The use of dry film resist with such low sensitivity will have a significant 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 a layer of, for example, a polyethylene thin film protective layer is adhered to the surface. For example, as described in a patent application with publication number CN113557474A, when the dry film resist contains 9,10-dibutoxyanthracene (DBA), the phenomenon of DBA permeating into the polyethylene thin film is unavoidable, and the sensitivity of the dry film resist continues to decrease, and problems such as the inability to form a desired pattern shape may occur. Such a permeation problem is particularly noticeable when the protective layer is a polyethylene film.

[0011] Due to the negative impact of light scattering on the analysis performance of dry film resist, the analysis ability of dry film resist decreases obviously with the increase of thickness. The analysis ability of conventional dry film resist is generally 0.8-1.0 times the thickness of dry film resist, and carrier board and substrate-like PCB require the analysis ability of the dry film resist used to be 0.5 times or less of the film thickness due to the process and precision requirements. The film thickness of the dry film resist used in the manufacture of conventional carrier board and substrate-like PCB is generally 20-29μm, so the analysis ability is required to be 15μm or less, and 10μm / 10μm circuit technology has already been put on the schedule, and in the near future, the circuit precision of IC carrier board will reach 5μm / 5μm.

[0012] Several kinds of initiator systems for PCB pattern transfer dry film resist suitable for LDI 405nm exposure light source reported in the prior art all have obvious advantages, but also obvious disadvantages. At present, acridine and its derivatives are generally used as initiator systems for high resolution and high sensitivity dry film resists for making high precision HDI inner layer boards. Although acridine initiators have high photosensitivity under 405nm wavelength exposure light source, they cannot promote the oxidation development of leuco developer after exposure, so the contrast of the patterns before and after exposure is poor, and the domestic LDI exposure machine cannot recognize the alignment, and 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] In addition, as electronic devices progress toward becoming lighter, thinner, shorter, and smaller, PCBs are required to have higher definition, higher density, and more layers. Conventional photomask exposure methods consume a large amount of film, have high manufacturing costs, and have limitations in the precision of the circuit patterns obtained through exposure using this method, so they are being replaced by laser direct imaging (LDI), which does not require film and uses digital data to directly irradiate actinic images. This direct writing exposure method can form resist patterns with high productivity and high resolution. A laser with a wavelength of 405 nm is generally used as the exposure light source, which has better exposure precision and can form high-density photosensitive resist patterns that are difficult to produce using conventional technology.

[0014] Automotive PCB panels account for a large proportion of the total PCB demand, and the volume continues to grow, but plating processes are generally used in the manufacture of PCB panels that require thick copper plates, such as automotive PCB panels and industrial control boards. Up until now, the exposure method corresponding to the manufacturing process of such PCB panels has been the traditional photomask exposure method, and the exposure light source is UV mercury lamp irradiation or LED light source, but in recent years, in order to improve the level of production automation by PCB manufacturing clients and increase efficiency and accuracy, laser direct imaging (LDI) is gradually replacing the traditional photomask exposure method.

[0015] In order to meet the process optimization needs of PCB manufacturing clients, dry film resists must simultaneously have high photosensitivity to the laser light source of the laser direct imaging method (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 had excellent electroplating resistance, but had very poor photosensitivity to exposure in laser direct imaging (LDI) with a laser wavelength of 405 nm. The initiator system used in the patent is 4,4'-bis(diethylamino)benzophenone, which is the same initiator commonly used in conventional dry film resists, and such initiator has seriously insufficient photosensitivity to a 405 nm laser light source, and therefore cannot be used to directly image the dry film resist by LDI.

[0017] In short, there is still a need for improvement in the dry film resist resin composition containing DBA, in order to obtain the dry film resist with relatively more stable sensitivity and obtain the resist pattern with higher precision.Therefore, in order to obtain the comprehensive performance with more stability and higher precision, the dry film resist used for the preparation of high precision carrier board is an urgent problem to be solved to further optimize the initiator system. Summary of the Invention [Problem to be solved by the invention]

[0018] SUMMARY OF THE PRESENT EMBODIMENT The primary objective of the present invention is to provide a dry film resist, a photosensitive dry film and a copper clad laminate, which overcomes the need for improved performance of conventional dry film resists. [Means for solving the problem]

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

[0020] Further, (D) the sensitizer comprises a compound containing an anthracene-substituted and / or triarylamine-substituted pyrazoline structure, Preferably, the (D) sensitizer comprises any one or more of the compounds 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 independently represents one or more of a hydrogen atom, a halogen atom, a nitro group, a C1-C8 alkyl group, and a C1-C4 alkoxy group, a represents any one integer of 0 to 5, b represents any one integer of 0 to 4, c represents any one integer of 0 to 5, and d represents any one integer of 0 to 4, and when a is greater than or equal to 2, a plurality of R 01 may be the same or different, and when b is greater than or equal to 2, there are multiple R 02 may be the same or different, and when c is greater than or equal to 2, there are multiple R 04 may be the same or different, and when d is greater than or equal to 2, there are multiple R 05 may be the same or different, each M is independently a benzene ring, a biphenyl group, a fused ring functional group, or an electron-rich heterocyclic or fused heterocyclic functional group; Preferably, M is a phenyl group, a biphenyl group, or a fused ring functional group having one or more of a C1-C4 alkoxy group, an amino group, or an alkyl group, or a heterocycle or a fused heterocycle functional group having furan, thiophene, indole, thiazole, benzofuran, benzothiazole, or fluorene; More preferably, the sensitizer comprises a compound having the structure: [ka]

[0021] Optionally, the benzene ring, biphenyl ring, fused ring, and heterocyclic ring in the above structures contain a substituent, the substituent being any one or more of halogen, C1-C8 alkyl group, and C1-C4 alkoxy group, and preferably the substituent is located at the para position.

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

[0023] Further, 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, preferably 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, 2.0 to 5.0 parts by weight of (C) photopolymerization initiator, and 0.01 to 0.5 parts by weight of (D) sensitizer, preferably the content of the sensitizer is 0.01 wt% to 0.5 wt% of the total weight of the dry film resist.

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

[0025] Preferably, the (C) photopolymerization initiator includes 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] Further, 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, the (B) photopolymerizable monomer comprises an EO segment and a PO segment, the EO segment represents an oxyethylene group, and the PO segment represents an oxypropylene group, preferably, the weight part of the (E) copper complex is 0.01 to 0.5, preferably, the compound forming a complex with copper in the (E) copper complex simultaneously contains a nitrogen-containing heterocyclic ring and a mercapto group, more preferably, the compound forming 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]

[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 a single bond or a double bond, Y is one or more selected from an oxygen atom, a sulfur atom, a carbon atom, and a nitrogen atom, and the hydrogen atoms of the ring formed by X, Y, and -C=NH- are a carboxy group, an amino group, a C1 to C2 group, 12 Alkyl groups, C1-C 12 Alkoxy group, C6-C 12 aryl group, or hydrazino group, and M is a single bond, C1 to C 12 Alkyl groups, C1-C 12 Ester group or C2-C 12 ether groups,

[0028] In formula IV, the ring constituted by X, Y, and Z is a benzene ring or a heterocycle, and the benzene ring and the heterocycle may have one or more of a C1-C6 alkyl group, a C1-C6 alkoxy group, an amino group, a carboxylic acid, a nitro group, and a halogen;More preferably, the compound forming 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-mercaptoindole, 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-hydrazine 5-mercapto-1,2,4-triazole, 1-methyl-5-mercapto-1H-tetrazole, 1-hydroxyethyl-5-mercapto-1H-tetrazole, 1-(2-dimethylaminoethyl)-1H-5-mercapto-tetrazole, 1-phenyl-5-mercaptotetrazole, 1,2-dihydro-1-(4-methoxyphenyl)-5H-tetraaza-5-thione, 1-ethyl-5-mercapto-1,2,3,4-tetrazole, 5-mercapto-1,2,3,4-tetrazole, 5-mercapto-1H-tetrazole-1-acetic acid, 5-mercapto-1,2,3,The compound is at least one selected from the group consisting of 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-thione, 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 H or CH3, EO represents an oxyethylene group, PO represents an oxypropylene group, the arrangement of EO and PO repeating units is random or block, m1 and m2 are each an arbitrary integer of 1 to 20, n1 and n2 are each an arbitrary integer of 0 to 20, and m1+m2 is an arbitrary integer of 2 to 20, n1+n2 is an arbitrary integer of 0 to 20, a1 is an arbitrary integer of 4 to 20, b1 is an arbitrary integer of 0 to 20, a2 is an arbitrary integer of 3 to 20, b2 is an arbitrary integer of 0 to 20, and c2 is an arbitrary integer of 3 to 20.

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

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

[0032] More preferably, the (B) photopolymerizable monomer is one or more selected from the group consisting of 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, the (B) photopolymerizable monomer contains 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 each an arbitrary integer of 1 to 20, n1 and n2 are each an arbitrary integer of 0 to 20, and m1+m2 is an arbitrary integer of 2 to 20, and n1+n2 is an arbitrary integer of 0 to 20, EO represents an oxyethylene group, PO represents an oxypropylene group, and the arrangement of EO and PO repeating units is random or block. Preferably, the photopolymerizable monomer having the structure represented by structural formula B1 accounts for 20% to 80% of the total amount of the photopolymerizable monomer, more preferably 40% to 80%, and 10% to 35% of the total weight of the (B) photopolymerizable monomer and the (A) alkali-soluble resin, and more preferably, the (B) photopolymerizable monomer further comprises lauryl (meth)acrylate, stearyl (meth)acrylate, nonylphenol acrylate, isobornyl ester, tetrahydrofuran methyl acrylate, bisphenol A di(meth)acrylate, or the like. The acrylate or acrylate copolymer may include one or more selected from the group consisting of 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 formula, R1 is independently H or CH3, and the arrangement of the EO segment and the PO segment repeat unit is random or block. In the structural formula IV, m1 and m2 are each an arbitrary integer of 0 to 30, n1 and n2 are each an arbitrary integer of 0 to 20, and m1+m2 is an arbitrary integer of 0 to 30, and n1+n2 is an arbitrary integer of 0 to 20. In the structural formula B5, a5 is an arbitrary integer of 0 to 30, and b5 is an arbitrary integer of 0 to 20. In the structural formula B6, a6 is an arbitrary integer of 0 to 30, and b6 is an arbitrary integer of 0 to 20. In the structural formula B7, a7 is an arbitrary integer of 0 to 20, and b7 is an arbitrary integer of 0 to 20. Preferably, 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; More preferably, the photopolymerizable monomer further includes 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, the alkali-soluble resin (A) is obtained by copolymerizing (meth)acrylic acid, (meth)acrylate, and styrene or a styrene derivative, and the alkali-soluble resin (A) contains one or more of the compounds represented by structural formula A1, [ka] In the formula, R2, R3, R5, and R7 each independently represent a hydrogen atom or a methyl group, R4 and R6 each independently represent 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, and a halogen atom, p and q each independently represent an integer of 0 to 5, R8 is one of a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, x, y, z, and u each independently represent a ratio of each copolymerization component in the alkali-soluble resin, with the proviso that 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%; The alkali-soluble resin (A) preferably has an acid value of 120 to 250 mgKOH / g, more preferably has a weight average molecular weight of 30,000 to 120,000, a molecular weight distribution of 1.3 to 2.5, and further preferably has a polymerization conversion rate of ≧97%.

[0036] Further, in the structural formula A1, x is 15 to 35 wt%, z is 0 to 50 wt%, u is 0 to 80 wt%, y is 0 to 25 wt%, and the value of z+u is 40 wt% to 80 wt%, Preferably, the copolymerization unit of the alkali-soluble resin (A) 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 ethyl (meth)acrylate, N,N-diethyl ethyl (meth)acrylate, N,N-diethyl propyl (meth)acrylate, N,N-dimethyl butyl (meth)acrylate, and N,N-diethyl butyl (meth)acrylate; Preferably, 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.

[0037] Further, in the structural formula A1, R3 is hydrogen, x is 15 to 40 wt%, z is 0 to 40 wt%, u is 0, and y is 20 to 60 wt%, Preferably, the copolymerization unit of the alkali-soluble resin (A) is selected from a (meth)acrylic acid alkyl ester and styrene and / or a derivative thereof, and the (meth)acrylic acid alkyl ester is 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, and 2-hydroxyethyl (meth)acrylate. , 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, glycidyl (meth)acrylate, N,N-dimethyl ethyl (meth)acrylate, N,N-diethyl ethyl (meth)acrylate, N,N-diethyl propyl (meth)acrylate, N,N-dimethyl butyl (meth)acrylate and N,N-diethyl butyl (meth)acrylate, and the styrene derivative is one or more selected from α-methylstyrene and benzyl (meth)acrylate, More preferably, the content of styrene in the copolymerization units of the alkali-soluble resin (A) is 0 to 40 wt % of the total weight of the copolymerization units, Preferably, 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.

[0038] Further, in the structural formula A1, R3 is hydrogen, x is 15 to 40 wt%, z is 0 to 40 wt%, u is 0, and y is 20 to 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, N,N-dimethyl ethyl (meth)acrylate, N,N-diethyl ethyl (meth)acrylate, N,N-diethyl propyl (meth)acrylate, N,N-dimethyl butyl (meth)acrylate, and N,N-diethyl butyl (meth)acrylate; Preferably, 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.

[0039] Furthermore, the dry film resist further includes an additive, and the additive includes any one or more of a free radical polymerization inhibitor, a color former, a dye, a plasticizer, a photothermal stabilizer, an adhesion promoter, a leveling agent, and an antifoaming agent, and the content of the additive is preferably 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 inhibitor is 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- The resorcinol is any 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] In order to achieve the above object, another aspect of the present application provides a photosensitive dry film, the photosensitive dry film including 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 includes any of the dry film resists described above.

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

[0042] Furthermore, the compound that forms a complex with copper in the copper complex (E) simultaneously contains a nitrogen-containing heterocycle and a mercapto group, and preferably, the compound that forms a complex with copper in the copper complex (E) 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 a single bond or a double bond, Y is one or more selected from an oxygen atom, a sulfur atom, a carbon atom, and a nitrogen atom, and the hydrogen atoms of the ring formed by X, Y, and -C=NH- are a carboxy group, an amino group, a C1 to C2 group, 12 Alkyl groups, C1-C 12 Alkoxy group, C6-C 12 aryl group, or hydrazino group, and M is a single bond, C1 to C 12 Alkyl groups, C1-C 12 Ester group or C2-C 12 ether groups, In formula IV, the ring constituted by X, Y, and Z is a benzene ring or a heterocycle, and the benzene ring and the heterocycle may have one or more of a C1-C6 alkyl group, a C1-C6 alkoxy group, an amino group, a carboxylic acid, a nitro group, and a halogen; More preferably, the compound forming 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-mercaptoindole, 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-hydrazine 5-mercapto-1,2,4-triazole, 1-methyl-5-mercapto-1H-tetrazole, 1-hydroxyethyl-5-mercapto-1H-tetrazole, 1-(2-dimethylaminoethyl)-1H-5-mercapto-tetrazole, 1-phenyl-5-mercaptotetrazole, 1,2-dihydro-1-(4-methoxyphenyl)-5H-tetraaza-5-thione, 1-ethyl-5-mercapto-1,2,3,4-tetrazole, 5-mercapto-1,2,3,4-tetrazole, 5-mercapto-1H-tetrazole-1-acetic acid, 5-mercapto-1,2,3,The compound is at least one selected from the group consisting of 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-thione, 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, and 4-amino-2-mercaptopyrimidine.

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

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

[0045] More preferably, the modifying functional group M1 is a fused ring functional group having one or more of a C1 to C4 alkoxy group, an amino group, and an alkyl group, or is any one of furan, thiophene, indole, thiazole, benzofuran, benzothiazole, indene, anthracene, acridine, and an aromatic amine, and the specific structural formula of the modifying functional group M1 and / or M2 is still more preferably: [ka] Including, During the ceremony, [ka] is a bonding position of a functional group, and optionally, the benzene ring, biphenyl ring, fused ring, and heterocyclic ring in the specific structural formula of the modifying functional group M1 and / or M2 contain one or more kinds of substituents selected from halogen, C1-C8 alkyl groups, and C1-C4 alkoxy groups, and preferably, the substituents are located at the para position.

[0046] Furthermore, the (C) photopolymerization initiator contains a compound represented by the following structural formula C1: [ka] In the formula, each substituent A in the benzene ring is independently a hydrogen atom, a methoxy group, or a halogen atom; Preferably, 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, Optionally, (C) the photoinitiator is further selected from the group consisting of 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 The compound includes one or more 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, benzil dimethyl ketal, 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane, N-phenylglycine, coumarin-based compounds, and oxazole-based compounds.

[0047] Further, the photopolymerizable monomer includes one or more of the compounds represented by structural formulas B1, B2, B3, and B4, [ka] [ka] [ka] [ka] In the formula, R1 is independently H or CH3, and the arrangement of the EO segment and the PO segment repeating units is random or block. In the structural formula B1, m1 and m2 are each an arbitrary integer of 0 to 30, n1 and n2 are each an arbitrary integer of 0 to 20, and m1+m2 is an arbitrary integer of 0 to 30, and n1+n2 is an arbitrary integer of 0 to 20. In the structural formula B5, a5 is an arbitrary integer of 0 to 30, and b5 is an arbitrary integer of 0 to 20. In the structural formula B6, a6 is an arbitrary integer of 0 to 30, and b6 is an arbitrary integer of 0 to 20. In the structural formula B7, a7 is an arbitrary integer of 0 to 20, and b7 is an arbitrary integer of 0 to 20. Preferably, 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; More preferably, the (B) photopolymerizable monomer further includes 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, the alkali-soluble resin (A) is obtained by copolymerizing (meth)acrylic acid, (meth)acrylate, and styrene or a styrene derivative, and the alkali-soluble resin includes any one or more of structures represented by structural formula A2, [ka] In the formula, R2 and R7 are each independently a hydrogen atom or a methyl group, and R8 is a C1-C18 Straight chain alkyl groups and C3-C 18 A branched alkyl group, a benzyl group, and a substituted C1-C aryl group containing a hydroxyl group and / or an amino group. 18 Straight chain alkyl group or C3-C 18 and a branched alkyl group, R4 is any one of a C1-C3 alkyl group, a C1-C3 alkoxy group, an amino group, and a halogen atom, and the structural formula is A2 the number of substituents in the benzene ring is 0 to 5, x, y, and z each represent a ratio of each copolymerization 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, N,N-dimethyl ethyl (meth)acrylate, N,N-diethyl ethyl (meth)acrylate, N,N-diethyl propyl (meth)acrylate, N,N-dimethyl butyl (meth)acrylate, and N,N-diethyl butyl (meth)acrylate; The alkali-soluble resin more preferably has an acid value of 120 to 250 mgKOH / g, more preferably has a weight average molecular weight of 50,000 to 120,000 and a molecular weight distribution of 1.3 to 2.5, and even more preferably has a polymerization conversion rate of ≧97%.

[0049] Furthermore, the dry film resist further contains an additive, and the additive includes any one or more of a color former, a dye, a plasticizer, a photothermal stabilizer, an adhesion promoter, a leveling agent, a polymerization inhibitor, and an antifoaming agent, and preferably, the content of the additive is 0.5 to 5.0 parts by weight.

[0050] Yet another aspect of the present application provides a photosensitive dry film, the photosensitive dry film including 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 includes any of the dry film resists described above.

[0051] Yet another aspect of the present application provides a copper-clad laminate, the copper-clad laminate being provided with any of the dry film resists described above. Effect of the Invention

[0052] The dry film resist of the present invention uses a specific type of sensitizer, and therefore has good overall performance, particularly outstanding in photosensitivity, resolution, alignment recognition adaptability and electroplating resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0053] In addition, the embodiments and features of the embodiments of the present application can be combined with each other as long as there is no contradiction.

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

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

[0056] The dry film resist includes a sensitizer containing a pyrazoline structure, and when used in combination with an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator, the overall performance of the dry film resist can be effectively improved.

[0057] In some exemplary embodiments of the present application, the above sensitizer (D) comprises a compound containing an anthracene-substituted and / or triarylamine-substituted pyrazoline structure. The present application optimizes the structure of anthracene-based and triarylamine-based sensitizers that are commonly used in dry film resists for high-end PCBs such as carrier boards and substrate-like PCBs by introducing pyrazoline structures into anthracene and / or triarylamine, and the imidazoline compound has good photosensitivity, so its photosensitivity to the LDI 405 nm 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 large π-conjugated electronic effect, the maximum absorption wavelength of the modified sensitizer compound is shifted to the red side, and is closer to the wavelength of the 405 nm laser light source. Therefore, the present application introduces pyrazoline structures into specific anthracene and triarylamine molecules, which can obviously improve the photosensitivity of the resulting dry film resist to the LDI 405 nm laser light source.

[0058] Since the structure of the above sensitizer simultaneously contains a pyrazoline ring structure and an anthracene or triarylamine structure, the sensitizer compound after optimization modification has dual active functional groups, and effectively combines the photosensitivity of the pyrazoline structure and the high-precision analysis ability of the anthracene or triarylamine structure, thereby ensuring the high-precision analysis ability of the dry film resist containing it, and can improve the production efficiency of clients who manufacture high-end PCBs such as carrier boards and substrate-like PCBs.

[0059] Analysis of the causes of the harmful issue of migration and penetration of the sensitizer 9,10-dibutoxyanthracene (DBA) revealed that, on the one hand, DBA has very low sensitivity, and in order to reach a certain degree of hardening and form a resist pattern with good appearance, a large amount of DBA is required to be added; on the other hand, DBA is a small molecule and its molecular structure contains a long alkyl chain, and due to molecular movement and the theory that similar molecules dissolve, DBA molecules are prone to migration into the polyethylene protective film, which also has an alkyl group structure. Based on the mechanism of molecular motion and the theory that similar things dissolve in each other, the present application introduces a pyrazoline structure into an anthracene compound to modify the structure of the anthracene sensitizer DBA. The introduced pyrazoline functional group also generally has another aromatic ring structure, so that the molecular weight of the anthracene sensitizer increases, and a large aromatic ring structure is introduced into the DBA molecular structure. Both of these can significantly reduce the harmful problem of the pyrazoline structure sensitizer of the present application migrating and penetrating into the polyethylene protective film, and thus a dry film resist with more stable properties in each aspect such as sensitivity and resist pattern can be obtained.

[0060] The compound containing the above anthracene-substituted and / or triarylamine-substituted pyrazoline structure only needs to have a corresponding chemical structure, so that a compound having a corresponding structure may be selected from conventional compounds. In some preferred embodiments of the present application, the sensitizer (D) has one or more of the structures represented by the 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 independently represents one or more of a hydrogen atom, a halogen atom, a nitro group, a C1-C8 alkyl group, and a C1-C4 alkoxy group, a represents any one integer of 0 to 5, b represents any one integer of 0 to 4, c represents any one integer of 0 to 5, and d represents any one integer of 0 to 4, and when a is greater than or equal to 2, a plurality of R 01 may be the same or different, and when b is greater than or equal to 2, there are multiple R 02 may be the same or different, and when c is greater than or equal to 2, there are multiple R 04 may be the same or different, and when d is greater than or equal to 2, there are multiple R 05 may be the same or different, and M is each independently a benzene ring, a biphenyl group, a fused ring functional group, or an electron-rich heterocyclic ring or a fused heterocyclic ring functional group, where the benzene ring represents a phenyl group or a derivative functional group of a phenyl group, the biphenyl group represents a biphenyl group or a derivative functional group of a biphenyl group, the fused ring functional group represents a fused ring or a derivative functional group of a fused ring, and the electron-rich heterocyclic ring or a fused heterocyclic ring functional group represents a derivative functional group of an electron-rich heterocyclic ring or a fused heterocyclic ring. For example, the above-mentioned derivative functional group may be a functional group containing a substituent such as a C1-C4 alkoxy group, an amino group, a C1-C8 alkyl group, or a halogen, and the number of the substituents may be one or more.

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

[0062] The above-mentioned benzene ring, biphenyl ring, fused ring, and heterocyclic ring may further contain a substituent, which is any one or more of halogen, C1-C8 alkyl group, and C1-C4 alkoxy group, and the number of the substituents is not limited. Preferably, the substituent is located at the para position, which has a better effect.

[0063] In some exemplary embodiments of the present application, the (D) sensitizer comprises any one or more of the compounds represented by the following structural formula I or II: [ka] [ka] In the formula, R0 is independently hydrogen, halogen, C1-C8 alkyl group or C1-C4 alkoxy group; the modifying functional group M1 in the structural formula I is independently biphenyl functional group, fused ring functional group, or substituted benzene ring having one or more of electron-rich heterocyclic ring, fused heterocyclic ring, C1-C4 alkoxy group, and amino group; the modifying functional group M2 in the structural formula II is selected from biphenyl, fused ring functional group, or electron-rich heterocyclic ring, fused heterocyclic ring, or substituted benzene ring having one or more of C1-C4 alkoxy group, C1-C3 alkyl group, and amino group; and the modifying functional group W is one of benzene ring and fluorene ring, or benzene ring, biphenyl ring, or fluorene ring having one or more of halogen, C1-C8 alkyl group, and C1-C4 alkoxy group.

[0064] The present application introduces several modified functional groups, such as biphenyl, fused ring functional group, electron-rich heterocycle or fused heterocycle and benzene ring with amino group, into pyrazoline-based compound, so that the sensitizer compound shown in formula I or II has an electron-rich conjugated system as a whole molecular structure after modification, and such electron-rich conjugation effect is helpful to promote the red shift of the absorption spectrum of the sensitizer, and its absorption spectrum extends to the visible light region. After modification, the maximum absorption wavelength of the sensitizer is closer to the exposure light source with a wavelength of 405 nm, so 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. In addition, by selecting the sensitizer with the above specific structure, not only does the dry film resist have high photosensitivity and resolution, but such a sensitizer can effectively promote the oxidative development of the leuco developer after exposure, and further enhance the contrast of the pattern before and after exposure, which is more helpful for its alignment recognition in domestic LDI exposure machine, and ensures its alignment accuracy in domestic LDI exposure machine. In addition, the dry film resist containing the above-mentioned sensitizer of the present application has a rich source of components. In particular, the sensitizer not only provides the dry film resist with both high photosensitivity and high alignment recognition adaptability, but also has a rich source and low cost, which can effectively reduce the production cost of high-end dry film sensitizers, and has very good market application value.

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

[0066] In some preferred embodiments, the specific structural formula of the modifying functional group M1 and / or M2 is: [ka] wherein: [ka] is a bonding position of a functional group, and optionally, the benzene ring, biphenyl ring, fused ring, and heterocycle in the specific structural formula of the modifying functional group M1 and / or M2 contain one or more substituents selected from the group consisting of halogen, C1-C8 alkyl group, and C1-C4 alkoxy group, and there is no limitation on the number of the substituents. Preferably, the substituents are located at the para position.

[0067] In the dry film resist of the present application, the contents of (A) the alkali-soluble resin, (B) the photopolymerizable monomer, (C) the photopolymerization initiator, and (D) the sensitizer may be determined based on the conventional technology, and are not limited in the present application. In some embodiments of the present application, in order to better exert the synergistic effect of each component, the above dry film resist comprises 45-65 parts by weight of (A) alkali-soluble resin, 30-50 parts by weight of (B) photopolymerizable monomer, 1.0-5.0 parts by weight of (C) photopolymerization initiator, and 0.01-0.5 parts by weight of (D) sensitizer. If the amount of the sensitizer added is too low, the obtained dry film resist has poor photosensitivity. If the amount added is too high, the surface layer of the dry film resist hardens too quickly, which affects the depth of hardening and there is a risk of reducing the adhesion of the dry film resist to the copper surface. In order to improve the sensitivity, resolution, and adhesion in a more balanced manner, the content of the sensitizer is preferably 0.01wt%-0.5wt% 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 contains 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.

[0069] The above-mentioned (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 the present 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 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 and (3,4-dimethoxyphenyl)-4',5'-diphenyl-1,1'-diimidazole. In addition to the above photopolymerization initiators, a small amount of other types of photopolymerization initiators, such as thioxanthone, benzoin phenyl ether, benzophenone, benzoin methyl ether, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, One or more of the following benzyl derivatives may be used in combination: xophenone, 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, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzil dimethyl ketal, and benzoyl dimethyl ether; 9-phenylacridine, and 1,7-bis(9,9'-acridinyl)heptane; N-phenylglycine, coumarin compounds, and oxazole compounds; and the specific amount of use may be determined based on the prior art and is not limited here.

[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 includes (E) a copper complex, wherein the compound that forms a complex with copper in the (E) copper complex includes a nitrogen-containing heterocyclic compound, and (B) the photopolymerizable monomer includes an EO segment and a PO segment, wherein the EO segment represents an oxyethylene group and the PO segment represents an oxypropylene group, and the above EO segment and PO segment may be derived from one or more specific photopolymerizable monomers simultaneously containing an EO segment and a PO segment, or a photopolymerizable monomer containing an EO segment and a PO segment, respectively, may be blended, or a photopolymerizable monomer containing an EO segment and a PO segment in different ratios may be blended.

[0072] The dry film resist containing the complex formed by the above nitrogen-containing heterocyclic compound and copper has the following characteristics: on the one hand, the nitrogen-containing heterocyclic structure has high polarity, so the copper complex can enhance the action force between the metal copper, and on the other hand, the lone pair 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 bond force between the compound and the copper atom. Due to these two effects, the addition of the above copper coordination compound can significantly strengthen the bond force of the dry film resist to the copper surface, and can alleviate the phenomenon that the side wall of the bottom part is slightly warped during the electroplating process of the dry film, thereby improving the electroplating resistance of the dry film resist.

[0073] In addition, the photopolymerizable monomer contains hydrophilic functional group ethylene oxide (EO) and hydrophobic functional group propylene oxide (PO) at the same time. On the one hand, if the photopolymerizable monomer contains hydrophilic functional group ethylene oxide (EO) segment, it can improve the water solubility of the dry film resist, thereby improving the developability and resolution of the dry film resist. On the other hand, if the photopolymerizable monomer contains only ethylene oxide segment, the water solubility of the dry film resist is improved, and the dry film resist is prone to warping of the side wall due to swelling, which causes a harmful problem called cementation. However, if the photopolymerizable monomer contains hydrophobic functional group propylene oxide (PO) segment, it can improve the hydrophobicity of the dry film resist to a certain extent, thereby improving the electroplating resistance of the dry film resist. Furthermore, the photopolymerizable monomer has a good balance between hydrophilicity and hydrophobicity of the dry film resist from the chemical structure, which allows the dry film resist photosensitive material to be obtained with balanced developability, analysis ability and electroplating resistance.

[0074] In order to further improve the electroplating resistance of the dry film resist, in some embodiments of the present application, the weight part of (E) the copper complex is 0.01 to 0.5. There is no special requirement for the nitrogen-containing heterocyclic compound complexed with copper, and it may be a saturated nitrogen-containing heterocyclic ring or an unsaturated nitrogen-containing heterocyclic ring, and the heterocyclic ring may contain one nitrogen atom or multiple nitrogen atoms. In some preferred embodiments of the present application, the compound that forms a complex with copper in the copper complex simultaneously contains a nitrogen-containing heterocyclic ring and a mercapto group, and the number of mercapto groups may be one or multiple.

[0075] In some preferred embodiments, the compound that forms a complex with copper in the (E) copper complex has one or more of the structures shown in 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 a single bond or a double bond, Y is one or more selected from an oxygen atom, a sulfur atom, a carbon atom, and a nitrogen atom, and the hydrogen atoms of the ring formed by X, Y, and -C=NH- are a carboxy group, an amino group, a C1 to C2 group, 12 Alkyl groups, C1-C 12 Alkoxy group, C6-C 12 aryl group, or hydrazino group, and M is a single bond, C1 to C 12 Alkyl groups, C1-C 12 Ester group or C2-C 12 In the structural formula IV, the ring formed by X, Y, and Z is a benzene ring or a heterocycle, and the benzene ring and the heterocycle may have one or more of a C1-C6 alkyl group, a C1-C6 alkoxy group, an amino group, a carboxylic acid, a nitro group, and a halogen.

[0077] In formula IV, Z is not limited to a single atom or functional group, and the ring formed by Z, X, and Y is a benzene ring or a heterocycle, where the heterocycle may be saturated or unsaturated, and the benzene ring and the heterocycle may have one or more of C1-C6 alkyl groups, C1-C6 alkoxy groups, amino groups, carboxylic acids, nitro groups, and halogens, that is, formula IV represents a heterocyclic compound in which a benzene ring or a heterocycle and a nitrogen-containing heterocycle are condensed. In formula III or IV above, the number of mercapto groups may be 1 to 6.

[0078] Examples of the compound that forms a complex with 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-mercaptoindole, 1,3,5-tris(mercaptoethyl)-1,3,5-trimethylphenylacetamide, 1,3,5-tris(phenylacetamide), ... riazine-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 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-tetrazole, 1-hydroxyethyl-5-mercapto-1H-tetrazole, 1-(2-dimethylaminoethyl)-1H-5-mercapto-tetrazole, 1-phenyl-5-mercaptotetrazole, 1,2-dihydro-1-(4-methoxyphenyl)-5H-tetraaza-5-thione, 1-ethyl-5-mercapto-1,2,3,4-tetrazole, 5-mercapto-1H-tetrazole-1-acetic acid, 5-mercapto-1,2,3,One or more of 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-thione, 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, and 4-amino-2-mercaptopyrimidine may be selected from the group consisting of 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-thione, 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 the rearrangement of electrons, the chemical structural formulas show that the sulfur atom and the heterocycle may be connected to the nitrogen-containing heterocycle by a single bond or a double bond. [ka]

[0079] The photopolymerizable monomer may be selected from the prior art. In some embodiments of the present application, when the sensitizer in the dry film resist includes the compound containing the anthracene-substituted and / or triarylamine-substituted pyrazoline structure, in order to further improve the resolution and adhesion of the dry film resist, the photopolymerizable monomer (B) 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 H or CH3, EO represents an oxyethylene group, PO represents an oxypropylene group, the arrangement of EO and PO repeating units is random or block, m1 and m2 are each any integer from 1 to 20, n1 and n2 are each any integer from 0 to 20, and m1+m2 is any integer from 2 to 20, n1+n2 is any integer from 0 to 20, a1 is any integer from 4 to 20, b1 is any integer from 0 to 20, a2 is any integer from 3 to 20, b2 is any integer from 0 to 20, and c2 is any integer from 3 to 20.

[0080] In the above-mentioned dry film resist system, in order to improve the resolution and adhesion in a more balanced manner, the photopolymerizable monomer (B) having a structure represented by structural formula B1 accounts for 40% to 90% of the total amount of the photopolymerizable monomer (B), more preferably 50% to 80%, and is 20% to 40% of the total weight of the photopolymerizable monomer (B) and the alkali-soluble resin (A).

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

[0082] Preferably, in addition to the above photopolymerizable monomer, the photopolymerizable monomer further comprises some other commonly used monofunctional, difunctional or polyfunctional (meth)acrylate-based ethylenically unsaturated double bond monomers.The above polyfunctional photopolymerizable monomer can be the trifunctional photopolymerizable monomer represented by structural formula B4, or can be other tetrafunctional photopolymerizable monomer, pentafunctional photopolymerizable monomer 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 of low sensitivity and low resolution, whereas if the weight is too high, the adhesive is likely to overflow onto the photosensitive layer.

[0085] When the sensitizer in the 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., EO / PO modified bisphenol A structure (meth)acrylate. [ka] In the formula, R1 is independently H or CH3, m1 and m2 are each an integer of 1 to 20, n1 and n2 are each an integer of 0 to 20, and m1+m2 is an integer of 2 to 20, and n1+n2 is an integer of 0 to 20, EO represents an oxyethylene group, PO represents an oxypropylene group, and the arrangement of EO and PO repeating units is random or block.

[0086] In order to improve the resolution and adhesion in a more balanced manner in the dry film resist system, the photopolymerizable monomer having the structure represented by Structural Formula IV accounts for 20% to 80% of the total amount of the photopolymerizable monomer (B), more preferably 40% to 80%, and 10% to 35% of the total weight of the photopolymerizable monomer (B) and the alkali-soluble resin (A). Preferably, in addition to the above photopolymerizable monomer, the photopolymerizable monomer (B) may further include some other commonly used monofunctional, bifunctional or polyfunctional (meth)acrylate-based ethylenically unsaturated double bond monomers. In some embodiments of the present application, the photopolymerizable monomer further includes 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 the dry film resist system in which the sensitizer contains the compound represented by the 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 of low sensitivity and low resolution, whereas if the weight is too high, the adhesive is likely to overflow onto the photosensitive layer.

[0088] When the dry film resist of the present application contains the above-mentioned copper complex, in order to better exert the synergistic effect of each component and further improve the electroplating resistance, developing ability and analyzing ability of the dry film resist, (B) the photopolymerizable monomer contains any one or more of the compounds represented by structural formulas B1, B5, B6 and B7, [ka] [ka] [ka] [ka] In the formula, R1 is independently H or CH3, the arrangement of the EO segment and the PO segment repeating unit is random or block, in the structural formula B1, m1 and m2 are each an arbitrary integer of 0 to 30, n1 and n2 are each an arbitrary integer of 0 to 20, and m1+m2 is an arbitrary integer of 0 to 30, and n1+n2 is an arbitrary integer of 0 to 20, in the structural formula B5, a5 is an arbitrary integer of 0 to 30, and b5 is an arbitrary integer of 0 to 20, in the structural formula B6, a6 is an arbitrary integer of 0 to 30, and b6 is an arbitrary integer of 0 to 20, in the structural formula B7, a7 is an arbitrary integer of 0 to 20, and b7 is an arbitrary integer of 0 to 20. Preferably, 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. More preferably, the (B) photopolymerizable monomer further includes 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 any 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 each independently represent a hydrogen atom or a methyl group, R4 and R6 each independently represent 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 each independently represent an integer of 0 to 5, R8 is any one of linear, branched, and cyclic alkyl groups having 1 to 18 carbon atoms, x, y, z, and u each independently represent a ratio of each copolymerization 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, the acid value of the alkali-soluble resin (A) is 120 to 250 mgKOH / g. This is because if the acid value of the alkali-soluble resin is too small, the solubility in alkali deteriorates and the development and film removal times tend to be long, whereas if the acid value of the alkali-soluble resin is too large, 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 (A) alkali-soluble resin is 30,000 to 120,000, and the molecular weight distribution is 1.3 to 2.5. The (A) alkali-soluble resin may be one type of copolymer resin represented by structural formula A1, or may be an alkali-soluble copolymer resin obtained by blending two or more types of such copolymer resins having different molecular weights, different acid values, or different styrene contents, and preferably has a polymerization conversion rate of 97% or more.

[0092] 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 better exert a synergistic effect, in the structural formula A1 representing the above 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 is helpful in further improving the photosensitivity, resolution, sensitivity, and stability of the resist pattern of the dry film resist. When the dry film resist system is used, the copolymerization unit of the alkali-soluble resin (A) is preferably 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 ethyl (meth)acrylate, N,N-diethyl ethyl (meth)acrylate, N,N-diethyl propyl (meth)acrylate, N,N-dimethyl butyl (meth)acrylate, and N,N-diethyl butyl (meth)acrylate. Preferably, the alkali-soluble resin has a weight average molecular weight of 30,000 to 80,000 and a molecular weight distribution of 1.3 to 2.5. A narrow molecular weight distribution is useful for improving the resolution of the dry film resist.

[0093] When the sensitizer in the dry film resist contains the compound represented by the above structural formula I or II, in order to further improve the overall performance of the dry film resist, in the structural formula A1 representing the above 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%. In the case where the dry film resist system is used, the copolymerization unit of the alkali-soluble resin (A) preferably contains an alkyl (meth)acrylate, for example, selected from an alkyl (meth)acrylate and styrene and / or a derivative thereof, and the alkyl (meth)acrylate is, for example, 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 ... The copolymerization unit of the alkali-soluble resin contains styrene or its derivative, and preferably, the styrene derivative is one or more selected from α-methylstyrene and benzyl (meth)acrylate, and when benzyl (meth)acrylate is selected as the copolymerization unit, the styrene copolymerization unit may be absent. In addition, compared with the styrene derivative, styrene has a better effect as a copolymerization monomer, and in some preferred embodiments of the present application, the content of styrene in the copolymerization unit of the alkali-soluble resin is 0-40wt% of the total weight of the copolymerization unit. Preferably, the alkali-soluble resin has a weight average molecular weight of 30,000 to 80,000 and a molecular weight distribution of 1.3 to 2.5. A narrow molecular weight distribution is useful for improving the resolution of the dry film resist.

[0094] When the dry film resist of the present application contains a copper complex, in order to further exert a synergistic effect between the respective components, in the structural formula A1 representing the above (A) alkali-soluble resin, R3 is hydrogen, x is 15 to 40 wt%, z is 0 to 40 wt%, u is 0, and y is 20 to 70 wt%, that is, the alkali-soluble resin (A) is obtained by copolymerizing (meth)acrylic acid, (meth)acrylate, and styrene or a styrene derivative, and preferably, the above (meth)acrylate may be an alkyl (meth)acrylate ester, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, or alkyl (meth)acrylate. The alkali-soluble resin may be any one or more of 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 ethyl (meth)acrylate, N,N-diethyl ethyl (meth)acrylate, N,N-diethyl propyl (meth)acrylate, N,N-dimethyl butyl (meth)acrylate, and N,N-diethyl butyl (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 the dry film resist.

[0095] In order to further improve the resolution, adhesion, and characteristics 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 the unexposed parts during resist pattern formation. From the viewpoint of the manufacturing process, the additive of the present application may further contain one or more of a color former, a dye, a plasticizer, a photothermal stabilizer, an adhesion promoter, a leveling agent, and an antifoaming agent, and the compounding ratio may be that of the conventional technology. Preferably, the content of the above additives is 0.5 to 5.0 parts by weight.

[0096] The free radical polymerization inhibitor 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 ... resorcinol, 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 the present application, the content of the above-mentioned free radical polymerization inhibitor is 0.001wt%-0.005wt% of the total weight of the dry film resist. If the amount is too low, the resolution of the obtained dry film resist is insufficient, and if the amount is too high, the photosensitivity of the dry film resist is not very good.

[0097] Another exemplary embodiment of the present application provides a photosensitive dry film, the photosensitive dry film including a dry film resist layer, and a support layer and a protective layer located on either side of the dry film resist layer, wherein the dry film resist layer includes any of the dry film resists described above.

[0098] The photosensitive dry film of the present application uses a dry film resist that has high photosensitivity, high resolution, and more stable properties in terms of sensitivity, resist pattern, etc., and therefore has excellent performance in photosensitivity, resolution and stability. It is suitable for the production of high-end PCBs such as carrier boards and substrate-like PCBs, and can improve the yield rate and significantly improve the production efficiency and reduce production costs in the fields of PCB manufacturing, lead frame manufacturing, semiconductor packaging, and the production of parts such as ITO in the flat panel display fields.

[0099] The photosensitive dry film of the present application uses an imaging type dry film resist by direct imaging exposure, which has high photosensitivity, high resolution, and high adaptability to alignment recognition in different types of LDI exposure machines, and therefore has good photosensitivity, resolution, and alignment accuracy, and can be used with different types of LDI exposure machines to achieve comprehensive performance such as excellent adaptability to alignment recognition, thereby improving the yield rate and significantly improving the production efficiency of parts such as ITO in the fields of PCB manufacturing, lead frame manufacturing, semiconductor packaging, and flat panel display, and reducing production costs.

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

[0101] This dry film resist contains a complex formed by a nitrogen-containing heterocyclic compound and copper, on the one hand, the nitrogen-containing heterocyclic structure has high polarity, so that this copper complex can enhance the action force between the metal copper, and on the other hand, the lone pair 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 binding force between this compound and the copper atom. Due to these two actions, the addition of the above-mentioned copper complex can significantly strengthen the binding force of the dry film resist to the copper surface, and can improve the phenomenon that the sidewall of the bottom part is slightly warped during the electroplating process of the dry film, thereby improving the electroplating resistance of the dry film resist.

[0102] In addition, the photopolymerizable monomer in the above dry film resist contains hydrophilic functional group ethylene oxide (EO) and hydrophobic functional group propylene oxide (PO) at the same time. On the one hand, if the photopolymerizable monomer contains hydrophilic functional group ethylene oxide (EO) segment, it can improve the water solubility of the dry film resist, thereby improving the developability and resolution of the dry film resist. On the other hand, if the photopolymerizable monomer only contains ethylene oxide segment, the water solubility of the dry film resist is improved, and the dry film resist is prone to warping of the side wall due to swelling, which causes a harmful problem called cementation. However, if the photopolymerizable monomer contains hydrophobic functional group propylene oxide (PO) segment, it can improve the hydrophobicity of the dry film resist to a certain extent, thereby improving the electroplating resistance of the dry film resist. Furthermore, the photopolymerizable monomer has a good balance between the hydrophilicity and hydrophobicity of the dry film resist from the chemical structure, and thus a dry film resist photosensitive material with balanced developability, analysis ability and electroplating resistance can be obtained.

[0103] The specific selection of (A) alkali-soluble resin, (B) photopolymerizable monomer, (C) photopolymerization initiator, and (E) copper complex in the above dry film resist may refer to the above contents of the present application. In some preferred embodiments of the present application, the dry film resist contains, on a weight part 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, so that the overall performance of the dry film resist is good. Preferably, the dry film resist may further contain 0.01 to 0.5 parts by weight of (D) sensitizer, and preferably, the (D) sensitizer has one or more of the structures represented by structural formula I or II, [ka] [ka] In the formula, R0 is independently hydrogen, halogen, a C1-C8 alkyl group, or a C1-C4 alkoxy group; the modifying functional group M1 in structural formula I is independently biphenyl, a fused ring functional group, an electron-rich heterocyclic ring, a fused heterocyclic ring, or a C1-C4 alkoxy group, or a benzene ring having an amino group; the modifying functional group M2 in structural formula II is selected from biphenyl, a fused ring functional group, an electron-rich heterocyclic ring, a fused heterocyclic ring, or a C1-C4 alkoxy group, a benzene ring having an amino group, or a substituted phenyl group having a C1-C4 alkoxy group; and the modifying functional group W is a benzene ring or a fluorene ring, or a benzene ring, biphenyl ring, or fluorene ring having one or more substituents selected from halogen, a C1-C8 alkyl group, and a C1-C4 alkoxy group. The biphenyl functional group in the above modified functional groups M1 and M2 represents biphenyl or a derivative thereof, the corresponding fused ring functional group and electron-rich heterocyclic ring, the fused heterocyclic ring functional group represents the corresponding functional group or a derivative thereof, and the types of derivatives of the above functional groups may be the common types in the art, for example, containing substituents such as halogen, C1-C8 alkyl group or C1-C4 alkoxy group.

[0104] The above sensitizer is a pyrazoline-based compound that is provided with several modified functional groups, such as an electron-donating substituent, a benzene ring, a condensed ring functional group, or an electron-rich heterocycle or a condensed heterocycle compound, so that the entire molecular structure is an electron-rich conjugated system. This electron-rich conjugation effect is helpful in promoting the red shift of the absorption spectrum of the sensitizer, and the absorption spectrum extends to the visible light region, and the absorption wavelength is closer to the wavelength of the 405 nm exposure light source, so that the dry film resist is more sensitive to the LDI 405 nm exposure light source, thereby improving the photosensitivity of the dry film resist to the LDI 405 nm exposure light source.

[0105] Preferably, the modifying functional group M1 is a fused ring functional group having one or more of a C1 to C4 alkoxy group, an amino group, and an alkyl group, or is any one of furan, thiophene, indole, thiazole, benzofuran, benzothiazole, indene, anthracene, acridine, and an aromatic amine, and more preferably, the specific structural formula of the modifying functional group M1 and / or M2 is: [ka] Including, During the ceremony, [ka] is a bonding position of a functional group, and optionally, the benzene ring, biphenyl ring, fused ring, and heterocyclic ring in the specific structural formula of the modifying functional group M1 and / or M2 contain one or more kinds of substituents selected from halogen, C1-C8 alkyl groups, and C1-C4 alkoxy groups, and preferably, the substituents are located at the para position.

[0106] Furthermore, the applicant has conducted many studies and tests and has found the following: When using the above sensitizer, if the weight ratio of the sensitizer to the copper complex is in the range of 30:1 to 1:50, the overall performance of the dry film resist, especially the electroplating resistance, is good, for example, the weight ratio of the sensitizer to the copper complex is 20:1, 10:1, 5:1, 2:1, 1:1, 1:5, 1:10, 1:20.

[0107] In another exemplary embodiment of the present application, a photosensitive dry film is provided, the photosensitive dry film includes a dry film resist layer, and a support layer and a protective layer located on both sides of the dry film resist layer, where the dry film resist layer contains any of the above dry film resists. The above dry film resist contains a complex formed by a nitrogen-containing heterocyclic compound and copper, so that on the one hand, the nitrogen-containing heterocyclic structure has high polarity, so that the copper complex can increase the action force between the metal copper, and on the other hand, the lone electron pair of the nitrogen atom can be coordinated with the copper atom, and the formation of such coordinate chemical bonds can further improve the binding force between such compounds and the copper atom. Due to both of these actions, the addition of the above copper complex can significantly strengthen the binding force of the dry film resist to the copper surface, and can improve the phenomenon that the bottom sidewall is micro-warped during the electroplating process of the dry film, thereby improving the electroplating resistance of the dry film resist.

[0108] In yet another exemplary embodiment of the present application, a copper clad laminate is provided, and the copper clad laminate is provided with any one of the dry film resists described above. Since the copper clad laminate of the present application is provided with the 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 by the present invention are further illustrated in the following examples and comparative examples.

[0110] The synthesis method of the sensitizer compound is as follows.

[0111] Synthesis of sensitizer compound D-1: In a 500mL three-neck flask, add the raw material 9-anthracenecarboxaldehyde (62g), acetone (7g) and ethanol (150mL), put the flask in a water bath at room temperature and stir for 15 minutes, when the raw material is dissolved, add 10% NaOH aqueous solution (120g) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to react at room temperature with stirring for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the reaction is no change again, stop the reaction. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (100mL), stirred at room temperature for 30 minutes, then suction filtered, the solid was collected, dried in a rotary evaporator to remove a small amount of solvent contained in the solid, and the intermediate product compound 1 (49g, purity 91%) represented by the following reaction structure was obtained.

[0112] In a 500mL three-neck flask, add intermediate compound 1 (49g) and glacial acetic acid (150g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (22g), the dropwise addition time lasts for 1 hour, and after the dropwise addition is completed, raise the temperature to 80℃ and react for 8 hours. The reaction is monitored by putting a drop on a TLC plate, and when the raw material is completely consumed, the reaction is stopped, cooled to room temperature, and then diluted with ethanol (200mL). The resulting suspension is stirred at room temperature for 30 minutes, and then suction filtered under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then suction filtered. The solid is collected and dried in a rotary evaporator to remove a small amount of solvent contained in the solid, and the sensitizer compound D-1 (44g, purity 95%) shown in the following reaction structure is obtained.

[0113] The specific reaction structure I is as follows: [ka]

[0114] The structure of the sensitizer compound of the above formula is merely illustrative, however, the anthracene ring may have a substituent such as a halogen, an alkyl group having a carbon chain length of C1 to C8, or an alkoxy group having a carbon chain length of C1 to C4, and the number of the substituents may be 1 or 1 to 5.

[0115] Synthesis of sensitizer compound D-2: In a 250mL three-neck flask, add the raw materials 2-acetylfluorene (21.8g), 9-anthracenecarboxaldehyde (20.6g) and ethanol (100mL), place the flask in a water bath at room temperature and stir for 15 minutes, when the raw materials are dissolved, add 3mol / L NaOH aqueous solution (66mL) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the raw material p-anisaldehyde is completely consumed, the reaction was stopped. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (100mL), stirred at room temperature for 30 minutes, then suction filtered, the solid was collected, dried in a rotary evaporator, and the small amount of solvent contained in the solid was removed, and the intermediate product compound 2 (36g, purity 90%) represented by the following reaction structure was obtained.

[0116] In a 250mL three-neck flask, add intermediate compound 2 (36g) and glacial acetic acid (100g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (19g), the dropwise addition time lasts for 30 minutes, and after the dropwise addition is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (150mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction, collect the solid, dry it in a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the sensitizer compound D-2 (28g, purity 96%) represented by the following reaction structure.

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

[0118] The structure of the sensitizer compound of the above formula is merely illustrative, however, the anthracene ring and the fluorene ring may have a substituent such as a halogen, an alkyl group having a carbon chain length of C1 to C8, or an alkoxy group having a carbon chain length of C1 to C4, and the number of the substituents may be 1 or 1 to 5.

[0119] Synthesis of sensitizer compound D-3: In a 250mL three-neck flask, add raw materials acetophenone (12.6g), 9-anthracenecarboxaldehyde (20.6g) and ethanol (100mL), place the flask in a water bath at room temperature and stir for 15 minutes, when the raw materials are dissolved, add 3mol / L NaOH aqueous solution (66mL) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the raw material p-anisaldehyde is completely consumed, the reaction was stopped. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (100mL), stirred at room temperature for 30 minutes, then suction filtered, the solid was collected, dried in a rotary evaporator to remove a small amount of solvent contained in the solid, and the intermediate product compound 3 (24g, purity 91%) represented by the following reaction structure was obtained.

[0120] In a 250mL three-neck flask, add intermediate compound 3 (24g) and glacial acetic acid (100g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (15g), the drop time lasts for 20 minutes, and after the drop time is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (150mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction, collect the solid, dry it in a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the sensitizer compound D-3 (19g, purity 97%) represented by the following reaction structure.

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

[0122] The structure of the sensitizer compound of the above formula is merely illustrative, however, the benzene ring and the anthracene ring may have a substituent such as a halogen, an alkyl group having a carbon chain length of C1 to C8, or an alkoxy group having a carbon chain length of C1 to C4, and the number of the substituents may be 1 or 1 to 5.

[0123] Synthesis of sensitizer compound D-4: In a 250mL three-neck flask, add the raw materials 4-acetylbiphenyl (20.5g), 9-anthracenecarboxaldehyde (20.6g) and ethanol (100mL), place the flask in a water bath at room temperature and stir for 15 minutes, when the raw materials are dissolved, add 3mol / L NaOH aqueous solution (66mL) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the raw material p-anisaldehyde is completely consumed, the reaction was stopped. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (100mL), stirred at room temperature for 30 minutes, then suction filtered, the solid was collected, dried in a rotary evaporator to remove a small amount of solvent contained in the solid, and the intermediate product compound 4 (32g, purity 92%) represented by the following reaction structure was obtained.

[0124] In a 250mL three-neck flask, add intermediate compound 4 (32g) and glacial acetic acid (100g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (17g), the drop time lasts for 20 minutes, and after the drop time is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (150mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction, collect the solid, dry it in a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the sensitizer compound D-4 (26g, purity 96%) shown in the following reaction structure.

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

[0126] The structure of the sensitizer compound of the above formula is merely illustrative, however, the biphenyl ring and the anthracene ring may have a substituent such as a halogen, an alkyl group having a carbon chain length of C1 to C8, or an alkoxy group having a carbon chain length of C1 to C4, and the number of the substituents may be 1 or 1 to 5.

[0127] Synthesis of sensitizer compound D-5: In a 250mL three-neck flask, add the raw materials 2'-acetonaphthone (17.8g), 4-(N,N-diphenylamino)benzaldehyde (27.3g) and ethanol (100mL), place the flask in a water bath at room temperature and stir for 15 minutes, when the raw materials are dissolved, add 3mol / L NaOH aqueous solution (66mL) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the raw material p-anisaldehyde is completely consumed, the reaction was stopped. The suspended matter obtained in the reaction was suction filtered under reduced pressure, and the obtained crude solid product was dispersed in a small amount of ethanol (100mL) and stirred at room temperature for 30 minutes, and the intermediate product compound 5 (30g, purity 91%) shown in the reaction structure was obtained.

[0128] In a 250mL three-neck flask, add intermediate compound 5 (30g) and glacial acetic acid (100g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (14.7g), the drop time lasts for 20 minutes, and after the drop time is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (150mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction, collect the solid, dry it in a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the sensitizer compound D-5 (33g, purity 95%) represented by the following reaction structure.

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

[0130] The structure of the sensitizer compound of the above formula is merely illustrative, however, the naphthalene ring and the benzene ring may have a substituent such as a halogen, an alkyl group having a carbon chain length of C1 to C8, or an alkoxy group having a carbon chain length of C1 to C4, and the number of the substituents may be 1 or 1 to 5.

[0131] Synthesis of sensitizer compound D-6: In a 250mL three-neck flask, add the raw materials 3-acetylthiophene (13.2g), 4-(N,N-diphenylamino)benzaldehyde (27.3g) and ethanol (100mL), place the flask in a water bath at room temperature and stir for 15 minutes, when the raw materials are dissolved, add 3mol / L NaOH aqueous solution (66mL) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the raw material p-anisaldehyde is completely consumed, the reaction was stopped. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (100mL), stirred at room temperature for 30 minutes, then suction filtered, the solid was collected, dried in a rotary evaporator, and a small amount of solvent contained in the solid was removed, and the intermediate product compound 6 (26g, purity 90%) represented by the following reaction structure was obtained.

[0132] In a 250mL three-neck flask, add intermediate compound 6 (26g) and glacial acetic acid (100g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (14g), the drop time lasts for 20 minutes, and after the drop time is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (150mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction, collect the solid, dry it in a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the sensitizer compound D-6 (21g, purity 96%) represented by the following reaction structure.

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

[0134] The structure of the sensitizer compound of the above formula is merely illustrative, however, the benzene ring and the heterocycle may have a substituent such as a halogen, an alkyl group having a carbon chain length of C1 to C8, or an alkoxy group having a carbon chain length of C1 to C4, and the number of the substituents may be 1 or 1 to 5.

[0135] Synthesis of sensitizer compound D-7: In a 500mL three-neck flask, add the raw material 4-(N,N-diphenylamino)benzaldehyde (49.6g), acetone (5.8g) and ethanol (150mL), put the flask in a water bath at room temperature and stir for 15 minutes, when the raw material is dissolved, add 10% NaOH aqueous solution (160g) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the reaction is no change again, stop the reaction. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (150mL), stirred at room temperature for 30 minutes, suction filtered, collect the solid, dry it with a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the intermediate product compound 7 (41g, purity 91%) represented by the following reaction structure.

[0136] In a 500mL three-neck flask, add intermediate compound 7 (41g) and glacial acetic acid (150g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (16g), the drop time lasts for 1 hour, and after the drop time is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (200mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction. The solid is collected and dried in a rotary evaporator to remove a small amount of solvent contained in the solid, and the sensitizer compound D-7 (34g, purity 95%) shown in the following reaction structure is obtained.

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

[0138] The structure of the sensitizer compound of the above formula is merely illustrative, however, the benzene ring may have a substituent such as a halogen, an alkyl group having a carbon chain length of C1 to C8, or an alkoxy group having a carbon chain length of C1 to C4, and the number of the substituents may be 1 or 1 to 5.

[0139] The components were mixed in a predetermined ratio according to the formulations in Tables 1 and 2 below, and 60 parts by weight of a solvent was added, whereby the solvent suitable for preparing the coating adhesive solution may be acetone, butanone, methanol, ethanol, isopropyl alcohol, toluene, etc., and then thoroughly stirred to completely dissolve, preparing a resin composition solution with a solid content of 40%. The mixture was left to stand for 30 minutes to thoroughly degas, and then uniformly coated on the surface of a 16 μm-thick PET support film using a coating device, 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 attached to the surface, resulting in a three-layer photosensitive dry film. [Table 1] [Table 2]

[0140] Here, the alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, sensitizer and additives are as follows. A-1: Methacrylic acid:methyl methacrylate:styrene:benzyl methacrylate=25:15:40:20, acid value was 163 mgKOH / g, weight average molecular weight measured by GPC was 50,000 g / mol, molecular weight distribution (PID) was 1.8, and conversion rate was 97.0%. A-2: Methacrylic acid:methyl methacrylate:styrene:benzyl methacrylate=25:15:40:20, acid value was 163 mgKOH / g, weight average molecular weight measured by GPC was 100,000 g / mol, molecular weight distribution (PID) was 2.0, and 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 50,000 g / mol, the molecular weight distribution (PID) was 2.0, and the conversion rate was 95%. B-1: (4) Ethoxybisphenol A diacrylate (Miwon Chemicals), 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), in the corresponding photopolymerizable monomer structural formula B1, n1+n2=0, m1+m2=10, and R1 is CH3. B-3: (6) Ethoxy polypropylene 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), 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 Power Electronic Materials). C-2: Benzoyl dimethyl ether (also known as a,a-dimethoxy-a-phenylacetophenone, Shanghai McLin Biochemical Materials Co., Ltd.). D-1: 1-phenyl-3-(9-anthracenylvinyl)-5-(9-anthracenyl)pyrazoline. See Synthesis Example D-1. D-2: 1-phenyl-3-(2-fluorenyl)-5-(9-anthracenyl)pyrazoline. See Synthesis Example D-2. D-3: 1-phenyl-3-phenyl-5-(9-anthracenyl)pyrazoline. See Synthesis Example D-3. D-4: 1-phenyl-3-biphenyl-5-(9-anthracenyl)pyrazoline. See Synthesis Example D-4. D-5: 1-phenyl-3-(2-naphthyl)-5-(4-dianilinophenyl)pyrazoline, see Synthesis Example D-5. D-6: 1-phenyl-3-(3-thienyl)-5-(4-dianilinophenyl)pyrazoline, see Synthesis Example D-6. D-7: 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: Pigment brilliant green (Shanghai Bailingwei Chemical Technology Co., Ltd.). F-3: Leuco crystal violet (Shanghai Bailingwei Chemical Technology Co., Ltd.). F-4: p-toluenesulfonamide (Shanghai Tekiai Chemical).

[0141] The methods for producing samples of Examples 1 to 14 and Comparative Examples 1 to 3 (including film attachment, exposure, development, and electrolytic copper plating), and the methods and results of evaluating the samples will be described below.

[0142] (1) How to prepare the sample (Film attachment) The copper surface of the copper-clad laminate was polished using a grinder, rinsed with water, and wiped clean to obtain a bright and innovative copper surface. The press roller temperature of the film attachment machine was set to 110°C and the conveying speed was set to 1.5 meters / min, and the PE protective film on the surface was removed from the photosensitive dry films obtained in the above examples and comparative examples. The films were then attached to the copper-clad laminate with heat under standard pressure to obtain samples with the films attached.

[0143] (exposure) The sample with the film attached was left to stand for 15 minutes or more, and the resolution and adhesion performance were examined by exposing it to a 405 nm wavelength laser direct imaging (LDI) exposure machine (Model IP-6, manufactured by Adtec Japan). A photosensitivity test was performed using a Stouffer 41 step exposure scale, with the exposure scale set to 13 to 17 scales.

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

[0145] (etching) The developed copper plate was subjected to an etching process, the etching solution was copper chloride, the etching speed was 1.0 meters / 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 ions were 140 g / L, and the etching machine was model GL181946 manufactured by Dongguan Space.

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

[0147] (2) Evaluation method (Sensitivity evaluation) The sample with the film attached was left to stand for 15 minutes or more, exposed with an Adtec IP-6 405 nm LDI exposure machine, and a sensitivity test was performed using a Stouffer 41 step exposure scale. After exposure, a 1 wt% aqueous sodium carbonate solution was sprayed at 30°C, and the development time was 2.0 times the minimum development time, thus removing the unexposed parts. Through these steps, a hardened film consisting of the hardened products of each component of the dry film resist was formed on the copper surface of the substrate. The exposure dose (mJ / cm2) when the remaining number of steps on the step exposure tablet of the obtained hardened film was 15 was calculated. 2 The sensitivity of the photosensitive resin composition was evaluated using the following equation. The smaller the value, the better the sensitivity.

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

[0149] (resolution evaluation) The sample is exposed using a mask with a wiring pattern in which the width of the exposed and unexposed parts is 1:1, and developed for twice the minimum development time. The minimum mask width at which a hardened resist line is normally formed is taken as the resolution value, and the sample is observed using a 2D imager or a scanning electron microscope (SEM). The smaller the reading, the better the resolution.

[0150] (Adhesion evaluation) A photosensitive dry film resist is laminated on a copper plate by hot pressing, and exposed to light with a mask having a wiring pattern with a width of n:400 between the exposed and unexposed parts. The corresponding sensitivity is 15 degrees. After developing for twice the minimum developing time, the resist is observed with a magnifying glass. The minimum mask width at which a complete hardened resist line is formed is taken as the value of adhesion. The smaller the reading, the better the adhesion.

[0151] (Side appearance 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 with the width of the exposed and unexposed parts being n:400, the exposure energy was 15 times the corresponding sensitivity, and after developing 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 15 μm was taken with a scanning electron microscope (SEM) at 1000 times magnification.

[0152] 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 inverted trapezoidal. ×: The cross section of the tip of the dry film is severely trapezoidal or the bottom is gouged out, or there is an obvious crack on the side wall.

[0153] (Initiator migration evaluation) The 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 which the polyethylene thin film protective layer on the surface of the resist was removed and the ultraviolet absorption spectrum of the polyethylene thin film protective layer was detected using a UV-visible spectrophotometer; the detection wavelength was 380 to 450 nm.

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

[0155] (3) See Tables 3 and 4 for the results of characterization such as sensitivity, resolution, adhesion, lateral appearance, 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, the Examples all provided dry film resists that were excellent in all important overall performance aspects, such as sensitivity, resolution, adhesion performance, lateral profile, and initiator migration, and were suitable for the production of high-end PCBs, such as carrier boards and substrate-like PCBs.

[0157] In Comparative Example 1, the initiator system is a combination of a hexaarylbisimidazole derivative and an anthracene system (DBA), which is a commonly used initiator system for preparing dry film resists for high-end PCBs such as carrier boards and substrate-like PCBs. When the amount of DBA added is the same as that of the sensitizer in the examples, the sensitivity of the corresponding dry film resist is very low, and there is a harmful issue of DBA migrating to the polyethylene protective film.

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

[0159] In Comparative Example 3, the conventional pyrazoline compound reported in the patent is used, and although the sensitivity is good, when this initiator system is used, even if it is combined with a high resolution alkali-soluble resin and a photopolymerizable monomer, 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 in the production of high-end PCBs such as carrier boards and substrate-like PCBs are not met.

[0160] From the above description, it can be seen that the above embodiments of the present invention achieve the following technical effects: By introducing pyrazoline structure into anthracene and triarylamine, the structure of anthracene-based and triarylamine-based sensitizers, which are commonly used in dry film resists for high-end PCBs such as carrier boards and substrate-like PCBs, is optimized, and the imidazoline compound has good photosensitivity, so its photosensitivity to LDI 405nm laser light source is higher than that of anthracene-based and triarylamine-based sensitizers; the modified sensitizer compound of the present application generally has a large π-conjugated structure, and due to such large π-conjugated electronic effect, the maximum absorption wavelength of the modified sensitizer compound is shifted to the red side, and is closer to the wavelength of 405nm laser light source; therefore, by introducing pyrazoline structure into specific anthracene and triarylamine molecules, the photosensitivity of the obtained dry film resist to LDI 405nm laser light source can be obviously improved.

[0161] In the present application, the sensitizer compound obtained through the optimization modification simultaneously contains a pyrazoline ring structure and an anthracene or triarylamine structure in its structure, so that the sensitizer compound after the optimization modification has dual active functional groups, and effectively combines the photosensitivity of the pyrazoline structure and the high-precision resolution ability of the anthracene or triarylamine structure, thereby ensuring that the obtained dry film resist has high-precision resolution ability and can improve the production efficiency of clients who manufacture high-end PCBs such as carrier boards and substrate-like PCBs.

[0162] Synthesis of sensitizer compound D-21: In a 500mL three-neck flask, add the raw material 4-acetylbiphenyl (117g), p-anisaldehyde (68g) and ethanol (200mL), put the flask in a water bath at room temperature and stir for 15 minutes, when the raw material is dissolved, add 40% NaOH aqueous solution (40g) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the raw material p-anisaldehyde is completely consumed, the reaction was stopped. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (150mL), stirred at room temperature for 30 minutes, then suction filtered, the solid was collected, dried in a rotary evaporator to remove a small amount of solvent contained in the solid, and the intermediate product compound 21 (145g, purity 92%) represented by the following reaction structure was obtained.

[0163] In a 500mL three-neck flask, add intermediate compound 21 (145g) and glacial acetic acid (300g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (95g), the drop time lasts for 1 hour, and after the drop time is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (300mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction, collect the solid, dry it in a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the sensitizer compound D-21 (122g, purity 95.5%) represented by the following reaction structure.

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

[0165] The sensitizer compound structure shown in the above formula is merely illustrative, however, the benzene ring and the biphenyl ring may have a substituent such as a halogen, a C1-C8 alkyl group, or a C1-C4 alkoxy group, and the number of the substituents may be 1 or 1-5.

[0166] Synthesis of sensitizer compound D-22: In a 1000mL three-neck flask, add raw material p-anisaldehyde (182g), acetone (29g) and ethanol (300mL), put the flask in a water bath at room temperature and stir for 15 minutes, when the raw material is dissolved, add 10% NaOH aqueous solution (480g) dropwise to the flask, the drop time is 2 hours, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the reaction is no change again, stop the reaction. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (150mL), stirred at room temperature for 30 minutes, then suction filtered, the solid was collected, dried in a rotary evaporator to remove a small amount of solvent contained in the solid, and the intermediate product compound 22 (180g, purity 90%) represented by the following reaction structure was obtained.

[0167] In a 500mL three-neck flask, add intermediate compound 22 (120g) and glacial acetic acid (300g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (55g), the dropwise addition time lasts for 1 hour, and after the dropwise addition is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (300mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction, collect the solid, dry it in a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the sensitizer compound D-22 (101g, purity 96%) shown in the following reaction structure.

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

[0169] The sensitizer compound structure shown in the above formula is merely illustrative, however, the benzene ring and the biphenyl ring may have a substituent such as a halogen, a C1-C8 alkyl group, or a C1-C4 alkoxy group, and the number of the substituents may be 1 or 1-5.

[0170] Synthesis of sensitizer compound D-23: In a 500mL three-neck flask, add the raw material acridine-9-carbaldehyde (124g), acetone (14g) and ethanol (200mL), put the flask in a water bath at room temperature and stir for 15 minutes, when the raw material is dissolved, add 10% NaOH aqueous solution (240g) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the reaction is no change again, stop the reaction. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (150mL), stirred at room temperature for 30 minutes, suction filtered, collect the solid, dry it with a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the intermediate product compound 23 (94g, purity 91%) represented by the following reaction structure.

[0171] In a 500mL three-neck flask, add intermediate compound 23 (80g) and glacial acetic acid (200g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (34g), the drop time lasts for 1 hour, and after the drop time is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (200mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction. The solid is collected and dried in a rotary evaporator to remove a small amount of solvent contained in the solid, and then obtain the sensitizer compound D-23 (57g, purity 95%) represented by the following reaction structure.

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

[0173] The sensitizer compound structure shown in the above formula is merely illustrative, however, the benzene ring and the acridine ring may have a substituent such as a halogen, a C1-C8 alkyl group, or a C1-C4 alkoxy group, and the number of the substituents may be 1 or 1-5.

[0174] Synthesis of sensitizer compound D-24: In a 500mL three-neck flask, add the raw material 2-acetylfluorene (62g), p-anisaldehyde (34g) and ethanol (200mL), put the flask in a water bath at room temperature and stir for 15 minutes, when the raw material is dissolved, add 40% NaOH aqueous solution (20g) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the raw material p-anisaldehyde is completely consumed, the reaction was stopped. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (150mL), stirred at room temperature for 30 minutes, then suction filtered, the solid was collected, dried in a rotary evaporator to remove a small amount of solvent contained in the solid, and the intermediate product compound 24 (78g, purity 90%) represented by the following reaction structure was obtained.

[0175] In a 500mL three-neck flask, add intermediate compound 24 (78g) and glacial acetic acid (150g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (40g), the drop time lasts for 1 hour, and after the drop time is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (150mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction, collect the solid, dry it in a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the sensitizer compound D-24 (65g, purity 96%) shown in the following reaction structure.

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

[0177] The sensitizer compound structure shown in the above formula is merely illustrative, however, the benzene ring and the fluorene ring may have a substituent such as a halogen, a C1-C8 alkyl group, or a C1-C4 alkoxy group, and the number of the substituents may be 1 or 1-5.

[0178] Synthesis of sensitizer compound D-25: In a 500mL three-neck flask, add the raw materials 4-acetylbiphenyl (58g), benzothiophene-2-carbaldehyde (40g) and ethanol (150mL), place the flask in a water bath at room temperature and stir for 15 minutes, when the raw materials are dissolved, add 40% NaOH aqueous solution (20g) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the raw material benzothiophene-2-carbaldehyde is completely consumed, the reaction is stopped. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (150mL), stirred at room temperature for 30 minutes, suction filtered, the solid was collected, dried in a rotary evaporator, and the small amount of solvent contained in the solid was removed, and the intermediate product compound 25 (83g, purity 93%) represented by the following reaction structure was obtained.

[0179] In a 500mL three-neck flask, add intermediate compound 25 (83g) and glacial acetic acid (200g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (42g), the dropwise addition time lasts for 1 hour, and after the dropwise addition is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (200mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction, collect the solid, dry it in a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the sensitizer compound D-25 (67g, purity 95%) represented by the following reaction structure.

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

[0181] The sensitizer compound structure shown in the above formula is merely illustrative, however, the benzene ring and the biphenyl ring may have a substituent such as a halogen, a C1-C8 alkyl group, or a C1-C4 alkoxy group, and the number of the substituents may be 1 or 1 to 5. Also, the benzothiophene heterocycle may be replaced with a heterocyclic functional group having an extra electron, such as furan, thiophene, indole, thiazole, benzofuran, benzothiazole, indene, anthracene, acridine, or an aromatic amine.

[0182] Synthesis of sensitizer compound D-26 represented by the following formula: In a 1000mL three-neck flask, add the raw materials 6-methoxy-2-naphthaldehyde (112g), acetone (14g) and ethanol (300mL), put the flask in a water bath at room temperature and stir for 15 minutes, when the raw materials are dissolved, add 10% NaOH aqueous solution (240g) dropwise to the flask, the drop time is 2 hours, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the reaction is no change again, stop the reaction. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (150mL), stirred at room temperature for 30 minutes, then suction filtered, the solid was collected, dried in a rotary evaporator, and the small amount of solvent contained in the solid was removed, and the intermediate product compound 26 (82g, purity 91%) represented by the following reaction structure was obtained.

[0183] In a 500mL three-neck flask, add intermediate compound 26 (82g) and glacial acetic acid (200g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (34g), the dropwise addition time lasts for 1 hour, and after the dropwise addition is completed, raise the temperature to 80℃ and react for 8 hours. The reaction is monitored by putting a drop on a TLC plate, and when the raw material is completely consumed, the reaction is stopped, cooled to room temperature, and then diluted with ethanol (200mL). The resulting suspension is stirred at room temperature for 30 minutes, and then suction filtered under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then suction filtered. The solid is collected and dried in a rotary evaporator to remove a small amount of solvent contained in the solid, and the sensitizer compound D-26 (74g, purity 96%) shown in the following reaction structure is obtained.

[0184] The specific reaction structure is as 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 a substituent such as a halogen, a C1-C8 alkyl group, or a C1-C4 alkoxy group, and the number of the substituents may be 1 or 1 to 5. In addition, the naphthalene ring may be replaced with a functional group of a condensed aromatic ring structure.

[0186] According to the formulations in Tables 5 and 6 below, the alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator and additive were mixed in a predetermined ratio, and 60 parts by weight of a solvent was added, whereby the solvent suitable for preparing the coating adhesive solution may be acetone, butanone, methanol, ethanol, isopropyl alcohol, toluene, etc., and then thoroughly stirred to completely dissolve, preparing a resin composition solution with a solid content of 40%. The mixture was left to stand for 30 minutes to thoroughly degas, and then uniformly coated on the surface of a 16 μm-thick PET support film using a coating device, 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 attached to the surface, resulting in a three-layer photosensitive dry film. [Table 5] [Table 6]

[0187] Here, the alkali-soluble resin, photopolymerizable monomer, photopolymerization initiator, sensitizer and additives are as follows. A-21: Methacrylic acid:methyl methacrylate:butyl acrylate:styrene=25:40:7:28, acid value was 131 mgKOH / g, weight average molecular weight measured by GPC was 55000 g / mol, molecular weight distribution (PID) was 1.8, and conversion rate was 97.0%. B-21:(4) Ethoxybisphenol A diacrylate (Miwon Chemicals). B-22: (10) Ethoxybisphenol A diacrylate (Miwon Chemicals). B-23: (6) Ethoxy polypropylene 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 Powerful Electronic Materials). C-22: 9-Phenylacridine (Changzhou Powerful Electronic Materials). C-23: N-phenylglycine (Nishi Chemical). D-21: 1-phenyl-3-biphenyl-5-(4-methoxyphenyl)pyrazoline, see Synthesis Example D-21. D-22: 1-phenyl-3-(biphenylvinyl)-5-biphenylpyrazoline, see Synthesis Example D-22. D-23: 1-phenyl-3-(9-acridinylvinyl)-5-(9-acridinyl group)pyrazoline. See Synthesis Example D-23. D-24: 1-phenyl-3-(2-fluorenyl)-5-(4-methoxyphenyl)pyrazoline, see Synthesis Example D-24. D-25: 1-phenyl-3-(biphenyl)-5-(2-benzothienyl)pyrazoline, see Synthesis Example D-25. D-26: 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 patent CN101652715, R = tert-butyl group). F-21: Pigment brilliant green (Shanghai Bailingwei Chemical Technology Co., Ltd.). F-22: Leucocrystal violet (Shanghai Bailingwei Chemical Technology Co., Ltd.). F-23: Tribromomethyl phenyl sulfone (Shanghai Tsinghai Chemical Industry). F-24: p-Toluenesulfonamide (Shanghai Tekiai Chemical).

[0188] The methods for preparing samples of Examples 15 to 27 and Comparative Examples 4 to 8 (including film attachment, exposure, development, and electrolytic copper plating), and the methods and results of evaluating the samples will be described below.

[0189] (1) How to prepare the sample (Film attachment) The copper surface of the copper-clad laminate was polished using a grinder, rinsed with water, and wiped clean to obtain a bright and innovative copper surface. The press roller temperature of the film attachment machine was set to 110°C and the conveying speed was set to 1.5 meters / min, and the PE protective film on the surface was removed from the photosensitive dry films obtained in the above examples and comparative examples. The films were then attached to the copper-clad laminate with heat under standard pressure to obtain samples with the films attached.

[0190] (exposure) The sample with the film attached was left to stand for 15 minutes or more, and the resolution and adhesion performance were examined by exposing it to a 405 nm wavelength laser direct imaging (LDI) exposure machine (Model IP-6, manufactured by Adtec Japan). A photosensitivity test was performed using a Stouffer 41 step exposure scale, with the exposure scale set to 14 to 20.

[0191] The alignment recognition characteristic test of the sample was performed using a domestically produced exposure machine, and the sample was exposed using a laser direct imaging (LDI) exposure machine manufactured by Wuxi Yingsuo Semiconductor Co., Ltd. The exposure machine was model IC2000, the wavelength was 405 nm, and the number of exposure units was controlled to 14 to 20 units.

[0192] (developing) The exposed sample was left to stand for 15 minutes or more, and the development temperature was 30°C and the pressure was 1.2Kg / cm 2 The developing solution was a 1% wt aqueous solution of sodium carbonate, the developing time was 1.5 to 2.0 times the minimum developing time, and after development, the resist layer was washed with water and dried. The minimum developing time was defined as the minimum time required for the resist layer in the unexposed area to completely dissolve.

[0193] (etching) The developed copper plate was subjected to an etching process, the etching solution was copper chloride, the etching speed was 1.0 meters / 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 ions were 140 g / L, and the etching machine was model GL181946 manufactured by Dongguan Space.

[0194] (Film withdrawal) The film stripping solution was NaOH, the concentration was 3.0 wt%, the temperature was 50°C, and the pressure was 1.2 Kg / cm 2 The film removal time was 1.5 to 2.0 times the minimum film removal time, and after the film removal, the sample was washed with water and dried.

[0195] (2) Evaluation method (Sensitivity evaluation) The sample with the film attached was left to stand for 15 minutes or more, exposed with an Adtec IP-6 405 nm LDI exposure machine, and a sensitivity test was performed using a Stouffer 41 step exposure scale. After exposure, a 1% wt aqueous solution of sodium carbonate was sprayed at 30°C, and the development time was 2.0 times the minimum development time, thus removing the unexposed parts. Through these steps, a cured film made of a cured product of the photosensitive resin composition was formed on the copper surface of the substrate. The exposure dose (mJ / cm2) when the remaining number of steps on the step exposure tablet of the obtained cured film was 17 was calculated. 2 The sensitivity of the photosensitive resin composition was evaluated by the following equation. The smaller the value, the better the sensitivity.

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

[0197] (resolution evaluation) The sample is exposed using a mask with a wiring pattern in which the width of the exposed and unexposed parts is 1:1, and developed for twice the minimum development time. The minimum mask width at which a hardened resist line is normally formed is taken as the resolution value, and the sample is observed using a 2D imager or a scanning electron microscope (SEM). The smaller the reading, the better the resolution.

[0198] (Adhesion evaluation) A photosensitive dry film resist is laminated on a copper plate by hot pressing, and exposed to light using a mask with a wiring pattern in which the width of the exposed and unexposed areas is n:400. The corresponding sensitivity is 17 degrees. After developing for twice the minimum developing time, the resist is observed under a magnifying glass. The minimum mask width at which a complete hardened resist line is formed is taken as the value of adhesion. The smaller the reading, the better the adhesion.

[0199] (Alignment recognition using domestic LDI exposure equipment) The exposure was done by a H-9300D LDI exposure machine manufactured by Shadow Speed ​​Technology, the exposure energy was measured by a Stouffer 41-grade exposure ruler, and the number of exposure grades was 17. While side A was exposed, side B was irradiated with a UV LED lamp to complete color printing, and then the exposure machine automatically used red or yellow light to perform point capture and identification. The shorter the color printing time by irradiation, the higher the contrast of the image after irradiation and the clearer the boundary of the irradiation point. In addition, if the points can be captured and identified by both red and yellow light after color printing, it shows that the alignment recognition characteristics of the domestic LDI exposure machine are excellent.

[0200] Criteria: ○: The color burning time by irradiation is 0.5 to 2.0 seconds, and after the color burning, point capture and identification is possible with either red or yellow light. Δ: The color burning time by irradiation is 2.0 to 3.0 seconds, and after the color burning, the point capture and identification is not possible with red light, and can only be identified with yellow light. ×: The color burning time by irradiation is longer than 3.0 seconds, and after the color burning, the dot capture and identification cannot be performed with either red light or yellow light.

[0201] (Side appearance evaluation) After removing the PE film from the prepared photosensitive dry film resist, the dry film was laminated onto a copper plate using a heated press roller. Here, it was exposed with a mask having a wiring pattern with the width of the exposed and unexposed parts being n:400, and developed for 2.0 times the minimum development time, after which a dry film image was obtained, and a side view of the dry film with a line width of 25 μm was photographed with a scanning electron microscope (SEM) at 1000 times magnification.

[0202] 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 inverted trapezoidal. ×: The cross section of the tip of the dry film is severely trapezoidal or the bottom is gouged out, or there is an obvious crack on the side wall.

[0203] (Film removal speed evaluation) The film withdrawal speed is evaluated by testing the film withdrawal time; the shorter the film withdrawal time, the faster the film withdrawal speed.

[0204] (3) For the results of characteristic evaluation such as sensitivity, resolution, adhesion, side profile, and alignment recognition using a domestic LDI exposure tool, see Tables 7 and 8. [Table 7] [Table 8]

[0205] As can be seen from the comparison between the Examples and Comparative Examples, the Examples produced dry film resists that were excellent in all key overall performance aspects, such as sensitivity, resolution, adhesion performance, side profile, and alignment recognition characteristics in domestic LDI exposure machines, and were applicable to LDI exposure machines.

[0206] In Comparative Examples 4 and 5, a pyrazoline compound of the prior art was used as a sensitizer. The test results showed that the test data was almost consistent with the data provided in the patent, and the alignment recognition characteristics of the domestic LDI exposure machine were good, but the sensitivity was obviously insufficient, and the resolution and adhesion needed to be further improved.

[0207] In Comparative Example 6, the amount of sensitizer was increased based on Comparative Example 4 in order to further improve the sensitivity, but the test results showed that after the amount of sensitizer was greatly increased, the sensitivity improved, but the adhesion strength was greatly reduced, 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. It is speculated that the reason for this is that the hardening of the resist is limited to the surface, and when the color of the surface becomes dark, the depth of hardening is insufficient, and the dry film pattern after exposure cannot adhere to the copper surface at all.

[0208] In Comparative Example 7, the initiator was hexaaryl imidazole, and no sensitizer was used. Looking at the results of the example, the corresponding dry film resist had very poor photosensitivity, and the properties such as analysis, adhesion, and side profile were all poor.

[0209] Comparative Example 8 is a conventional solution for producing a high-sensitivity, high-resolution dry film resist for use in the manufacture of HDI inner layer boards, and the test results are consistent with those of PCB clients, with high sensitivity at 405 nm and excellent resolution accuracy, but with this formulation, even if a certain amount of tribromomethylphenylsulfone is added to enhance the contrast of the image before and after exposure, alignment recognition cannot be performed in domestic LDI exposure machines, and dry film resists using this formulation cannot be used in domestic LDI exposure machines that are currently widely introduced in PCB clients. The reason for this is that an acridine-based initiator system is used in this formulation, and when this initiator initiates photopolymerization, the development becomes too slow after exposure, and the contrast of the pattern before and after exposure becomes too weak, causing alignment recognition to be impossible in domestic LDI exposure machines.

[0210] As can be seen from the above description, the above embodiments of the present application achieve the following technical effects. By introducing several modified functional groups, such as biphenyl, fused ring functional group, electron-rich heterocycle or benzene ring with fused heterocycle and amino group, into pyrazoline-based compound, the entire molecular structure of the sensitizer compound represented by structural formula I or II after modification is an electron-rich conjugated system, and such electron-rich conjugation effect is helpful to promote the red shift of the sensitizer absorption spectrum, and its absorption spectrum extends to the visible light region. After modification, the maximum absorption wavelength of the sensitizer is closer to the exposure light source with a wavelength of 405 nm, so 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. In addition, the present application selects a specific sensitizer, so that the dry film resist not only has high photosensitivity and resolution, but also further enhances the contrast of the pattern before and after exposure, which is more helpful for its alignment recognition in domestic LDI exposure machine, and ensures its alignment accuracy in domestic LDI exposure machine.

[0211] Synthesis of sensitizer compound D-27: In a 1000mL three-neck flask, add raw material p-anisaldehyde (68g), acetone (14g) and ethanol (150mL), put the flask in a water bath at room temperature and stir for 15 minutes, when the raw material is dissolved, add 10% NaOH aqueous solution (240g) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, when the reaction is no change again, stop the reaction. The suspended matter obtained in the reaction was suction filtered under reduced pressure, the obtained crude solid product was dispersed in a small amount of ethanol (100mL), stirred at room temperature for 30 minutes, then suction filtered, the solid was collected, dried in a rotary evaporator, and a small amount of solvent contained in the solid was removed, and the intermediate product compound 27 (56g, purity 90%) represented by the following reaction structure (2) was obtained.

[0212] In a 500mL three-neck flask, add intermediate compound 27 (56g) and glacial acetic acid (150g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (29g), the drop time lasts for 30 minutes, and after the drop time is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (150mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction, collect the solid, dry it in a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the sensitizer compound D-27 (52g, purity 97%) shown in the following reaction structure.

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

[0214] The sensitizer compound structure shown in the above formula is merely illustrative, however, the benzene ring may have a substituent such as a halogen, an alkyl group having a carbon chain length of C1 to C8, or an alkoxy group having a carbon chain length of C1 to C4, and the number of the substituents may be 1 or 1 to 5.

[0215] Synthesis of sensitizer compound D-28: In a 500mL three-neck flask, add the raw material indole-3-carbaldehyde (72g), acetone (14g), and ethanol (100mL), place the flask in a water bath at room temperature and stir for 15 minutes, when the raw material is dissolved, add 10% NaOH aqueous solution (240g) dropwise to the flask, the drop time is 1 hour, after the drop is completed, continue to stir at room temperature and react for 8 hours, monitor the reaction by putting a drop on a TLC plate, and when the reaction is no longer different, stop the reaction. The suspended matter obtained in the reaction was suction filtered under reduced pressure, and the obtained crude solid product was dispersed in a small amount of ethanol (200mL), stirred at room temperature for 30 minutes, then suction filtered, the solid was collected, dried in a rotary evaporator, and a small amount of solvent contained in the solid was removed, and the intermediate product compound 28 (63g, purity 89%) represented by the following reaction structure was obtained.

[0216] In a 500mL three-neck flask, add intermediate compound 28 (63g) and glacial acetic acid (200g), put it in an oil bath and stir to raise the temperature to 50℃. At 50℃, slowly add phenylhydrazine (33g), the dropwise addition time lasts for 1 hour, and after the dropwise addition is completed, raise the temperature to 80℃ and react for 8 hours. Monitor the reaction by putting a drop on a TLC plate, and when the raw material is completely consumed, stop the reaction, cool to room temperature, add ethanol (200mL) to dilute, stir the resulting suspension at room temperature for 30 minutes, and then filter with suction under reduced pressure. The obtained crude solid product needs to be further purified, which is dispersed in a small amount of methanol (150mL), stirred at room temperature for 30 minutes, and then filter with suction, collect the solid, dry it in a rotary evaporator to remove a small amount of solvent contained in the solid, and obtain the sensitizer compound D-28 (55g, purity 95%) shown in the following reaction structure.

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

[0218] The sensitizer compound structure shown in the above formula is merely illustrative, however, the benzene ring and the indole ring may have a substituent such as a halogen, an alkyl group having a carbon chain length of C1 to C8, or an alkoxy group having a carbon chain length of C1 to C4, and the number of the substituents may be 1 or 1 to 5.

[0219] The components were mixed in a given ratio according to the formulations in Tables 9 and 10 below, and 60 parts by weight of a solvent was added, where the solvent suitable for preparing the coating adhesive solution may be acetone, butanone, methanol, ethanol, isopropyl alcohol, toluene, etc., and then thoroughly stirred to completely dissolve the mixture to prepare a solution with a solid content of 40%. The mixture was left to stand for 30 minutes to fully degas, and then uniformly coated on the surface of a 16 μm thick PET support film using a coating device, and then 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 attached 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 additives are as follows. A-31: Methacrylic acid:methyl methacrylate:butyl acrylate:butyl acrylate:styrene=22:40:20:11:7, acid value was 127 mgKOH / g, weight average molecular weight measured by GPC was 91000 g / mol, molecular weight distribution (PID) was 2.0, and conversion rate was 97.0%. B-31: (10) Ethoxybisphenol A dimethacrylate (Miwon Chemicals), the corresponding photopolymerizable monomer structure VI, m1+m2=10, n1+n2=0, and R1=methyl group. B-32: (10) ethoxy (4) propoxy bisphenol A dimethacrylate (Miwon Chemicals), and in the corresponding photopolymerizable monomer structure VI, m1 + m2 = 10, n1 + n2 = 4, and R1 = methyl group. B-33: (6) Ethoxy polypropylene glycol (700) dimethacrylate (Miwon Chemicals), and the corresponding photopolymerizable monomer structure VIII, a2=6, b2=12, and R1=methyl group. B-34: (8) ethoxy (4) propoxynonylphenol acrylate (Miwon Chemicals), and the corresponding photopolymerizable monomer structure VII has a1=8, b1=4, and R1=H. B-35: (3) Ethoxylated trimethylolpropane trimethacrylate (Miwon Chemicals), and 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 Powerful Electronic Materials). C-32: 4,4'-Bis(diethylamino)benzophenone. C-33: 9-Phenylacridine (Changzhou Powerful Electronic Materials). C-34: N-phenylglycine (Nishi-Akagaku). D-21: 1-phenyl-3-biphenyl-5-(4-methoxyphenyl)pyrazoline, see Synthesis Example D-21, purity 95%. D-27: 1-phenyl-3-(4-methoxyvinyl)-5-(4-methoxyphenyl)pyrazoline, see Synthesis Example D-27. D-22: 1-phenyl-3-(biphenylvinyl)-5-biphenylpyrazoline, see Synthesis Example D-22, purity 95.5%. D-23: 1-phenyl-3-(9-acridinylvinyl)-5-(9-acridinyl group)pyrazoline, see Synthesis Example D-23, purity 94%. D-28: 1-phenyl-3-(3-indolylvinyl)-5-(3-indolyl)pyrazoline, see Synthesis Example D-28. D-26: 1-phenyl-3-(6-methoxy-2-naphthylvinyl)-5-(6-methoxy-2-naphthyl)pyrazoline, see Synthesis Example D-26, purity 96%. D-12: 1-phenyl-3-(4-methoxyvinyl)-5-(4-methoxyphenyl)pyrazoline, a sensitizer reported in Hitachi Chemical's patent CN104111583. E-1: 2-mercaptobenzimidazole-4-carboxylic acid, which belongs to structural formula IV. E-2: Mercaptobenzothiazole, which belongs to structural formula IV. E-3: 6-thioguanine, which belongs to structural formula IV. E-4: Mercaptotriazole, which belongs to structural formula III. E-5: 1-hydroxyethyl-5-mercapto-1H-tetrazole, which belongs to the structural formula III. F-31: Pigment brilliant green (Shanghai Bailingwei Chemical Technology Co., Ltd.). F-32: Leucocrystal violet (Shanghai Leuco Chemical Technology Co., Ltd.). F-33: p-toluenesulfonamide (Shanghai Tekiai Chemical).

[0221] The methods for preparing samples of Examples 28 to 46 and Comparative Examples 9 to 11 (including film attachment, exposure, development, electrolytic copper plating, and electrolytic tin plating), and the methods and results of evaluating the samples will be described below.

[0222] (1) How to prepare the sample (Film attachment) The copper surface of the copper-clad laminate was polished using a grinder, rinsed with water, and wiped clean to obtain a bright and innovative copper surface. The press roller temperature of the film attachment machine was set to 110°C and the conveying speed was set to 1.5 meters / min, and the PE protective film on the surface was removed from the photosensitive dry films obtained in the above examples and comparative examples. The films were then attached to the copper-clad laminate with heat under standard pressure to obtain samples with the films attached.

[0223] (exposure) The sample with the film attached was left to stand for 15 minutes or more, and then exposed to light using a 405 nm wavelength laser direct imaging (LDI) exposure machine (Model IP-6, manufactured by Adtec Japan). A photosensitivity test was performed using a Stouffer 41 step exposure scale, and the exposure scale was controlled to 17 to 20 scales.

[0224] (developing) The exposed sample was left to stand for 15 minutes or more, and the development temperature was 30°C and the pressure was 1.2Kg / cm 2 The developing solution was a 1% wt aqueous solution of sodium carbonate, the developing time was 1.5 to 2.0 times the minimum developing time, and after development, the resist layer was washed with water and dried. The minimum developing time was defined as the minimum time required for the resist layer in the unexposed area to completely dissolve.

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

[0226] (etching) The developed copper plate was subjected to an etching process, the etching solution was copper chloride, the etching speed was 1.0 meters / 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 ions were 140 g / L, and the etching machine was model GL181946 manufactured by Dongguan Space.

[0227] (Film withdrawal) The film stripping solution was NaOH, the concentration was 3.0 wt%, the temperature was 50°C, and the pressure was 1.2 Kg / cm 2 The film removal time was 1.5 to 2.0 times the minimum film removal time, and after the film removal, the sample was washed with water and dried.

[0228] (2) Evaluation method (Sensitivity evaluation) The sample with the film attached was left to stand for 15 minutes or more, exposed with an Adtec IP-6 405 nm LDI exposure machine, and a sensitivity test was performed using a Stouffer 41 step exposure scale. After exposure, a 1% wt aqueous solution of sodium carbonate was sprayed at 30°C, and the development time was 2.0 times the minimum development time, thus removing the unexposed parts. Through these steps, a cured film made of a cured product of the photosensitive resin composition was formed on the copper surface of the substrate. The exposure dose (mJ / cm2) when the remaining number of steps on the step exposure tablet of the obtained cured film was 18 was calculated. 2The sensitivity of the photosensitive resin composition was evaluated by the following equation. The smaller the value, the better the sensitivity.

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

[0230] (resolution evaluation) The sample is exposed using a mask with a wiring pattern in which the width of the exposed and unexposed parts is 1:1, and developed for twice the minimum development time. The minimum mask width at which a hardened resist line is normally formed is taken as the resolution value, and the sample is observed using a 2D imager or a scanning electron microscope (SEM). The smaller the reading, the better the resolution.

[0231] (Adhesion evaluation) A photosensitive dry film resist is laminated on a copper plate by hot pressing, and exposed to light using a mask with a wiring pattern in which the width of the exposed and unexposed areas is n:400. The corresponding sensitivity is 18 levels. After developing for twice the minimum developing time, the resist is observed under a magnifying glass. The minimum mask width at which a complete hardened resist line is formed is taken as the value of adhesion. The smaller the reading, the better the adhesion.

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

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

[0234] (Electroplating Contamination Evaluation) Dry film resist sample after exposure (exposure number 20) 0.8m 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 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: ○: After subtracting the blank, the TOC value < 500 ppm Δ: After subtracting the blank, 500 ppm < TOC value < 1000 ppm ×: After subtracting the blank, the TOC value > 1000 ppm.

[0236] (Morphology evaluation of the side surface) 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 were n:400, developed at 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) at a magnification of 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 severely trapezoidal in reverse or the bottom is dug out, 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 Examples and the Comparative Examples, the Examples provided dry film resists with excellent essential properties such as sensitivity, resolution, adhesion performance, side profile, electroplating resistance, and electroplating contamination resistance.

[0240] In Example 40, the ratio of sensitizer and complex is beyond the preferred ratio range, and the obtained dry film resist has high photosensitivity, but the corresponding analysis, adhesion and electroplating resistance are not good. In Example 43, the ratio of PO segment in photocurable monomer is beyond the preferred ratio range, and the obtained dry film resist has poor analysis, adhesion and lateral shape. In Example 44, the pyrazoline sensitizer reported in Hitachi Chemical's patent CN104111583 is used, and the obtained dry film resist has poor sensitivity, analysis, adhesion and lateral shape. In Example 45, the initiator system used is the initiator system currently commonly used in high-sensitivity LDI laser direct imaging resist, but its properties in terms of electroplating resistance and electroplating contamination are not good, and it is not suitable for electroplating process. The reason for this is that, on the one hand, the molecular weight of the acridine initiator is small and the amount used is large, so that the initiator fragments in the dry film resist after exposure are likely to penetrate into the electroplating solution and cause contamination of the electroplating solution, and on the other hand, with such an initiator, the side of the bottom of the dry film after exposure is slightly irregular, which may cause minor cementation. In Example 46, the initiator system used is the initiator system currently commonly used in electroplating dry films, which has very poor photosensitivity to the LDI 405nm laser light source, but because a complexing agent is added, the obtained dry film resist has excellent electroplating resistance properties.

[0241] On the other hand, in Comparative Examples 9 and 10, no complex was added, and the resulting dry film resists had poor electroplating resistance. In Comparative Example 11, the photocurable monomer contained no hydrophobic PO segment, but only hydrophilic EO segments, and the resulting dry film resist had excellent properties such as sensitivity, resolution, and adhesion, but had poor electroplating resistance and suffered from slight cementation.

[0242] The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention. Those skilled in the art can make various modifications and changes to the present invention. Any modifications, equivalent replacements, improvements, etc. made without departing from the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. 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 sensitizer (D) contains a compound containing a pyrazoline structure.

2. the sensitizer (D) contains a compound containing an anthracene-substituted and / or triarylamine-substituted pyrazoline structure, Preferably, the sensitizer (D) includes one or more of the compounds represented by structural formulas D1, D2, D3, D4, and D5, 【Chemistry 1】 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 In the formula, R ０１ , R ０２ , R ０３ , R ０４ , R ０５ are each independently hydrogen, halogen, a nitro group, or C １ ~C ８ Alkyl group, C １ ~C ４ alkoxy groups, a represents an integer of 0 to 5, b represents an integer of 0 to 4, c represents an integer of 0 to 5, and d represents an integer of 0 to 4. When a is greater than or equal to 2, a plurality of R ０１ may be the same or different, and when b is greater than or equal to 2, there are multiple R ０２ may be the same or different, and when c is greater than or equal to 2, there are multiple R ０４ may be the same or different, and when d is greater than or equal to 2, there are multiple R ０５ may be the same or different, each M is independently a benzene ring, a biphenyl group, a fused ring functional group, or an electron-rich heterocyclic ring or fused heterocyclic ring functional group; Preferably, M is C １ ~C ４ a phenyl group, a biphenyl group or a fused ring functional group having one or more of an alkoxy group, an amino group or an alkyl group, or a heterocyclic ring or a fused heterocyclic ring functional group having a furan, a thiophene, an indole, a thiazole, a benzofuran, a benzothiazole or a fluorene; More preferably, the sensitizer comprises a compound having the structure: 【Chemistry 6】 Optionally, the benzene ring, biphenyl ring, fused ring, and heterocyclic ring in the above structures contain substituents, the substituents being halogen, C １ ~C ８ Alkyl group, C １ ~C ４ 2. The dry film resist according to claim 1, wherein the substituent is any one or more of alkoxy groups, and preferably the substituent is located at the para position.

3. The sensitizer (D) includes one or more of the compounds represented by the following structural formula I or II: 【Chemistry 7】 【Chemistry 8】 In the formula, R ０ are each independently hydrogen, halogen, or C １ ~C ８ Alkyl group or C １ ~C ４ The modifying functional group M in the structural formula I is an alkoxy group. １ each independently represents a biphenyl functional group, a fused ring functional group, or an electron-rich heterocycle, a fused heterocycle, or a C １ ~C ４ The modified functional group M in the structural formula II is a substituted benzene ring having one or more of an alkoxy group and an amino group. ２ is a biphenyl, a fused ring functional group or an electron-rich heterocycle, a fused heterocycle or a C １ ~C ４ Alkoxy group, C １ ~C ３ The modified functional group W is selected from a substituted benzene ring having one or more of an alkyl group and an amino group, and the modified functional group W is one of a benzene ring and a fluorene ring, or a halogen, C １ ~C ８ Alkyl group, C １ ~C ４ a benzene ring, a biphenyl ring, or a fluorene ring having one or more substituents selected from the group consisting of alkoxy groups; Preferably, the modifying functional group M １ are each independently C １ ~C ４ a fused ring functional group having one or more of an alkoxy group, an amino group, or an alkyl group, or a furan, a thiophene, an indole, a thiazole, a benzofuran, a benzothiazole, an indene, an anthracene, an acridine, or an aromatic amine; Preferably, the modifying functional group M １ And / or M ２ The specific structural formula is: 【Chemistry 9】 wherein: 【Chemistry 10】 is the attachment site of a functional group, and optionally, the modifying functional group M １ And / or M ２ In the specific structural formula, the benzene ring, the biphenyl ring, the condensed ring, and the heterocyclic ring are halogen, C １ ~C ８ Alkyl group, C １ ~C ４ 2. The dry film resist according to claim 1, which contains one or more substituents selected from the group consisting of alkoxy groups, and which are preferably located at the para position.

4. the dry film resist comprises 45 to 65 parts by weight of an alkali-soluble resin (A), 30 to 50 parts by weight of a photopolymerizable monomer (B), 1.0 to 5.0 parts by weight of a photopolymerization initiator (C), and 0.01 to 0.5 parts by weight of a sensitizer (D); Preferably, the dry film resist comprises 45 to 65 parts by weight of an alkali-soluble resin (A), 30 to 50 parts by weight of a photopolymerizable monomer (B), 2.0 to 5.0 parts by weight of a photopolymerization initiator (C), and 0.01 to 0.5 parts by weight of a sensitizer (D); The dry film resist according to any one of claims 1 to 3, characterized in that the content of the sensitizer is preferably 0.01 wt % to 0.5 wt % of the total weight of the dry film resist.

5. The photopolymerization initiator (C) contains a compound represented by the following structural formula C1, 【Chemistry 11】 In the formula, each substituent A in the benzene ring is independently one or more of a hydrogen atom, a methoxy group, and a halogen atom; The dry film resist according to any one of claims 1 to 3, characterized in that the (C) photopolymerization initiator contains 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.

6. the dry film resist further comprises (E) a copper complex, in which a compound that forms a complex with copper in the copper complex comprises a nitrogen-containing heterocyclic compound; the (B) photopolymerizable monomer comprises an EO segment and a PO segment, the EO segment represents an oxyethylene group, and the PO segment represents an oxypropylene group; Preferably, the weight part of the (E) copper complex is 0.01 to 0.5, Preferably, the compound forming a complex with copper in the copper complex (E) contains a nitrogen-containing heterocycle and a mercapto group at the same time, More preferably, the compound forming a complex with copper in the copper complex (E) has one or more of the structures represented by structural formula III or IV, 【Chemistry 12】 【Chemistry 13】 In the 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 a single bond or a double bond, Y is one or more selected from an oxygen atom, a sulfur atom, a carbon atom, and a nitrogen atom, and the hydrogen atoms of the ring formed by X, Y, and -C=NH- are a carboxy group, an amino group, a C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C ６ ~C １２ aryl group, or hydrazino group; M is a single bond, C １ ~C １２ Alkyl group, C １ ~C １２ Ester group or C ２ ~C １２ ether groups, In the structural formula IV, the ring constituted by X, Y, and Z is a benzene ring or a heterocycle, and the benzene ring and the heterocycle are C １ ~C ６ Alkyl group, C １ ~C ６ may have one or more of an alkoxy group, an amino group, a carboxylic acid, a nitro group, and a halogen; More preferably, the compound forming a complex with copper in the copper complex (E) 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-mercaptoindole, 1,3,5-tris(mercaptoethyl) 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-hydrazine 5-mercapto-1,2,4-triazole, 1-methyl-5-mercapto-1H-tetrazole, 1-hydroxyethyl-5-mercapto-1H-tetrazole, 1-(2-dimethylaminoethyl)-1H-5-mercapto-tetrazole, 1-phenyl-5-mercaptotetrazole, 1,2-dihydro-1-(4-methoxyphenyl)-5H-tetraaza-5-thione, 1-ethyl-5-mercapto-1,2,3,4-tetrazole, 5-mercapto-1H-tetrazole-1-acetic acid, 5-mercapto-1,2,3,The dry film resist according to any one of claims 1 to 3, characterized in that the compound is one or more selected from the group consisting of 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-thione, 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, and 4-amino-2-mercaptopyrimidine.

7. The photopolymerizable monomer (B) includes 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 are each independently H or CH ３ wherein EO represents an oxyethylene group, PO represents an oxypropylene group, the arrangement of the EO and PO repeating units is random or block, m １ , m ２ Each n is an integer from 1 to 20, １ , n ２ Each is an integer from 0 to 20, and m １ +m ２ is any integer from 2 to 20, n １ +n ２ is any integer from 0 to 20, １ is any integer from 4 to 20, b １ is any integer from 0 to 20, ２ is any integer from 3 to 20, b ２ is any integer from 0 to 20, c ２ is any integer from 3 to 20, Preferably, 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, more preferably 50% to 80%, and is 20% to 40% of the total weight of the (B) photopolymerizable monomer and the (A) alkali-soluble resin; More preferably, the photopolymerizable monomer (B) further contains one or more of the structures represented by structural formula B4, 【Chemistry 17】 In the formula, R １ are each independently H or CH ３ and a ３ are each independently any integer from 1 to 10, More preferably, the photopolymerizable monomer (B) is one or more selected from the group consisting of 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. The dry film resist according to claim 2,

8. The photopolymerizable monomer (B) contains one or more of the compounds represented by structural formula B1, 【Chemistry 18】 In the formula, R １ are each independently H or CH ３ and m １ , m ２ Each n is an integer from 1 to 20, １ , n ２ Each is an integer from 0 to 20, and m １ +m ２ is any integer from 2 to 20, n １ +n ２ represents any one integer from 0 to 20, EO represents an oxyethylene group, PO represents an oxypropylene group, and the repeating units of EO and PO are arranged randomly or in a block; Preferably, the photopolymerizable monomer having the structure represented by Structural Formula B1 accounts for 20% to 80% of the total amount of the photopolymerizable monomers, more preferably 40% to 80%, and is 10% to 35% of the total weight of the (B) photopolymerizable monomer and the (A) alkali-soluble resin; More preferably, the photopolymerizable monomer (B) further comprises one or more selected from the group consisting of 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. The dry film resist according to claim 3,

9. The photopolymerizable monomer (B) includes one or more of the compounds represented by structural formulas B1, B5, B6, and B7, 【Chemistry 19】 【Chemistry 20】 【Chemistry 21】 【Chemistry 22】 In the formula, R １ are each independently H or CH ３ The repeating units of the EO segment and the PO segment are arranged randomly or in blocks, and in the structural formula IV, １ , m ２ Each is an arbitrary integer from 0 to 30, n １ , n ２ Each is an 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 the structural formula B5, ５ is any integer from 0 to 30, b ５ is any integer from 0 to 20, and in the structural formula B6, ６ is any integer from 0 to 30, b ６ is any integer from 0 to 20, and in the structural formula B7, ７ is any integer from 0 to 20, b ７ is any integer from 0 to 20, Preferably, 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; More preferably, the photopolymerizable monomer further comprises one or more selected from the group consisting of 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. The dry film resist according to claim 6,

10. 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】 In the formula, R ２ , R ３ , R ５ , R ７ are each independently a hydrogen atom or a methyl group; R ４ , R ６ each independently represents one or more of 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 each independently represent an integer of 0 to 5; R ８ represents any one of linear, branched, and cyclic alkyl groups having 1 to 18 carbon atoms; x, y, z, and u each represent a ratio of each copolymerization component in the alkali-soluble resin, where 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 3, characterized in that the alkali-soluble resin (A) has an acid value of 120 mgKOH / g to 250 mgKOH / g, more preferably a weight average molecular weight of 30,000 to 120,000, a molecular weight distribution of 1.3 to 2.5, and further preferably a polymerization conversion rate of ≧97%.

11. In the formula A1, x is 15 wt % to 35 wt %, z is 0 wt % to 50 wt %, u is 0 wt % to 80 wt %, y is 0 wt % to 25 wt %, and the value of z + u is 40 wt % to 80 wt %; Preferably, the copolymerization unit of the alkali-soluble resin (A) 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 ethyl (meth)acrylate, N,N-diethyl ethyl (meth)acrylate, N,N-diethyl propyl (meth)acrylate, N,N-dimethyl butyl (meth)acrylate, and N,N-diethyl butyl (meth)acrylate; The dry film resist according to claim 10, wherein 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.

12. In the structural formula A1, R ３ 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 60 wt %; Preferably, the copolymerization unit of the alkali-soluble resin (A) is selected from a (meth)acrylic acid alkyl ester and styrene and / or a derivative thereof, and the (meth)acrylic acid alkyl ester is 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, the styrene derivative is one or more selected from α-methylstyrene and benzyl (meth)acrylate, More preferably, the content of styrene in the copolymerization units of the alkali-soluble resin (A) is 0 wt % to 40 wt % of the total weight of the copolymerization units, The dry film resist according to claim 10, wherein 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.

13. In the structural formula A1, R ３ 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 %; 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, N,N-dimethyl ethyl (meth)acrylate, N,N-diethyl ethyl (meth)acrylate, N,N-diethyl propyl (meth)acrylate, N,N-dimethyl butyl (meth)acrylate, and N,N-diethyl butyl (meth)acrylate; Preferably, 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.

14. The dry film resist further includes an additive, the additive including any one or more of a free radical polymerization inhibitor, a color former, a dye, a plasticizer, a photothermal stabilizer, an adhesion promoter, a leveling agent, and an antifoaming agent, and the content of the additive is preferably 0.5 parts by weight 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 inhibitor is 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-ethylresorcinol ...resorcinol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcatechol, 2-propylcate The dry film resist according to any one of claims 1 to 3, characterized in that the resorcinol is one or more selected from the group consisting of 4-methyl-2,2-diphenyl-6-tert-butylphenol, 4-propyl ...

15. 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 according to any one of claims 1 to 3.

16. 1. A dry film resist comprising: (A) an alkali-soluble resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; and (E) a copper complex, wherein in the copper complex (E), a compound that forms a complex with copper contains a nitrogen-containing heterocyclic compound; and the (B) photopolymerizable monomer contains an EO segment and a PO segment, wherein the EO segment represents an oxyethylene group and the PO segment represents an oxypropylene group.

17. The compound that forms a complex with copper in the copper complex (E) contains a nitrogen-containing heterocycle and a mercapto group at the same time, and preferably, the compound that forms a complex with copper in the copper complex (E) has one or more of the structures represented by structural formula III or IV, 【Chemistry 24】 【Chemistry 25】 In the 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 a single bond or a double bond, Y is one or more selected from an oxygen atom, a sulfur atom, a carbon atom, and a nitrogen atom, and the hydrogen atoms of the ring formed by X, Y, and -C=NH- are a carboxy group, an amino group, a C １ ~C １２ Alkyl group, C １ ~C １２ Alkoxy group, C ６ ~C １２ aryl group, or hydrazino group; M is a single bond, C １ ~C １２ Alkyl group, C １ ~C １２ Ester group or C ２ ~C １２ ether groups, In the structural formula IV, the ring formed by X, Y, and Z is a benzene ring or a heterocycle, and the benzene ring and the heterocycle are C １ ~C ６ Alkyl group, C １ ~C ６ may have one or more of an alkoxy group, an amino group, a carboxylic acid, a nitro group, and a halogen; More preferably, the compound forming a complex with copper in the copper complex (E) 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-mercaptoindole, 1,3,5-tris(mercaptoethyl) 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-hydrazine 5-mercapto-1,2,4-triazole, 1-methyl-5-mercapto-1H-tetrazole, 1-hydroxyethyl-5-mercapto-1H-tetrazole, 1-(2-dimethylaminoethyl)-1H-5-mercapto-tetrazole, 1-phenyl-5-mercaptotetrazole, 1,2-dihydro-1-(4-methoxyphenyl)-5H-tetraaza-5-thione, 1-ethyl-5-mercapto-1,2,3,4-tetrazole, 5-mercapto-1H-tetrazole-1-acetic acid, 5-mercapto-1,2,3,The dry film resist according to claim 16, characterized in that the compound is one or more selected from the group consisting of 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-thione, 1-(4-carboxyphenyl)-5-mercapto-1H-tetrazole, and 4-amino-2-mercaptopyrimidine.

18. The dry film resist according to claim 16, characterized in that the dry film resist comprises, on a weight part basis, 40 to 65 parts by weight of the alkali-soluble resin (A), 35 to 60 parts by weight of the photopolymerizable monomer (B), 2.0 to 4.5 parts by weight of the photopolymerization initiator (C), and 0.01 to 0.5 parts by weight of the copper complex (E).

19. The dry film resist further comprises 0.01 to 0.5 parts by weight of a sensitizer (D), and preferably, the sensitizer (D) comprises one or more of the compounds represented by structural formula I or II; 【Chemistry 26】 【Chemical 27】 In the formula, R ０ are each independently hydrogen, halogen, or C １ ~C ８ Alkyl group or C １ ~C ４ is an alkoxy group, The modifying functional group M in the structural formula I １ each independently represents biphenyl, a fused ring functional group or an electron-rich heterocycle, a fused heterocycle or C １ ~C ４ A benzene ring having an alkoxy group and an amino group; The modifying functional group M in the structural formula II ２ is a biphenyl, a fused ring functional group or an electron-rich heterocycle, a fused heterocycle or a C １ ~C ４ A benzene ring having an alkoxy group or an amino group, or C １ ~C ４ The modified functional group W is any one of a benzene ring and a fluorene ring, or a halogen, C １ ~C ８ Alkyl group, C １ ~C ４ a benzene ring, a biphenyl ring, or a fluorene ring having one or more substituents selected from the group consisting of alkoxy groups; More preferably, the modifying functional group M １ are each independently C １ ~C ４ The modified functional group M is preferably a condensed ring functional group having one or more of an alkoxy group, an amino group, or an alkyl group, or is preferably any one of furan, thiophene, indole, thiazole, benzofuran, benzothiazole, indene, anthracene, acridine, and an aromatic amine. １ and / or M ２ The specific structural formula is: 【Chemistry 28】 Including, During the ceremony, 【Chemical 29】 is the attachment site of the functional group, Optionally, the modifying functional group M １ And / or M ２ In the specific structural formula, the benzene ring, the biphenyl ring, the condensed ring, and the heterocyclic ring are halogen, C １ ~C ８ Alkyl group, C １ ~C ４ 17. The dry film resist according to claim 16, further comprising one or more substituents of an alkoxy group, the substituents being preferably located at the para position.

20. The (C) photopolymerization initiator includes a compound represented by the following structural formula C1, 【Chemistry 30】 In the formula, each substituent A in the benzene ring is independently a hydrogen atom, a methoxy group, or a halogen atom; Preferably, 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, Optionally, the photopolymerization initiator (C) may further include 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-benzoanthraquinone, 2,3-benzylanthraquinone, octamethylanthraquinone, 1,2-benzoanthraquinone, octamethyl ...

17. The dry film resist according to claim 16, comprising at least one selected from the group consisting of triphenylanthraquinone, 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, benzyl dimethyl ketal, 9-phenylacridine, 1,7-bis(9,9'-acridinyl)heptane, N-phenylglycine, coumarin-based compounds, and oxazole-based compounds.

21. The photopolymerizable monomer includes one or more of the compounds represented by structural formulas B1, B2, B3, and B4, 【Chemistry 31】 【Chemistry 32】 【Chemical 33】 【Chemical Formula 34】 In the formula, R １ are each independently H or CH ３ The repeating units of the EO segment and the PO segment are arranged randomly or in blocks, and in the structural formula B1, １ , m ２ Each is an arbitrary integer from 0 to 30, n １ , n ２ Each is an 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 the structural formula B5, ５ is an integer between 0 and 30, and b ５ is an arbitrary integer of 0 to 20, and in the structural formula B6, ６ is an integer between 0 and 30, and b ６ is an arbitrary integer of 0 to 20, and in the structural formula B7, ７ is an integer between 0 and 20, and b ７ is any integer from 0 to 20, Preferably, 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; More preferably, the photopolymerizable monomer (B) further comprises one or more selected from the group consisting of 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. The dry film resist according to claim 16,

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 includes any one or more of structures represented by Structural Formula A2, 【Chemistry 35】 In the formula, R ２ , R ７ are each independently a hydrogen atom or a methyl group; R ８ is C １ ~C １８ A straight chain alkyl group and ３ ~C １８ Substituted C containing a branched alkyl group, a benzyl group, and a hydroxyl group and / or an amino group １ ~C １８ Linear alkyl group or C ３ ~C １８ and a branched alkyl group, R ４ is C １ ~C ３ Alkyl group, C １ ~C ３ the number of substituents on the benzene ring of the structural formula A2 is 0 to 5; x, y, and z each represent a ratio of each copolymerization component in the alkali-soluble resin, where x is 15 wt % to 40 wt %, y is 20 wt % to 70 wt %, and z is 0 wt % 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, N,N-dimethyl ethyl (meth)acrylate, N,N-diethyl ethyl (meth)acrylate, N,N-diethyl propyl (meth)acrylate, N,N-dimethyl butyl (meth)acrylate, and N,N-diethyl butyl (meth)acrylate; More preferably, the acid value of the alkali-soluble resin is 120 mgKOH / g to 250 mgKOH / g, more preferably, the weight average molecular weight is 50,000 to 120,000, the molecular weight distribution is 1.3 to 2.5, and even more preferably, the polymerization conversion rate is ≧97%.

23. The dry film resist according to claim 16, further comprising an additive, the additive comprising one or more of a color former, a dye, a plasticizer, a photothermal stabilizer, an adhesion promoter, a leveling agent, a polymerization inhibitor and an antifoaming agent, and preferably the content of the additive is 0.5 parts by weight to 5.0 parts by weight.

24. 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 according to any one of claims 16 to 21.

25. A copper-clad laminate comprising the dry film resist according to any one of claims 16 to 21.

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