A photosensitive resin composition for dual-wavelength exposure

Abstract

The present invention discloses a photosensitive resin composition suitable for dual-wavelength exposure, with a first wavelength range of 350 nm - 370 nm and a second wavelength range of 390 nm - 410 nm. The photosensitive resin composition also has excellent exposure sensitivity, resolution, adhesion, and peelability. The above-mentioned photosensitive resin composition comprises: (A) an alkali-soluble polymer resin; (B) a photopolymerizable monomer containing an ethylenically unsaturated double bond; (C) a photoinitiator; (D) a sensitizer; (E) other optional additives. The above-mentioned (D) sensitizer comprises two pyrazoline derivatives.

Description

Technical Field

[0001] The present invention relates to the fields of photocuring and anti-corrosion coatings, and particularly to a photosensitive resin composition suitable for dual-wavelength exposure. Background Art

[0002] In recent years, with the miniaturization of the wiring pitch of printed circuit boards, more and more manufacturers use laser direct imaging exposure machines for exposure production. As a maskless exposure light source, most laser direct imaging exposure machines use lasers with a wavelength range of 350 nm - 410 nm, especially 355 nm and 405 nm laser light sources, which are widely used in laser direct imaging exposure machines. Correspondingly, the anti-corrosion dry films designed for laser direct imaging exposure machines are also divided into anti-corrosion dry films suitable for 355 nm and 405 nm exposures. Therefore, users need to purchase anti-corrosion dry films suitable for different exposure wavelengths for different exposure machines.

[0003] During the actual production process using anti-corrosion dry films, it is necessary to identify the applicable exposure wavelength corresponding to the anti-corrosion dry film, which increases the identification process and there is a risk of wasting raw materials and working hours due to incorrect identification. If there is an anti-corrosion dry film applicable to both 355 nm and 405 nm laser light sources, the identification process for the applicable wavelength of the dry film during use can be reduced, and the waste of raw materials and working hours caused by incorrect identification can also be effectively reduced.

[0004] In addition, from the perspective of the exposure process, when using a 355 nm light source for exposure, the absorbance is high, the exposure sensitivity of the dry film is high, and there is a good curing effect at a lower exposure energy; when using a 405 nm light source for exposure, the absorbance is low, and more light reaches the bottom of the anti-corrosion dry film. Therefore, there is a tendency for the adhesion to be improved.

[0005] With the further requirement of miniaturization of anti-corrosion patterns, new exposure technologies may emerge. If two lasers with wavelengths of 350 nm - 370 nm and 390 nm - 410 nm are used for exposure simultaneously, the advantages of both high absorbance and low absorbance can be taken into account. However, the anti-corrosion dry films designed for laser direct imaging exposure machines in the past are all designed to exhibit good performance for a specific single wavelength (such as 355 nm or 405 nm wavelength), and cannot be applied to the process of simultaneous exposure with two different wavelength lasers.

[0006] Patent CN106909026A discloses a resist composition capable of directly depicting exposure imaging. The composition contains a photopolymerizable component, a photoinitiator, and an alkali-soluble copolymer resin. This patent claims that the composition can have comprehensive properties such as high sensitivity, high resolution, and good stripping characteristics at both 355 nm and 405 nm. However, the examples of this patent do not verify that the composition has good properties at both 355 nm and 405 nm wavelengths. In fact, the composition of this patent cannot achieve good exposure sensitivity at both 355 nm and 405 nm wavelengths.

[0007] Patent CN110446976A discloses a photosensitive resin composition, claiming that the invention can be used for dual-wavelength exposure and can impart excellent exposure sensitivity, adhesion, and resolution. Although this patent achieves the effect of being applicable to exposure at both 355 nm and 405 nm exposure wavelengths, its exposure sensitivity is low and no longer meets the requirements of the current PCB production industry for high sensitivity of laser direct imaging resist dry film.

[0008] In view of this, there is an urgent need in the art for a new photosensitive resin composition applicable to two different exposure wavelength bands of 350 nm - 370 nm and 390 nm - 410 nm. Summary of the Invention

[0009] In view of the problems existing in the prior art, the present invention provides a new photosensitive resin composition applicable to two different exposure wavelength bands. This photosensitive resin composition can be exposed in two bands. The first wavelength range is 350 nm - 370 nm, and the second wavelength range is 390 nm - 410 nm. This photosensitive resin composition also has excellent exposure sensitivity, resolution, adhesion, and stripping fragmentation resistance.

[0010] To achieve the above object, the technical solution adopted by the present invention is as follows:

[0011] A photosensitive resin composition applicable to dual-wavelength exposure, with the first wavelength range being 350 nm - 370 nm and the second wavelength range being 390 nm - 410 nm. The photosensitive resin composition comprises:

[0012] (A) An alkali-soluble polymer resin;

[0013] (B) A photopolymerizable monomer containing an ethylenically unsaturated double bond;

[0014] (C) A photopolymerization initiator;

[0015] (D) A sensitizer;

[0016] (E) Other optional auxiliaries.

[0017] Among them, the above-mentioned (D) sensitizer contains pyrazoline derivatives.

[0018] According to an embodiment of the present invention, in the (A) alkali-soluble polymer resin, the content of methacrylic acid monomer is 20%-30%, the content of methyl methacrylate monomer is 30%-60%, the content of n-butyl acrylate monomer is 7%-15%, the content of styrene monomer is 10%-30%, and the content of 2-hydroxyethyl acrylate monomer is 1%-10%; its weight average molecular weight ranges from 30,000 to 100,000; its dispersity is less than 3.

[0019] (A) The alkali-soluble polymer resin can be used alone or in combination of two or more. Based on the total mass parts of 100 parts of the (A) alkali-soluble polymer resin and the (B) ethylenically unsaturated double bond-containing photopolymerizable monomer, the mass parts of the (A) alkali-soluble polymer resin are 40-70 parts, preferably 50-60 parts.

[0020] The mass parts of subsequent other components are all measured based on this standard.

[0021] According to an embodiment of the present invention, the (B) ethylenically unsaturated double bond-containing photopolymerizable monomer includes ethylenically unsaturated double bond photopolymerizable monomers having monofunctional groups, bifunctional groups, and trifunctional groups. Preferably, the (B) ethylenically unsaturated double bond-containing photopolymerizable monomer is selected from one or more of bisphenol A type (meth)acrylate compounds, nonylphenol acrylate compounds containing multiple ethoxy groups, aliphatic polyurethane acrylate compounds, trimethylolpropane tri(meth)acrylate compounds containing multiple ethoxy groups, etc.

[0022] According to an embodiment of the present invention, the (C) photopolymerization initiator contains 2,4,5-triaryl imidazole dimers; the structure of the 2,4,5-triaryl imidazole dimers can be symmetric or asymmetric. Preferably, the structure of the 2,4,5-triaryl imidazole dimer is selected from 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-bromophenyl)-4,5-diphenyl imidazole dimer, etc. From the viewpoint of improving the exposure sensitivity during the formation of the resist pattern and the resolution and adhesion of the formed resist pattern, 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer is preferred.

[0023] According to an embodiment of the present invention, the addition amount of the (C) photopolymerization initiator is 0.5-10 parts, preferably 1-5 parts.

[0024] According to an embodiment of the present invention, the (D) sensitizer includes a (D-1) pyrazoline derivative having a maximum absorption at 350 nm - 370 nm and a (D-2) pyrazoline derivative having a maximum absorption at 390 nm - 410 nm. The inventors have found that by adding the above two pyrazoline derivatives as sensitizers, the photosensitive resin composition can have good exposure sensitivity in the above two exposure wavelength bands.

[0025] The above (D-1) pyrazoline derivative is represented by the general formula (I):

[0026]

[0027] In the above general formula (I), R1 - R3 each independently represent hydrogen, a linear or branched alkyl group having 1 - 12 carbon atoms, a linear or branched alkoxy group having 1 - 10 carbon atoms, a halogen atom, or a phenyl group. From the viewpoint of improving the exposure sensitivity during the formation of the resist pattern, R1 - R3 are preferably hydrogen, tert-butyl, isopropyl, methoxy, and ethoxy.

[0028] Preferably, the (D-1) pyrazoline derivative is 1-phenyl-3-phenyl-5-(4-methoxyphenyl)pyrazoline, 1-phenyl-3-phenyl-5-(4-tert-butylphenyl)pyrazoline, 1-phenyl-3-phenyl-5-(4-isopropylphenyl)pyrazoline, and more preferably 1-phenyl-3-phenyl-5-(4-methoxyphenyl)pyrazoline.

[0029] The mass fraction of the (D-1) pyrazoline derivative is 0.01 - 1 part, preferably 0.05 - 0.2 part.

[0030] The above (D-2) pyrazoline derivative is represented by the general formula (II):

[0031]

[0032] In the above general formula (II), R4 - R6 each independently represent hydrogen, a linear or branched alkyl group having 1 - 12 carbon atoms, a linear or branched alkoxy group having 1 - 10 carbon atoms, a halogen atom, or a phenyl group. From the viewpoint of improving the exposure sensitivity during the formation of the resist pattern, R4 - R6 are preferably hydrogen, tert-butyl, isopropyl, methoxy, and ethoxy.

[0033] Preferably, the (D-2) pyrazoline derivative is 1-phenyl-3-styryl-5-(4-methoxyphenyl)pyrazoline, 1-phenyl-3-styryl-5-(4-tert-butylphenyl)pyrazoline, 1-phenyl-3-styryl-5-(4-isopropylphenyl)pyrazoline, and more preferably 1-phenyl-3-styryl-5-(4-tert-butylphenyl)pyrazoline.

[0034] (D-2) pyrazoline derivative is 0.01 - 1 part by mass, preferably 0.05 - 0.2 part by mass.

[0035] Further preferably, the mass ratio of (D-1) to (D-2) is 1:1 - 1:2, more preferably 1:1.3 - 1:1.6.

[0036] The inventors have found that by using two pyrazoline derivatives with specific structures and controlling their dosages, the exposure sensitivity of the photoresist dry film can be significantly improved while taking into account the adhesion.

[0037] The inventors have also found that among various pyrazoline derivative structures, the combination of (D-1) pyrazoline derivative with a methoxy structure and (D-2) pyrazoline derivative with a tert-butyl structure has the best sensitizing effect for both the 350nm - 370nm and 390nm - 410nm wavelength bands.

[0038] The above-mentioned (D-1) and (D-2) pyrazoline derivatives can be obtained commercially or synthesized by methods commonly used in the art, such as the methods disclosed in patents JP2931693B2, JP3312756B2, JP2757528B2, etc.

[0039] According to an embodiment of the present invention, the (E) other optional additives include one or more of other photoinitiators and / or sensitizers, hydrogen donors, dyes, pigments, photochromic agents, plasticizers, stabilizers, coating aids, etc.

[0040] The other photoinitiators and / or sensitizers include, but are not limited to: aromatic ketones, anthraquinones, coumarins, acridines, and other photoinitiators and sensitizers known to those skilled in the art. Exemplarily, benzophenone, tetraethyl methylene ketone, 9,10-dibutylanthracene, 7-diethylamino-4-methylcoumarin, 9-phenylacridine, 1,7-bis(9-acridinyl)heptane, etc. can be listed. These photoinitiators and / or sensitizers can be used alone or in combination of two or more.

[0041] The hydrogen donors include, but are not limited to: amine compounds, carboxylic acid compounds, sulfone compounds, and alcohol compounds. Exemplarily, triethanolamine, N-phenylglycine, phenylthioacetic acid, tribromomethylphenyl sulfone, dodecyl mercaptan, etc. can be listed. These hydrogen donors can be used alone or in combination of two or more.

[0042] For the dyes, pigments, and photochromic agents, exemplarily, malachite green, brilliant green, invisible crystal violet (LCV), basic fuchsin, crystal violet, etc. can be listed. These dyes, pigments, and photochromic agents can be used alone or in combination of two or more.

[0043] The plasticizers, by way of example, may include: dibutyl phthalate, p-toluenesulfonamide, benzenesulfonamide, trimethyl phosphate, etc. These plasticizers can be used alone or in combination of two or more.

[0044] The stabilizers, by way of example, may include: p-methylphenol, tert-butylcatechol, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, aluminum N-nitroso-N-phenylhydroxylamine, diethylhydroxylamine, etc. These stabilizers can be used alone or in combination of two or more.

[0045] The coating aids, by way of example, may include: acetone, methanol, ethanol, toluene, dichloromethane, cyclohexanone, etc. These coating aids can be used alone or in combination of two or more.

[0046] The present invention also provides a photosensitive resin laminate composed of the above photosensitive resin composition: The photosensitive resin composition is coated on a support (usually a PET tape base), dried through a drying channel to form a photosensitive resin layer. On one side of the photosensitive resin layer, a protective film (generally a PE protective film) is laminated. The resulting support - photosensitive resin layer - protective film laminate is the final photosensitive resin laminate. The coating thickness of the photosensitive resin layer is preferably 10 μm - 80 μm, more preferably 20 μm - 50 μm.

[0047] The present invention also provides a method for manufacturing an etching pattern, which includes the following steps:

[0048] (1) Laminating step: The protective film of the above photosensitive resin laminate is peeled off, and the photosensitive resin layer is laminated on a copper-clad laminate or a flexible substrate.

[0049] (2) Exposure step: The photosensitive resin laminate is exposed and cured with a first laser of 350 nm or more and 370 nm or less and a second laser of 390 nm or more and 410 nm or less, respectively.

[0050] (3) Developing step: The exposed photosensitive resin composition is developed (usually potassium carbonate or sodium carbonate is used as the developer) to form an etching pattern.

[0051] The present invention also provides a method for manufacturing a printed circuit board, which includes the following steps:

[0052] (1) Laminating step: The protective film of the above photosensitive resin laminate is peeled off, and the photosensitive resin layer is laminated on a copper-clad laminate or a flexible substrate.

[0053] (2) Exposure process: The photosensitive resin laminate is exposed and cured with a first laser of 350 nm or more and 370 nm or less and a second laser of 390 nm or more and 410 nm or less, respectively.

[0054] (3) Development process: The exposed photosensitive resin composition is developed (usually using potassium carbonate or sodium carbonate as the developer) to form an etching resist pattern.

[0055] (4) Conductor pattern formation process: The portion of the surface of the copper-clad laminate or flexible substrate that is not covered by the protective pattern is etched or plated.

[0056] (5) Stripping process: The protective pattern is stripped from the surface of the copper-clad laminate or flexible substrate (usually using sodium hydroxide as the stripping solution).

[0057] The present invention also provides a method for manufacturing a conductor pattern, including the above-mentioned lamination process, exposure process, development process, conductor pattern formation process, and stripping process. The difference lies in that: in the lamination process, the photosensitive resin laminate is laminated on a metal plate or a metal-coated insulating plate.

[0058] The present invention also provides a method for manufacturing a lead frame, including the above-mentioned lamination process, exposure process, development process, conductor pattern formation process, and stripping process. The difference lies in that: in the lamination process, the photosensitive resin laminate is laminated on a metal plate.

[0059] The present invention also provides a method for manufacturing a semiconductor package, including the above-mentioned lamination process, exposure process, development process, conductor pattern formation process, and stripping process. The difference lies in that: in the lamination process, the photosensitive resin laminate is laminated on a wafer having a large-scale integrated circuit.

[0060] Compared with the prior art, the present invention has the following beneficial effects:

[0061] The photosensitive resin composition provided by the present invention can be simultaneously applied to two exposure bands of 350 nm - 370 nm and 390 nm - 410 nm. Especially at the wavelengths of 355 nm and 405 nm commonly used in current mainstream laser direct writing exposure machines, it has good resolution, adhesion, and stripping breakage, and excellent exposure sensitivity at both wavelengths. Detailed implementation manners

[0062] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without making creative efforts belong to the protection scope of the present invention. In addition, it is worth noting that the raw materials involved in the present invention are all ordinary commercially available products unless otherwise specified.

[0063] 1. Preparation of photosensitive resin composition

[0064] 1.1(A) Synthesis of alkali-soluble polymer resin

[0065] 1.1.1(A-1) Synthesis of alkali-soluble polymer resin

[0066] Mix 252 g of ethylene glycol methyl ether and 168 g of toluene as solvents evenly (mass ratio is 3:2), and the obtained mixed solution is used as "solution a".

[0067] Mix 130 g of methacrylic acid, 235 g of methyl methacrylate, 45 g of n-butyl acrylate, 75 g of styrene, 15 g of 2-hydroxyethyl acrylate (mass ratio is 26:47:9:15:3) as monomers for synthesizing polymer resin and 3 g of azobisisobutyronitrile as an initiator evenly and dissolve them. The obtained mixed solution is used as "solution b".

[0068] Mix 72 g of ethylene glycol methyl ether, 48 g of toluene (mass ratio is 3:2) as solvents and 2.0 g of azobisisobutyronitrile as an initiator evenly and dissolve them. The obtained mixed solution is used as "solution c".

[0069] Mix 42 g of ethylene glycol methyl ether and 28 g of toluene as solvents evenly (mass ratio is 3:2), and the obtained mixed solution is used as "solution d".

[0070] Add "solution a" to a 2 L reaction flask equipped with a stirring paddle, a reflux condenser, a thermocouple thermometer, a constant pressure dropping funnel and a nitrogen inlet tube. While introducing nitrogen into the reaction flask and stirring (200 rpm), heat it with a water bath to 80 °C. All subsequent reaction processes are carried out under stirring at 200 rpm.

[0071] Using a constant pressure dropping funnel, "Solution b" was evenly added dropwise to the reaction flask over 4 hours, with the temperature controlled at 80°C ± 2°C. After the addition was complete, it was kept at 80°C for 2 hours. Then, using a constant pressure dropping funnel, "Solution c" was evenly added dropwise to the reaction flask over 10 minutes. After the addition was complete, it was kept at 80°C for 3 hours. After the heat preservation was completed, using a constant pressure dropping funnel, "Solution d" was evenly added dropwise to the reaction flask over 10 minutes, with the temperature controlled at 80°C ± 2°C. After the addition was complete, the temperature was raised to 90°C within 30 minutes and kept at this temperature for 2 hours.

[0072] After the heat preservation was completed, it was cooled to obtain the (A-1) alkali-soluble polymer resin.

[0073] Among them, the weight-average molecular weight (M w ) was determined by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene standard curve. The specific chromatographic conditions are as follows:

[0074] Pump: Agilent 1260 Infinity Ⅱ type

[0075] Chromatographic column: PLgel 5μm MIXED-D 300×7.5mm gel chromatography columns, 2 columns in series

[0076] Sample injection volume: 20 μL

[0077] Mobile phase: Tetrahydrofuran (HPLC grade)

[0078] Flow rate: 1.0 mL / min

[0079] Column oven (test temperature): 40°C

[0080] Detector: Agilent 1260 Infinity Ⅱ type, RID detector

[0081] 1.1.2 Synthesis of (A-2) to (A-4) alkali-soluble polymer resins

[0082] As the polymer monomer, using the raw materials shown in Table 1 in the mass ratio shown in Table 1, except for this, the synthesis operation for obtaining the alkali-soluble polymer resin (A-1) was the same, and (A-2) to (A-4) alkali-soluble polymer resins were obtained.

[0083] Among them, the weight-average molecular weight (M w ) was determined by gel permeation chromatography (GPC) and derived by conversion using a standard polystyrene standard curve. The specific chromatographic conditions were the same as those of the above-mentioned (A-1) alkali-soluble polymer resin. The weight-average molecular weight and dispersity of the alkali-soluble polymer resins are shown in Table 2 below.

[0084] The "initiator" in Table 1 refers to the initiator in "Solution b", and the "additional initiator" refers to the initiator in "Solution c".

[0085] Table 1. Mass ratio of alkali-soluble polymer resin monomers

[0086]

[0087] Table 2. Performance indicators of alkali-soluble polymer resin

[0088]

[0089]

[0090] 1.2 (B) Photopolymerizable monomers containing ethylenically unsaturated double bonds

[0091] Photopolymerizable monomer 1: 30 (ethoxy) bisphenol A dimethacrylate

[0092] Photopolymerizable monomer 2: 10 (ethoxy) bisphenol A dimethacrylate

[0093] Photopolymerizable monomer 3: (3) ethoxylated trimethylolpropane triacrylate

[0094] Photopolymerizable monomer 4: 8 (ethoxy) nonylphenol acrylate

[0095] Photopolymerizable monomer 5: 9 (ethoxy) trimethylolpropane triacrylate

[0096] 1.3 (C) Photopolymerization initiator

[0097] BCIM: 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer

[0098] 1.4 (D) Sensitizer

[0099] ZG-1 (synthesized by Baoding Lucky Film Co., Ltd.): 1-phenyl-3-phenyl-5-(4-methoxyphenyl)pyrazoline;

[0100] As shown in the following chemical formula (Ⅲ):

[0101]

[0102] ZG-2 (synthesized by Baoding Lucky Film Co., Ltd.): 1-phenyl-3-styryl-5-(4-tert-butylphenyl)pyrazoline;

[0103] As shown in the following chemical formula (Ⅳ):

[0104]

[0105] ZG-3 (synthesized by Baoding Lucky New Materials Co., Ltd.): 1-phenyl-3-phenyl-5-(4-ethoxyphenyl)pyrazoline;

[0106] As shown in the following chemical formula (Ⅴ):

[0107]

[0108] ZG-4 (synthesized by Baoding Lucky New Materials Co., Ltd.): 1-phenyl-3-styryl-5-(4-isopropylphenyl)pyrazoline;

[0109] As shown in the following chemical formula (Ⅵ):

[0110]

[0111] 1.5 (E) Other optional auxiliaries

[0112] NPG: N-phenylglycine

[0113] LCV: Leuco Crystal Violet

[0114] MKG: Malachite Green

[0115] PTSA: p-Toluenesulfonamide

[0116] Polymerization inhibitor 510: N-nitroso-N-phenylhydroxyaluminum

[0117] The mass parts of each component in Examples 1-2 and Comparative Examples 1-6 are shown in Tables 3 and 4 below:

[0118] Table 3 Examples

[0119]

[0120]

[0121] Table 4 Comparative Examples

[0122]

[0123]

[0124] 2. Manufacturing method of photosensitive resin laminate

[0125] The photosensitive resin composition prepared above was uniformly coated on a support of a 15-μm-thick PET film (Shandong Fuwei Film Co., Ltd.), and dried in an oven at 90 °C for 3 min to form a photosensitive resin composition layer with a film thickness of 38 μm. A 15-μm-thick PE protective film (Foshan Xinchangsheng Plastic Film Co., Ltd.) was overlaid on the photosensitive resin composition layer, thereby forming a photosensitive resin laminate of PET support - photosensitive resin layer - PE protective film.

[0126] According to the above method, photosensitive resin laminates of Examples 1-2 and Comparative Examples 1-6 were obtained respectively.

[0127] 3. Manufacturing method of resist pattern

[0128] 3.1 Laminating process

[0129] Using a pretreatment machine, the substrate laminated with a 40-μm-thick copper layer was sprayed, washed, and brushed to clean and roughen the surface of the copper layer of the substrate.

[0130] Using a laminating machine, the protective film of the photosensitive resin laminate was peeled off and laminated on the copper-clad substrate. The laminating speed was 1.0 m / min, the temperature of the laminating roller was 110 °C, and the laminating pressure was 0.4 kg.

[0131] 3.2 Exposure process

[0132] Using an exposure machine, the photosensitive resin laminate laminated on the substrate was exposed. 355-nm light source and 405-nm light source were used respectively, and exposure was carried out with a 41-step exposure scale. Exposure was carried out with the energy value corresponding to the maximum remaining 20 steps as the exposure energy.

[0133] 3.3 Development process

[0134] Using a developing machine, the photosensitive resin laminate with the PET support peeled off was developed. The nozzle was a fan-shaped nozzle, the developing solution was an aqueous solution of Na2CO3 with a mass concentration of 1%, and the developing pressure was 0.18 kg. The shortest time required for the completely developed removal of the unexposed part of the photosensitive resin layer was measured as the shortest developing time, and development was carried out for a time twice the shortest developing time.

[0135] 4. Performance evaluation

[0136] 4.1 Evaluation of exposure sensitivity

[0137] After the laminating process, the photosensitive resin laminates of Examples 1-2 and Comparative Examples 1-6 were exposed using a 355-nm light source and classified according to the following criteria:

[0138] ○ (Good): The energy value corresponding to the maximum residual order of 20 levels is less than or equal to 20 mj / cm 2 .

[0139] △ (Acceptable): The energy value corresponding to the maximum residual order of 20 levels is greater than 20 mj / cm 2 and less than 40 mj / cm 2 .

[0140] × (Poor): The energy value corresponding to the maximum residual order of 20 levels is greater than or equal to 40 mj / cm 2 .

[0141] After the lamination process, the photosensitive resin laminates of Examples 1-2 and Comparative Examples 1-6 were subjected to an exposure process using a 405 nm light source and classified according to the following criteria:

[0142] ○ (Good): The energy value corresponding to the maximum residual order of 20 levels is less than or equal to 25 mj / cm 2 .

[0143] △ (Acceptable): The energy value corresponding to the maximum residual order of 20 levels is greater than 25 mj / cm 2 and less than 50 mj / cm 2 .

[0144] × (Poor): The energy value corresponding to the maximum residual order of 20 levels is greater than or equal to 50 mj / cm 2 .

[0145] 4.2 Resolution evaluation

[0146] After the lamination process, the photosensitive resin laminates of Examples 1-2 and Comparative Examples 1-6 were subjected to an exposure process using 355 nm and 405 nm light sources respectively, and the energy value corresponding to the maximum residual order of 20 levels was used as the exposure energy. The exposure pattern was a line with a line width: line pitch ratio of 1:1. After the development process, the minimum line pitch at which the anti-etching layer lines were normally formed was used as the resolution value and classified according to the following criteria:

[0147] ○ (Good): The resolution value is less than or equal to 40 μm.

[0148] △ (Acceptable): The resolution value is greater than 40 μm and less than 60 μm.

[0149] × (Poor): The resolution value is greater than or equal to 60 μm.

[0150] 4.3 Adhesion evaluation

[0151] For the photosensitive resin laminates of Examples 1-2 and Comparative Examples 1-6, after the lamination process, the exposure process was carried out using a 355 nm light source and a 405 nm light source respectively, and the energy value corresponding to the maximum remaining order of 20 levels was used as the exposure energy. The exposure pattern was a line with a fixed line pitch of 500 μm and a line width ranging from 10 μm to 100 μm. After the development process, the minimum line width of the resist layer line formed normally was used as the value of the adhesion, and the classification was carried out according to the following criteria:

[0152] ○ (Good): The adhesion value is less than or equal to 30 μm.

[0153] △ (Acceptable): The adhesion value is greater than 30 μm and less than 50 μm.

[0154] × (Poor): The adhesion value is greater than or equal to 50 μm.

[0155] 4.4 Evaluation of peeling and fragmentation

[0156] For the photosensitive resin laminates of Examples 1-2 and Comparative Examples 1-6, after the lamination process, the exposure process was carried out using a 355 nm light source and a 405 nm light source respectively, and the energy value corresponding to the maximum remaining order of 20 levels was used as the exposure energy. The exposure pattern was a square with a side length of 10 cm. After the development process, the square cured pattern with a side length of 10 cm together with the substrate was cut off with scissors and placed in a beaker containing 3% NaOH aqueous solution, and the film removal experiment was carried out by ultrasonic oscillation. After the square cured pattern was completely peeled off from the copper layer of the substrate, the fragmentation situation of the square pattern of the cured resist layer was observed, and the classification was carried out according to the following criteria:

[0157] ○ (Good): The cured resist layer pattern is completely fragmented or the number of broken holes is greater than or equal to 10.

[0158] △ (Acceptable): The number of broken holes in the cured resist layer pattern is less than 10 and greater than 3.

[0159] × (Poor): The number of broken holes in the cured resist layer pattern is less than or equal to 3 or there is no fragmentation at all.

[0160] Table 5 Performance evaluation results

[0161]

[0162] As can be seen from Table 5, Examples 1-2 showed good performance in terms of exposure sensitivity, resolution, adhesion, and peelability, while Comparative Examples 1-6 were inferior to Examples 1-2 in some aspects of exposure sensitivity, resolution, adhesion, and peelability. The photosensitive resin composition and the photosensitive resin laminate can be simultaneously applied to 355 nm and 405 nm exposure machines, and are widely used in the manufacture of resist patterns, printed circuit boards, conductor patterns, lead frame lines, and semiconductor packages, and can effectively avoid production accidents caused by misidentification of the applicable wavelength type of dry film.

[0163] In addition, with the development of exposure technology in the future, the photosensitive resin composition and the photosensitive resin laminate can also be exposed using both 355 nm and 405 nm lasers simultaneously, taking into account the advantages of both high absorbance and low absorbance, and manufacturing resist patterns with higher precision.

[0164] Finally, it should be noted that the above content is only used to illustrate the technical solution of the present invention, rather than limiting the protection scope of the present invention. Any simple modification or equivalent replacement of the technical solution of the present invention by those of ordinary skill in the art does not depart from the essence and scope of the technical solution of the present invention.

Claims

1. A photosensitive resin composition suitable for dual-wavelength exposure, with the first wavelength range being 350 nm - 370 nm and the second wavelength range being 390 nm - 410 nm. The photosensitive resin composition comprises: (A)An alkali-soluble polymer resin; (B)A photopolymerizable monomer containing an ethylenically unsaturated double bond; (C)A photopolymerization initiator; (D)A sensitizer; (E)Other optional additives; Among them, The above-mentioned (D) sensitizer contains two pyrazoline derivatives, namely one of the (D-1) pyrazoline derivatives represented by the general formula (I) and one of the (D-2) pyrazoline derivatives represented by the general formula (II): (I) (II); Wherein, R1, R2, R4, and R5 each independently represent hydrogen, tert-butyl, isopropyl, methoxy, or ethoxy, R3 is methoxy, and R6 is tert-butyl; The mass ratio of (D-1) to (D-2) is 1:1 - 1:2; It is characterized in that: The comonomers of the (A) alkali-soluble polymer resin contain, by mass percentage: 20% - 30% of methacrylic acid monomers, 30% - 60% of methyl methacrylate monomers, 7% - 15% of n-butyl acrylate monomers, 10% - 30% of styrene monomers, and 1% - 10% of 2-hydroxyethyl acrylate monomers; The weight-average molecular weight range of the alkali-soluble polymer resin is 30,000 - 100,000, and the dispersity is less than 3; The (A) alkali-soluble polymer resin can be used alone or in combination of two or more.

2. The photosensitive resin composition according to claim 1, wherein: The (D-1) pyrazoline derivative is specifically 1-phenyl-3-phenyl-5-(4-methoxyphenyl)pyrazoline, and the (D-2) pyrazoline derivative is specifically 1-phenyl-3-styryl-5-(4-tert-butylphenyl)pyrazoline.

3. The photosensitive resin composition according to claim 1 or 2, characterized in that: Based on the total mass parts of 100 parts of the (A) alkali-soluble polymer resin and the (B) photopolymerizable monomer containing an ethylenically unsaturated double bond, the mass parts of the (D-1) pyrazoline derivative are 0.01 - 1 part, and the mass parts of the (D-2) pyrazoline derivative are 0.01 - 1 part.

4. The photosensitive resin composition according to claim 3, wherein: The mass parts of the (D-1) pyrazoline derivative are 0.05 - 0.2 part, and the mass parts of the (D-2) pyrazoline derivative are 0.05 - 0.2 part.

5. The photosensitive resin composition according to claim 4, wherein: The mass ratio of (D-1) to (D-2) is 1:1.3 - 1:1.

6.

6. The photosensitive resin composition according to claim 1, wherein: Based on the total mass parts of 100 parts of the (A) alkali-soluble polymer resin and the (B) photopolymerizable monomer containing an ethylenically unsaturated double bond, the mass parts of the (A) alkali-soluble polymer resin are 40 - 70 parts.

7. The photosensitive resin composition according to claim 6, wherein: The mass parts of the (A) alkali-soluble polymer resin are 50 - 60 parts.

8. The photosensitive resin composition according to claim 1, wherein: The (B) photopolymerizable monomer containing an ethylenically unsaturated double bond includes ethylenically unsaturated double bond photopolymerizable monomers with mono-functional groups, di-functional groups, and tri-functional groups.

9. The photosensitive resin composition according to claim 8, wherein: The (B) photopolymerizable monomer containing an ethylenically unsaturated double bond is selected from one or more of: bisphenol A type (meth)acrylate compounds, nonylphenol acrylate compounds containing multiple ethoxy groups, aliphatic polyurethane acrylate compounds, and trimethylolpropane tri(meth)acrylate compounds containing multiple ethoxy groups.

10. The photosensitive resin composition according to claim 1, wherein: The (C) photopolymerization initiator includes 2,4,5-triaryl imidazole dimers.

11. The photosensitive resin composition according to claim 10, wherein: The structure of the 2,4,5-triaryl imidazole dimer is selected from one of 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenyl imidazole dimer, and 2-(o-bromophenyl)-4,5-diphenyl imidazole dimer.

12. The photosensitive resin composition according to claim 11, wherein: The structure of the 2,4,5-triaryl imidazole dimer is 2-(o-chlorophenyl)-4,5-diphenyl imidazole dimer.

13. The photosensitive resin composition according to claim 12, wherein: Based on the total mass parts of 100 parts of the (A) alkali-soluble polymer resin and the (B) photopolymerizable monomer containing an ethylenically unsaturated double bond, the addition amount of the (C) photopolymerization initiator is 0.5 - 10 parts.

14. The photosensitive resin composition according to claim 13, characterized in that: The addition amount of the (C) photopolymerization initiator is 1 - 5 parts.

15. The photosensitive resin composition according to claim 1, wherein: The (E) other optional additives include one or several of other photoinitiators and / or sensitizers, hydrogen donors, dyes, pigments, photochromic agents, plasticizers, stabilizers, and coating aids.

16. A photosensitive resin laminate composed of the photosensitive resin composition according to any one of claims 1 - 15, and the photosensitive resin laminate is prepared by the following method: Coating the photosensitive resin composition on a support, drying to form a photosensitive resin layer; laminating a protective film on one side of the photosensitive resin layer; the resulting support - photosensitive resin layer - protective film laminate is the final photosensitive resin laminate.

17. The photosensitive resin laminate according to claim 16, wherein: The coating thickness of the photosensitive resin layer is 10 μm - 80 μm.

18. The photosensitive resin laminate according to claim 17, wherein: The coating thickness of the photosensitive resin layer is 20 μm - 50 μm.

19. A method for manufacturing an etching pattern, which includes the following steps: (1) Laminating step, removing the protective film from the photosensitive resin laminate according to any one of claims 16 - 18, and laminating the photosensitive resin layer on a copper-clad laminate or a flexible substrate. (2) Exposure step, exposing and curing the photosensitive resin laminate with a first laser of 350 nm or more and 370 nm or less and a second laser of 390 nm or more and 410 nm or less respectively. (3) Development step, developing the exposed photosensitive resin composition to form an etching pattern.

20. A method for manufacturing a printed circuit board, which includes the following steps: (1) Laminating step, removing the protective film from the photosensitive resin laminate according to any one of claims 16 - 18, and laminating the photosensitive resin layer on a copper-clad laminate or a flexible substrate. (2) Exposure step, exposing and curing the photosensitive resin laminate with a first laser of 350 nm or more and 370 nm or less and a second laser of 390 nm or more and 410 nm or less respectively. (3) Development step, developing the exposed photosensitive resin composition to form an etching pattern. (4) Conductor pattern forming step, etching or plating the part of the surface of the copper-clad laminate or the flexible substrate that is not covered by the protective pattern. (5) Peeling step, peeling the protective pattern from the surface of the copper-clad laminate or the flexible substrate.

21. A method for manufacturing a conductor pattern, which includes the following steps: (1) Laminating step, removing the protective film from the photosensitive resin laminate according to any one of claims 16 - 18, and laminating the photosensitive resin layer on a metal plate or a metal-coated insulating board. (2) Exposure process: The photosensitive resin laminate is exposed and cured with a first laser of 350 nm or more and 370 nm or less and a second laser of 390 nm or more and 410 nm or less, respectively. (3) Development process: The exposed photosensitive resin composition is developed to form an etching resist pattern. (4) Conductor pattern forming process: The portion of the surface of the copper-clad laminate or flexible substrate not covered by the protective pattern is etched or plated. (5) Stripping process: The protective pattern is stripped from the surface of the copper-clad laminate or flexible substrate.

22. A method for manufacturing a lead frame, comprising the following processes: (1) Lamination process: The protective film is removed from the photosensitive resin laminate according to any one of claims 16-18, and the photosensitive resin layer is laminated on a metal plate. (2) Exposure process: The photosensitive resin laminate is exposed and cured with a first laser of 350 nm or more and 370 nm or less and a second laser of 390 nm or more and 410 nm or less, respectively. (3) Development process: The exposed photosensitive resin composition is developed to form an etching resist pattern. (4) Conductor pattern forming process: The portion of the surface of the copper-clad laminate or flexible substrate not covered by the protective pattern is etched or plated. (5) Stripping process: The protective pattern is stripped from the surface of the copper-clad laminate or flexible substrate.

23. A method for manufacturing a semiconductor package, comprising the following processes: (1) Lamination process: The protective film is removed from the photosensitive resin laminate according to any one of claims 16-18, and the photosensitive resin layer is laminated on a wafer having a large-scale integrated circuit. (2) Exposure process: The photosensitive resin laminate is exposed and cured with a first laser of 350 nm or more and 370 nm or less and a second laser of 390 nm or more and 410 nm or less, respectively. (3) Development process: The exposed photosensitive resin composition is developed to form an etching resist pattern. (4) Conductor pattern forming process: The portion of the surface of the copper-clad laminate or flexible substrate not covered by the protective pattern is etched or plated. (5) Stripping process: The protective pattern is stripped from the surface of the copper-clad laminate or flexible substrate.

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