A dry film type photosensitive resin composition and its preparation method and application

Abstract

The present invention relates to the field of photoengraving technology for patterned surfaces, in particular to the field of IPCG03F, and more specifically to a dry film type photosensitive resin composition and its preparation method and application. In parts by weight, the components include: 100 parts of polyamic acid ester, 100-200 parts of solvent, 1-8 parts of initiator, 20-60 parts of acrylate monomer, and 2-15 parts of auxiliary agent. The acrylate monomer includes pentaerythritol tetraacrylate and ethoxylated bisphenol A diacrylate, and the weight ratio of the pentaerythritol tetraacrylate and ethoxylated bisphenol A diacrylate is 1: (2-3); the mass ratio of the polyamic acid ester to the initiator is 100: (5-10), the structure of the formed polymer film is solid, the width loss before and after baking is small, the overall polymer is better, the resolution is high during the development process, the width loss before and after baking is small, and the overall polymer is better.

Description

Technical Field

[0001] The present invention relates to the technical field of pattern surface photoengraving technology, in particular to the field of IPC G03F, and more specifically to a dry film type photosensitive resin composition and a preparation method and application thereof. Background Art

[0002] The semiconductor electronic packaging industry is gradually developing towards high density, high power, and lightness. In order to ensure that electronic components have sufficient mechanical strength in the use environment, electronic packaging must have high reliability, excellent heat dissipation, and low cost. There are two types of existing polyimide resin packaging materials. Traditional polyimide needs to be combined with a photoresist to obtain the target circuit pattern, while photosensitive resin can omit the three steps of photoresist coating, polyimide etching, and photoresist removal. Graphics can be made through direct exposure and development, reducing the complexity of processing, improving the yield rate, and reducing costs. However, the existing negative-type photosensitive resin is limited by structure, the operating space for analytical attachment is limited, and there is a problem of poor resolution of exposure and development.

[0003] CN115561966B discloses a chemically amplified negative photosensitive polyimide coating adhesive and its application. By using a polyimide resin containing phenolic hydroxyl groups together with a photoacid generator and a cross-linking agent, the prepared photolithographic pattern has high resolution, a high and adjustable angle between the bevel and the bottom edge, a low curing shrinkage rate, good adhesion to different substrate interfaces, and good resistance to chemical corrosion. However, the analytical process is complex and the yield rate is low and the cost is high.

[0004] CN114316263B discloses a cross-linked polyamic acid ester, a preparation method thereof, a polyimide composition containing the same, and a preparation method of a polyimide resin film. The cross-linked polyamic acid ester is formed by cross-linking the polyphenol cross-linking agent residues and the carboxyl residues of the originally complete polyamic acid units. The cross-linked polyamic acid ester can effectively resist development with alkaline developer, has good heat resistance, high resolution, high sensitivity, and large contrast, but has poor adhesion to electronic substrates. Summary of the invention

[0005] The first aspect of the present invention provides a dry film type photosensitive resin composition, which comprises, by weight, 100 parts of polyamic acid ester, 100-200 parts of solvent, 1-8 parts of initiator, 20-60 parts of acrylate monomer, and 2-15 parts of auxiliary agent.

[0006] Preferably, the dry film type photosensitive resin composition comprises, by weight, 100 parts of polyamic acid ester, 120-180 parts of solvent, 5-8 parts of initiator, 30-60 parts of acrylate monomer, and 2-6 parts of auxiliary agent.

[0007] The structural unit of the polyamic acid ester is shown in formula (1):

[0008] wherein R1 comprises a tetravalent organic group, R2 comprises a divalent organic group, and R3 comprises a hydrogen atom,

[0009] The general structural formula of R4 is shown in formula (2):

[0010] Wherein R5 includes one of an alkyl group and an alkoxy group, R6 includes a monovalent organic group, R7 includes a carbon-carbon unsaturated double bond, and p includes a methylene group.

[0011] The R6 includes an alkyl group or an aromatic hydroxyl group.

[0012] The weight average molecular weight of the polyamic acid ester is 20000-50000 Da.

[0013] The raw materials for preparing the polyamic acid ester include: dianhydride monomer, photosensitive resin, diamine monomer, polar solvent, catalyst and dehydrating agent.

[0014] Preferably, the raw materials for preparing the polyamic acid ester include, by weight: 5-30 parts of dianhydride monomer, 5-30 parts of photosensitive resin, 10-25 parts of diamine monomer, 30-60 parts of polar solvent, 0.5-3 parts of catalyst, and 10-20 parts of dehydrating agent.

[0015] The dianhydride monomer includes one or more of pyromellitic dianhydride (PMDA), 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), and 4,4'-oxydiphthalic anhydride (ODPA).

[0016] The diamine monomer includes one or more of m-phenylenediamine, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 2,2'-bis(trifluoromethyl)-4,4'-diaminophenyl ether (6FODA) and 4,4'-diaminodiphenyl ether (ODA).

[0017] The polar solvent includes one or more of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP).

[0018] The catalyst includes at least one of dibutyltin diacetate, dibutyltin dilaurate, triethanolamine, triethylamine, and triethylenediamine.

[0019] The photosensitive resin includes one of glycidyl methacrylate (GMA) and hydroxyethyl methacrylate (HEMA).

[0020] The dehydrating agent includes at least one of acetic anhydride, formic anhydride and trifluoroacetic anhydride.

[0021] The preparation method of the polyamic acid ester comprises the following steps:

[0022] S1: Add part of polar solvent, dianhydride monomer, part of photosensitive resin and catalyst into a flask and mix them evenly;

[0023] After S2 is cooled, the diamine monomer and the remaining polar solvent are added to react;

[0024] S3 After cooling, add dehydrating agent dropwise, stir evenly, then add remaining photosensitive resin to react;

[0025] S4: Distilled water is added dropwise to the reaction solution, and the precipitate is collected, filtered, and dried under reduced pressure to obtain polyamic acid ester.

[0026] Preferably, the preparation method of the polyamic acid ester comprises the following steps:

[0027] S1: Add part of NMP, ODPA, part of HEMA, and triethylenediamine into a flask and stir at 45 °C for 1 hour;

[0028] S2 is cooled to 25°C, m-phenylenediamine, 4,4'-diaminodiphenyl ether and the remaining NMP are added, and stirred at 45°C for 150 minutes;

[0029] S3 was cooled to room temperature, trifluoroacetic anhydride was added dropwise to the solution, stirred for 20 minutes, and then the remaining HEMA was added, and stirred at 45°C for 20 hours;

[0030] S4: Distilled water is added dropwise to the reaction solution, and the precipitate is collected, filtered, and dried under reduced pressure to obtain polyamic acid ester.

[0031] Preferably, the solvent comprises N-methylpyrrolidone.

[0032] The initiator includes a hydroxyimino-type initiator.

[0033] Preferably, the structure of the initiator is as shown in formula (3):

[0034]

[0035] The acrylate monomer includes at least one of triethylene glycol dimethacrylate, pentaerythritol tetraacrylate, ethoxylated trimethylolpropane triacrylate, ditrimethylolpropane acrylate, and ethoxylated bisphenol A diacrylate.

[0036] Preferably, the general structural formula of the ethoxylated bisphenol A diacrylate is as shown in formula (4):

[0037] The values ​​of a and b are both 1 to 15.

[0038] Preferably, the acrylate monomer comprises pentaerythritol tetraacrylate and ethoxylated bisphenol A diacrylate, and the weight ratio of the pentaerythritol tetraacrylate to the ethoxylated bisphenol A diacrylate is 1:(2-3).

[0039] The mass ratio of the polyamic acid ester to the initiator is 100:(1-10).

[0040] The auxiliary agent includes at least one of a silane coupling agent, a leveling agent, and a photoinitiator.

[0041] The auxiliary agent includes a silane coupling agent, a leveling agent, and a photoinitiator, and the mass ratio of the photoinitiator, the silane coupling agent, and the leveling agent is 0.4:(2-5):(0.1-1).

[0042] The applicant has found that by introducing polyamic acid ester polymer and acrylate monomer and using them in combination with a coupling agent [3-(triethoxysilyl)propyl] urea, the adhesion to the substrate can be improved, and it can be applied to a sandwich state with polyester film and polyethylene film as the upper and lower layers and a photoresist layer (the dry film type photosensitive resin composition of the present application) in the middle. It can also form a tough film when coated on PET, which can be closely attached to the PE film and can be peeled off before use. The dissolution rate ratio of the unexposed part to the exposed part is excellent, photodevelopment can be achieved in a solvent, and the resolution and photosensitivity performance are good. In particular, the acrylate monomer includes pentaerythritol tetraacrylate and ethoxylated bisphenol A diacrylate, the weight ratio of the pentaerythritol tetraacrylate to the ethoxylated bisphenol A diacrylate is 1:(2-3); the mass ratio of the polyamic acid ester to the initiator is 100:(5-10), the structure of the formed polymer film is solid, the width loss before and after baking is small, the overall polymer is better, the resolution is high during the development process, the width loss before and after baking is small, and the overall polymer is better, which may be because the hard segment part of the initiator and the soft segment part of the acrylic resin have reached a balance.

[0043] The second aspect of the present invention provides a method for preparing a dry film type photosensitive resin composition, comprising the following steps: adding a solvent, an initiator, an auxiliary agent, and an acrylate monomer to polyamic acid ester, and stirring to completely dissolve the polyamic acid ester to obtain the dry film type photosensitive resin composition.

[0044] The third aspect of the present invention provides an application of a dry film type photosensitive resin composition, characterized in that it is applied to a photoresist solution of electronic equipment.

[0045] Preferably, the photoresist liquid is coated on PET to form a tough coating layer, and can cover the tightly attached PE film to form a three-layer dry film roll. During testing, the PE film can be separated, and the coating layer can be transferred to the silicon wafer via a laminator. After exposure, the PET is torn off and the pattern is developed.

[0046] Beneficial Effects

[0047] 1. The polyamic acid ester prepared in the present application can improve the adhesion to the substrate, and has an excellent dissolution rate ratio between the unexposed part and the exposed part, and has good resolution and sensitivity performance.

[0048] 2. The acrylate monomer includes pentaerythritol tetraacrylate and ethoxylated bisphenol A diacrylate, and the weight ratio of the pentaerythritol tetraacrylate to the ethoxylated bisphenol A diacrylate is (2-3):1; the mass ratio of the polyamic acid ester to the initiator is 100:(5-10), and the structure of the formed polymer film is solid, the width loss before and after baking is small, the overall polymer is better, the resolution is high during the development process, the width loss before and after baking is small, and the overall polymer is better.

[0049] 3. The composition prepared by the present application can be coated on the surface of PET to form a uniform and smooth coating. After coating and baking, a photoresist film layer can be closely attached to a PE film. When used, the PE film can be completely released and then the

[0050] The coating is transferred to the surface of the silicon wafer by a laminator. After lamination, the coating layer can be completely transferred to the silicon surface.

[0051] 4. The present invention provides a photoresist component in the form of a dry film of the photosensitive resin. In particular, in recent years, the photosensitive resin composition in the form of a dry film has the advantages of convenience and high productivity and has been widely used in the printed circuit board process. In semiconductor applications, liquid photoresists are the main form, and the application of dry film is less common.

[0052] 5. The present invention uses photosensitive photoresist in dry film photoresist. Due to the structure of photosensitive dry film, polyester film and polyethylene film are used as upper and lower layers, and the middle layer is a sandwich state of photoresist layer. These three layers are PET layer, photoresist is coated on PET, dried, pressed on PP and rolled into a roll form, which improves the convenience of use. At the same time, after rolling, the middle layer resin has a sandwich layer that is not easy to be squeezed and seeped out at the edge of the roll.

[0053] 6. The composition prepared in the present application is applied to the photoresist liquid of electronic devices and has excellent dissolution rate ratio, sensitivity, resolution, adhesion, and good storage stability of the photoresist in the form of a dry film covered with a PE film. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] Figure 1 It is a three-layer structure of photoresist films coated on PET and covered with PE films, wherein from top to bottom are PET layer, coating layer (resin composition prepared in Example), and PE layer.

[0055] Figure 2 This is a photograph of the resin composition of Example 19 after being coated on a silicon wafer.

[0056] Figure 3 for Figure 2 Exposed photos.

[0057] Figure 4 for Figure 3 Photo after development.

[0058] Figure 5 for Figure 4 Magnified image of circuit attachment under a microscope.

[0059] Figure 6 for Figure 4 Magnified image of circuit attachment under a microscope after baking.

[0060] Figure 7 This is a photograph showing that the coating flatness of the silicon wafer in Example 1 was NG.

[0061] Figure 8 This is a micrograph of the NA attached in Example 1.

[0062] Fig. 9 This is a photo of the PET-coated, dried and transferred silicon wafer with a rate of 30% in Example 11.

[0063] Fig.10 This is a photo of the circuit cracking in Example 4.

[0064] Fig.11 This is a photo of the circuit crack analyzed in Example 4. DETAILED DESCRIPTION

[0065] Examples 1-19

[0066] A dry film type photosensitive resin composition, the components of which are shown in Table 1-3 in parts by weight.

[0067] Among them, the auxiliary agent includes a silane coupling agent, a leveling agent, and a photoinitiator. The silane coupling agent is [3-(triethoxysilyl)propyl] urea, the leveling agent model is: MODAFLOW9200, brand: Allnex, and the photoinitiator is 4,4'-di(N,N-diethylamino)benzophenone.

[0068] Wherein M1 is triethylene glycol dimethacrylate, M2 is pentaerythritol tetraacrylate, M3 is ethoxylated trimethylolpropane triacrylate, M4 is ditrimethylolpropane acrylate, M5 is ethoxylated bisphenol A diacrylate, and the values ​​of a and b are 2.

[0069] The initiator is P1, and its structure is shown in formula (1):

[0070]

[0071] Table 1

[0072] Table 2

[0073]

[0074]

[0075] Table 3

[0076]

[0077] The weight average molecular weight of the polyamic acid ester is 35000 Da, which is measured in terms of standard polystyrene by a GPC method.

[0078] The preparation of the polyamic acid ester comprises the following steps:

[0079] S1, in a 1.0L flask equipped with a stirrer and a thermometer, 49.6g (160mmol) of ODPA, 4.16g (32.0mmol) of HEMA, and 3.2g of triethylenediamine were dissolved in 200.0g of NMP, and stirred at 45°C for 1 hour.

[0080] S2, cooled to 25°C, added 4.4 g (47.2 mmol) of m-phenylenediamine, 19.04 g (95.12 mmol) of 4,4'-diaminodiphenyl ether and 100 g of NMP, stirred at 45°C for 150 minutes, and then cooled to room temperature.

[0081] S3, 62.8 g (299.04 mmol) of trifluoroacetic anhydride was added dropwise to the solution, stirred for 20 minutes, then 42.48 g (326 mmol) of HEMA was added, and stirred at 45° C. for 20 hours. Distilled water was added dropwise to the reaction solution, and the precipitate was collected, filtered, and dried under reduced pressure to obtain a polyamic acid ester polymer.

[0082] A preparation method of a dry film type photosensitive resin composition comprises the following steps: adding a solvent, an initiator, an auxiliary agent and an acrylate monomer into polyamic acid ester, stirring and completely dissolving the polyamic acid ester to obtain the dry film type photosensitive resin composition.

[0083] The invention discloses an application of a dry film type photosensitive resin composition, which is applied to a photoresist liquid of electronic equipment.

[0084] Performance Testing Methods

[0085] 1. Silicon wafer coating: Spin-coat the photosensitive resin composition prepared in the example onto the silicon wafer, and pre-bake at 80°C for 4 minutes to form a 10 μm wide photoresist film layer. Then use a mask to expose the film under UV ultra-high pressure mercury lamp (Zhisheng M5525KW mercury xenon short arc lamp) at 400mj / cm 2The film is exposed with energy, and then developed with PGMEA (1,2-propylene glycol methyl ether acetate) for twice TTC (cleaning time, for example, the coating layer can be completely dissolved and cleaned with PGMEA in 30 seconds, and 60 seconds is used to develop the exposure pattern) to form a pattern film, which is then baked in a nitrogen oven at 225°C for 1 hour.

[0086] 2. PET coating: The photosensitive resin composition prepared in the embodiment is coated on the PET surface, and then pre-baked at 80°C for 7 minutes to form a photoresist film layer with a width of 10 μm, and then covered with a PE film to test the adhesion of the PE film. The PE film is then torn off to observe whether the release is complete, and then the coating layer and the silicon wafer are bonded to each other, and the PET upper coating layer is transferred to the silicon wafer surface by a laminator (the transferred area is calculated, and the transfer rate of the PET-coated silicon wafer is = (the area of ​​the coating layer after transfer / the area of ​​the PET upper coating layer) × 100%. The test results are shown in Tables 4-6. Fig. 9 This is a photo of the PET-coated, dried and transferred silicon wafer with a transfer rate of 30% in Example 11. The parameters of the laminating machine are roller temperature 110°C, 2kg / cm pressure, and 0.6m / min speed. After transfer, the exposure and development are performed in the same manner as above to form a circuit.

[0087] 3. Observe the flatness of the silicon wafer coating (if the surface is smooth, it is OK, otherwise it is NG. NG is Figure 7 As shown), test the resolution and attached line width (if there is no pattern, it is recorded as NA, where NA is Figure 8 As shown, if Figure 10-11 If cracking occurs, it is recorded as line cracking), width after development, width after baking, and test results are shown in Table 4-6.

[0088] The three-layer structure of the photoresist film coated on PET and covered with PE film is as follows Figure 1 As shown; the process flow of photoetching is: tear off the PE layer, transfer the coating layer to the silicon wafer, tear off the PET layer, cover the upper part of the coating layer with a mask, and after exposure to light, use a solvent to clean the uncured part.

[0089] See the photo after coating Figure 2 , see the photos after exposure Figure 3 , the developed photos are shown in Figure 4 .

[0090] Example 19: The width of the attached line (37.79 microns, 36.52 microns) was measured under a microscope. Figure 5 ; The width of the slices after baking (6.2 microns, 6.04 microns) was measured under a microscope. Figure 6 The loss of development width before and after baking is small, where adhesion and analysis are the data read from the exposed film, and the values ​​are rounded to 5um and recorded in Table 4.

[0091] Performance test data

[0092] Table 4

[0093] Table 5

[0094] Test items Example 8 Example 9 Example 10 Embodiment 11 Example 12 Embodiment 13 Silicon wafer coating flatness NG NG OK OK OK OK Adhesion (micrometer) NA 40 25 55 55 30 Resolution (micrometer) NA 35 30 40 55 75 PET coated, dried and transferred silicon wafer rate (%) 0 0 0 30 0 0

[0095] Table 6

[0096]

[0097]

Claims

1. A dry film type photosensitive resin composition, characterized in that: The components include, by weight: 100 parts of polyamic acid ester, 100-200 parts of solvent, 1-8 parts of initiator, 20-60 parts of acrylate monomer, and 2-15 parts of auxiliary agent; The acrylate monomer includes pentaerythritol tetraacrylate and ethoxylated bisphenol A diacrylate, and the weight ratio of the pentaerythritol tetraacrylate to the ethoxylated bisphenol A diacrylate is 1:(2-3); The general structural formula of the ethoxylated bisphenol A diacrylate is shown in formula (4): (4), where the values ​​of a and b are both 1 to 15; The auxiliary agent includes a silane coupling agent, a leveling agent and a photoinitiator, and the mass ratio of the photoinitiator, the silane coupling agent and the leveling agent is 0.4: (2-5): (0.1-1).

2. The dry film type photosensitive resin composition according to claim 1, characterized in that: The structural unit of the polyamic acid ester is shown in formula (1): (1); wherein R1 comprises a tetravalent organic group, R2 comprises a divalent organic group, and R3 comprises a hydrogen atom, The general structural formula of R4 is shown in formula (2): (2); Wherein R5 includes one of an alkyl group and an alkoxy group, R6 includes a monovalent organic group, R7 is a methyl group, and p is 2.

3. The dry film type photosensitive resin composition according to claim 2, characterized in that: The R6 includes an alkyl group or an aromatic hydroxyl group.

4. The dry film type photosensitive resin composition according to claim 1 or 2, characterized in that: The weight average molecular weight of the polyamic acid ester is 20000-50000 Da.

5. The dry film type photosensitive resin composition according to claim 4, characterized in that: The initiator includes a hydroxyimino-type initiator.

6. A method for preparing the dry film type photosensitive resin composition according to any one of claims 1 to 5, characterized in that: The method comprises the following steps: adding a solvent, an initiator, an auxiliary agent and an acrylate monomer into polyamic acid ester, stirring and completely dissolving the polyamic acid ester, and obtaining the polyamic acid ester.

7. An application of the dry film type photosensitive resin composition according to any one of claims 1 to 5, characterized in that: Used in photoresist liquid for electronic equipment.

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