Photosensitive resin composition, photosensitive film and application thereof

Abstract

The invention provides a photosensitive resin composition, a photosensitive film and application thereof. The photosensitive resin composition comprises the following components: resin containing a benzocyclobutene group, resin containing a # imgabs0 # group, a photoinitiator and an organic solvent, wherein R1 is a hydrogen atom, a bromine atom, a fluorine atom, a substituted or unsubstituted C1-C18 alkyl group, an alkenyl group, a cycloalkyl group or an aryl group, and a substituent group is halogen or a C1-C10 alkyl group; in the photosensitive resin composition, the molar content of the # imgabs2 # group is greater than 50% on the basis that the total mole number of the # imgabs1 # group and the benzocyclobutene group is 100%. The photocuring degree of a photocuring system and a thermocuring system can be effectively adjusted by adjusting the proportion of the photocuring and thermocuring # imgabs3 group and the pure thermocuring benzocyclobutene group in the photosensitive resin composition system, the subsequent exposure, development and thermocuring adjustment of the system is facilitated, and the subsequent thermocuring conditions are relatively simple.

Description

Technical Field

[0001] The present invention belongs to the technical field of lithographic patterning materials, and relates to a photosensitive resin composition, a photosensitive film and their applications, and particularly to a photosensitive resin composition with low dielectric loss, a photosensitive film and their applications in lithographic patterning. Background Art

[0002] The integrated circuit material industry is the foundation for the development of the integrated circuit industry, and the quality of materials directly affects the performance of integrated circuit products. With the rapid development of the microelectronics industry, corresponding electronic devices and integrated circuits are developing towards miniaturization, high speed, and high density, and dielectric materials with lower dielectric constants and loss factors are required to accommodate more metal lines in narrower spaces.

[0003] The ultraviolet curing technology has low cost and is relatively environmentally friendly, and can form a three-dimensional network structure by curing in a short time. The core of ultraviolet curing is photoresist. During the integrated circuit manufacturing process, a photochemical reaction occurs in the exposed area of the photoresist, resulting in a solubility difference between the exposed area and the unexposed area in the developer, and the resulting lithographic pattern can be used as the dielectric insulating layer of the integrated circuit. Due to its structural characteristics, organic polymer materials exhibit excellent performance. Since the lateral diffusion of macromolecules is inhibited, the patterns of polymer polymers usually have high resolution.

[0004] Benzocyclobutene (BCB) groups can be crosslinked and cured by heating without generating small molecules, which has little impact on the performance of the resin. The photosensitive resin prepared with benzocyclobutene as the base material has the advantages of low dielectric constant, low dielectric loss, low moisture absorption rate, high thermal stability, etc., and has important application value in microelectronic packaging. On the other hand, the photosensitive resin with low dielectric loss has the advantages of low chemical polarity and low polarizability under the condition of an external electric field, which is beneficial to reducing the dielectric constant.

[0005] CN115826359A discloses the preparation and application of a fully hydrocarbon low dielectric loss photosensitive resin for lithographic patterning, D f which can reach 0.001 - 0.002. However, the proportion of C═C double bonds that can undergo photocuring in this resin composition is relatively low, and the proportion of purely thermosetting benzocyclobutene is relatively high, resulting in a low curing degree during the photocuring process, and thus relatively harsh conditions are required for the subsequent thermal curing of BCB.

[0006] Therefore, in this field, there is a desire to develop a photosensitive resin composition with simple thermal curing conditions, and the photosensitive film prepared therefrom has excellent dielectric properties, mechanical properties and heat resistance. Summary of the Invention

[0007] In view of the deficiencies of the prior art, the purpose of the present invention is to provide a photosensitive resin composition, a photosensitive film and their applications, and in particular to provide a photosensitive resin composition with low dielectric loss, a photosensitive film and their applications in lithographic patterning.

[0008] To achieve this purpose, the present invention adopts the following technical solutions:

[0009] In a first aspect, the present invention provides a photosensitive resin composition, which comprises the following components: a resin containing a benzocyclobutene group, a resin containing a group, a photoinitiator and an organic solvent;

[0010] Among them, R1 is a hydrogen atom, a bromine atom, a fluorine atom, a substituted or unsubstituted C1-C18 (for example, it can be C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17 or C18) alkyl group, alkenyl group, cycloalkyl group or aromatic group, and the substituent is a halogen (such as fluorine, chlorine, bromine, iodine) or a C1-C10 (for example, it can be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10) alkyl group;

[0011] In the photosensitive resin composition, based on the total number of moles of the group and the benzocyclobutene group being 100%, the molar content of the group is greater than 50%, such as 51%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%, and the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0012] It should be noted that the molar content of the group (or vinyl group) mentioned below in the present invention is based on the total number of moles of the group and the benzocyclobutene group, and will not be elaborated one by one.

[0013] It should be noted that the resin containing the group in the present invention does not include the resin containing the benzocyclobutene group.

[0014] The present invention adjusts the proportion of the group that is cured by light and heat and the pure thermosetting benzocyclobutene group in the photosensitive resin composition system (that is, based on the total number of moles of the group and the benzocyclobutene group being 100%, the (where the molar content of the group is greater than 50%) can effectively adjust the photocuring degree of the photo-thermal curing system, which is beneficial to the adjustment of subsequent exposure, development, and thermal curing of the system, making the conditions for subsequent thermal curing relatively simple.

[0015] By adjusting the content of each resin component in the system, the electrical properties of the cured product can be effectively adjusted in the present invention, and the final electrical properties can be reduced to 0.00065 @ 10 GHZ.

[0016] The photosensitive resin composition provided by the present invention has excellent dielectric properties, mechanical properties, and heat resistance, and is expected to be applied in the microelectronics field.

[0017] Preferably, the resin containing benzocyclobutene groups has the structure shown in the following formula (I):

[0018]

[0019] Wherein, R is a hydrogen atom, a bromine atom, a fluorine atom, an alkyl group, an alkenyl group, an aromatic group, a polyphenylene ether segment, a polybutadiene segment, a styrene-butadiene resin segment, an SBS segment, or an SEBS segment.

[0020] The resin containing benzocyclobutene groups can be prepared by the methods of the prior art. Exemplarily, the preparation method of the benzocyclobutene resin includes: coupling reaction of polybutadiene with 4-halobenzocyclobutene to obtain the benzocyclobutene resin; wherein, Hal is a halogen, for example, it can be Cl, Br, or I.

[0021] Preferably, the Hal is Br, that is, the raw material is 4-bromobenzocyclobutene

[0022] Preferably, the coupling reaction is carried out in the presence of a palladium catalytic system.

[0023] Preferably, the palladium catalytic system includes a palladium catalyst and an organic phosphine ligand.

[0024] Preferably, the palladium catalyst is palladium acetate, and the organic phosphine ligand is tris(o-tolyl)phosphine.

[0025] Preferably, the coupling reaction is carried out in the presence of an acid-binding agent.

[0026] Preferably, the acid-binding agent includes an organic base, and more preferably triethylamine.

[0027] Preferably, the coupling reaction is carried out in an inert protective atmosphere, and the inert protective atmosphere includes any one of a nitrogen atmosphere, an argon atmosphere, and a helium atmosphere.

[0028] Preferably, the temperature of the coupling reaction is 60 - 100 °C, for example, it can be 65 °C, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C or 95 °C, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0029] Preferably, the time of the coupling reaction is 5 - 36 h, for example, it can be 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 24 h, 28 h, 32 h or 34 h, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0030] Preferably, the resin containing benzocyclobutene group further includes group.

[0031] Preferably, in the photosensitive resin composition, based on the total molar amount of group and benzocyclobutene group being 100%, the molar content of the group is 60 - 95%, more preferably 70 - 90%.

[0032] Preferably, the resin containing group includes any one or at least two combinations of polybutadiene resin, polybutadiene resin derivatives, styrene - butadiene resin, styrene - butadiene resin derivatives, styrene - butadiene - styrene block copolymer, styrene - butadiene - styrene random copolymer, resin containing single or at least two styrene functional groups, polyfunctional vinyl compounds, allyl compounds, resin containing isopropenyl functional group, resin containing one or at least two methacrylic acid functional groups, resin derivatives containing one or at least two methacrylic acid functional groups, resin containing one or at least two acrylic acid functional groups, resin derivatives containing one or at least two acrylic acid functional groups.

[0033] Preferably, the polyfunctional vinyl compounds include any one or at least two combinations of trimethacrylic acid, divinylbenzene, polyfunctional acrylate, P,P'-divinyl - 1,2 - diphenylethane (BVPE).

[0034] Preferably, the allyl compounds include any one or at least two combinations of triallyl isocyanurate (TAIC), trimethallyl isocyanate (TMAIC), triallyl cyanurate (TAC), polyisocyanuric acid triallyl ester, triallyl ester cyanurate, diallyl phthalate.

[0035] Preferably, the photoinitiator includes any one or a combination of at least two of 1-hydroxy-cyclohexyl-phenyl ketone, 2,6-bis(4-azobenzylidene)cyclohexanone, 3,3'-carbonylbis(7-diethylaminocoumarin), benzophenone, or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide.

[0036] Preferably, based on 100 parts by mass of the organic components in the photosensitive resin composition, the amount of the photoinitiator is 1-10 parts, for example, it can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, or 10 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0037] It should be noted that in the present invention, the organic components in the photosensitive resin composition refer to resins containing benzocyclobutene groups, resins containing groups, and other resins that may be included (such as the thermoplastic resins described later).

[0038] Preferably, the organic solvent includes any one or a combination of at least two of toluene, xylene, chloroform, dichloromethane, n-hexane, ethyl acetate, butyl acetate, petroleum ether, cyclohexanone, or cyclohexane.

[0039] Preferably, the amount of the organic solvent is such that the solid content of the glue solution in the photosensitive resin composition is 60-70%, for example, it can be 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, or 69%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0040] Preferably, the photosensitive resin composition further includes a thermoplastic resin.

[0041] Preferably, based on 100% by weight of the total weight of the photosensitive resin composition, the mass percentage content of the thermoplastic resin ≤80%, for example, it can be 0, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, or 75%, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range.

[0042] Preferably, the thermoplastic resin includes hydrogenated styrene-butadiene block copolymer (SEBS) and / or thermoplastic polyphenylene oxide (PPO).

[0043] Preferably, the hydrogenated styrene-butadiene block copolymer includes unmodified SEBS and / or modified SEBS.

[0044] Preferably, the modified SEBS includes any one or a combination of at least two of maleic anhydride modified SEBS, epoxy modified SEBS, amino modified SEBS, and carboxyl modified SEBS.

[0045] Preferably, the photosensitive resin composition further includes a filler.

[0046] Preferably, based on 100 parts by mass of the organic components in the photosensitive resin composition, the mass of the filler is 5 - 100 parts, for example, it can be 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 70 parts, 80 parts, or 90 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Preferably, it is 10 - 100 parts, and more preferably 15 - 100 parts.

[0047] Preferably, the filler is an inorganic filler and / or an organic filler, and more preferably an inorganic filler.

[0048] Preferably, the inorganic filler includes any one or a combination of at least two of non-metal oxides, metal oxides, metal hydroxides, metal nitrides, non-metal nitrides, inorganic hydrates, inorganic salts, metal hydrates, and inorganic phosphorus.

[0049] Preferably, the inorganic filler includes any one or a combination of at least two of silica powder, silica, aluminum hydroxide, alumina, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, and mica.

[0050] Preferably, the silica can be any one or a combination of at least two of fused silica, crystalline silica, spherical silica, and hollow silica.

[0051] Preferably, the organic filler includes any one or a combination of at least two of polyphenylene ether fillers (powder and / or microspheres), polytetrafluoroethylene fillers (powder), polyetheretherketone fillers, polyphenylene sulfide fillers, and polyethersulfone fillers (powder);

[0052] Preferably, the median particle size (D50) of the filler is 0.01 - 5 μm, for example, it can be 0.05 μm, 0.1 μm, 0.5 μm, 1 μm, 2 μm, 3 μm, or 4 μm, as well as the specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the range. Preferably, it is 0.01 - 2 μm, more preferably 0.02 - 1 μm, and even more preferably 0.02 - 0.5 μm.

[0053] Exemplarily, the particle size of the filler is measured by an MS3000 Malvern laser particle size analyzer.

[0054] Preferably, the filler includes a surface-treated filler.

[0055] Preferably, the surface treatment agent for the surface treatment includes any one or a combination of at least two of a silane coupling agent, an organosilicon oligomer, and a titanate coupling agent;

[0056] Preferably, based on 100 parts by mass of the filler to be treated, the mass of the surface treatment agent is 0.1 - 5 parts, such as 0.2 parts, 0.5 parts, 0.8 parts, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, or 4.5 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range. Further preferably, it is 0.5 - 3 parts, and even more preferably 0.75 - 2 parts.

[0057] Preferably, the photosensitive resin composition further includes a flame retardant.

[0058] Preferably, based on 100 parts by mass of the resin in the photosensitive resin composition, the mass of the flame retardant is 1 - 50 parts, such as 5 parts, 10 parts, 15 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, or 45 parts, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the range.

[0059] Preferably, the flame retardant includes any one or a combination of at least two of a nitrogen-based flame retardant, a halogen-based flame retardant, a phosphorus-based flame retardant, and a metal hydroxide flame retardant.

[0060] The photosensitive resin composition provided by the present invention is prepared by the following method. The preparation method includes: mixing and dispersing the components in the photosensitive resin composition evenly to obtain the photosensitive resin composition.

[0061] Preferably, the preparation process of the photosensitive resin composition is carried out in the dark.

[0062] In a second aspect, the present invention provides a photosensitive film, and the material of the photosensitive film includes the photosensitive resin composition as described in the first aspect.

[0063] Preferably, the photosensitive film is prepared by coating the photosensitive resin composition on a release material (such as a PET release film, a PI release film) and drying.

[0064] Preferably, the thickness of the photosensitive film is 5-50 μm, such as 8 μm, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm or 48 μm, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range.

[0065] In a third aspect, the present invention provides a multilayer printed circuit board, which includes an interlayer insulating layer formed by using the photosensitive film as described in the second aspect.

[0066] In a fourth aspect, the present invention provides a method for manufacturing a multilayer printed circuit board, which comprises the following steps (1)-(3):

[0067] Step (1): A step of laminating the photosensitive film as described in the second aspect on one or both sides of a circuit board by using a vacuum laminating machine;

[0068] Step (2): A step of exposing and developing the photosensitive film in step (1) to form an interlayer insulating layer with vias;

[0069] Step (3): A step of forming a circuit pattern on the interlayer insulating layer.

[0070] Preferably, between step (2) and step (3), there is also included step (2-1): a heat treatment step for the interlayer insulating layer;

[0071] Preferably, between step (2) and step (3), there is also included step (2-2): a roughening treatment step for the vias and the interlayer insulating layer.

[0072] Preferably, the exposure and development in step (2) are specifically to expose the photosensitive film through a photomask using a UV-LED light source. The exposed area crosslinks and cures and is insoluble in the developer, while the unexposed area is soluble in the developer. After development with the developer, a pattern consistent with the photomask is obtained. The developer for the development includes any one or a combination of at least two of toluene, xylene, chloroform, n-hexane, cyclohexane, butyl acetate, ethyl acetate, and petroleum ether, preferably toluene, xylene, and cyclohexane.

[0073] Preferably, the wavelength of the UV-LED light source is 300-400 nm, such as 300 nm, 310 nm, 320 nm, 330 nm, 340 nm, 350 nm, 360 nm, 365 nm, 370 nm, 380 nm, 390 nm or 400 nm, as well as the specific point values between the above point values. Due to space limitations and for the sake of brevity, the present invention does not exhaustively list the specific point values included in the above range.

[0074] Preferably, the temperature of the heat treatment in step (2-1) is 190-230°C. For example, it can be 195°C, 200°C, 205°C, 210°C, 215°C, 220°C or 225°C, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range. The time of the heat treatment is 30-300 min. For example, it can be 40 min, 60 min, 90 min, 120 min, 150 min, 180 min, 210 min, 240 min or 270 min, as well as specific point values between the above point values. Due to space limitations and for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the above range.

[0075] The pattern obtained after photocuring the photosensitive resin composition of the present invention has high clarity. Through the photo-thermal double crosslinking process, the obtained photosensitive film has high heat resistance; at the same time, during the heat treatment process, the unreacted photoinitiator will thermally decompose and will not affect the dielectric properties of the photosensitive film.

[0076] The photosensitive resin described in the present invention can crosslink the double bonds in the polymer chain through photocuring and is insoluble in the developing solution, so a pattern with neat edges and high precision is obtained. Compared with the prior art, the present invention has at least the following beneficial effects:

[0077] (1) By adjusting the proportion of the photocuring and thermosetting groups and the pure thermosetting benzocyclobutene group in the photosensitive resin composition system of the present invention (that is, based on the total molar amount of the photocuring and thermosetting groups and the benzocyclobutene group being 100%, the molar content of the photocuring group is greater than 50%), the degree of photocuring of the photocuring and thermosetting system can be effectively adjusted, which is beneficial to the adjustment of subsequent exposure, development, and thermosetting of the system, making the subsequent thermosetting conditions relatively simple. group and the proportion of the pure thermosetting benzocyclobutene group (that is, based on the total molar amount of the photocuring and thermosetting groups and the benzocyclobutene group being 100%, the molar content of the photocuring group is greater than 50%), the degree of photocuring of the photocuring and thermosetting system can be effectively adjusted, which is beneficial to the adjustment of subsequent exposure, development, and thermosetting of the system, making the subsequent thermosetting conditions relatively simple. group and the benzocyclobutene group being 100% by total molar amount, the molar content of the photocuring group is greater than 50%), the degree of photocuring of the photocuring and thermosetting system can be effectively adjusted, which is beneficial to the adjustment of subsequent exposure, development, and thermosetting of the system, making the subsequent thermosetting conditions relatively simple. group and the benzocyclobutene group being 100% by total molar amount, the molar content of the photocuring group is greater than 50%), the degree of photocuring of the photocuring and thermosetting system can be effectively adjusted, which is beneficial to the adjustment of subsequent exposure, development, and thermosetting of the system, making the subsequent thermosetting conditions relatively simple.

[0078] (2) The pattern obtained after photocuring the photosensitive resin composition of the present invention has high clarity. Through the photo-thermal double crosslinking process, the obtained photosensitive film has high heat resistance; at the same time, during the heat treatment process, the unreacted photoinitiator will thermally decompose and will not affect the dielectric properties of the photosensitive film. Detailed Embodiments

[0079] The technical solutions of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.

[0080] In the following specific embodiments of the present invention, the specific information of the resin used to prepare the resin containing benzocyclobutene groups is as follows:

[0081] B1000: Polybutadiene, the molar percentage content of the structural unit formed by 1,2-polymerization of butadiene ( the same below) is 85%, and the molar percentage content of the structural unit formed by 1,4-polymerization ( the same below) is 15%, Nippon Soda Co., Ltd.;

[0082] B3000: B3000, Polybutadiene, the molar percentage content of the structural unit formed by 1,2-polymerization is 92%, and the molar percentage content of the structural unit formed by 1,4-polymerization is 8%, Nippon Soda Co., Ltd.

[0083] BCBS: DS5202, Wuhan Disai New Materials.

[0084] Preparation Example 1

[0085] A resin BCB1 containing benzocyclobutene groups, and its preparation method is as follows:

[0086] Add 6.29 g of 4-bromobenzocyclobutene, 100 g of polybutadiene B1000, 0.607 g of tris(o-methylphenyl)phosphine, 0.278 g of palladium acetate, 20 mL of triethylamine and 68 mL of acetonitrile into a flask, and stir at 85 °C for 24 hours in an argon atmosphere. Cool and spin-dry the solvent. Quickly pass through a column with neutral alumina, spin-dry the solvent to obtain a viscous liquid, dissolve it in toluene, add methanol with a volume 4 times that of toluene, shake well and let stand, and separate the toluene layer. Then spin-dry and concentrate, and dry under vacuum to obtain a colorless viscous liquid, that is, the resin BCB1 containing benzocyclobutene groups.

[0087] Preparation Example 2

[0088] A resin BCB2 containing benzocyclobutene groups, and its preparation method is as follows:

[0089] Add 70 g of polybutadiene B1000, 30 g of BCBS, and 80 mL of toluene into a flask to dissolve them into a homogeneous solution, and heat to the reflux temperature in an argon atmosphere. Dissolve 0.5 g of tert-butyl isopropyl phenyl peroxide BIPB in 20 mL of toluene, then add it dropwise within 35 min, react at the toluene reflux temperature, monitor the reaction by TLC chromatography column until the BCBS raw material spot disappears, stop the reaction, and cool to obtain the resin BCB2 containing benzocyclobutene groups, which can be used without separation.

[0090] Preparation Example 3

[0091] A resin BCB3 containing benzocyclobutene groups, and its preparation method is as follows:

[0092] Add 271.11 g of 4-bromobenzocyclobutene, 100 g of polybutadiene B3000, 26.15 g of tris(o-methylphenyl)phosphine, 11.97 g of palladium acetate, 800 ml of triethylamine and 2000 ml of acetonitrile into a flask, and stir at 85 °C for 24 hours under an argon atmosphere. Cool and rotary evaporate the solvent. Perform flash column chromatography with neutral alumina, rotary evaporate the solvent to obtain a viscous liquid, dissolve it in toluene, add methanol in an amount 4 times that of toluene, shake well and let stand, and separate the toluene layer. Then rotary evaporate and concentrate, and dry under vacuum to obtain a colorless viscous liquid, namely resin BCB3 containing benzocyclobutene groups.

[0093] Preparation Example 4

[0094] A resin BCB4 containing benzocyclobutene groups is prepared as follows:

[0095] Synthesize the resin BCB4 containing benzocyclobutene groups by the method in Example 1 of the prior art CN107501459A, which is copolymerized from 4-vinylbiphenyl and 4-vinylbenzocyclobutene.

[0096] Preparation Example 5

[0097] A resin BCB5 containing benzocyclobutene groups is prepared as follows:

[0098] Synthesize the resin BCB5 containing benzocyclobutene groups by the method in Preparation Example 1.2 of the prior art CN114736096A Among them, the molar ratio of -CH=CH2 to benzocyclobutene groups is 1:1.

[0099] Preparation Example 6

[0100] A resin BCB6 containing benzocyclobutene groups is prepared as follows:

[0101] Synthesize the resin BCB6 containing benzocyclobutene groups by the method in Example 1 of the prior art CN114478178A

[0102] In the following specific embodiments of the present invention, the materials involved are as follows:

[0103] (1) Resin containing benzocyclobutene groups

[0104] Resins BCB1 to BCB6 containing benzocyclobutene groups provided in Preparation Examples 1-6;

[0105] BCB1: The vinyl molar content is 0, and the number average molecular weight is 170;

[0106] BCB2: The vinyl molar content is 82.35%, and the number average molecular weight is 14500;

[0107] BCB3: The vinyl molar content is 56.52%, and the number-average molecular weight is 3,655;

[0108] BCB4: A copolymer of 4-vinylbiphenyl and 4-vinylbenzocyclobutene, with a vinyl molar content of 0 and a number-average molecular weight of 13,500;

[0109] BCB5: Benzocyclobutene monosubstituted divinylbiphenyl, with a vinyl molar content of 50% and a number-average molecular weight of 308;

[0110] BCB6: Benzocyclobutene monosubstituted trivinylcyclohexane, with a vinyl molar content of 66.67% and a number-average molecular weight of 264.

[0111] (2) Resins containing groups

[0112] MX9000: M-PPO resin, supplied by Sabic;

[0113] OPE-2ST: M-PPO resin, supplied by Mitsubishi Gas Chemical;

[0114] BVPE: p,p-divinyl-1,2-diphenylethane, supplied by Shandong Xingshun New Materials;

[0115] TAIC: Triallyl isocyanurate, supplied by Sartomer;

[0116] B3000: Polybutadiene, with a molar percentage of 92% of the structural units formed by 1,2-polymerization and 8% of the structural units formed by 1,4-polymerization, supplied by Nippon Soda Co., Ltd.;

[0117] Ricon 100: A copolymer of butadiene and styrene, with a molar percentage of 70% of the structural units formed by 1,2-polymerization, 8% of the structural units formed by 1,4-polymerization, and 22% of the styrene structural units, supplied by Sartomer Company, USA;

[0118] ODV: CH resin, supplied by Nippon Steel & Sumitomo Metal Corporation.

[0119] (3) Thermoplastic resins:

[0120] SEBS-MA: KIC19-023: Maleic anhydride grafted SEBS, supplied by Shanghai Keter.

[0121] (4) Fillers:

[0122] HM052BYJ: Spherical silica powder, supplied by Jiangsu Huimai.

[0123] (5) Photoinitiators

[0124] Diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; Macklin reagent;

[0125] IRGACURE 184, BASF, Germany.

[0126] (6) Flame retardant:

[0127] JH-100, Guangzhou Juhang.

[0128] (7) Organic solvent:

[0129] Toluene.

[0130] Example 1

[0131] A photosensitive resin composition, the specific components and dosages (parts by weight) of the photosensitive resin composition are shown in Table 1.

[0132] A photosensitive film comprising the photosensitive resin composition, and the preparation method is as follows:

[0133] (1) Mix the resin containing benzocyclobutene groups, the resin containing groups, the thermoplastic resin, the filler, the photoinitiator, the flame retardant and the organic solvent (toluene) in the formula amounts uniformly to obtain a photosensitive solution with a solid content of 65%;

[0134] (2) Coat the photosensitive solution on a PET release film to obtain a photosensitive film (with a thickness of 38 μm) with a size of 300 mm X 300 mm.

[0135] Put the obtained photosensitive film into an oven at 110 °C and bake for 3 minutes; after the organic solvent is volatilized, expose the photosensitive film with a 365 nm UV LED light source for 240 s. The resin containing double bonds is crosslinked and cured by exposure and is insoluble in the developer, while the unexposed resin is soluble in the developer; develop for 4 min with the developer (cyclohexane) to elute the uncured resin, and obtain a film surface with a certain roughness. Then perform electroless copper plating on this surface, dry the solvent, and then perform electroplating, and the electroplated copper thickness is 35 μm. Finally, perform programmed temperature curing on the above copper-plated sample, the curing temperature is 230 °C, the curing time is 60 min, and then cool down to obtain a copper-plated foil film with a high crosslinking density. Make the film into a test PS spline to test the copper plating adhesion PS; etch off the copper plated on the remaining part to make samples for testing Dk / Df and Tg (DMA) to test the above properties.

[0136] (3) Expose the photosensitive thin film to a 365 nm UV-LED point light source through a mask for 240 s. The exposed area crosslinks and cures, becoming insoluble in the developer, while the unexposed area is soluble in the developer. Place the exposed thin film in the developer (cyclohexane) for 4 min to develop a pattern consistent with the mask. Then, thermally cure the developed thin film at 230 °C for 120 min, and then cool it down to obtain a lithographically patterned thin film.

[0137] Perform the following performance tests on the photosensitive thin films and lithographically patterned thin films provided in the foregoing examples and comparative examples:

[0138] (1) Resolution of the lithographic pattern: Observe the stereolithographic pattern after development with an optical microscope. Set the minimum size at which the edge of the pattern can be observed smoothly without scum as the pattern resolution L / S (μm).

[0139] (2) Glass transition temperature Tg: Test using a dynamic mechanical analyzer (DMA) Rheometric RSAIII.

[0140] (3) Dielectric constant Dk and dielectric loss tangent Df: Measure using the split post dielectric resonator (SPDR) method with a dielectric analyzer (Dielectric Analyzer) HP Agilent E4991A at a frequency of 10 GHz.

[0141] (4) PS: Test according to the IPC-TM-650 2.4.8C5 standard.

[0142] The test results are shown in Table 1.

[0143] Examples 2-9, Comparative Examples 1-2

[0144] A photosensitive resin composition and a photosensitive thin film and a lithographically patterned thin film containing the same, which are different from those in Example 1 in that the formulation of the photosensitive resin composition is different, as specifically shown in Table 1 and Table 2. Among them, the dosage unit of each component is "parts", and "--" means that the component is not added. The preparation methods and performance test methods of the photosensitive thin film and the lithographically patterned thin film are the same as those in Example 1.

[0145] Table 1

[0146]

[0147]

[0148] Table 2

[0149]

[0150]

[0151] Combined with the foregoing performance test data, it can be seen that the photosensitive resin composition provided by the present invention is used for photosensitive films and for preparing copper clad laminates and lithographically patterned films, such that the copper clad laminate has a Dk of 2.43 - 2.72, a Df of 0.00064 - 0.0013, a glass transition temperature Tg of 220 - 265 °C, a peel strength of 0.32 - 0.5 N / mm, and the lithographically patterned film has a resolution of 8 - 25 μm, and has excellent dielectric properties, mechanical properties and heat resistance at the same time.

[0152] The photosensitive resin composition provided in Comparative Example 1 has a C=C double bond content of 47.77%. The photocuring step is not sufficient to cure the adhesive film sufficiently, resulting in the elution of BCB1 during the development process for the cured part, leading to a subsequent decrease in Tg, a deterioration in Df, a decrease in PS, and a decrease in resolution; the photosensitive resin composition provided in Comparative Example 2 has a C=C double bond content of 42%. The adhesive film is not cured sufficiently in the photocuring step, and the developing solution cyclohexane has a strong developing effect, resulting in the elution of the cured part during the development process and making it impossible to perform the next operation.

[0153] The applicant declares that the present invention uses the above embodiments to illustrate the photosensitive resin composition, photosensitive film and its applications of the present invention, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must rely on the above embodiments to be implemented. Those skilled in the art should understand that any improvement to the present invention, the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific methods, etc., all fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A photosensitive resin composition, characterized in that, The photosensitive resin composition comprises the following components: a resin containing a benzocyclobutene group, a resin containing a group, a photoinitiator, and an organic solvent; group, a photoinitiator, and an organic solvent; Wherein, R1 is a hydrogen atom, a bromine atom, a fluorine atom, a substituted or unsubstituted C1-C18 alkyl group, alkenyl group, cycloalkyl group or aromatic group, and the substituent is a halogen or a C1-C10 alkyl group; In the photosensitive resin composition, based on the total molar amount of the group and the benzocyclobutene group being 100%, the molar content of the group is greater than 50%.

2. The photosensitive resin composition according to claim 1, wherein The resin containing a benzocyclobutene group has a structure shown in the following formula (I): Wherein, R is a hydrogen atom, a bromine atom, a fluorine atom, an alkyl group, an alkenyl group, an aromatic group, a polyphenylene ether segment, a polybutadiene segment, a styrene-butadiene resin segment, an SBS segment or an SEBS segment; Preferably, the resin containing benzocyclobutene groups further includes groups.

3. The photosensitive resin composition according to claim 1 or 2, characterized in that, In the photosensitive resin composition, based on the total molar amount of the group and the benzocyclobutene group being 100%, the molar content of the group is 60-95%, more preferably 70-90%.

4. The photosensitive resin composition according to any one of claims 1 to 3, characterized in that, The resin containing the group includes any one or a combination of at least two of polybutadiene resin, polybutadiene resin derivatives, styrene-butadiene resin, styrene-butadiene resin derivatives, styrene-butadiene-styrene block copolymer, styrene-butadiene-styrene random copolymer, resin containing single or at least two styrene functional groups, polyfunctional vinyl compounds, allyl compounds, resin containing isopropenyl functional groups, resin containing one or at least two methacrylic acid functional groups, resin derivatives containing one or at least two methacrylic acid functional groups, resin containing one or at least two acrylic acid functional groups, and resin derivatives containing one or at least two acrylic acid functional groups.

5. The photosensitive resin composition according to any one of claims 1-4, characterized in that, The photoinitiator includes any one or a combination of at least two of 1-hydroxy-cyclohexyl-phenylmethanone, 2,6-bis(4-azobenzylidene)cyclohexanone, 3,3'-carbonylbis(7-diethylaminocoumarin), benzophenone or diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide; Preferably, based on 100 parts by mass of the organic components in the photosensitive resin composition, the amount of the photoinitiator is 1-10 parts; Preferably, the organic solvent includes any one or a combination of at least two of toluene, xylene, chloroform, dichloromethane, n-hexane, ethyl acetate, butyl acetate, petroleum ether, cyclohexanone or cyclohexane; Preferably, the amount of the organic solvent is such that the solid content of the glue in the photosensitive resin composition is 60-70%; 6. The photosensitive resin composition according to any one of claims 1-5, characterized in that, The photosensitive resin composition further includes a thermoplastic resin; Preferably, based on 100% of the total weight of the photosensitive resin composition, the mass percentage content of the thermoplastic resin ≤ 80%; Preferably, the thermoplastic resin includes a hydrogenated styrene-butadiene block copolymer and / or a thermoplastic polyphenylene ether; 7. The photosensitive resin composition according to any one of claims 1-6, characterized in that, The photosensitive resin composition further includes a filler; Preferably, based on 100 parts by mass of the organic components in the photosensitive resin composition, the mass of the filler is 5-100 parts; Preferably, the filler is an inorganic filler and / or an organic filler, and more preferably an inorganic filler; Preferably, the inorganic filler includes any one or a combination of at least two of silica powder, silicon dioxide, aluminum hydroxide, aluminum oxide, talc powder, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica; Preferably, the organic filler includes any one or a combination of at least two of a polyphenylene ether filler, a polytetrafluoroethylene filler, a polyether ether ketone filler, a polyphenylene sulfide filler, a polyethersulfone filler; Preferably, the median particle size of the filler is 0.01-5 μm; Preferably, the filler includes a surface-treated filler; Preferably, the surface treatment agent for the surface treatment includes any one or a combination of at least two of a silane coupling agent, an organosilicon oligomer, a titanate coupling agent; Preferably, based on 100 parts by mass of the filler to be treated, the mass of the surface treatment agent is 0.1-5 parts; Preferably, the photosensitive resin composition further includes a flame retardant; Preferably, based on 100 parts by mass of the resin in the photosensitive resin composition, the mass of the flame retardant is 1-50 parts.

8. A photosensitive film, characterized in that, The material of the photosensitive film includes the photosensitive resin composition according to any one of claims 1-7; Preferably, the photosensitive film is obtained by coating the photosensitive resin composition on a release material and drying it. Preferably, the thickness of the photosensitive film is 5 - 50 μm.

9. A multilayer printed circuit board, characterized in that, The multilayer printed circuit board includes an interlayer insulating layer, and the interlayer insulating layer is formed using the photosensitive film as described in claim 8.

10. A method for preparing a multi-layer printed circuit board, characterized in that, The preparation method has the following steps (1) to (3): Step (1): A step of laminating the photosensitive film as described in claim 8 on one side or both sides of a circuit board. Step (2): A step of exposing and developing the photosensitive film in step (1) to form an interlayer insulating layer having through holes. Step (3): A step of forming a circuit pattern on the interlayer insulating layer. Preferably, between step (2) and step (3), there is also included step (2 - 1): A step of heat-treating the interlayer insulating layer. Preferably, between step (2) and step (3), there is also included step (2 - 2): A step of roughening the through holes and the interlayer insulating layer.

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