Dielectric copolymer material

Abstract

The present invention relates to a polymerizable mixture that can be used to form dielectric materials to prepare passivation layers in electronic devices.

Description

Technical Field

[0001] This invention provides a novel dielectric polymer material, particularly suitable for the manufacture of electronic devices. The dielectric copolymer material can be prepared from a polymerizable mixture comprising a polymerizable compound, a second compound, and a third compound. The polymerizable compound is one or more polymerizable maleimide compounds having mesogenic (mesocrystalline) groups. The second compound is a bifunctional or polyfunctional compound capable of reacting with the polymerizable compound. The third compound is a polyfunctional compound capable of reacting with the polymerizable compound. The polymerizable compound can also be referred to as a reactive liquid crystal moiety (RM). This dielectric material exhibits excellent and balanced material properties, particularly meeting the requirements of advanced electronic packaging applications (e.g., wafer-level packaging (WLP)) and low-dielectric-constant adhesive applications. For example, compared with existing materials, the materials of the present invention have: (a) excellent thermomechanical properties, such as high glass transition temperature (Tg), low coefficient of thermal expansion (CTE), high elongation at break and high tensile strength; (b) good dielectric properties, such as low dielectric constant and low dielectric loss tangent; (c) high adhesive strength; and / or (d) good spin coating performance. Background Technology

[0002] Reactive liquid crystal building blocks (RMs) can be polymerized at temperatures exhibiting thermotropic liquid crystal (LC) phases (typically nematic, cholesteric, or smectic phases) to obtain anisotropic polymers that retain their liquid crystal state. In particular, optical anisotropy has been widely applied in the field of optical thin films to compensate for and enhance the brightness of flat panel displays (especially liquid crystal displays).

[0003] Besides their widespread use in liquid crystal displays and screens, liquid crystal materials exhibit advantages in other application areas due to their unique physical properties (R. Stannarius, Nat. Mat. 2009, 8, 617-618; and J.P. F. Ageralwall et al., Current Appl. Phys. 2012, 12, 1387-1412). In particular, highly ordered anisotropic polymer networks are a class of widely used materials (D.J. Broer et al., Lagmuir 2014, 30, 13499-13509; and R. Zentel et al., Adv. Mater. 2010, 22, 3366-3387). However, in most cases, liquid crystal polymers or the corresponding monomers constituting these polymers do not possess the optimal properties required for a specific application.

[0004] WO2012 / 152409A1 relates to polymer particles having optical anisotropy and shape anisotropy, the polymer particles comprising a monomer unit of at least one reactive liquid crystal moiety; methods for preparing the same; uses of these particles in the preparation of optical, electro-optical, electronic, electrochemical, electrophotographic, electrowetting, and electrophoretic displays and / or devices, as well as in safety, cosmetic, decorative, and diagnostic applications; and electrophoretic solutions and displays comprising said polymer particles. Specifically, the polymer particles have at least one monomer unit of RM having at least two polymerizable groups; at least one polymerizable dye as a comonomer; optionally, at least one comonomer; optionally, at least one crosslinking comonomer; optionally, at least one ionic comonomer; and optionally, at least one polymerizable stabilizer.

[0005] Various methods for preparing liquid crystal polymers from RM and for preparing RM starting materials are known in the prior art. For example, Siemensmeyer et al. described a method for preparing a mixture of liquid crystal compounds, wherein at least one starting component consists of a mixture of at least two compounds, and the mixture reacts with at least one other starting component to form a statistical mixture (WO96 / 04351A1).

[0006] Besides efficient methods for preparing liquid crystal compounds, suitable polymerization methods for forming anisotropic polymer networks have also attracted much attention. Researchers have investigated the applicability of various active functional groups in photoinitiated polymerization reactions. Acrylates and methacrylates are the most commonly used active functional groups, and due to their high polymerization rates, they are particularly suitable for UV-initiated free radical polymerization (DJ Broer et al., Lagmuir 2014, 30, 13499-13509). However, UV curing is not suitable for all applications.

[0007] Mixtures of polymerizable liquid crystal monomers (reactive liquid crystal building blocks) can be used to prepare thin films, which can be cured by thermally or photoinitiated polymerization. Films prepared in this way are relatively thin and contain highly cross-linked rigid polymers, exhibiting significant dimensional stability. However, these films are relatively brittle and have low elasticity. On the other hand, if the degree of cross-linking is reduced, dimensionally stable polymer films cannot be obtained.

[0008] US6,261,481B1 describes an organic insulating composition with good thermal conductivity. This insulating composition comprises a liquid crystal (LC) resin polymerized from a resin composition containing monomers having liquid crystal moiety groups. The composition has a thermal conductivity ≥0.4 W / mK in mutually perpendicular directions. The monomers included in the resin composition have liquid crystal moiety groups, and preferably also have epoxy groups, which can be thermally polymerized under acid catalysis. Preferably, at the start of polymerization, the resin composition is heated to conditions that cause the monomers containing liquid crystal moiety groups to partially align, thereby freezing the anisotropic properties based on this partial alignment within the polymer.

[0009] US2008 / 0075961A1 and US2017 / 0152418A1 relate to maleimide adhesive films prepared from thermosetting maleimide resins containing imide-extended mono, bis, and polymaleimide compounds. These maleimide adhesive films possess photostructured capabilities and are suitable for the production of electronic devices, integrated circuits, semiconductor devices, passive devices, solar cells, solar modules, and / or light-emitting diodes. However, these maleimide compounds do not contain any liquid crystal building blocks, thus preventing the imparting of preferred orientation or partial alignment of the compounds within the film. This results in poor mechanical stability and thermal conductivity. Furthermore, the glass transition temperatures of these materials are typically low, which also affects their thermal expansion properties.

[0010] KR20160052234A describes a photocurable insulating resin composition and a printed circuit board using the same. This photocurable insulating resin composition comprises a photocurable liquid crystal oligomer, a photocurable graphene oxide, and a photocurable metal alkoxide. However, the photocurable liquid crystal oligomer does not contain multiple liquid crystal moieties linked by spacer groups. This results in poor solubility and very high energy requirements for photocuring.

[0011] - Electronic Packaging

[0012] As solid-state transistors began to replace vacuum tube technology, electronic components such as resistors, capacitors, and diodes could be directly mounted onto printed circuit boards or expansion cards via pins, establishing a basic packaging unit or level that remains in use today. Complex electronic functions often require a greater number of independent components than a single printed circuit expansion card can interconnect. The advent of multilayer expansion card technology was accompanied by the development of three-dimensional packaging of daughter cards on multilayer motherboards. Integrated circuits enable many discrete circuit elements (such as resistors and diodes) to be embedded in a single, relatively small component called an integrated circuit chip (wafer) or die. However, despite the extremely high integration density, multiple packaging levels are often still required, partly due to the nature of integrated circuit technology itself. Integrated circuit chips are very fragile, with extremely small pins. The primary function of the first-level package is mechanical protection, heat dissipation, and providing electrical connections for the delicate integrated circuit. At least one additional packaging level, such as a printed circuit expansion card, is required because some components (such as high-power resistors, mechanical switches, and capacitors) are not easily integrated onto the chip. For very complex applications, such as large computers, multilayer packaging structures are necessary.

[0013] Due to the influence of Moore's Law, advanced electronic packaging strategies are playing an increasingly important role in developing more powerful electronic products. In other words, as the demand for smaller, faster, and more powerful mobile and portable electronic devices continues to grow, so too does the demand for more cost-effective packaging technologies.

[0014] To meet the demands of today's semiconductor industry, a plethora of advanced packaging technologies are emerging. Leading advanced packaging technologies—wafer-level packaging (WLP), fan-out wafer-level packaging (FOWLP), 2.5D interposers, chip stacking, package stacking, and embedded integrated circuits—all require structuring of thin substrates, redistribution layers, and other components such as high-resolution interconnects. The end-consumer market continuously demands lower prices, higher functionality, and smaller, thinner devices / equipment. This drives the demand for next-generation packaging technologies that require finer features, higher reliability, and more competitive manufacturing costs.

[0015] Wafer-level packaging (WLP) is a technology that packages integrated circuits while they are still part of a wafer, unlike traditional chip-level packaging, which involves dicing the wafer into individual circuits (bare dies) before packaging. WLP offers numerous advantages over chip-level packaging and is essentially a true chip-level packaging (CSP) technology because the final package size is almost identical to the bare die itself. Wafer-level packaging allows for the integration of wafer fabrication, packaging, testing, and aging processes at the wafer level, simplifying the entire device manufacturing process from silicon to customer delivery. Due to the size constraints of smartphones and wearable devices, WLP is primarily used in these applications. Functions provided by WLP for smartphones or wearable devices include: compasses, sensors, power management, wireless connectivity, etc. Wafer-level chip-scale packaging (WL-CSP) is one of the smallest packages currently on the market. WLP can be divided into fan-in WLP and fan-out WLP (Figure 1). Both use redistribution technology to form the connection between the chip and the solder balls.

[0016] Fan-out wafer-level packaging (FOWLP) is one of the latest packaging trends in the microelectronics field: FOWLP has extremely high miniaturization potential in terms of package size and thickness. The technology basis of FOWLP is a reconfigured spray-coated wafer with embedded chips and a thin-film redistribution layer, which together form a package compatible with surface mount devices (SMD). The main advantages of FOWLP are: very thin package (because no substrate is required), low thermal resistance, excellent high-frequency performance (thanks to its short and flat electrical connections), and bump-free chip connections (rather than traditional wire bonding or solder joint connections).

[0017] With existing materials, wafer-level lithography (WLP) is limited to applications with medium-sized chips. The primary reason for this limitation is the mismatch between the coefficient of thermal expansion (CTE) of currently selected materials and silicon grains (CTE: 3 ppm / K), leading to performance degradation and stress on the grain. Therefore, there is an urgent need for novel materials with superior physical properties, particularly a CTE closer to that of silicon and high mechanical flexibility. Currently, redistribution layers (RDLs) are typically made of copper layers (CTE: 16.5 ppm / K), deposited on polymer passivation layers such as polyimide (PI), butylcyclobutane (BCB), or polybenzoxazole (PBO) via electroplating. Photolithographic patterning capability and low curing temperature are two other important requirements for processing such materials.

[0018] Polyimide has become the standard passivation layer for memory chips and other devices that require surface protection during operation and testing. The development of photosensitive resins aims to reduce processing costs.

[0019] Polyimide-ODA is the first member of a series of novel high-performance polymers developed by DuPont based on alternating aromatic homocyclic and heterocyclic compounds:

[0020]

[0021] The unique feature of polyimide is its extremely high decomposition temperature, which can reach over 400°C. Furthermore, its excellent mechanical properties ensure high flexibility (elongation at break up to 100%) and ultra-high tensile strength exceeding 200 MPa. PI remains the most commonly used polymer in IC passivation.

[0022] The negatively sensitive polymer PI was modified by polybenzoxazole (PBO), which is sometimes also referred to as positively sensitive PI:

[0023]

[0024] Polymer films can be developed using aqueous developers after exposure.

[0025] The so-called BCB (benzocyclobutene) is an example of a siloxane polymer group that also has a vinyl and benzocyclobutene ring system:

[0026]

[0027] Its main advantage lies in its polymerization reaction (Diesel-Alder reaction), which has high atom economy because it does not produce byproducts. This highly cross-linked thermosetting polymer has excellent electrical properties, but it is brittle, has low elongation at break (8%), and low tensile strength (87 MPa).

[0028] Another existing technological exploration involves the use of imide-extended bismaleimide resins, a method proposed in US2008 / 0075961A1 and US2017 / 0152418A1. These have shown promising application potential in low-stress wafer passivation coatings. However, despite these improvements, there is still room for further development to meet the stringent requirements of the industry.

[0029] In summary, the materials in the prior art have the following drawbacks:

[0030] Polyimide and polybenzoxazole typically require extremely high processing temperatures, which increases the risk of warpage, especially in multilayer redistribution layers (RDLs). Furthermore, polyimide has a high water absorption rate, which can affect device reliability.

[0031] Benzocyclobutene derivatives and polynorbornene exhibit very low dielectric constants, but this advantage is offset by their extremely poor adhesion to metals.

[0032] Currently, imide-extended bismaleimide resins have not yet exhibited a good combination of excellent mechanical and thermal properties. They are either highly flexible (low modulus) but have high CTE values, or brittle (high modulus) and have low CTE values.

[0033] Therefore, there is a need to continuously develop new dielectric materials that do not exhibit the aforementioned drawbacks known in the prior art.

[0034] - Photolithography

[0035] Photolithography has long been a key patterning technology for building inorganic and organic materials in advanced packaging applications such as flip chip wafer bumping, electroplating gold, solder bumping, copper pillar technology, and redistribution layers. Photolithography is a significant manufacturing process and cost factor; in today's industrial photolithography applications, careful selection of the appropriate exposure solution is crucial for achieving optimal cost structure.

[0036] Current drivers and trends in the semiconductor industry clearly indicate that performance improvements in microelectronic devices are imperative to meet the needs of future end users. For example, consumer electronics devices such as tablets and smartphones are becoming thinner and lighter while boasting greater computing power, larger data storage capacity, and more sophisticated communication capabilities. Furthermore, cost factors are becoming increasingly important for all participants in the supply chain, from chip manufacturers, foundries, packaging and testing suppliers to equipment manufacturers, in a highly competitive market environment. Therefore, the entire industry is striving to find innovative ways to reduce manufacturing costs and enable technologies to meet challenging technical requirements.

[0037] For decades, photolithography has been a fundamental process in the fabrication and packaging of microelectronic devices. A key component of any photolithography process is the exposure tool, which uses light in the ultraviolet wavelength range to pattern photoresist or polymers. The exposure tool must be able to precisely create the desired features and align them with the pre-fabricated structure in the underlying layer. Several exposure techniques exist: proximity or contact printing, direct laser imaging, and projection lithography. The corresponding toolkits vary in technical capabilities (optical resolution, overlay accuracy, and effective throughput) and exposure process costs (see H. Hichri et al., SÜSS Micro Tec Photonic System Inc., Corona, CA, USA).

[0038] Patent documents

[0039] 1. WO2012 / 152409A1

[0040] 2. WO96 / 04351A1

[0041] 3. US6,261,481B1

[0042] 4. US2008 / 0075961A1

[0043] 5. US2017 / 0152418A1

[0044] 6. KR20160052234A

[0045] Non-patent literature

[0046] 1. R. Stannarius, Nat. Mat. 2009, 8, 617-618; and JPF Lagerwallet al., Current Appl. Phys. 2012, 12, 1387-1412

[0047] 2. DJ Broer et al., Lagmuir 2014, 30, 13499-13509

[0048] 3. R. Zentel et al., Adv. Mater. 2010, 22, 3366-3387. Summary of the Invention

[0049] However, the inventors have recently discovered that one or more important problems still need to be addressed, as described below; to overcome the shortcomings and deficiencies of the prior art and provide a new material that can be used as a multifunctional dielectric material in various electronic packaging applications; to provide a novel dielectric material that, when used for the formation of a passivation layer for packaged electronic devices, exhibits excellent film-forming properties, excellent thermal properties such as a low coefficient of thermal expansion (CTE), and excellent mechanical properties such as excellent flexibility. Another object of the present invention is to provide a novel dielectric material that can be easily processed using conventional solvents; to achieve linear CET behavior before and after Tg; to provide a novel photostructured material mixture that is particularly suitable for various applications in electronic packaging, such as passivation of conductive or semiconductor elements, die bonding, and as a major component in the preparation of printed circuit board substrates. One of its important application areas is as a dielectric material for RDL structures in packaged microelectronic devices; to provide a polymerizable mixture from which the novel material is composed. Furthermore, an object of the present invention is to provide a method for forming the novel material using the polymerizable mixture. Finally, one of the objectives of this invention is to provide an electronic device comprising the novel material as a dielectric material, a manufacturing method for preparing a packaged microelectronic structure, and a microelectronic device comprising the packaged microelectronic structure obtained by the manufacturing method.

[0050] Then, the inventors unexpectedly discovered that the features defined in the claims can solve one or more of the above-mentioned technical problems.

[0051] That is, a novel polymerizable mixture has been discovered, comprising a polymerizable compound, a second compound, and a third compound, wherein the polymerizable compound is the compound represented by formula (1).

[0052] P 1 -Sp 1 -(MG-Sp 1 ) m -P 1 Equation (1)

[0053] in:

[0054] m is an integer from 2 to 60;

[0055] P 1 express V 1 and V 2 Independent of each other, they are H, alkyl groups having 1 to 6 carbon atoms, F, Cl, or CN;

[0056] Sp 1 Each occurrence represents a spacer group;

[0057] MG is a rod-shaped liquid crystal building block; and

[0058] The second compound is a bifunctional or multifunctional compound, the third compound is a multifunctional compound, and the second and third compounds can react with polymerizable compounds to form copolymers.

[0059] The polymerizable mixture is used as a starting material to form a novel class of copolymers that exhibit both a low coefficient of thermal expansion and high mechanical flexibility. The copolymers are prepared by a method that is also part of this invention:

[0060] A method for forming a copolymer, wherein the method includes the following steps:

[0061] (i) To provide a polymerizable mixture according to the present invention;

[0062] (ii) The polymerizable mixture is polymerized to obtain a copolymer.

[0063] In addition, a copolymer is provided that can be obtained by the above-described method for forming copolymers or obtained by the method described above.

[0064] In addition, an electronic device comprising the copolymer according to the present invention is also provided.

[0065] Finally, a method for fabricating a packaged microelectronic structure is provided, wherein a dielectric layer is provided on a substrate, and the method includes the following steps:

[0066] (1) Applying the polymerizable mixture according to the invention to a substrate surface; and

[0067] (2) The polymerizable composition is polymerized to form a dielectric layer.

[0068] The present invention also provides a microelectronic device comprising a packaged microelectronic structure, which can be obtained by the manufacturing method of the present invention or by the method thereof.

[0069] Preferred embodiments of the present invention are described below and in the dependent claims.

[0070] Technical effects of the present invention

[0071] This invention provides one or more of the following technical effects: overcoming the shortcomings and deficiencies of the prior art, providing a new material that can be used as a multifunctional dielectric material in various electronic packaging applications; providing a novel dielectric material that, when used for the formation of a passivation layer for packaged electronic devices, exhibits excellent film-forming properties, excellent thermal properties such as a low coefficient of thermal expansion (CTE), and excellent mechanical properties such as excellent flexibility. Another object of this invention is to provide a novel dielectric material that can be easily processed using conventional solvents; to match the coefficient of thermal expansion of the dielectric material with, for example, that of silicon (Si: 3 ppm / K) or copper (Cu: 16.5 ppm / K) without adversely affecting mechanical properties (e.g., elongation at break after UV curing or thermal curing at temperatures below 200°C); to provide a novel photostructured material mixture that is particularly suitable for various applications in electronic packaging, such as passivation of conductive or semiconductor elements, die bonding, and as a major component in the preparation of printed circuit board substrates. One of its important application areas is as a dielectric material for RDL structures in packaged microelectronic devices; and to provide a polymerizable mixture from which the novel material is composed. Furthermore, an object of the present invention is to provide a method for forming the novel material using the polymerizable mixture. Finally, one object of the present invention is to provide an electronic device comprising the novel material as a dielectric material, a manufacturing method for preparing an encapsulated microelectronic structure, and a microelectronic device comprising the encapsulated microelectronic structure obtained by the manufacturing method. Detailed Implementation

[0072] -definition

[0073] Unless otherwise stated, the following terms used in the specification and claims shall have the following meanings for the purposes of this specification.

[0074] In this specification, unless otherwise specified, the use of the singular includes the plural, and the words “a,” “an,” and “the” mean “at least one.” Furthermore, the use of the term “comprising” and other forms of use such as “including” and “containing” are not restrictive. Additionally, unless otherwise specified, terms such as “element” or “component” cover: an element or component comprising one unit, and an element or component comprising more than one unit. As used herein, unless otherwise specified, the conjunction “and” is intended to be inclusive, while the conjunction “or” is not intended to be exclusive. For example, the phrase “or, alternatively” is intended to be exclusive. As used herein, the term “and / or” refers to any combination of elements, including the use of a single element. The terms “about” or “approximately,” when used in conjunction with a measurable numerical variable, refer to the indicated value of the variable and all values ​​of the variable within the experimental error of the indicated value (e.g., within the 95% confidence limit of the mean) or within ±10% or ±5% of the indicated value, whichever is greater.

[0075] As used in this article, “Cx-y” (where x and y are integers) represents the number of carbon atoms in a carbon chain. For example, C 1-6 Alkyl refers to an alkyl chain with a carbon chain length of 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, and hexyl). Unless otherwise explicitly stated, the chain can be straight or branched. Unless otherwise stated, "alkyl" refers to a hydrocarbon group, which can be straight, branched (e.g., methyl, ethyl, propyl, isopropyl, tert-butyl, etc.), cyclic (e.g., cyclohexyl, cyclopropyl, cyclopentyl, etc.), or polycyclic (e.g., norbornyl, adamantyl, etc.). Suitable acyclic groups can be methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl or tert-butyl, and straight or branched pentyl, hexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, and hexadecyl. Unless otherwise stated, alkyl refers to a group having 1 to 10 carbon atoms. Cyclic alkyl groups can be monocyclic or polycyclic. Suitable examples of monocyclic alkyl groups include substituted cyclopentyl, cyclohexyl, and cycloheptyl. As mentioned earlier, cyclic alkyl groups can be substituents of any acyclic alkyl group. These alkyl moieties can be substituted or unsubstituted.

[0076] "Alkoxy" (also known as "alkyloxy group") refers to an alkyl group (e.g., methoxy, ethoxy, propoxy, butoxy, 1,2-isopropoxy, cyclopentoxy, cyclohexyloxy, etc.) linked by an oxygen (-O-) moiety as described above.

[0077] "Halogenated" or "halogenated" refers to halogens (such as F, Cl, Br, and I).

[0078] "Hydroxyl" (also known as "hydroxyl group") refers to the -OH group.

[0079] The term "aryl" refers to an aromatic cyclic functional group having 4 to 10 carbon atoms, 5 to 10 carbon atoms, or 6 to 10 carbon atoms. Exemplary aryl groups include, but are not limited to, phenyl, tolyl, furanyl, benzyl, and o-xylyl.

[0080] In addition to known and understood methods for representing covalent bond connection points, the connection points (binding sites) of the structural elements proposed in this patent application can also be represented using... The symbol represents a structural element. Indicates the binding site.

[0081] Unless otherwise stated, "alkylene" refers to a straight-chain saturated divalent hydrocarbon group of one or more carbon atoms, or a branched saturated divalent hydrocarbon group of three to six carbon atoms (e.g., methylene, ethylene, propylene, 1-methylpropylene, 2-methylpropylene, butylene, pentylene, etc.). In the disclosed and claimed compounds, alkylene is used as R. 1 With R 2 Linking groups between alkyl groups, such as ethylene bridges. Specific examples of alkylene linking groups include methylene (-CH2), ethylene (-CH2CH2-), and substituted ethylenes (e.g., -CH(CH3)CH2-, etc.).

[0082] "Heteroalkylene" refers to the -(alkylene)- radical as defined above, wherein one, two, or three carbon atoms in the alkylene chain are replaced by -O-, N (H, alkyl, or substituted alkyl), S, SO, SO2, or CO. In some preferred embodiments, the carbon atoms are replaced by O or N.

[0083] Unless otherwise stated, the term "(substituted)" refers to alkyl, substituted alkyl, unsubstituted aryl, substituted aryl, alkyloxy, alkylaryl, haloalkyl, halide, hydroxyl, amino, or aminoalkyl. Similarly, the term "unsubstituted" refers to the same structural unit that has no substituents other than hydrogen.

[0084] The terms "liquid crystal," "mesocrystalline compound," or "liquid crystal element compound" (also simply "liquid crystal element") refer to compounds that can exist in a mesocrystalline phase, or particularly an LC phase, under suitable temperature, pressure, and concentration conditions. Non-amphiphilic liquid crystal element compounds contain, for example, one or more rod-shaped, banana-shaped, or disc-shaped liquid crystal element groups.

[0085] The term "calamitic" refers to a rod-shaped or plate / strip-shaped compound or group. The term "banana-shaped" refers to a curved group in which two (typically rod-shaped) liquid crystal unit groups are connected by a semi-rigid group, and the connection is not collinear. The term "disc-shaped" refers to a dish-shaped or sheet-shaped compound or group.

[0086] The term "liquid crystal matrix group" or its abbreviation "MG" refers to a group capable of inducing liquid crystal (LC) phase behavior. Liquid crystal matrix groups, especially non-amphiphilic liquid crystal matrix groups, are typically rod-shaped or disc-shaped. The compounds constituting the liquid crystal matrix group do not necessarily possess an LC phase themselves. They may only exhibit LC phase behavior when mixed with other compounds or when the liquid crystal matrix compound or mixture thereof polymerizes. For simplicity, the term "liquid crystal" will refer to both liquid crystal matrix and LC material in the following text.

[0087] Rod-shaped liquid crystal matrix compounds typically comprise rod-shaped (i.e., rod-shaped or plate-shaped) liquid crystal modules, which are formed by one or more aromatic or alicyclic groups directly or through linking groups. Optionally, they may include terminal groups attached to the short end of the rod and one or more lateral groups attached to the long end of the rod. These terminal and lateral groups are typically selected from, for example, carbonyl or hydrocarbon groups, polar groups (such as halogens, nitro groups, hydroxyl groups, etc.), or polymerizable groups.

[0088] Disc-shaped liquid crystal compounds typically comprise a disc-shaped, i.e., relatively flat, dish-shaped or sheet-shaped liquid crystal cell, for example, composed of one or more fused aromatic or alicyclic groups (such as triphenylene), and optionally include one or more terminal groups attached to the liquid crystal cell, these terminal groups being selected from the aforementioned terminal groups and lateral groups.

[0089] The term "reactive liquid crystal moiety" or its abbreviation "RM" refers to a polymerizable liquid crystal moiety or liquid crystal compound, preferably a monomer or oligomer.

[0090] The term “spacer group” or “spacer group”, also referred to below as “Sp”, is known to those skilled in the art and has been described in the literature.

[0091] Unless otherwise stated, the terms “spacer group” or “spacer group” used above and below refer to a flexible organic group that connects a liquid crystal matrix group and a polymerizable group in a polymerizable liquid crystal matrix compound (“RM”).

[0092] The term "polymer" includes, but is not limited to, homopolymers, copolymers (e.g., block, random, and alternating copolymers), terpolymers, quaternary copolymers, and their blends and modifications. Furthermore, unless explicitly stated otherwise, the term "polymer" should include all possible configurational isomers of the material. These configurations include, but are not limited to, isotactic, syndiotactic, and atactic symmetries. A polymer is a molecule with a relatively high molecular weight whose structure is primarily composed of multiple repeating units (i.e., repeating units), which are actually or conceptually derived from molecules with a relatively low molecular weight (i.e., monomers). In the context of this invention, a polymer consists of more than 60 monomers.

[0093] The term "oligomer" refers to a molecular complex composed of a small number of monomeric units, unlike polymers, which in principle have an unlimited number of monomers. For example, dimers, trimers, and tetramers are oligomers composed of two, three, and four monomers, respectively. In the context of this invention, oligomers may consist of up to 60 monomers.

[0094] The term "polymerizable compound" refers to a compound capable of undergoing polymerization, thereby providing the building blocks (repeating units) for the basic structure of polymers or oligomers. A polymerizable compound is a functionalized compound having one or more polymerizable groups. Numerous compounds combine through polymerization to form polymers. A polymerizable compound with one polymerizable group is also called a "monofunctional" or "monoreactive" compound; a compound with two polymerizable groups is called a "bifunctional" or "bireactive" compound; and a compound with more than two polymerizable groups is called a "polyfunctional" or "polyreactive" compound. Compounds without polymerizable groups are also called "nonfunctional" or "nonreactive" compounds.

[0095] As used herein, the term "homogeneous polymer" refers to a polymer derived from a single monomer (real, implicit, or hypothetical).

[0096] As used herein, the term "copolymer" generally refers to any polymer derived from more than one monomer, wherein the polymer contains more than one corresponding repeating unit. In one embodiment, the copolymer is the reaction product of two or more monomers, and therefore contains two or more corresponding repeating units. Preferably, the copolymer contains two, three, four, five, or six repeating units. A copolymer obtained by copolymerizing three monomers may also be called a ternary copolymer. A copolymer obtained by copolymerizing four monomers may also be called a quaternary copolymer. Copolymers can exist in the form of block, random, and / or alternating copolymers.

[0097] As used herein, the term "block copolymer" refers to a copolymer in which adjacent blocks have different compositions, i.e., adjacent blocks contain repeating units derived from different types of monomers or the same type of monomers, but the composition or sequence distribution of the repeating units is different.

[0098] Furthermore, as used herein, the term "random copolymer" refers to a polymer composed of macromolecules in which the probability of finding a given repeating unit at any position in the chain is independent of the properties of adjacent repeating units. Typically, in random copolymers, the sequence distribution of repeating units follows Bernoulli statistics.

[0099] As used herein, the term "alternating copolymer" refers to a copolymer composed of macromolecules consisting of two repeating units arranged in an alternating sequence.

[0100] Electronic packaging is an important branch of electronic engineering, encompassing a variety of technologies. It refers to the insertion of discrete components, integrated circuits, and MSI (Medium-Size Integrated Circuit) and LSI (Large-Size Integrated Circuit) chips (usually connected to a lead frame via wires) into plated through-holes on a multilayer circuit board (also known as an expansion card), and then soldering them in place. The packaging of electronic systems must consider factors such as protection against mechanical damage, heat dissipation, radio frequency noise radiation, electrostatic discharge protection, maintenance, ease of operation, and cost.

[0101] As used herein, the term "microelectronic device" refers to electronic devices with extremely small electronic designs and component sizes. This typically (but not always) means micrometers or smaller. These devices usually contain one or more microelectronic components made of semiconductor materials and interconnected in a packaged structure to form the microelectronic device. Many electronic components in common electronic designs have corresponding microelectronic versions. These components include transistors, capacitors, inductors, resistors, diodes, and of course, insulators and conductors are also present in microelectronic devices. Due to the exceptionally small size of components, pins, and pads, unique wiring techniques, such as wire bonding, are often used in microelectronic devices.

[0102] The chapter headings used herein are for organizational purposes only and should not be construed as limiting the subject matter. All documents or portions thereof cited in this application, including but not limited to patents, patent applications, articles, books, and monographs, are incorporated herein by reference in their entirety for any purpose. If any definition of a term in any incorporated reference or similar material conflicts with the definition in this application, the definition in this application shall prevail.

[0103] Detailed description

[0104] It should be understood that the above general description and the following detailed description are exemplary and explanatory, and are not intended to limit the subject matter as defined in the claims. Those skilled in the art should be able to readily understand the purpose, features, advantages, and ideas of the disclosed subject matter based on the description herein; and those skilled in the art can easily put the disclosed subject matter into practice based on the description herein. The description of any "preferred embodiment" and / or example is intended to illustrate preferred implementations of the disclosed subject matter and is not intended to limit the scope of the claims.

[0105] Preferred implementation scheme

[0106] -polymerizable compounds

[0107] The present invention relates to a polymerizable mixture comprising a polymerizable compound, a second compound, and a third compound.

[0108] polymerizable compounds

[0109] Polymerizable compounds are compounds represented by formula (1).

[0110] P 1 -Sp 1 -(MG-Sp 1 ) m -P 1 Equation (1)

[0111] in:

[0112] m is an integer from 2 to 60, preferably an integer from 2 to 50, more preferably an integer from 2 to 30, and most preferably an integer from 3 to 20;

[0113] P 1 express V 1 For H, V 2 It is an alkyl group, F, Cl or CN having 1 to 6 carbon atoms; or V 1 and V 2 They are independent of each other and are all alkyl, F, Cl or CN with 1 to 6 carbon atoms;

[0114] Sp 1 Each occurrence represents a spacer group (Sp) or a single bond;

[0115] MG is a rod-shaped liquid crystal building block, preferably selected from formula (2):

[0116] -(A 21 -Z 21 ) k -A 22 -(Z 22 -A23 ) l -Equation (2)

[0117] in:

[0118] A 21 To A 23 Each group is independent of the others, and each time they appear independently of each other, they are aryl, heteroaryl, heterocyclic, alicyclic or cyclic imide groups, which are optionally substituted with one or more of the same or different groups L;

[0119] Z 21 and Z 22 The following are independent of each other, and each occurrence is independent of the others: -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 01 -、-NR 01 -CO-、-NR 01 -CO-NR 02 -NR 01 -CO-O-、-O-CO-NR 01 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2)4-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 01 -、-CY 01 =CY 02 -, CH=CH-COO-, -OCO-CH=CH-, or single bonds;

[0120] R 01 and R 02 Each can be independently represented by an H or alkyl group having 1 to 12 carbon atoms;

[0121] L is F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR xx R yy -C(=O)OR xx -C(=O)R xx -NR xx R yy-OH, -SF5, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may optionally be replaced by F or Cl, -CN, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 6 carbon atoms;

[0122] R xx and R yy Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms;

[0123] Y 01 and Y 02 Each can be represented independently of H, alkyl, aryl, F, Cl, or CN having 1 to 12 carbon atoms;

[0124] k and l are independent of each other and can be 0, 1, 2, 3 or 4.

[0125] polymerizable group P 1 It is capable of undergoing polymerization reactions, such as free radical or ionic chain polymerization, or polymerization addition reactions (e.g., cycloaddition reactions, such as 2+2 cycloaddition, 4+2 cycloaddition, or 1,3-dipolar cycloaddition, or nucleophilic addition), or polymerization-like reactions, such as addition to the polymer backbone via one of the above reaction types.

[0126] Preferably, V 1 and V 2 The alkyl groups are independently selected from alkyl groups having 1 to 3 carbon atoms, F, Cl, or CN. Preferred alkyl groups having 1 to 3 carbon atoms are methyl, ethyl, and propyl. Preferably, V 1 and V 2 same.

[0127] Preferably, Z 21 and Z 22 Each is independent of the others, and each occurrence is independently -COO-, -OCO-, -O-CO-, -OCH2-, -CH2O, -CH2CH2-, -(CH2)4-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH-, or a single bond. More preferably, Z 21 and Z 22 They are independent of each other, and each time they appear, they are independently -COO-, -OCO-, or single bonds.

[0128] Preferably, k and l are independently 0, 1, or 2; more preferably, k and l are each 1.

[0129] Preferred spacer group Sp1 Select from the formula Sp'-X', such that "P 1 -Sp 1 -" corresponds to "P" 1 -Sp'-X'-", where:

[0130] Sp' means

[0131] (a) A straight-chain or branched alkylene group having 1 to 40 carbon atoms, optionally monosubstituted or polysubstituted with F, Cl, Br, I or CN, wherein one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, or -NR. 01 -、SiR 01 R 02 -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR 01 -CO-O-、-O-CO-NR 01 -、-NR 01 -CO-NR 01 -, -CH=CH- or -C≡C- substitution, so that O and / or S atoms are not directly connected to each other;

[0132] (b) -Sp x -G-Sp y -, where Sp x and Sp y Each of the above can independently represent an alkylene group or a single bond having 1 to 20 carbon atoms; G represents a cycloalkylene group having 3 to 20 carbon atoms, which may optionally be mono- or poly-substituted with an alkyl group having 1 to 20 carbon atoms.

[0133] X' represents -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 01 -、-NR 01 -CO-、-NR 01 -CO-NR 01 -, -OCH2, CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=C-, -N=N-, -CH=CR 01 -、-CY 01 =CY 02 -、-C≡C-、-CH=CH-COO-、-OCO-CH=CH- or single bonds;

[0134] R 01 and R 01Each can be used independently to represent hydrogen or an alkyl group having 1 to 12 carbon atoms;

[0135] Y 01 and Y 02 Each can be represented independently as H, F, Cl, or CN.

[0136] The preferred groups Sp' are selected from linear methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, cyclohexylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethylene, propylene, and butylene.

[0137] More preferably, the spacer group Sp 1 Choose from the list containing the following ingredients:

[0138] -(CH2) p1 -、-(CH2CH2O) q1 -CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2-, -(SiR 01 R 02 -O) p1 -、-(CH2) p1 -(ring-C6H8R) 01 R 02 )-(CH2) p1 -,and

[0139] ,

[0140] in:

[0141] p1 is an integer from 1 to 60, preferably an integer from 1 to 36, and more preferably an integer from 1 to 12;

[0142] q1 is an integer from 1 to 12, preferably an integer from 1 to 3; and

[0143] R 01 and R 02 Each can be represented independently by H or an alkyl group having 1 to 12 carbon atoms.

[0144] The best option Sp 1 The functional group is -(CH2). p1 -、-O-(CH2) p1 -、-O-(CH2) p1 -O-, -OCO-(CH2) p1 -、-OCOO-(CH2) p1 - and -(CH2)p1 -(ring-C6H8R) 01 R 02 )-(CH2) p1 Where p1 is an integer from 1 to 36, preferably an integer from 1 to 12, and R 01 and R 02 Each can be represented independently by H or an alkyl group having 1 to 12 carbon atoms.

[0145] In a preferred embodiment of the present invention, group A 21 To A 23 Each group independently represents a portion selected from the following groups a) to e), and in the case of multiple occurrences, they are independent of each other:

[0146] a) trans-1,4-cyclohexylene, 1,4-cyclohexylene, and 4,4'-bicyclohexylene, wherein one or more non-adjacent CH2 groups may be substituted with -O- and / or -S-, and one or more H atoms may be substituted with L groups;

[0147] b) 1,4-phenylene, 1,3-phenylene, 4,4'-biphenyl, 2,5-thiophene and 2,6-dithiopheno[3,2-b:2',3'-d]thiophene, wherein one or two CH groups may be replaced by N and one or more H atoms may be replaced by L groups;

[0148] c) Tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrofuran-2,5-diyl, cyclobutane-1,3-diyl, piperidine-1,4-diyl, thiophene-2,5-diyl, and selenophene-2,5-diyl, wherein one or more L groups may be substituted thereon;

[0149] d) A saturated, partially unsaturated, or fully unsaturated polycyclic group having 5 to 20 ring carbon atoms, optionally substituted, wherein one or more carbon atoms may also be replaced by heteroatoms, preferably selected from bicyclo[1.1.1]pentane-1,3-diyl, bicyclo[2.2.2]octane-1,4-diyl, spiro[3.3]heptane-2,6-diyl,

[0150]

[0151] One or more hydrogen atoms may be replaced by an L group, and / or one or more double bonds may be replaced by a single bond, and / or one or more CH groups may be replaced by an N group, and wherein

[0152] M represents -O-, -S-, -CH2-, -CHY 03 -or-CY 03 Y 04 -;

[0153] Y03 Y 04 The above are represented independently of each other as R. 01 One of the given meanings: F, Cl, CN, OCF3, or CF 3 H, F, Cl, CN, OCF3 or CF3 are preferred;

[0154] W 5 W 6 Independently represented by -CH2CH2-, -CH=CH-, -CH2-O-, O-CH2-, -C(R) c R d - or -O-;

[0155] R c R d Each of the above can independently represent H or an alkyl group having 1 to 6 carbon atoms, preferably H, methyl or ethyl;

[0156] R 03 R 04 Independent of each other, H, F, and straight-chain or branched alkyl groups having 1 to 12 carbon atoms, wherein one or more hydrogen atoms may be replaced by fluorine atoms;

[0157] e) Cyclic imides selected from the following:

[0158]

[0159] One or more H atoms may be replaced by L groups, and / or one or more double bonds may be replaced by single bonds, and / or one or more CH groups may be replaced by N groups.

[0160] The preferred compound according to formula (1) is:

[0161]

[0162]

[0163]

[0164]

[0165]

[0166]

[0167]

[0168] The groups and subscripts have the following meanings:

[0169] L is F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR xx R yy -C(=O)OR xx -C(=O)R xx -NR xx R yy -OH, -SF5, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyl or alkoxy carbonyl group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms), wherein one or more hydrogen atoms are optionally replaced by F or Cl, preferably F, -CN or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyl or alkoxy carbonyl group having 1 to 6 carbon atoms;

[0170] R xx and R yy Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms;

[0171] r can be 0, 1, 2, 3, or 4;

[0172] s can be 0, 1, 2, or 3;

[0173] t is 0, 1, or 2;

[0174] Z 21 and Z 22 The following are independent of each other, and each occurrence is independent of the others: -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 01 -、-NR 01 -CO-、-NR 01 -CO-NR 02 -NR 01 -CO-O-、-O-CO-NR 01 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2)4-, -CF2CH2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 01 -、-CY 01 =CY 02-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or single bond, preferably -COO-, -OCO-, -CO-O-, -O-CO-, -OCH2-, -CH2O-, -CH2CH2-, -(CH2)4-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or single bond;

[0175] R 01 and R 02 Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms;

[0176] Sp 1 Each occurrence represents either a spacer group (Sp) as defined above, or a single bond;

[0177] P 1 express V 1 For H, V 2 It is an alkyl group, F, Cl or CN having 1 to 6 carbon atoms; or V 1 and V 2 Each of the following is independently an alkyl group, F, Cl, or CN having 1 to 6 carbon atoms; and

[0178] m is an integer from 1 to 60, preferably an integer from 1 to 50, more preferably an integer from 2 to 30, and most preferably an integer from 3 to 20.

[0179] A more preferred compound according to formula (1) is:

[0180]

[0181]

[0182] Among them, the group and the subscript have one of the meanings defined above.

[0183] The further preferred compound according to formula (1) is:

[0184]

[0185] in

[0186] Z 21 and Z 22 They are independent of each other, and each time they appear, they are independently -O-, -COO-, or -OCO-;

[0187] m is an integer from 1 to 60, preferably an integer from 1 to 50, more preferably an integer from 2 to 30, and most preferably an integer from 3 to 20.

[0188] P 1 express V 1 and V 2 Each is independently H or an alkyl group having 1 to 6 carbon atoms;

[0189] Sp 1 From -(CH2) p1 -、-O-(CH2) p1 -、-O-(CH2) p1 -O-, -OCO-(CH2) p1 -、-OCOO-(CH2) p1 - and -(CH2) p1 -(ring-C6H8R) 01 R 02 )-(CH2) p1 Selected from the group, where p1 is an integer from 1 to 60, preferably an integer from 1 to 36, more preferably an integer from 6 to 12, R 01 and R 02 Each can be represented independently by H or an alkyl group having 1 to 12 carbon atoms.

[0190] The most preferred compound of formula (1) is selected from:

[0191]

[0192] in

[0193] n is an integer from 1 to 60, preferably an integer from 1 to 36, and more preferably an integer from 6 to 12;

[0194] m is an integer from 1 to 60, preferably an integer from 1 to 50, more preferably an integer from 2 to 30, and most preferably an integer from 3 to 20.

[0195] As polymerizable compounds of this type of chemical formula (1), known compounds such as those described in WO2019 / 141833A1 can be used and manufactured.

[0196] -Second compound

[0197] The second compound included in the polymerizable mixture according to the invention is a bifunctional or polyfunctional compound capable of reacting with the polymerizable compound to form a copolymer. The second compound has at least two polymerizable groups (P... 2 For example, two, three, four, five, etc., these groups are selected from groups containing C=C double bonds, preferably with P. 1 It undergoes free radical or ionic chain polymerization or 2+2 cycloaddition reaction; it contains groups with two conjugated C=C double bonds, preferably with P. 1A 4+2 cycloaddition reaction occurs (Diesel-Alder reaction); nucleophilic group, preferably with P 1 Nucleophilic addition reaction (Michael reaction) occurs; and a 1,3-dipolar group, preferably with P 1 A 1,3-dipolar cycloaddition reaction occurs.

[0198] Preferred polymerizable groups containing C=C double bonds (P) 2 (Selected from:)

[0199] CH2=CW 1 -COO-、CH2=CW 1 -CO-、 , ,

[0200] CH2=CW 2 -(O) k3 -、CW 1 2=CH-CO-(O) k3 -、CW 1 2=CH-CO-NH-, CH2=CW 1 -CO-NH-, CH3-CH=CH-O-, CH2=CH-CH2-O-, (CH2=CH)2CH-O-CO-, (CH2=CH-CH2)2CH-O-CO-, (CH2=CH)2CH-O-, (CH2=CH-CH2)2N-, (CH2=CH-CH2)2N-CO-, CH2=CW 1 -CO-NH-, CH2=CH-(CO-O) k1 -Phe-(O) k2 -, CH2=CH-(CO) k1 -Phe-(O) k2 -, or Phe-CH=CH-; where

[0201] W 1 It represents H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 carbon atoms, preferably H or CH3;

[0202] W 2 The symbol represents H or an alkyl group having 1 to 5 carbon atoms, preferably H or CH3;

[0203] W 3 and W 4 Each of the above can be independently represented by H, Cl or an alkyl group having 1 to 5 carbon atoms, preferably H or CH3;

[0204] Phe represents 1,4-phenylene, optionally substituted with one or more L groups as defined above; and

[0205] k1, k2, and k3 independently represent 0 or 1; and

[0206] k4 is an integer from 1 to 10.

[0207] Preferred groups containing two conjugated C=C double bonds are selected from: CW 1 2=CW 1 -CW 1 =CW 1 -;in

[0208] W 1 It represents H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 carbon atoms, preferably H or CH3.

[0209] The preferred nucleophilic group is selected from: HS-(CH2) k5 -CO-(O) k3 - HS-(CH2) k5 -CO-, HS-(CH2) k5 -(O) k3 - HS-(CH2) k5 -O-CO-, HS-(CH2) k5 -CO-NH-, HS-(CH2) k5 -NH-CO-, HS-Phe-(O) k2 -、H2N-(CH2) k5 -CO-(O) k3 -、H2N-(CH2) k5 -CO-, H2N-(CH2) k5 -(O) k3 -、H2N-(CH2) k5 -O-CO-、H2N-(CH2) k5 -CO-NH-, H2N-(CH2) k5 -NH-CO-, or H2N-Phe-(O) k2 -;in

[0210] k2 and k3 represent 0 or 1 independently of each other;

[0211] k5 is an integer from 0 to 10, preferably an integer from 0 to 5, and more preferably 0, 1 or 2.

[0212] Preferred 1,3-dipolar groups are selected from:

[0213] (Ylide) and (Nitrileimide) (Nitrile oxides) (diazo compounds) (Azides) and (Methylimino ylide) and and (Methylimide) and (nitroketone) (Carbonyl ylide) (Carbonyl oxide), (Nitro) and (carbonylimine) and (Azimines) (nitrosimine) and (azo compounds) or (nitrosoxide); where:

[0214] W 5 Each time it appears, it independently represents H, phenyl, or an alkyl group having 1 to 5 carbon atoms, preferably phenyl or CH3.

[0215] Particularly preferred polymerizable groups (P) 2 (Selected from:)

[0216] CH2=CW 1 -COO-、CH2=CW 1 -CO-、 CH2=CW 2 -(O) k3 -、

[0217] CW 1 2=CH-CO-(O) k3 -, CH3-CH=CH-O-, CH2=CH-CH2-O-, HS-(CH2) k5 -CO-(O) k3 - HS-(CH2) k5 -CO-, HS-(CH2) k5 -(O) k3 - HS-(CH2) k5 -O-CO-、H2N-(CH2) k5 -CO-(O) k3 -、H2N-(CH2) k5 -CO-, H2N-(CH2) k5 -(O) k3 -or H2N-(CH2)k5 -O-CO-; where

[0218] W 1 It represents H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 carbon atoms, preferably H or CH3;

[0219] W 2 The symbol represents H or an alkyl group having 1 to 5 carbon atoms, preferably H or CH3;

[0220] W 3 and W 4 Each of the above can be independently represented by H, Cl or an alkyl group having 1 to 5 carbon atoms, preferably H or CH3;

[0221] k3 represents 0 or 1;

[0222] k5 is an integer from 0 to 10, preferably an integer from 0 to 5, and more preferably 0, 1 or 2.

[0223] Most preferably, P 2 express V 1 and V 2 Independent of each other, they are H, alkyl groups having 1 to 6 carbon atoms, F, Cl, or CN;

[0224] In one embodiment, the second compound is represented by formula (3).

[0225] Equation (3)

[0226] Where X a express

[0227] (a) A straight-chain or branched alkylene group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, optionally monosubstituted or polysubstituted with F, Cl, Br, I or CN, wherein one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, NR-. 01 -、-SiR 01 R 02 -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S, -NR 01 -CO-O-、-O-CO-NR 01 -、-NR 01 -CO-NR 01 -, -CH=CH- or -C≡C- substitution, so that O and / or S atoms are not directly connected to each other; or

[0228] (b) -R a -R b -Rc -, where R a and R c Each can be independently represented as an alkylene group or a single bond having 1 to 20 carbon atoms; R b This refers to a cycloalkylene group having 3 to 20 carbon atoms, which may optionally be mono- or poly-substituted with an alkyl group having 1 to 20 carbon atoms. It is preferred to use publicly available compounds conforming to chemical formula (3).

[0229] The preferred monomer represented by equation (3) is,

[0230] .

[0231] In one embodiment, the second compound is represented by formula (5).

[0232] Equation (5)

[0233] in:

[0234] Xb represents -(A) 41 -Z 41 ) m1 -(A 42 ) m2 -(Z 42 -A 43 ) m3 -,in:

[0235] A 41 To A 43 They are independent of each other, and each time they appear independently of each other, they are aryl or heteroaryl, which are optionally substituted with one or more of the same or different groups L;

[0236] L is F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR xx R yy -C(=O)OR xx -C(=O)R xx -NR xx R yy -OH, -SF5, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may optionally be replaced by F or Cl, -CN, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 6 carbon atoms;

[0237] R xx and R yy Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms;

[0238] Z 41 and Z 42 They are independent of each other, and each time they appear, they are independently -O-, -CO-, -COO-, -OCO-, -CH2, (CH2)2-, -(CH2)2- or a single bond;

[0239] m 1 It can be 1, 2, 3, 4, 5, 6, or 7;

[0240] m 2 and m 3 Each can be 0, 1, 2, 3, or 4 independently.

[0241] The preferred monomer represented by equation (5) is

[0242] .

[0243] - Third compound

[0244] The third compound included in the polymerizable mixture according to the invention is a multifunctional compound capable of reacting with the polymerizable compound to form a copolymer. This third compound has at least three polymerizable groups (P...). 3 These groups are selected from groups containing C=C double bonds, preferably with P. 1 It undergoes free radical or ionic chain polymerization or 2+2 cycloaddition reaction; it contains groups with two conjugated C=C double bonds, preferably with P. 1 A 4+2 cycloaddition reaction occurs (Diesel-Alder reaction); nucleophilic group, preferably with P 1 Nucleophilic addition reaction (Michael reaction) occurs; and a 1,3-dipolar group, preferably with P 1 A 1,3-dipolar cycloaddition reaction occurs. As this type of third compound, publicly available compounds are preferred.

[0245] Preferred polymerizable groups containing C=C double bonds (P) 3 (Selected from:)

[0246] CH2=CW 1 -COO-、CH2=CW 1 -CO-、 , ,

[0247] CH2=CW 2 -(O) k3 -、CW 1 2=CH-CO-(O) k3 -、CW 1 2=CH-CO-NH-, CH2=CW 1-CO-NH-, CH3-CH=CH-O-, CH2=CH-CH2-O-, (CH2=CH)2CH-O-CO-, (CH2=CH-CH2)2CH-O-CO-, (CH2=CH)2CH-O-, (CH2=CH-CH2)2N-, (CH2=CH-CH2)2N-CO-, CH2=CW 1 -CO-NH-, CH2=CH-(CO-O) k1 -Phe-(O) k2 -, CH2=CH-(CO) k1 -Phe-(O) k2 -, or Phe-CH=CH-; where

[0248] W 1 It represents H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 carbon atoms, preferably H or CH3;

[0249] W 2 The symbol represents H or an alkyl group having 1 to 5 carbon atoms, preferably H or CH3;

[0250] W 3 and W 4 Each of the above can be independently represented by H, Cl or an alkyl group having 1 to 5 carbon atoms, preferably H or CH3;

[0251] Phe represents 1,4-phenylene, optionally substituted with one or more L groups as defined above; and

[0252] k1, k2, and k3 represent 0 or 1 independently of each other;

[0253] k4 is an integer from 1 to 10.

[0254] Preferred groups containing two conjugated C=C double bonds are selected from: CW 1 2=CW 1 -CW 1 =CW 1 -;in

[0255] W 1 It represents H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 carbon atoms, preferably H or CH3.

[0256] The preferred nucleophilic group is selected from: HS-(CH2) k5 -CO-(O) k3 - HS-(CH2) k5 -CO-, HS-(CH2) k5 -(O) k3 - HS-(CH2) k5-O-CO-, HS-(CH2) k5 -CO-NH-, HS-(CH2) k5 -NH-CO-, HS-Phe-(O) k2 -、H2N-(CH2) k5 -CO-(O) k3 -、H2N-(CH2) k5 -CO-, H2N-(CH2) k5 -(O) k3 -、H2N-(CH2) k5 -O-CO-、H2N-(CH2) k5 -CO-NH-, H2N-(CH2) k5 -NH-CO-, or H2N-Phe-(O) k 2-; where

[0257] k2 and k3 represent 0 or 1 independently of each other;

[0258] k5 is an integer from 0 to 10, preferably an integer from 0 to 5, and more preferably 0, 1 or 2.

[0259] Preferred 1,3-dipolar groups are selected from:

[0260] (Cryptolite) and (Nitrileimide) (Nitrile oxides) (diazo compounds) (Azides) and (Methylimino ylide) and and (Methylimide) and (nitroketone) (Carbonyl ylide) (Carbonyl oxide), (Nitro) and (carbonylimine) and (Azoimine) (nitrosamines) and (azo compounds) or (nitrosooxides); where:

[0261] W 5Each time it appears, it independently represents H, phenyl, or an alkyl group having 1 to 5 carbon atoms, preferably phenyl or CH3.

[0262] The particularly preferred polymerizable groups (P) are selected from:

[0263] CH2=CW 1 -COO-、CH2=CW 1 -CO-、 CH2=CW 2 -(O) k3 -、

[0264] CW 1 2=CH-CO-(O) k3 -, CH3-CH=CH-O-, CH2=CH-CH2-O-, HS-(CH2) k5 -CO-(O) k3 - HS-(CH2) k5 -CO-, HS-(CH2) k5 -(O) k3 - HS-(CH2) k5 -O-CO-、H2N-(CH2) k5 -CO-(O) k3 -、H2N-(CH2) k5 -CO-, H2N-(CH2) k5 -(O) k3 -or H2N-(CH2) k5 -O-CO-; where

[0265] W 1 It represents H, F, Cl, CN, CF3, phenyl or alkyl having 1 to 5 carbon atoms, preferably H or CH3;

[0266] W 2 The symbol represents H or an alkyl group having 1 to 5 carbon atoms, preferably H or CH3;

[0267] W 3 and W 4 Each of the above can be independently represented by H, Cl or an alkyl group having 1 to 5 carbon atoms, preferably H or CH3;

[0268] k3 represents 0 or 1;

[0269] k5 is an integer from 0 to 10, preferably an integer from 0 to 5, and more preferably 0, 1 or 2.

[0270] Most preferably, P 3 express V 1 and V 2Independent of each other, they are H, alkyl groups having 1 to 6 carbon atoms, F, Cl, or CN.

[0271] In one embodiment, the third compound is represented by formula (4).

[0272] Equation (4)

[0273] Where Ya represents -(A) 31 -Z 31 ) m1 -(Z 32 -A 32 ) m2 -(Z 33 -A 33 ) m3 -,in:

[0274] A 31 and A 33 They are independent of each other, and each time they appear independently of each other, they are aryl or heteroaryl, which are optionally substituted with one or more of the same or different groups L;

[0275] L is F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR xx R yy -C(=O)OR xx -C(=O)R xx -NR xx R yy -OH, -SF5, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may optionally be replaced by F or Cl, -CN, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 6 carbon atoms;

[0276] R xx and R yy Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms;

[0277] A 32 It is an aryl group, substituted with a maleimide moiety.

[0278] Z 31 To Z 33 They are independent of each other, and each time they appear, they are independently -O-, -CO-, -COO-, -OCO-, -CH2, -(CH2)2-, -(CH2)2- or a single bond;

[0279] m 1 and m3 Each value can independently take the values ​​0, 1, 2, 3, or 4;

[0280] m 2 The number is 0, 1, 2, 3, 4, 5, 6, or 7. As a third compound, a publicly available compound conforming to chemical formula (4) is more preferred.

[0281] The optimal monomer / compound represented by equation (4) is:

[0282] .

[0283] In one embodiment, the third compound is represented by formula (6):

[0284] Equation (6)

[0285] Where Y b express

[0286] A straight-chain or branched alkylene group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, which is partially mono- or poly-substituted with bismaleimide and optionally further mono- or poly-substituted with F, Cl, Br, I or CN. Furthermore, one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, or NR. 01 -、-SiR 01 R 02 -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR 01 -CO-O-、-O-CO-NR 01 -、-NR 01 -CO-NR 01 -, -CH=CH- or -C≡C- substitutions prevent O and / or S atoms from being directly connected to each other.

[0287] The preferred monomer / compound represented by formula (6) is:

[0288] .

[0289] - Polymerizable mixtures

[0290] As described above, the disclosed subject matter relates to polymerizable mixtures comprising the first, second, and third compounds described herein.

[0291] The inventors unexpectedly discovered that the presence of at least one multifunctional monomer / compound can ensure that the desired degree of branching is achieved during polymerization.

[0292] Furthermore, the inventors unexpectedly discovered that the simultaneous presence of monomers / compounds containing aliphatic groups and monomers containing aromatic groups can further improve film retention performance and have a positive impact on the glass transition temperature (Tg) of copolymers obtained from polymerizable mixtures.

[0293] In a preferred embodiment, the polymerizable mixture comprises a polymerizable compound represented by formula (1), a second compound represented by formula (3), and a third compound represented by formula (4).

[0294] In other preferred embodiments, the polymerizable mixture comprises a polymerizable compound represented by formula (1), a second compound represented by formula (5), and a third compound represented by formula (6).

[0295] In a particularly preferred embodiment, the polymerizable mixture comprises a polymerizable compound, a second compound, and a third compound to form a copolymer, wherein the polymerizable compound is:

[0296]

[0297] in

[0298] m is an integer from 2 to 60, preferably an integer from 2 to 50, more preferably an integer from 2 to 30, and most preferably an integer from 2 to 20.

[0299] P 1 express V 1 and V 2 Each is independently H or an alkyl group having 1 to 6 carbon atoms;

[0300] Sp 1 From -(CH2) p1 -、-O-(CH2) p1 -、-O-(CH2) p1 -O-, -OCO-(CH2) p1 -、-OCOO-(CH2) p1 - and -(CH2) p1 -(ring-C6H8R) 01 R 02 )-(CH2) p1 Select from the group, where p1 is an integer from 1 to 36, preferably an integer from 1 to 12, R 01 and R 02 Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms;

[0301] The second compound is represented by formula (3):

[0302] Equation (3)

[0303] Where X a express

[0304] (a) A straight-chain or branched alkylene group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, optionally monosubstituted or polysubstituted with F, Cl, Br, I or CN, wherein one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, NR-. 01 -、-SiR 01 R 02 -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S, -NR 01 -CO-O-、-O-CO-NR 01 -、-NR 01 -CO-NR 01 -, -CH=CH- or -C≡C- substitution, so that O and / or S atoms are not directly connected to each other; or

[0305] (b) -R a -R b -R c -, where R a and R c Each can be independently represented as an alkylene group or a single bond having 1 to 20 carbon atoms; R b This indicates a cycloalkylene group having 3 to 20 carbon atoms, optionally mono- or poly-substituted with an alkyl group having 1 to 20 carbon atoms; and wherein...

[0306] The third compound is represented by formula (4):

[0307] Equation (4)

[0308] Where Y a Indicates -(A 31 -Z 31 ) m1 -(Z 32 -A 32 ) m2 -(Z 33 -A 33 ) m3 -

[0309] in:

[0310] A 31 and A 33 They are independent of each other, and each time they appear independently of each other, they are aryl or heteroaryl, which are optionally substituted with one or more of the same or different groups L;

[0311] L is F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR xx R yy -C(=O)OR xx -C(=O)R xx -NR xx R yy -OH, -SF5, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may optionally be replaced by F or Cl, -CN, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 6 carbon atoms;

[0312] R xx and R yy Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms;

[0313] A 32 It is an aryl group, substituted with a maleimide moiety.

[0314] Z 31 To Z 33 They are independent of each other, and each time they appear, they are independently -O-, -CO-, -COO-, -OCO-, -CH2, -(CH2)2-, -(CH2)2- or a single bond;

[0315] m 1 and m 3 Each value can independently take the values ​​0, 1, 2, 3, or 4;

[0316] m 2 It can be 0, 1, 2, 3, 4, 5, 6 or 7.

[0317] Preferably, the polymerizable compound is selected from:

[0318]

[0319] in

[0320] n is an integer from 1 to 60, preferably an integer from 1 to 36, and more preferably an integer from 6 to 12;

[0321] m is an integer from 2 to 60, preferably an integer from 2 to 50, more preferably an integer from 2 to 30, and most preferably an integer from 3 to 20.

[0322] In other particularly preferred embodiments, the polymerizable mixture comprises a polymerizable compound, a second compound, and a third compound to form a copolymer, wherein the polymerizable compound is:

[0323]

[0324] in

[0325] m is an integer from 2 to 60, preferably an integer from 2 to 50, more preferably an integer from 2 to 30, and most preferably an integer from 2 to 20.

[0326] P 1 express V 1 and V 2 Each is independently H or an alkyl group having 1 to 6 carbon atoms;

[0327] Sp 1 From -(CH2) p1 -、-O-(CH2) p1 -、-O-(CH2) p1 -O-, -OCO-(CH2) p1 -、-OCOO-(CH2) p1 - and -(CH2) p1 -(ring-C6H8R) 01 R 02 )-(CH2) p1 Select from the group, where p1 is an integer from 1 to 36, preferably an integer from 1 to 12, R 01 and R 02 Each of the above can independently represent H or an alkyl group having 1 to 12 carbon atoms; and wherein

[0328] The second compound is represented by formula (5).

[0329] Equation (5)

[0330] Where X b Indicates -(A 41 -Z 41 ) m1 -(A 42 ) m2 -(Z 42 -A 43 ) m3 -

[0331] in:

[0332] A 41 To A 43 They are independent of each other, and each time they appear independently of each other, they are aryl or heteroaryl, which are optionally substituted with one or more of the same or different groups L;

[0333] L is F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR xx R yy -C(=O)OR xx -C(=O)R xx -NR xx R yy -OH, -SF5, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may optionally be replaced by F or Cl, -CN, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 6 carbon atoms;

[0334] R xx and R yy Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms;

[0335] Z 41 and Z 42 They are independent of each other, and each time they appear, they are independently -O-, -CO-, -COO-, -OCO-, -CH2, (CH2)2-, -(CH2)2- or a single bond;

[0336] m 1 It can be 1, 2, 3, 4, 5, 6, or 7;

[0337] m 2 and m 3 Each of the compounds is independently 0, 1, 2, 3, or 4; and the third compound is represented by formula (6):

[0338] Equation (6)

[0339] Where Y b express

[0340] A straight-chain or branched alkylene group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, which is partially mono- or poly-substituted with bismaleimide and optionally further mono- or poly-substituted with F, Cl, Br, I or CN. Furthermore, one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, or NR. 01 -、-SiR 01 R 02 -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR 01 -CO-O-、-O-CO-NR 01 -、-NR 01-CO-NR 01 -, -CH=CH- or -C≡C- substitutions prevent O and / or S atoms from being directly connected to each other.

[0341] Preferably, the polymerizable compound is selected from:

[0342]

[0343] in

[0344] n is an integer from 1 to 60, preferably an integer from 1 to 36, and more preferably an integer from 6 to 12;

[0345] m is an integer from 2 to 60, preferably an integer from 2 to 50, more preferably an integer from 2 to 30, and most preferably an integer from 3 to 20.

[0346] In the most preferred embodiment, the polymerizable mixture comprises a polymerizable compound, a second compound, and a third compound to form a copolymer, wherein the polymerizable compound is:

[0347]

[0348] in

[0349] m is an integer from 2 to 60, preferably an integer from 2 to 50, more preferably an integer from 2 to 30, and most preferably an integer from 2 to 20.

[0350] P 1 express V 1 and V 2 Each is independently H or an alkyl group having 1 to 6 carbon atoms;

[0351] Sp 1 From -(CH2) p1 -、-O-(CH2) p1 -、-O-(CH2) p1 -O-, -OCO-(CH2) p1 -、-OCOO-(CH2) p1 - and -(CH2) p1 -(ring-C6H8R) 01 R 02 )-(CH2) p1 Select from the group, where p1 is an integer from 1 to 36, preferably an integer from 1 to 12, R 01 and R 02 Each of the above can independently represent H or an alkyl group having 1 to 12 carbon atoms; and

[0352] The second compound is:

[0353]

[0354] (BMI-689, from Designer Molecules Inc.); and

[0355] The third compound is:

[0356]

[0357] (Polyphenylmethane-bismaleimide, Homide 122, provided by HOS-technik).

[0358] Preferably, the polymerizable compound of formula (I) is selected from:

[0359]

[0360] in

[0361] n is an integer from 1 to 60, preferably an integer from 1 to 36, and more preferably an integer from 6 to 12;

[0362] m is an integer from 2 to 60, preferably an integer from 2 to 50, more preferably an integer from 2 to 30, and most preferably an integer from 3 to 20.

[0363] A more preferred polymerizable compound of formula (I) is:

[0364]

[0365] Preferably, the ratio of the second compound to the third compound in the polymerizable mixture is from 10:1 to 1:10. More preferably, the ratio of the second compound to the third compound is from 1:1 to 1:4.

[0366] Based on the total weight of the polymerizable mixture, the polymerizable mixture described herein preferably contains 5 to 95% by weight of a polymerizable compound, more preferably 30 to 50% by weight of a polymerizable compound.

[0367] Based on the total weight of the polymerizable mixture, the polymerizable mixture described herein preferably contains 0.1 to 50% by weight, more preferably 0.5 to 5% by weight of the second compound.

[0368] Based on the total weight of the mixture, the polymerizable mixture described herein preferably contains 0.1 to 50% by weight, more preferably 0.5 to 10% by weight, of a third compound.

[0369] The polymerizable mixtures described herein may also contain a curing agent. Alternatively, the polymerizable mixtures described herein may also contain a solvent, such as an organic solvent. The polymerizable mixtures of the present invention may be free of any curing agent and / or organic / inorganic solvents.

[0370] -Methods for forming copolymers

[0371] The method for forming copolymers includes the following steps:

[0372] (i) Provide the polymerizable mixtures described herein; and

[0373] (ii) The polymerizable mixture is polymerized to obtain a copolymer.

[0374] The polymerizable mixture comprises the polymerizable compound, the second compound, and the third compound as described above. Preferably, based on the total weight of the polymerizable monomers / compounds, the total content of the polymerizable compound in the polymerizable mixture is 5 to 95% by weight, more preferably 80 to 99% by weight, and most preferably 90 to 95% by weight. Preferably, based on the total weight of the polymerizable monomers / compounds, the total content of the second compound in the polymerizable mixture is 0.1 to 50% by weight, more preferably 0.5 to 10% by weight, and most preferably 0.5 to 5% by weight. Preferably, based on the total weight of the polymerizable monomers / compounds, the total content of the third compound in the polymerizable mixture is 0.1 to 50% by weight, more preferably 0.5 to 30% by weight, and most preferably 0.5 to 10% by weight.

[0375] Preferably, the polymerizable mixture provided in step (i) is substantially solvent-free. "Substantially solvent-free" means that, based on the total weight of the polymerizable monomers / compounds, the total residual solvent content in the polymerizable starting material does not exceed 10% by weight, preferably not more than 5% by weight, and more preferably not more than 1% by weight. Alternatively, preferably, based on the total weight of the polymerizable monomers / compounds, the polymerizable mixture provided in step (i) preferably contains one or more solvents in an amount exceeding 10% by weight, more preferably exceeding 25% by weight, and most preferably exceeding 50% by weight.

[0376] Preferably, in step (ii), the polymerizable mixture is polymerized by a free radical or ionic chain polymerization reaction or an addition polymerization reaction. Preferred addition polymerization reactions are cycloaddition reactions, such as 2+2 cycloaddition reactions, 4+2 cycloaddition reactions, or 1,3-dipolar cycloaddition reactions, or nucleophilic addition reactions, such as the Michael reaction.

[0377] The above-mentioned reaction types and related reaction conditions (such as catalyst, solvent, temperature, time, concentration, etc.) are well known to those skilled in the art.

[0378] For example, free radical polymerization or ionic polymerization can be carried out in the presence of free radical or ionic polymerization initiators, which can be activated thermally and / or photochemically. Those skilled in the art are familiar with suitable free radical and ionic polymerization initiators. For example, cycloaddition reactions can be carried out under photochemical conditions or in the presence of Lewis acids. Those skilled in the art are familiar with suitable photochemical conditions and suitable Lewis acids.

[0379] Preferably, the polymerizable mixture provided in step (i) further comprises one or more free radical initiators. Preferred free radical initiators are thermally activated free radical initiators and / or photochemically activated free radical initiators.

[0380] Preferred thermally activated free radical initiators are: tert-amyl peroxybenzoate, 4,4-azobis(4-cyanopentanoic acid), 1,1'-azobis(cyclohexanecarboxynitrile), 2,2'-azobisisobutyronitrile (AIBN), benzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3 - Hexyne, bis(1-(tert-butylperoxy)-1-methylethyl)benzene, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroperoxide, tert-butyl peracetic acid, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, cumene hydroperoxide (CHP), cyclohexanone peroxide, dicumene peroxide (DCP), lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, and potassium persulfate.

[0381] Preferred photochemically activated free radical initiators are: acetophenone, 4,4′-dimethoxybenzoin (p-anisil), benzoin (benzil), benzoin, benzophenone, 2-benzoylbenzoic acid, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(dimethylamino)benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin ethyl ether, 4-benzoylbenzoic acid, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, methyl 2-benzoylbenzoate, 2-(1,3-benzodioxane-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-benzyl-2-(dimethylamino)-4'-morpholinyl phenylbutanone, (±) - Camphorquinone, 2-chlorothioxanone, 4,4'-dichlorobenzophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,4-diethylthioxanone-9-one, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 1,4-dibenzoylbenzene, 2-ethylanthraquinone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methylphenylacetone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-isopropylthioxanone, lithium phenyl(2,4,6-trimethylbenzoyl)phosphine hypophosphite, 2-methyl-4'-(methylthio)-2-morpholinylphenylacetone, 2-isonitrosophenylacetone, 2-phenyl-2-(p-toluenesulfonyloxy)acetophenone, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide. Typically, these initiators are free radical polymerization initiators that can be activated by photochemical methods.

[0382] Other preferred photochemically activated free radical initiators are:

[0383] , , , , , , , ,and .

[0384] Preferably, the initiator for free radical polymerization is thermally activated by exposure to heat, or photochemically activated by exposure to radiation such as ultraviolet and / or visible light.

[0385] Exposure to heat refers to exposure to higher temperatures, preferably in the range of 40 to 200°C, and more preferably in the range of 50 to 180°C.

[0386] Exposure to radiation includes exposure to visible light and / or ultraviolet light. Preferably, visible light is electromagnetic radiation with wavelengths greater than 380 to 780 nm, more preferably greater than 380 to 500 nm. Preferably, ultraviolet light is electromagnetic radiation with wavelengths ≤ 380 nm, more preferably with wavelengths of 100 to 380 nm. More preferably, ultraviolet light is selected from UV-A light with wavelengths of 315 to 380 nm, UV-B light with wavelengths of 280 to 315 nm, and UV-C light with wavelengths of 100 to 280 nm.

[0387] For ultraviolet light sources, mercury vapor lamps or ultraviolet lasers can be selected; for infrared light sources, ceramic emitters or infrared laser diodes can be selected; and for visible light, laser diodes can be selected.

[0388] Preferred ultraviolet light sources are those with the following characteristics: a) single-wavelength radiation with a maximum wavelength less than 255 nm, such as mercury low-pressure discharge lamps at 254 nm and 185 nm, ArF excimer lasers at 193 nm, and Xe2 layers at 172 nm; or b) broad-wavelength distributed radiation with wavelength components less than 255 nm, such as undoped mercury low-pressure discharge lamps.

[0389] In a preferred embodiment of the invention, the light source is a xenon flash lamp. Preferably, the xenon flash lamp has a broad emission spectrum, with its short wavelength component as low as about 200 nm.

[0390] Preferably, the polymerization reaction in step (ii) is carried out within a time range of up to 5 hours, more preferably up to 1 hour, and most preferably up to 0.5 hours.

[0391] More preferably, the polymerization reaction of the polymerizable mixture in step (ii) is carried out at a higher temperature, preferably in the temperature range of 25 to 200°C, and more preferably in the temperature range of 25 to 150°C.

[0392] A copolymer is also provided, which can be obtained by the method according to the invention described above for forming the copolymer, or obtained by the method described above. The copolymer is preferably a linear copolymer or a crosslinked copolymer, more preferably a linear copolymer.

[0393] In addition, a copolymer is provided comprising at least one repeating unit derived from a polymerizable compound, at least one repeating unit derived from a second compound, and at least one repeating unit derived from a third compound, as defined above.

[0394] Preferably, the molecular weight Mw (determined by GPC) of the copolymer according to the invention is at least 2,000 g / mol, more preferably at least 4,000 g / mol, and even more preferably at least 5,000 g / mol. Preferably, the molecular weight Mw of the copolymer is less than 50,000 g / mol. More preferably, the molecular weight Mw of the copolymer is in the range of 5,000 to 20,000 g / mol.

[0395] Furthermore, an electronic device comprising the copolymer according to the invention is also provided. For the electronic device, it is preferable that the copolymer forms a dielectric layer, more preferably a dielectric layer forming part of a redistribution layer. This dielectric layer serves to electrically isolate one or more electronic components that are part of the electronic device from each other.

[0396] Finally, a method for fabricating a packaged microelectronic structure is provided, wherein a dielectric layer is provided on a substrate, and the method includes the following steps:

[0397] (1) Applying the polymerizable mixture according to the invention to a substrate surface; and

[0398] (2) The polymerizable mixture is cured to form a dielectric layer.

[0399] Preferably, the polymerizable mixture applied in step (1) is substantially solvent-free. "Substantially solvent-free" means that, based on the total weight of the polymerizable monomers / compounds, the total residual solvent content in the polymerizable mixture does not exceed 10% by weight, preferably not more than 5% by weight, and more preferably not more than 1% by weight.

[0400] However, depending on the application method used in step (1) to apply the polymerizable mixture, the polymerizable mixture preferably contains one or more solvents in an amount preferably greater than 10% by weight, more preferably greater than 25% by weight, and most preferably greater than 50% by weight, based on the total weight of the polymerizable monomers / compounds.

[0401] There are no particular limitations on the method of applying the polymerizable mixture in step (1). Preferred methods of application in step (1) include dispensing, dip coating, screen printing, stencil printing, roll coating, spraying, slot coating, spin coating, stereolithography, gravure printing, flexographic printing, or inkjet printing.

[0402] The polymerizable mixtures of the present invention can be provided in the form of formulations suitable for gravure printing, flexographic printing, and / or inkjet printing. In preparing such formulations, ink-based formulations known in the art can be used.

[0403] Alternatively, the polymerizable mixtures of the present invention can be provided in the form of formulations suitable for photolithography processes. Photolithography processes utilize light to transfer geometric patterns from a photomask onto a photocurable composition, thereby forming a photo-pattern. Typically, such photocurable compositions contain a photochemically activated free radical polymerization initiator. When preparing such formulations, photoresist-based formulations known in the art can be used.

[0404] The preferred average thickness of the polymerizable mixture layer applied in step (1) is 1 to 50 µm, more preferably 2 to 30 µm, and most preferably 3 to 15 µm.

[0405] Preferably, the curing reaction in step (2) is carried out by free radical or ionic chain polymerization or addition polymerization. Preferred addition polymerization reactions are cycloaddition reactions, such as 2+2 cycloaddition, 4+2 cycloaddition (Diesel-Alder reaction), or 1,3-dipolar cycloaddition, or nucleophilic addition reactions, such as the Michael reaction. Preferred curing conditions correspond to the preferred polymerization conditions given above regarding the copolymer formation method.

[0406] Preferably, the polymerizable mixture applied in step (1) further comprises one or more free radical initiators. Preferred free radical initiators are as described above.

[0407] In addition, a microelectronic device is provided, which includes an encapsulated microelectronic structure prepared according to the above-described manufacturing method.

[0408] The present invention is further illustrated below by way of examples, but these examples should not be construed as limiting the invention. Those skilled in the art will understand that various modifications, additions, and alterations can be made to the invention without departing from the spirit and scope of the invention as defined by the appended claims.

[0409] Example

[0410] Synthesis Examples Synthesis of the first polymerizable composition 1

[0411]

[0412] As described in WO2019 / 141833A1, dianhydride (10 g, 0.015 mol) was dissolved in a mixture of NMP / toluene (0.1 L, 1 / 1, v / v), followed by the addition of Priamine (16.5 g, 0.03 mol). The reaction mixture was refluxed for 12 hours using a Dean-Stark apparatus. The reaction mixture was cooled to room temperature, and maleic anhydride (3.7 g, 0.04 mol) was slowly added. The mixture was again refluxed for 12 hours using a Dean-Stark apparatus. After the mixture cooled to room temperature, 50 mL of toluene was added. Finally, the mixture was added dropwise to methanol (0.2 L) to precipitate the oligomers. After removing the solvent, the crude product was washed twice with methanol and dried under vacuum to give 20 g (71%) of a brown, waxy resin. Finally, the compound represented by formula (I) was obtained.

[0413] Refer to Example 1: Polymerizable composition 1 with BMI26 and Irgacure OXE 02

[0414]

[0415] Polymerizable Composition 1

[0416] (BMI 26)

[0417] A formulation consisting of 43% polymerizable composition 1, 4.3% BMI-26, 2.15% OXE02, and the remainder being CPN, was subjected to a reaction at 10 J / cm². 2 Mercury arc curing, development in CPN, and hard baking at 230°C for 1 hour under nitrogen atmosphere resulted in an E modulus of approximately 1600 MPa, a Tg of 72.2 °C, and αCTE < 100 ppm / K in the ranges of 80–150 and 150–200. -1 After being cured by i-line, it exhibits poor thermomechanical properties.

[0418] Refer to Example 2: Polymerizable composition 1 with BMI26 and Irgacure OXE 02

[0419] Apply 1J / cm 2 Using i-line exposure and the same development method described in Example 1, the resulting E modulus was approximately 1100 MPa and Tg was 63.5 °C. Compared to UV curing, the quality and film retention of the i-line cured film were significantly worse.

[0420] Working Example 1: Polymerizable composition 1 with a polymerizable mixture of Homide 122 and BMI-689

[0421]

[0422] Polymerizable Composition 1

[0423] BMI-689

[0424] Homide 122 (polyphenylene-bismaleimide)

[0425] Formula WE1 was prepared, which consisted of BMI-689 and Homide 122 in a 1:1 ratio used at 5% solid content and 95% by weight of polymerizable composition 1.

[0426] The E modulus and Tg can be increased to approximately 1700 MPa and 69.9 °C, respectively.

[0427] Working Example 2: Polymerizable composition 1 with a polymerizable mixture of Homide 122 and BMI-689

[0428] Formula WE2 was prepared, which consisted of BMI-689 and Homide 122 used in a 1:4 ratio at 5% solid content and 95% by weight of polymerizable composition 1.

[0429] The E modulus and Tg can be further improved to approximately 1900 MPa, with a Tg of 73.9, and improved linearity of CTE (coefficient of thermal expansion) is achieved after Tg.

[0430] Working Example 3: Polymerizable composition 1 with a polymerizable mixture of Homide 122 and BMI-689

[0431] Formula WE3 was prepared, which consisted of BMI-689 and Homide 122 used in a 1:1 ratio at 10% solid content and 95% by weight of polymerizable composition 1.

[0432] Increasing the solid content of BMI689 and Homide 122 crosslinking agents from 5% by weight (Example 1) to 10% by weight (Example 3) had a significant impact on Tg, increasing it to 83.1°C. An E modulus of approximately 1800 MPa was also obtained.

Claims

1. A polymerizable mixture comprising a polymerizable compound, a second compound, and a third compound, wherein the polymerizable compound is a compound represented by formula (1). P 1 -Sp 1 -(MG-Sp 1 ) m -P 1 Formula (1) in: m is an integer from 1 to 60; P 1 express V 1 and V 2 Independent of each other, they are H, alkyl groups having 1 to 6 carbon atoms, F, Cl, or CN; Sp 1 Each occurrence represents a spacer group; MG is a rod-shaped liquid crystal building block, preferably selected from formula (2): -(A 21 -Z 21 ) k -A 22 -(Z 22 -A 23 ) l -Formula (2) in: A 21 To A 23 Each group is independent of the others, and each time they appear independently of each other, they are aryl, heteroaryl, heterocyclic, alicyclic or cyclic imide groups, which are optionally substituted with one or more of the same or different groups L; Z 21 and Z 22 The following are independent of each other, and each occurrence is independent of the others: -O-, -S-, -CO-, -COO-, -OCO-, -S-CO-, -CO-S-, -O-COO-, -CO-NR 01 -、-NR 01 -CO-、-NR 01 -CO-NR 02 -NR 01 -CO-O-、-O-CO-NR 01 -, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -CH2CH2-, -(CH2)4-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=CH-, -N=N-, -CH=CR 01 -、-CY 01 =CY 02 -, CH=CH-COO-, -OCO-CH=CH-, or single bonds; R 01 and R 02 Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms; L is F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR xx R yy -C(=O)OR xx -C(=O)R xx -NR xx R yy -OH, -SF5, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may optionally be replaced by F or Cl, -CN, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 6 carbon atoms; R xx and R yy Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms; Y 01 and Y 02 Each can be represented independently of H, alkyl, aryl, F, Cl, or CN having 1 to 12 carbon atoms; k and l are independently 0, 1, 2, 3, or 4; and The second compound is a bifunctional or polyfunctional compound; the third compound is a polyfunctional compound, and The second and third compounds can react with the polymerizable compound to form a copolymer.

2. The polymerizable mixture according to claim 1, wherein the spacer group Sp 1 Selected from formula Sp'-X', such that the group "P 1 -Sp 1 -" corresponds to the formula "P" 1 -Sp'-X'-", where: Sp' means: (a) A straight-chain or branched alkylene group having 1 to 40 carbon atoms, optionally monosubstituted or polysubstituted with F, Cl, Br, I or CN, wherein one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, or -NR. 01 -、SiR 01 R 02 -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR 01 -CO-O-、-O-CO-NR 01 -、-NR 01 -CO-NR 01 -, -CH=CH- or -C≡C- substitution, so that O and / or S atoms are not directly connected to each other; (b) -Sp x -G-Sp y -, where Sp x and Sp y Each of the above can independently represent an alkylene group or a single bond having 1 to 20 carbon atoms; G represents a cycloalkylene group having 3 to 20 carbon atoms, which may optionally be mono- or poly-substituted with an alkyl group having 1 to 20 carbon atoms. X' represents -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR 01 -、-NR 01 -CO-、-NR 01 -CO-NR 01 -, -OCH2, CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, -N=C-, -N=N-, -CH=CR 01 -、-CY 01 =CY 02 -、-C≡C-、-CH=CH-COO-、-OCO-CH=CH- or single bonds; R 01 and R 01 Each can be used independently to represent hydrogen or an alkyl group having 1 to 12 carbon atoms; Y 01 and Y 02 Each can be represented independently as H, F, Cl, or CN.

3. The polymerizable mixture according to claim 1 or 2, wherein the spacer group Sp is selected from the following list: -(CH2) p1 -、-(CH2CH2O) q1 -CH2CH2-, -CH2CH2-S-CH2CH2-, -CH2CH2-NH-CH2CH2-, -(SiR 01 R 02 -O) p1 -、-(CH2) p1 -(ring-C6H8R) 01 R 02 )-(CH2) p1 - and ,in: p1 is an integer from 1 to 60; q1 is an integer from 1 to 12; and R 01 and R 02 Each can be represented independently by H or an alkyl group having 1 to 12 carbon atoms.

4. The polymerizable mixture according to any one of claims 1 to 3, wherein A 21 To A 23 They are independent of each other, and each time they appear, they are independently aryl, cyclic imide, or alicyclic groups; Z 21 and Z 22 They are independent of each other, and each time they appear, they are independently either -COO- or -OCO-; and Sp represents -(CH2) p1 -(ring-C6H8R) 01 R 02 )-(CH2) p1 - where p1 is an integer from 1 to 12, R 01 and R 02 Each can be represented independently by H or an alkyl group having 1 to 12 carbon atoms.

5. The polymerizable mixture according to any one of claims 1 to 4, wherein the polymerizable compound is selected from... ， Preferably, the polymerizable compound is 。 6. The polymerizable mixture according to any one of claims 1 to 5, wherein the second compound comprises two or more polymerizable groups (P... 2 The group selected from groups containing C=C double bonds, preferably those with P 1 It can undergo free radical or ionic chain polymerization or 2+2 cycloaddition reaction; it contains groups with two conjugated C=C double bonds, preferably with P 1 Performs a 4+3 cycloaddition reaction; nucleophilic group, preferably with P 1 Nucleophilic addition reaction; and 1,3-dipolar group, preferably with P 1 It undergoes a 1,3-dipolar cycloaddition reaction.

7. The polymerizable mixture according to any one of claims 1 to 6, wherein the third compound comprises three or more polymerizable groups (P... 3 The group selected from groups containing C=C double bonds, preferably those with P 1 It can undergo free radical or ionic chain polymerization or 2+2 cycloaddition reaction; it contains groups with two conjugated C=C double bonds, preferably with P 1 Performs a 4+3 cycloaddition reaction; nucleophilic group, preferably with P 1 Nucleophilic addition reaction; and 1,3-dipolar group, preferably with P 1 It undergoes a 1,3-dipolar cycloaddition reaction.

8. The polymerizable mixture according to any one of claims 1 to 7, wherein the polymerizable group P 1 P 2 and P 3 Each of them stated: ； Where V 1 and V 2 Independently, they are H, alkyl groups having 1 to 6 carbon atoms, F, Cl, or CN; preferably H or alkyl groups having 1 to 6 carbon atoms.

9. The polymerizable mixture according to any one of claims 1 to 8, wherein the second compound is represented by formula (3), Equation (3) Where X a express (c) A straight-chain or branched alkylene group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, optionally monosubstituted or polysubstituted with F, Cl, Br, I or CN, wherein one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, NR-. 01 -、-SiR 01 R 02 -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S, -NR 01 -CO-O-、-O-CO-NR 01 -、-NR 01 -CO-NR 01 -, -CH=CH- or -C≡C- substitution, so that O and / or S atoms are not directly connected to each other; or (d) -R a -R b -R c -, where R a and R c Each can be independently represented as an alkylene group or a single bond having 1 to 20 carbon atoms; R b This indicates a cycloalkylene group having 3 to 20 carbon atoms, optionally mono- or poly-substituted with an alkyl group having 1 to 20 carbon atoms; and wherein... The third compound is represented by formula (4): Equation (4) Where Y a Indicates -(A 31 -Z 31 ) m1 -(Z 32 -A 32 ) m2 -(Z 33 -A 33 ) m3 -, in: A 31 and A 33 They are independent of each other, and each time they appear independently of each other, they are aryl or heteroaryl, which are optionally substituted with one or more of the same or different groups L; L is F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR xx R yy -C(=O)OR xx -C(=O)R xx -NR xx R yy -OH, -SF5, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may optionally be replaced by F or Cl, -CN, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 6 carbon atoms; R xx and R yy Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms; A 32 It is an aryl group, substituted with a maleimide moiety. Z 31 To Z 33 They are independent of each other, and each time they appear, they are independently -O-, -CO-, -COO-, -OCO-, -CH2, -(CH2)2-, -(CH2)2- or a single bond; m 1 and m 3 Each is independently 0, 1, 2, 3, or 4; and m 2 It can be 0, 1, 2, 3, 4, 5, 6 or 7.

10. The polymerizable mixture according to any one of claims 1 to 9, wherein the second compound is: 。 11. The polymerizable mixture according to any one of claims 1 to 10, wherein the third compound is: 。 12. The polymerizable mixture according to any one of claims 1 to 8, wherein the second compound is represented by formula (5), Equation (5) Where X b Indicates -(A 41 -Z 41 ) m1 -(A 42 ) m2 -(Z 42 -A 43 ) m3 -, in: A 41 To A 43 They are independent of each other, and each time they appear independently of each other, they are aryl or heteroaryl, which are optionally substituted with one or more of the same or different groups L; L is F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=O)NR xx R yy -C(=O)OR xx -C(=O)R xx -NR xx R yy -OH, -SF5, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 20 carbon atoms, wherein one or more hydrogen atoms may optionally be replaced by F or Cl, -CN, or a straight-chain or branched alkyl, alkoxy, alkyl carbonyl, alkoxy carbonyl, alkyl carbonyloxy, or alkoxy carbonyloxy having 1 to 6 carbon atoms; R xx and R yy Each can be represented independently as H or an alkyl group having 1 to 12 carbon atoms; Z 41 and Z 42 They are independent of each other, and each time they appear, they are independently -O-, -CO-, -COO-, -OCO-, -CH2, (CH2)2-, -(CH2)2- or a single bond; m 1 It can be 1, 2, 3, 4, 5, 6, or 7; m 2 and m 3 Each of the following is independently 0, 1, 2, 3, or 4; and wherein the third compound is represented by formula (6): Equation (6) Where Y b express A straight-chain or branched alkylene group having 1 to 40 carbon atoms, preferably 1 to 30 carbon atoms, which is partially mono- or poly-substituted with bismaleimide and optionally further mono- or poly-substituted with F, Cl, Br, I or CN. Furthermore, one or more non-adjacent CH2 groups may be independently substituted with -O-, -S-, -NH-, or NR. 01 -、-SiR 01 R 02 -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -NR 01 -CO-O-、-O-CO-NR 01 -、-NR 01 -CO-NR 01 -, -CH=CH- or -C≡C- substitutions prevent O and / or S atoms from being directly connected to each other.

13. The polymerizable mixture according to any one of claims 1 to 8 and 12, wherein the second compound is: ； And the third compound is: 。 14. The polymerizable mixture according to any one of claims 1 to 13, wherein the ratio of the second compound to the third compound is 10:1 to 1:10, preferably 1:1 to 1:

4.

15. The polymerizable mixture according to any one of claims 1 to 14, wherein the content of the polymerizable compound is 5 to 95% by weight, preferably 30 to 50% by weight, based on the total weight of the mixture.

16. The polymerizable mixture according to any one of claims 1 to 15, wherein the content of the second compound is 0.1 to 50% by weight, preferably 0.5 to 5% by weight, based on the total weight of the mixture.

17. The polymerizable mixture according to any one of claims 1 to 16, wherein the content of the third compound is 0.1 to 50% by weight, preferably 0.5 to 10% by weight, based on the total weight of the mixture.

18. The polymerizable mixture according to any one of claims 1 to 17, wherein the mixture further comprises a curing agent.

19. The polymerizable mixture according to any one of claims 1 to 18, wherein the mixture further comprises a solvent, particularly an organic solvent.

20. A method for forming a dielectric polymer material, comprising the following steps: a. Providing a polymerizable mixture according to any one of claims 1 to 19; and b. Cure the polymerizable mixture.

21. A dielectric polymer material obtainable by the method of claim 20.

22. An electronic device comprising the dielectric polymer material of claim 21.

23. The electronic device of claim 22, wherein the electronic device is a microelectronic device, and the dielectric polymer material is included as a repassivation material in the redistribution layer of the microelectronic device.

Images