A photocurable high temperature resistant low dielectric material and its preparation method

Abstract

The present invention discloses a photocurable high-temperature resistant low-dielectric material and a preparation method thereof, and relates to the technical field of dielectric materials. The raw materials of the photocurable high-temperature resistant low-dielectric material include 100 parts of a high-temperature resistant photosensitive resin, 10 to 30 parts of polyvinylcarbazole-modified POSS, 1 to 3 parts of a photoinitiator, and 0.1 to 0.5 parts of a light stabilizer. Due to the synergistic effect of the various materials of the photocurable high-temperature resistant low-dielectric material of the present invention, the coating has good mechanical properties and good adhesion after curing, and the dielectric constant is lower than 2.25. It can withstand high temperatures of up to 350°C and can be used for a long time at a high temperature of 200°C. It can meet some occasions with high requirements for high temperature resistance and low dielectric, such as specific fields such as electronics and electrical, aerospace, and medical machinery.

Description

Technical Field

[0001] The present invention belongs to the technical field of dielectric materials, and in particular relates to a light-cured high-temperature-resistant low-dielectric material and a preparation method thereof. Background Art

[0002] With the development of industry and advancements in technology, the demand for coating materials is becoming increasingly important across various industries. Due to their environmentally friendly and efficient characteristics, light-curing coatings have gradually replaced traditional chemical reaction coatings and are now widely used in various fields. Light-curing materials are produced through photopolymerization, a process in which a free-flowing liquid is chemically polymerized and reacted to form a non-sticky solid by the addition reaction of light-curing monomers or copolymers under ultraviolet or visible light. In practical applications, their use is gaining increasing attention, particularly in high and low temperature environments.

[0003] Epoxy acrylate is synthesized from acrylic acid and epoxy resin. As a result, it combines the good adhesive properties of epoxy resin with the good weather resistance and excellent optical properties of acrylate, but its heat resistance is relatively poor. Silicone resin, on the other hand, is generally a thermosetting resin and exhibits excellent heat resistance, weather resistance, electrical insulation, and weather resistance. However, it also has some disadvantages, such as requiring high temperatures (150-200°C) for curing and a long curing time, which hinders its use over large areas. Silicone resin also has poor adhesion and is easily corroded by organic solvents. Its physical properties at high temperatures are poor, and it is relatively expensive. Ordinary epoxy acrylates have properties that complement these. Therefore, to achieve a high-performance resin, silicone resin and ordinary epoxy acrylates can be combined to form a silicone-modified resin, which fully utilizes the advantages of both and compensates for their shortcomings. Such high-performance and widely applicable resins are of great significance to the development of the organic polymer industry.

[0004] Low dielectric constant materials, or low-k materials (low-k materials), are a hot topic of research in the current semiconductor industry. By reducing the dielectric constant k of the dielectric materials used in integrated circuits, the integrated capacitance between devices and wires can be reduced, and the circuit operation speed can be improved. In recent years, with the increasing speed of aircraft, the new generation of antenna wave-transmitting technology has developed rapidly. Not only are the temperature resistance and dielectric properties of the material system increasingly demanding, but the ability to efficiently transmit electromagnetic waves at high frequencies and ultra-widebands has rapidly increased the integration of integrated circuits. The operating frequency range of RF connectors, microwave devices, etc. has also been greatly improved. In order to reduce the resulting impedance delay and power loss, high-temperature resistant low-dielectric constant materials are needed to protect various electronic components, thereby reducing impedance delay and meeting the needs of integrated circuit development.

[0005] Therefore, this puts forward technical requirements for the material system such as easy operation, low dielectric constant, low dielectric loss and high temperature resistance. Summary of the Invention

[0006] In order to solve the problems of poor high-temperature resistance, high dielectric constant and unstable long-term mechanical properties of existing photocurable coating materials, the present invention discloses a photocurable high-temperature resistant low-dielectric material and a preparation method thereof. The prepared photocurable coating has good mechanical properties, good adhesion, low dielectric constant and excellent high-temperature resistance, can withstand high temperatures of up to 350°C and can be used for a long time at high temperatures of 200°C.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a light-curable high-temperature resistant low-dielectric material, the raw materials for preparing the light-curable material include:

[0009]

[0010] Polyphenylene silsileoxane (POSS) used in the present invention is a kind of hollow nanoparticle with nanostructure, high specific surface area, belongs to nanometer-scale silicon dioxide / siloxane hybrid, molecule is cage-type structure, molecular size is generally 1~3nm, forms inorganic framework core by Si-O, and periphery is surrounded by organic group.This compound has excellent reactivity, heat resistance and flame retardancy, porosity and nanometer size effect.The nanoparticle with hollow structure is introduced into polymer, and ensures its good dispersion in composite material, can form nanopore structure and can effectively reduce the dielectric constant of material.The polyvinyl carbazole (PVK) selected for use in the present invention is formed by monomer N-vinyl carbazole (having good high temperature resistance) self-polymerization, is aromatic structure nitrogen-containing heterocyclic polymer, band π electron system side chain non-conjugated polymer, molecular weight cross-linking increases, has more than monomer molecule high temperature resistance, by polyvinyl carbazole physical winding POSS, not only reduces POSS agglomeration probability, simultaneously two high temperature resistant materials are organically combined, reach 1+1>2 high temperature resistance and improve. At the same time, the molecular structure has a vinyl structure, which can be well mixed and dispersed with high-temperature resistant photosensitive resin. After photopolymerization, polyvinylcarbazole-modified POSS can provide better cohesive strength for the cured coating, further improving the coating's high-temperature resistance and low dielectric constant.

[0011] In the present invention, the mass fraction of the high temperature resistant photosensitive resin is 100 parts, and correspondingly, the mass fraction of the polyvinylcarbazole-modified POSS is 10 to 30 parts, for example, it can be 10 parts, 12 parts, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 28 parts or 30 parts, etc.

[0012] The mass fraction of the photoinitiator is 1 to 3 parts, for example, it can be 1 part, 1.2 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.8 parts or 3 parts.

[0013] The mass fraction of the light stabilizer is 0.1 to 0.5 parts, for example, 0.1 parts, 0.15 parts, 0.2 parts, 0.25 parts, 0.3 parts, 0.35 parts, 0.4 parts, 0.45 parts or 0.5 parts.

[0014] As a preferred technical solution of the present invention, the raw materials of the high-temperature resistant photosensitive resin include: organosilicon-modified epoxy acrylate resin and acrylate monomer diluent.

[0015] The acrylate-modified silicone resin contained in the present invention has the advantages of both silicone resin and acrylic resin. The Si-O bond energy (450 kJ / mol) in the silicone polymer is much greater than the C-C bond energy (345 kJ / mol). It has the advantages of good thermal stability, oxidation resistance, weather resistance and low-temperature properties. Using it to modify epoxy acrylic resin can reduce internal stress, thereby lowering the dielectric constant of the resin, and increasing toughness and high-temperature resistance, which is superior to single acrylic resin.

[0016] Preferably, the mass ratio of the silicone-modified epoxy acrylate resin to the acrylate monomer diluent is 1:(0.2-1), for example, it can be 1:0.2, 1:0.4, 1:0.5, 1:0.6, 1:0.8 or 1:1.

[0017] For example, the weight portion of the organosilicon-modified epoxy acrylate resin is 50 to 80 parts, and the weight portion of the acrylate monomer diluent can be 20 to 50 parts.

[0018] Preferably, the acrylic acid ester monomer diluent includes acrylamide morpholine and tricyclodecane dimethanol diacrylate.

[0019] The resin is mixed with acrylamide morpholine and tricyclodecane dimethanol diacrylate. The nitrogen free radicals in the molecular structure can inhibit the occurrence of oxygen inhibition, increase the polymerization rate, and achieve full curing, thereby avoiding poor adhesion and high-temperature resistance of the coating caused by insufficient curing. The resulting material has moderate viscosity, good fluidity, fast curing speed, and small curing volume shrinkage. The diluent contains a nitrogen-containing heterocyclic structure, which can further improve the high-temperature resistance of the light-curing material.

[0020] Preferably, the mass ratio of acrylamide morpholine and tricyclodecane dimethanol diacrylate is (1-3):1, for example, it can be 1:1, 1.2:1, 1.5:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1 or 3:1.

[0021] As a preferred technical solution of the present invention, the raw materials for preparing the polyvinylcarbazole-modified POSS include polyvinylcarbazole with a molecular weight of 3500-4500 (for example, 3500, 3600, 3800, 3900, 4000, 4200, 4300 or 4500, etc.) and POSS.

[0022] Preferably, the mass ratio of polyvinylcarbazole to POSS is 1:(5-10), for example, it can be 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10.

[0023] Preferably, the photoinitiator includes a free radical photoinitiator and a cationic photoinitiator.

[0024] The present invention discloses a light-curable, high-temperature-resistant, low-dielectric material. The photoinitiator selected is a combination of a free radical photoinitiator and a cationic photoinitiator, and the usage ratio of the free radical photoinitiator to the cationic photoinitiator is limited. The siloxane with double bonds contained in the molecular chain of the matrix resin can be decomposed to form a large number of silane free radicals under the action of the cationic photoinitiator. The reaction rate of the generated macromolecular free radicals with the acrylate monomer can be increased by 1 to 2 orders of magnitude, and an interpenetrating network structure is formed upon curing, thereby greatly improving the high-temperature resistance of the cured coating.

[0025] Preferably, the mass ratio of the free radical photoinitiator to the cationic photoinitiator is 5:(1-3), for example, it can be 5:1, 5:1.2, 5:1.4, 5:1.5, 5:1.6, 5:1.8, 5:2, 5:2.4, 5:2.5, 5:2.8 or 5:3.

[0026] Preferably, the free radical photoinitiator includes one or more of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, methyl benzoylformate, isooctyl p-N,N-dimethylaminobenzoate, monoacylphosphine oxide, and bisacylphosphine oxide;

[0027] Preferably, the cationic photoinitiator is any one of diaryliodonium salts, triarylsulfonium salts, arylferrocenium salts, and aryldiazonium salts, or a combination of two or more thereof.

[0028] As a preferred technical solution of the present invention, the light stabilizer is any one or a combination of two or more of an amino-containing hindered amine light stabilizer (preferably BASF Tinuvin 292), a triazole ultraviolet light absorber (preferably BASF TINUVIN 326), or a benzophenone ultraviolet light absorber (preferably BASF Chimassorb 81).

[0029] Preferably, the raw materials of the photocurable high temperature resistant low dielectric material also include 0.1 to 0.3 parts of a leveling agent, for example, 0.1 parts, 0.12 parts, 0.13 parts, 0.15 parts, 0.18 parts, 0.2 parts, 0.24 parts, 0.25 parts, 0.28 parts or 0.3 parts, etc.

[0030] Preferably, the leveling agent is a silicone leveling agent, preferably any one of BASF EFKA-3777, BYK-361N, BYK-300, and Merck MOK-2028, or a combination of two or more thereof.

[0031] Preferably, the raw materials of the photocurable high temperature resistant low dielectric material also include 0.3 to 0.5 parts of defoaming agent, for example, it can be 0.3 parts, 0.32 parts, 0.35 parts, 0.38 parts, 0.4 parts, 0.42 parts, 0.45 parts, 0.48 parts or 0.5 parts.

[0032] Preferably, the defoaming agent is any one of BYK-052, BYK-1797 or BYK-A530, or a combination of two or more thereof.

[0033] As a preferred technical solution of the present invention, the organosilicon-modified epoxy acrylate resin is prepared by the following method:

[0034] Mixing the formulated amounts of bisphenol A epoxy acrylate, xylene, silane, dibutyltin dilaurate and p-hydroxyanisole;

[0035] The obtained mixture is then heated to react, and then distilled under reduced pressure to obtain an organosilicon-modified epoxy acrylate resin.

[0036] In the present invention, the organosilicon-modified epoxy acrylate resin can be prepared by the following method:

[0037] (1) Weighing bisphenol A epoxy acrylate, xylene, silane, dibutyltin dilaurate, and p-hydroxyanisole, respectively, and adding them into a reaction container, stirring and dissolving them to mix uniformly;

[0038] (2) Raising the temperature of the reaction system to 80-100° C. and reacting for 6-8 hours to obtain a yellow liquid, which is then subjected to reduced pressure distillation to obtain a viscous liquid, which is the silicone-modified epoxy acrylate resin.

[0039] As a preferred technical solution of the present invention, the molar ratio of bisphenol A epoxy acrylate to silane is (1.5-2):1, for example, it can be 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1 or 2:1.

[0040] Preferably, the silane is any one of vinyltriethoxysilane, vinyltributoxysilane, and 4-triethoxysilylvinylbenzocyclobutene.

[0041] Preferably, the mass ratio of bisphenol A epoxy acrylate, xylene, dibutyltin dilaurate and p-hydroxyanisole is 1:(2-6):(0.01-0.1):(0.001-0.01), preferably 1:5:0.01:0.001.

[0042] As a preferred technical solution of the present invention, the polyvinylcarbazole-modified POSS is prepared by the following method:

[0043] POSS is ultrasonically dispersed in toluene for 1.5 to 2 hours (for example, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours or 2.0 hours, etc.) to obtain a dispersion, polyvinyl carbazole is added to the dispersion containing POSS, and ultrasonic dispersion is continued for 3 to 5 hours (for example, 3 hours, 3.2 hours, 3.4 hours, 3.5 hours, 3.8 hours, 4 hours, 4.2 hours, 4.5 hours, 4.8 hours or 5 hours, etc.), centrifuged and then dried to obtain polyvinyl carbazole-modified POSS.

[0044] In a second aspect, the present invention provides a method for preparing the light-curable high-temperature resistant low-dielectric material as described in the first aspect, the preparation method comprising the following steps:

[0045] (1) Preparation of high temperature resistant photosensitive resin and polyvinylcarbazole modified POSS:

[0046] (2) mixing the high temperature resistant photosensitive resin and the polyvinylcarbazole-modified POSS according to the formula:

[0047] (3) The obtained mixture is mixed with a formulated amount of a light stabilizer, a photoinitiator, an optional leveling agent, and an optional defoaming agent, and the light is cured to obtain the light-cured high-temperature-resistant low-dielectric material.

[0048] As a preferred technical solution of the present invention, the preparation method comprises the following steps:

[0049] (1) Preparation of high temperature resistant photosensitive resin and polyvinylcarbazole modified POSS:

[0050] Adding organosilicon-modified epoxy acrylate resin and acrylate monomer diluent in parts by weight into a stirring kettle, controlling the temperature at 50-65° C., and stirring at a speed of 800-1000 r / min for 1-2 hours to obtain a high-temperature resistant photosensitive resin;

[0051] POSS was ultrasonically dispersed in toluene for 1.5 to 2 hours to obtain a dispersion, polyvinylcarbazole was added to the dispersion containing POSS, and ultrasonic dispersion was continued for 3 to 5 hours. The mixture was centrifuged and dried to obtain polyvinylcarbazole-modified POSS;

[0052] (2) mixing the high temperature resistant photosensitive resin and polyvinylcarbazole modified POSS:

[0053] The high temperature resistant photosensitive resin and the polyvinylcarbazole modified POSS are mixed at a stirring speed of 200 to 300 r / min, and then the stirring speed is adjusted to 1000 to 1200 r / min, the temperature is controlled at 50-65° C., and the stirring is continued for 3 to 5 hours;

[0054] (3) Adjust the stirring speed to 200-300 r / min, add light stabilizer, photoinitiator and optional leveling agent, control the temperature to 50-65°C, and adjust the stirring speed to 600-800 r / min to mix uniformly;

[0055] (4) adjusting the stirring speed to 200-300 r / min, lowering the temperature to room temperature, adding an optional defoaming agent, and stirring for 1-2 hours while evacuating the mixture to obtain a photocurable high-temperature resistant low-dielectric material composition; and then applying the obtained composition on a substrate, curing it under UV light to form a film, thereby obtaining a photocurable high-temperature resistant low-dielectric material.

[0056] As a preferred embodiment, the UV light curing film of the present invention is specifically performed as follows: using a UV mercury lamp for curing, controlling the irradiation distance and irradiation time, preferably using 40mW / cm 2 UV mercury lamp, irradiation distance 15 cm, irradiation time 10 to 600 seconds.

[0057] In a third aspect, the present invention further provides applications of the photocurable high-temperature resistant low-dielectric material as described in the first aspect in the fields of integrated circuits, electronics, aerospace, or medical machinery.

[0058] The numerical range described in the present invention includes not only the point values ​​listed above, but also any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0059] Compared with the prior art, the present invention has the following beneficial effects:

[0060] A kind of light-cured high temperature resistant low dielectric material of the present invention, selects POSS and high temperature resistant photosensitive resin modified by polyvinyl carbazole, the acrylate-modified organosilicon resin contained has the advantages of organosilicon resin and acrylic resin concurrently, by polyvinyl carbazole physical winding POSS, not only reduces POSS agglomeration probability, simultaneously two kinds of high temperature resistant materials are organically combined, reach 1+1>2 high temperature resistance performance improvement.Meanwhile, the POSS molecular structure modified by polyvinyl carbazole has vinyl structure, can be well mixed and dispersed with high temperature resistant photosensitive resin, after light polymerization, polyvinyl carbazole modifies POSS and can provide better cohesive strength for the coating formed by solidification, further promotes coating high temperature resistance and low dielectric constant. Therefore, the materials selected in the present invention work synergistically with each other, and the tensile strength of the cured material is higher than 43 MPa, with good mechanical properties and good adhesion. The dielectric constant of the cured coating is lower than 2.25, and can reach a minimum of 2.13. The dielectric loss tanδ is less than 0.010, and it can withstand high temperatures of up to 350°C and can be used for a long time at a high temperature of 200°C. It can meet some occasions with high requirements for high temperature resistance and low dielectric, such as application in specific fields such as electronics, aerospace, and medical machinery. DETAILED DESCRIPTION

[0061] The technical solution of the present invention is further illustrated below through specific implementation methods. However, the following examples are merely simplified examples of the present invention and do not represent or limit the scope of protection of the present invention. The scope of protection of the present invention shall be subject to the claims.

[0062] In the following examples, unless otherwise specified, all reagents and consumables used were purchased from conventional reagent manufacturers in the field; unless otherwise specified, all experimental methods and technical means used were conventional methods and means in the field.

[0063] Example 1

[0064] This embodiment provides a light-curable high-temperature resistant low-dielectric material, which is prepared from the following raw materials in parts by weight:

[0065]

[0066]

[0067] The preparation method comprises the following steps:

[0068] (1) Preparation of high temperature resistant photosensitive resin and polyvinylcarbazole modified POSS:

[0069] Weighing bisphenol A epoxy acrylate, xylene, vinyl triethoxysilane, dibutyltin dilaurate, and p-hydroxyanisole, respectively, and adding them to a reaction container, stirring and dissolving to mix uniformly; wherein the molar ratio of bisphenol A epoxy acrylate to vinyl triethoxysilane is 1.5:1, and the mass ratio of bisphenol A epoxy acrylate, xylene, dibutyltin dilaurate, and p-hydroxyanisole is 1:5:0.01:0.001; raising the temperature of the reaction system to 90° C., reacting for 7 hours to obtain a yellow liquid, and subjecting the obtained yellow liquid to reduced pressure distillation to obtain a viscous liquid, which is a silicone-modified epoxy acrylate resin;

[0070] Adding organosilicon-modified epoxy acrylate resin and acrylate monomer diluent in parts by weight into a stirring kettle, controlling the temperature to 50° C., and stirring at a speed of 800 r / min for 1.5 hours to obtain a high-temperature resistant photosensitive resin;

[0071] POSS was ultrasonically dispersed in toluene for 2 h to obtain a dispersion. Polyvinylcarbazole with a molecular weight of 4000 was added to the dispersion containing POSS, and ultrasonic dispersion was continued for 5 h. After centrifugation and drying, polyvinylcarbazole-modified POSS was obtained. The mass ratio of polyvinylcarbazole to POSS was 1:8. Infrared characterization showed that: 3081 cm -1 CH aromatic peak, 3040 cm -1 NH peak, 1153cm -1 CN peak, 1050cm -1 Si-O-Si peak, 751 cm -1 It is the CH peak of carbazole ring;

[0072] (2) mixing the high temperature resistant photosensitive resin and polyvinylcarbazole modified POSS:

[0073] The high temperature resistant photosensitive resin and the polyvinylcarbazole-modified POSS were mixed at a stirring speed of 200 r / min, and then the stirring speed was adjusted to 1000 r / min, the temperature was controlled at 60° C., and stirring was continued for 4 h;

[0074] (3) Adjust the stirring speed to 200 r / min, add light stabilizer, photoinitiator and leveling agent, control the temperature to 50°C, and adjust the stirring speed to 600 r / min to mix them evenly;

[0075] (4) adjusting the stirring speed to 200 r / min, lowering the temperature to room temperature, adding a defoaming agent, and stirring for 2 hours while evacuating the mixture to obtain a photocurable high-temperature resistant low-dielectric material composition; then applying the obtained composition on a substrate, and curing it under UV light to form a film, thereby obtaining a photocurable high-temperature resistant low-dielectric material.

[0076] Example 2

[0077] A light-curing high-temperature-resistant low-dielectric material is prepared from the following raw materials in parts by weight:

[0078]

[0079] Preparation method:

[0080] (1) Preparation of high temperature resistant photosensitive resin and polyvinylcarbazole modified POSS:

[0081] Bisphenol A epoxy acrylate, xylene, vinyl triethoxysilane, dibutyltin dilaurate and p-hydroxyanisole are weighed and added to a reaction container respectively, stirred and dissolved to mix evenly, the temperature of the reaction system is increased to 100° C., and the reaction is carried out for 6 hours to obtain a yellow liquid, and the obtained yellow liquid is subjected to reduced pressure distillation to obtain a viscous liquid, which is an organosilicon-modified epoxy acrylate resin, wherein the molar ratio of bisphenol A epoxy acrylate to vinyl triethoxysilane is 1.8:1, and the mass ratio of bisphenol A epoxy acrylate, xylene, dibutyltin dilaurate and p-hydroxyanisole is 1:5:0.01:0.001; the organosilicon-modified epoxy acrylate resin and the acrylate monomer diluent are added to the stirred tank in order according to parts by weight, the temperature is controlled to 50° C., and the mixture is stirred at a speed of 1000 r / min for 1 hour to obtain a high-temperature resistant photosensitive resin;

[0082] POSS was ultrasonically dispersed in toluene for 2 h to obtain a dispersion. Polyvinylcarbazole with a molecular weight of 3500 was added to the dispersion containing POSS, and ultrasonic dispersion was continued for 4 h. After centrifugation and drying, polyvinylcarbazole-modified POSS was obtained, wherein the mass ratio of polyvinylcarbazole to POSS was 1:5. Infrared characterization showed that: 3080 cm -1 The peaks are CH aromatics, 3041 cm -1 NH peak, 1153cm -1 CN peak, 1050cm -1 Si-O-Si peak, 750cm -1 It is the CH peak of carbazole ring;

[0083] (2) mixing the high temperature resistant photosensitive resin and polyvinylcarbazole modified POSS:

[0084] The high temperature resistant photosensitive resin and the polyvinylcarbazole-modified POSS were mixed at a stirring speed of 300 r / min, and then the stirring speed was adjusted to 1200 r / min, the temperature was controlled at 65° C., and stirring was continued for 5 h;

[0085] (3) Adjust the stirring speed to 300 r / min, add light stabilizer, photoinitiator and leveling agent, control the temperature to 65°C, and adjust the stirring speed to 800 r / min to mix them evenly;

[0086] (4) adjusting the stirring speed to 300 r / min, lowering the temperature to room temperature, adding a defoaming agent, and stirring for 2 hours while evacuating the mixture to obtain a photocurable high-temperature resistant low-dielectric material composition; then applying the obtained composition on a substrate, and curing it under UV light to form a film, thereby obtaining a photocurable high-temperature resistant low-dielectric material.

[0087] Example 3

[0088] A light-curing high-temperature-resistant low-dielectric material is prepared from the following raw materials in parts by weight:

[0089]

[0090]

[0091] The difference from Example 1 is that during the preparation process, the specific components of the high-temperature resistant photosensitive resin and the polyvinylcarbazole-modified POSS are somewhat different, and the other parameters remain the same. Specifically as follows:

[0092] The organosilicon-modified epoxy acrylate resin is prepared by the following method: bisphenol A epoxy acrylate, xylene, 4-triethoxysilyl vinylbenzocyclobutene, dibutyltin dilaurate, and p-hydroxyanisole are weighed and added to a reaction container respectively, stirred and dissolved to mix uniformly, the reaction system temperature is raised to 80° C., and the reaction is carried out for 8 hours to obtain a yellow liquid, and the obtained yellow liquid is subjected to reduced pressure distillation to obtain a viscous liquid, which is the organosilicon-modified epoxy acrylate resin; wherein the molar ratio of bisphenol A epoxy acrylate to 4-triethoxysilyl vinylbenzocyclobutene is 2:1, and the mass ratio of bisphenol A epoxy acrylate, xylene, dibutyltin dilaurate, and p-hydroxyanisole is 1:5:0.01:0.001;

[0093] The high-temperature resistant polymer material modified POSS is prepared by the following method: POSS is ultrasonically dispersed in toluene for 2 hours to obtain a dispersion, polyvinyl carbazole with a molecular weight of 4500 is added to the dispersion containing POSS, and ultrasonic dispersion is continued for 3 hours. After centrifugation, the polyvinyl carbazole-modified POSS is obtained, wherein the mass ratio of polyvinyl carbazole to POSS is 1:10. Infrared test characterization shows: 3081cm -1 The peaks are CH aromatics, 3041 cm -1 NH peak, 1152cm -1 CN peak, 1050cm -1 Si-O-Si peak, 750cm-1 It is the CH peak of the carbazole ring.

[0094] Example 4

[0095] A light-curing high-temperature-resistant low-dielectric material is prepared from the following raw materials in parts by weight:

[0096]

[0097] The difference from Example 1 is that during the preparation process, the specific components of the high-temperature resistant photosensitive resin and the polyvinylcarbazole-modified POSS are somewhat different, and the other parameters remain the same. Specifically as follows:

[0098] The organosilicon-modified epoxy acrylate resin is prepared by the following method: bisphenol A epoxy acrylate, xylene, vinyl triethoxysilane, dibutyltin dilaurate, and p-hydroxyanisole are weighed and added into a reaction container respectively, stirred and dissolved to mix uniformly, the temperature of the reaction system is increased to 100° C., and the reaction is carried out for 7 hours to obtain a yellow liquid, and the obtained yellow liquid is subjected to reduced pressure distillation to obtain a viscous liquid, which is the organosilicon-modified epoxy acrylate resin, wherein the molar ratio of bisphenol A epoxy acrylate to vinyl triethoxysilane is 2:1, and the mass ratio of bisphenol A epoxy acrylate, xylene, dibutyltin dilaurate, and p-hydroxyanisole is 1:5:0.01:0.001;

[0099] The high-temperature resistant polymer material modified POSS is prepared by the following method: POSS is ultrasonically dispersed in toluene for 2 hours to obtain a dispersion, polyvinyl carbazole with a molecular weight of 4200 is added to the dispersion containing POSS, and ultrasonic dispersion is continued for 5 hours. After centrifugation, the polyvinyl carbazole-modified POSS is obtained, wherein the mass ratio of polyvinyl carbazole to POSS is 1:9. Infrared test characterization shows: 3080cm -1 CH aromatic peak, 3042 cm -1 NH peak, 1152cm -1 CN peak, 1050cm -1 Si-O-Si peak, 750cm -1 It is the CH peak of the carbazole ring.

[0100] Example 5

[0101] A light-curing high-temperature-resistant low-dielectric material is prepared from the following raw materials in parts by weight:

[0102]

[0103] The difference from Example 1 is that during the preparation process, the specific components of the high-temperature resistant photosensitive resin and the polyvinylcarbazole-modified POSS are somewhat different, and the other parameters remain the same. Specifically as follows:

[0104] The organosilicon-modified epoxy acrylate resin is prepared by the following method: bisphenol A epoxy acrylate, xylene, vinyltributoxysilane, dibutyltin dilaurate, and p-hydroxyanisole are weighed and added into a reaction container respectively, stirred and dissolved to mix uniformly, the temperature of the reaction system is raised to 90° C., and the reaction is carried out for 8 hours to obtain a yellow liquid, and the obtained yellow liquid is subjected to reduced pressure distillation to obtain a viscous liquid, which is the organosilicon-modified epoxy acrylate resin, wherein the molar ratio of bisphenol A epoxy acrylate to vinyltributoxysilane is 1.8:1, and the mass ratio of bisphenol A epoxy acrylate, xylene, dibutyltin dilaurate, and p-hydroxyanisole is 1:5:0.01:0.001;

[0105] The high-temperature resistant polymer material modified POSS is prepared by the following method: POSS is ultrasonically dispersed in toluene for 2 hours to obtain a dispersion, polyvinyl carbazole with a molecular weight of 3800 is added to the dispersion containing POSS, and ultrasonic dispersion is continued for 3 hours. After centrifugation, the polyvinyl carbazole-modified POSS is obtained, wherein the mass ratio of polyvinyl carbazole to POSS is 1:6. Infrared test characterization shows: 3080cm -1 CH aromatic peak, 3040 cm -1 NH peak, 1154 cm -1 CN peak, 1050cm -1 Si-O-Si peak, 749 cm -1 It is the CH peak of the carbazole ring.

[0106] Comparative Example 1

[0107] Compared with Example 1, the difference of this comparative example is that the epoxy acrylate resin is not modified with silicone; the other parameters and steps are consistent with Example 1.

[0108] Comparative Example 2

[0109] Compared with Example 1, the difference is that the acrylate monomer diluent is acrylamide morpholine, and the weight portion of acrylamide morpholine is 30 parts; the other parameters and steps are consistent with Example 1.

[0110] Comparative Example 3

[0111] Compared with Example 1, the difference is that the acrylate monomer diluent is tricyclodecane dimethanol diacrylate, and the weight portion of tricyclodecane dimethanol diacrylate is 30 parts; the other parameters and steps are consistent with Example 1.

[0112] Comparative Example 4

[0113] Compared with Example 1, the difference is that: no polyvinylcarbazole-modified POSS is added, the weight portion of the high-temperature resistant photosensitive resin is 90 parts; and the other parameters and steps are consistent with Example 1.

[0114] Comparative Example 5

[0115] Compared with Example 1, the difference is that unmodified POSS is added; the other parameters and steps are consistent with Example 1.

[0116] Comparative Example 6

[0117] Compared with Example 1, the difference is that POSS modified with a vinyl silane coupling agent is added; the other parameters and steps are consistent with those in Example 1.

[0118] Comparative Example 7

[0119] Compared with Example 1, the difference is that polyvinylcarbazole-modified fumed silica is added; the other parameters and steps are consistent with Example 1.

[0120] Comparative Example 8

[0121] Compared with Example 1, the difference is that the initiator is only 2-hydroxy-2-methyl-1-phenylpropanone, and the weight proportion of 2-hydroxy-2-methyl-1-phenylpropanone is 3 parts; the other parameters and steps are consistent with Example 1.

[0122] Comparative Example 9

[0123] Compared with Example 1, the difference is that the initiator is only diaryliodonium salt, and the weight portion of diaryliodonium salt is 3 parts; the other parameters and steps are consistent with Example 1.

[0124] Performance Testing

[0125] High temperature resistance test: Bake at 200℃ for 360 hours continuously and observe whether the coating has cracks or discoloration.

[0126] Dielectric constant: The low dielectric constant coatings prepared in the embodiment and the comparative example of the same mass were tested according to the method of IPC-TM-6502.5.5.9 at a test frequency of 10 GHz.

[0127] The light-curable high-temperature-resistant low-dielectric material prepared in Examples 1-5 and Comparative Examples 1-9 was coated on the surface of a glass substrate by dipping, with a coating thickness of 30 μm.

[0128] With 40mW / cm 2The UV mercury lamp was used to irradiate the front and back surfaces at a distance of 15 cm for 20 seconds each. The performance of the formed cured coating was tested and evaluated. The results are shown in Table 1 below:

[0129] Table 1

[0130]

[0131] As can be seen from the data in Table 1, the coatings prepared in Examples 1-5 of the present invention have good mechanical properties, good adhesion, a dielectric constant lower than 2.25, can withstand high temperatures of up to 350°C and can be used for a long time at a high temperature of 200°C; however, the coatings in Comparative Examples 1-9 have a decline in comprehensive performance due to changes in composition and key components or lack thereof, especially in high temperature resistance and dielectric constant changes.

[0132] In conjunction with Example 1 and Comparative Examples 1~3, the high temperature resistant photosensitive resin that the present invention selects, at least need satisfy two conditions, and promptly epoxy acrylate resin need be through organosilicon modification, and acrylate monomer diluent is the combination of acrylamide morpholine and tricyclodecane dimethanol diacrylate; In conjunction with Example 1 and Comparative Examples 4~7, as can be known, the POSS that the polyvinyl carbazole of selecting among the present invention modifies, is a kind of special material with high temperature resistant characteristic, if do not modify or (Comparative Example 5) select other modifiers (as Comparative Example 6 has selected silane coupling agent) and do not select POSS for basic material (Comparative Example 7), its tensile strength, dielectric constant and high temperature resistance all can have decline in various degrees; Wherein silane coupling agent can cause slight change on polymer molecular structure and the POSS crystal structure, thereby helps dipole polarization under electric field action, improves polarizability, has increased polarizability, finally causes the dielectric constant of material to increase. Combining Example 1 with Comparative Examples 8 and 9, the effects of selecting a variety of photoinitiators and light stabilizers in the present invention are reflected. When two suitable photoinitiators and light stabilizers are used in combination with each other, they will also have a significant impact on the tensile strength, hardness, high temperature resistance and other properties of the material. This result also reminds those skilled in the art that the effects of photoinitiators and light stabilizers cannot be ignored during the preparation process. Selecting suitable photoinitiators and light stabilizers and cooperating with each other can also improve the performance of the material itself.

[0133] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the scope of protection and disclosure of the present invention.

Claims

1. A light-curable high-temperature resistant low-dielectric material, characterized in that: The raw materials of the photocurable high temperature resistant low dielectric material include, by weight: 100 copies of high temperature resistant photosensitive resin 10-30 parts of polyvinylcarbazole-modified POSS 1 to 3 parts of photoinitiator 0.1-0.5 parts of light stabilizer; The raw materials of the high temperature resistant photosensitive resin include: organosilicon modified epoxy acrylate resin and acrylate monomer diluent; The acrylic acid ester monomer diluent includes acrylamide morpholine and tricyclodecane dimethanol diacrylate; The polyvinylcarbazole-modified POSS is prepared by the following method: POSS was ultrasonically dispersed in toluene for 1.5 to 2 hours to obtain a dispersion, polyvinylcarbazole was added to the dispersion containing POSS, and ultrasonic dispersion was continued for 3 to 5 hours. The mixture was centrifuged and dried to obtain polyvinylcarbazole-modified POSS; The photoinitiator includes a free radical photoinitiator and a cationic photoinitiator.

2. The light-curable high-temperature resistant low-dielectric material according to claim 1, characterized in that: The mass ratio of the organosilicon-modified epoxy acrylate resin to the acrylate monomer diluent is 1:(0.2-1); The mass ratio of the acrylamide morpholine and tricyclodecane dimethanol diacrylate is (1-3):

1.

3. The light-curable high-temperature-resistant low-dielectric material according to claim 1 or 2, characterized in that: The raw materials for preparing the polyvinylcarbazole-modified POSS include polyvinylcarbazole with a molecular weight of 3500-4500 and POSS; The mass ratio of the polyvinyl carbazole to POSS is 1:(5-10).

4. The light-curable high-temperature-resistant low-dielectric material according to any one of claims 1 to 3, characterized in that: The mass ratio of the free radical photoinitiator to the cationic photoinitiator is 5:(1-3); The free radical photoinitiator includes one or more of 2-hydroxy-2-methyl-1-phenylpropanone, 1-hydroxycyclohexylphenyl ketone, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, methyl benzoylformate, isooctyl p-N,N-dimethylaminobenzoate, monoacylphosphine oxide, and bisacylphosphine oxide; The cationic photoinitiator is any one of diaryliodonium salts, triarylsulfonium salts, arylferrocenium salts, and aryldiazonium salts, or a combination of two or more thereof; The light stabilizer is any one of an amino-containing hindered amine light stabilizer, a triazole ultraviolet light absorber, and a benzophenone ultraviolet light absorber, or a combination of two or more thereof.

5. The light-curable high-temperature-resistant low-dielectric material according to any one of claims 1 to 4, characterized in that: The raw materials of the light-curing high-temperature resistant low-dielectric material also include 0.1 to 0.3 parts of a leveling agent; The leveling agent is an organic silicon leveling agent; The raw materials of the light-curing high-temperature resistant low-dielectric material also include 0.3 to 0.5 parts of a defoaming agent; The defoaming agent is any one of BYK052, BYK1797, and BYK-A530, or a combination of two or more thereof.

6. The light-curable high-temperature-resistant low-dielectric material according to any one of claims 1 to 5, characterized in that: The organosilicon-modified epoxy acrylate resin is prepared by the following method: Mixing the formulated amounts of bisphenol A epoxy acrylate, xylene, silane, dibutyltin dilaurate and p-hydroxyanisole; The obtained mixture is then heated to react, and then distilled under reduced pressure to obtain an organosilicon-modified epoxy acrylate resin.

7. The light-curable high-temperature-resistant low-dielectric material according to claim 6, characterized in that: The molar ratio of bisphenol A epoxy acrylate to silane is (1.5-2):1; The silane is any one of vinyltriethoxysilane, vinyltributoxysilane, and 4-triethoxysilylvinylbenzocyclobutene; The mass ratio of the bisphenol A epoxy acrylate, xylene, dibutyltin dilaurate and p-hydroxyanisole is 1:(2-6):(0.01-0.1):(0.001-0.01).

8. A method for preparing a light-curable high-temperature resistant low-dielectric material according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: (1) Preparation of high temperature resistant photosensitive resin and polyvinylcarbazole modified POSS: (2) mixing the high temperature resistant photosensitive resin and the polyvinylcarbazole-modified POSS according to the formula: (3) The obtained mixture is mixed with a formulated amount of a light stabilizer, a photoinitiator, an optional leveling agent, and an optional defoaming agent, and the light is cured to obtain the light-cured high-temperature-resistant low-dielectric material.

9. The preparation method according to claim 8, characterized in that The preparation method comprises the following steps: (1) Preparation of high temperature resistant photosensitive resin and polyvinylcarbazole modified POSS: Add silicone-modified epoxy acrylate resin and acrylate monomer diluent in parts by weight into a stirring kettle, control the temperature to 50-65° C., and stir at a speed of 800-1000 r / min for 1-2 hours to obtain a high-temperature resistant photosensitive resin; POSS was ultrasonically dispersed in toluene for 1.5 to 2 hours to obtain a dispersion, polyvinylcarbazole was added to the dispersion containing POSS, and ultrasonic dispersion was continued for 3 to 5 hours. The mixture was centrifuged and dried to obtain polyvinylcarbazole-modified POSS; (2) mixing the high temperature resistant photosensitive resin and polyvinylcarbazole modified POSS: The high temperature resistant photosensitive resin and the polyvinylcarbazole-modified POSS are mixed at a stirring speed of 200-300 r / min, and then the stirring speed is adjusted to 1000-1200 r / min, the temperature is controlled at 50-65° C., and the stirring is continued for 3-5 hours; (3) adjusting the stirring speed to 200-300 r / min, adding a light stabilizer, a photoinitiator, and an optional leveling agent, controlling the temperature to 50-65°C, and adjusting the stirring speed to 600-800 r / min to mix; (4) adjusting the stirring speed to 200-300 r / min, lowering the temperature to room temperature, adding an optional defoaming agent, and stirring for 1-2 hours while evacuating the mixture to obtain a photocurable high-temperature resistant low-dielectric material composition; then applying the obtained composition on a substrate, and curing it under UV light to form a film, thereby obtaining a photocurable high-temperature resistant low-dielectric material.

10. Use of the light-curable high-temperature-resistant low-dielectric material according to any one of claims 1 to 7 in the fields of integrated circuits, electronics and electrical equipment, aerospace, or medical machinery.

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