Curable siloxane resin composition and film comprising the same

Abstract

A curable silicone resin composition includes a silicone resin and a radical initiator. The siloxane resin is obtained by a hydrolytic condensation reaction of a mixture of a trialkoxysilane having an alkenyl group and a dialkoxysilane having at least one aryl group. Accordingly, the curable silicone resin composition can form a cured material having characteristics suitable for use in a low dielectric insulation material for ultra-high frequency / ultra-high speed electronic devices.

Description

Cross Reference to Related Applications

[0001] This application claims priority to and the benefit of Korean Patent Application No. 10-2024-0063788, filed on May 16, 2024, in the Korean Intellectual Property Office, under 35 U.S.C. §119, which is incorporated herein by reference in its entirety. BACKGROUND 1. TECHNICAL FIELD

[0002] The present application relates to a siloxane resin composition and a film having properties suitable for a material for a low dielectric insulating layer for ultra-high frequency / ultra-high speed electronic devices. 2. DESCRIPTION OF RELATED ART

[0003] Ultra-high frequency / ultra-high speed electronic devices, which can be essential for industries such as 5G / 6G communication, virtual reality (VR), artificial intelligence (AI), self-driving cars, high-performance computing (HPC), etc., are capable of rapidly transmitting, receiving, and processing a large amount of data and are capable of establishing hyper connectivity between a large number of devices. Accordingly, their market size is rapidly growing. Ultra-high frequency / ultra-high speed electronic devices can operate at a frequency band of gigahertz (GHz) or higher. In order to maintain the performance of electronic devices in a gigahertz or higher frequency band, it is necessary to minimize transmission loss occurring in internal circuits including printed circuit boards, integrated circuits, and semiconductor package redistribution layers (RDLs). Therefore, various research and development are being conducted to reduce circuit transmission loss in ultra-high frequency / ultra-high speed electronic devices.

[0004] Transmission loss can be expressed as the sum of conductor loss and dielectric loss. In a high frequency band, dielectric loss accounts for a large portion. Since dielectric loss is determined by the dielectric constant and the dielectric loss tangent of the insulating layer forming the circuit, a material having a low dielectric constant and a dielectric loss tangent can be used for an insulating material in order to minimize the transmission loss of ultra-high frequency / ultra-high speed electronic devices.

[0005] To date, many materials for insulating materials for ultra-high frequency / ultra-high speed electronic devices have been proposed. However, these materials have limitations in practical applications since they are difficult to satisfy suitable thermal, mechanical, and dielectric reliability at the same time. For example, the polyimide resin composition proposed in PCT Publication No. 2022-163335 does not have sufficient dielectric properties. The polyphenylene resin composition proposed in U.S. Patent Publication No. 2023-0312912 has a low glass transition temperature, making its thermal reliability low. Although the liquid crystal resin containing a filler proposed in U.S. Authorized Patent No. 11760932 has excellent dielectric properties, the reliability at a via hole is low due to the anisotropy of the chemical structure of the liquid crystal resin. In addition, the methacrylic resin proposed in U.S. Patent Publication No. 2022-0169769 has not been evaluated by general methods of measuring dielectric properties. The bismaleimide resin proposed in U.S. Authorized Patent No. 11678432 has not clearly shown experimental results regarding its thermal mechanical reliability, such as glass transition temperature. The epoxy resin composition proposed in Japanese Authorized Patent No. 6867459 has not clearly shown experimental results regarding its dielectric constant and reliability. Therefore, it is difficult to determine whether the above proposed materials are suitable for insulating materials for ultra-high frequency / ultra-high speed electronic devices.

[0006] Korean Patent Publication No. 2023-0039848 proposes a siloxane resin having a low dielectric constant and dielectric loss tangent, a low water absorption, and excellent thermal mechanical reliability in a high frequency band, which has shown a possibility for an insulating material for ultra-high frequency / ultra-high speed electronic devices. However, since the siloxane resin has fluidity with a high ratio of loss modulus to storage modulus at room temperature, it is difficult to form a free-standing film. Therefore, it is difficult to apply the siloxane resin to a process of depositing an insulating material to form a high integration circuit. In addition, since the precursor of the siloxane resin is high in cost, cost competitiveness can be low. Therefore, there is a need to develop a new resin which not only has a low dielectric constant and a low dielectric loss tangent in a gigahertz or higher frequency band, but also has excellent thermal mechanical properties and reliability, a possibility of forming a free-standing film, and cost competitiveness. SUMMARY

[0007] An object of the present application is to provide a curable siloxane resin composition having properties suitable for an insulating material for ultra-high frequency / ultra-high speed electronic devices, such as a low dielectric constant and dielectric loss tangent, a low water absorption, a high glass transition temperature, a low thermal expansion (coefficient of thermal expansion), a low ratio of loss modulus to storage modulus, cost competitiveness, etc.

[0008] According to one embodiment of the present application, the curable siloxane resin composition comprises a siloxane resin and a radical initiator. The siloxane resin is obtained by a hydrolytic condensation reaction of a mixture of trialkoxysilane having alkenyl group and dialkoxysilane having at least one aryl group. The siloxane resin is represented by the following Chemical Formula 1,

[0009] [Chemical Formula 1]

[0010]

[0011] In Chemical Formula 1, R1 comprises a linear or branched C 2-20 alkenyl group, R2 comprises a linear or branched C 6-20 aryl group, R3 comprises a linear or branched C 6-20 aryl group, C 1-20 alkyl group or C 2-20 alkenyl group, a and b are natural numbers, and b is greater than or equal to a.

[0012] In one embodiment, the number average molecular weight of the siloxane resin is 1000 g / mol to 15000 g / mol, and the weight average molecular weight of the siloxane resin is 1000 g / mol to 30000 g / mol.

[0013] In one embodiment, the trialkoxysilane comprises at least one of the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, trimethoxy(4-vinylphenyl)silane, and triethoxy(4-vinylphenyl)silane.

[0014] In one embodiment, the dialkoxysilane comprises at least one of the group consisting of methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,4-bis(methoxydimethylsilyl)benzene, 1,4-bis(ethoxydimethylsilyl)benzene, 4-vinylphenyldimethoxysilane, and 4-vinylphenyldiethoxysilane.

[0015] In one embodiment, the free radical initiator includes at least one of 2,3-dimethyl-2,3-diphenylbutane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di(tert-butylperoxy isopropyl)benzene, tert-butyl cumyl peroxide, di-tert-amyl peroxide, dicumyl peroxide, butyl 4,4-di(tert-butylperoxy)valerate, tert-butyl peroxyl benzoate, 2,2-di(tert-butylperoxy)butane, tert-amyl peroxyl benzoate, tert-butyl peroxyacetate, tert-butyl peroxy(2-ethylhexyl)carbonate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 1,1-di(tert-butylperoxy)cyclohexane, tert-amyl peroxyacetate, tert-amyl peroxy(2-ethylhexyl)carbonate, 1,1-di(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, tert-butyl monoperoxymalate, 1,1'-azobis(hexahydrobenzocinnoline), tert-butyl peroxyisobutyrate, tert-butyl peroxydiethylacetate, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, tert-amyl peroxy-2-ethylhexanoate, di(3-methylbenzoyl)peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, ammonium persulfate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), sebacoyl peroxide, lauroyl peroxide, di(3,5,5-trimethylhexanoyl)peroxide, tert-amyl peroxypivalate, tert-butyl peroxypimelic acid ester, 1,1,3,3-tetramethylbutyl peroxypivalate, tert-butyl peroxypivalate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxy carbonate, diisopropyl peroxydicarbonate, tert-butyl peroxypivalate, di-sec-butyl peroxydicarbonate, tert-amyl peroxypivalate, cumyl peroxypimelic acid ester, di(3-methoxybutyl)peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxypivalate, cumyl peroxypivalate, diisobutyryl peroxide, benzoin, benzoin ethyl ether, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, and an oxime ester compound.

[0016] In one embodiment, the ratio of the loss modulus to the storage modulus of the curable siloxane resin composition is 1 or less.

[0017] According to one embodiment of the present invention, the film comprises a cured material of the curable siloxane resin composition.

[0018] In one embodiment, the cured material has a dielectric constant of 3.3 or less and a dielectric loss tangent of 0.003 or less at a frequency of 10 GHz.

[0019] According to one embodiment of the present application, the composite film comprises a cured material of the curable siloxane resin composition, and at least one of a glass cloth and an inorganic filler.

[0020] According to one embodiment of the present application, the copper-clad laminate comprises the composite film.

[0021] According to the embodiments of the present application, the cured material of the curable siloxane resin composition can have a low dielectric constant and dielectric loss tangent, a low water absorption, a high glass transition temperature, a low thermal expansion, cost competitiveness, etc. Thus, the cured material can have properties suitable for an insulating material for ultra-high frequency / ultra-high speed electronic devices.

[0022] Further, since the curable siloxane resin composition can have a large storage modulus at room temperature, the ratio of loss modulus to storage modulus is small. Thus, the curable siloxane resin composition can exhibit as a solid, which is not tacky, without an additional curing process, thereby forming a film, a sheet, and a roll that can be easily handled. Thus, the curable siloxane resin composition can provide great convenience to the manufacturing process of forming a low-dielectric insulating layer of an ultra-high frequency / ultra-high speed electronic device. DETAILED DESCRIPTION

[0023] Exemplary embodiments of the present application will be described in detail, so that the present application can be easily practiced by one of ordinary skill in the art to which the present application belongs. As those skilled in the art will recognize, the described embodiments can be modified in various different ways without departing from the spirit or scope of the present application. Also, detailed descriptions of known technologies are omitted for brevity.

[0024] Throughout the specification, unless explicitly described to the contrary, the terms "comprise" and "include" and variations such as "comprises", "comprising", "includes", "including", and the like are to be construed in an open, non-exhaustive sense that does not exclude additional elements or steps.

[0025] Throughout the specification, the terms "about" and "substantially" are used in the sense of equal or nearly equal, when given manufacturing and material tolerances inherent in the described situation, and are used to prevent unscrupulous infringers from unfairly exploiting the present disclosure in which precise or absolute numerical values are disclosed to aid in the understanding of the present disclosure.

[0026] Throughout the specification, the term "step" or "of the steps" is not limited to mean "a step for".

[0027] Throughout the specification, it will be understood that when an element or layer is referred to as being "on", "connected to", or "coupled to" another element or layer, it can be directly on, connected, or coupled to the other element or layer, or intervening elements or layers can be present.

[0028] Throughout the specification, when an element is referred to as being "directly on", "directly connected to", or "directly coupled to" another element or layer, there are no intervening elements or layers present.

[0029] Throughout the specification, the term "combination thereof" included in the expression in the form of a Markush group will be understood to mean a mixture or combination of at least one selected from the group consisting of the constituent elements described in the expression in the form of a Markush group, and refers to include at least one selected from the group consisting of the constituent elements.

[0030] Throughout the specification, the term "alkyl" used herein can include a linear or branched C 1-7 alkyl or C 1-20 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, or all possible isomers thereof, but can not be limited thereto.

[0031] Throughout the specification, the term "alkenyl" used herein refers to a monovalent hydrocarbon group containing at least one carbon-carbon double bond in its multiple alkyl groups having two or more carbon atoms, and can include a linear or branched C 2-20 alkenyl, but is not limited thereto.

[0032] Throughout the specification, the term "aryl" used herein refers to a monovalent functional group formed by removing a hydrogen atom present in at least one cyclic arene, and can include a C 6-20 aryl, such as phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, or all possible isomers thereof, but can not be limited thereto. The arene is a hydrocarbon group having an aromatic ring, and includes a monocyclic or polycyclic hydrocarbon group, and the polycyclic hydrocarbon group can include at least one aromatic ring and can include an aromatic ring or a non-aromatic ring as an additional ring, but can not be limited thereto.

[0033] Throughout the specification, the term "alkoxy group or alkoxy" used herein refers to a form in which an alkyl group and an oxygen atom are bonded, and can include a C 1-20An alkoxy group, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, a pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, a nonadecyloxy group, an icosyloxy group, or all possible isomers thereof, but can not be limited thereto.

[0034] Throughout the specification, the term "curable silicone resin composition" refers to a composition comprising a curable silicone resin and / or a radical initiator for curing the silicone resin.

[0035] Hereinafter, a method of manufacturing a curable silicone resin composition according to one embodiment of the present application will be more fully described.

[0036] The curable silicone resin composition according to one embodiment comprises a silicone resin and a radical initiator. The silicone resin is obtained by a hydrolytic condensation reaction of a mixture of a trialkoxysilane having an alkenyl group, a dialkoxysilane having at least one aryl group, and a catalyst, and the catalyst comprises an acid or an aqueous base, and the silicone resin is represented by the following Chemical Formula 1,

[0037] [Chemical Formula 1]

[0038]

[0039] In Chemical Formula 1, R1comprises a linear or branched C 2-20 an alkenyl group, R2comprises a linear or branched C 6-20 an aryl group, R3comprises a linear or branched C 6-20 an aryl group, C 1-20 an alkyl group, or C 2-20 an alkenyl group, a and b are natural numbers, and b is greater than or equal to a.

[0040] The oxygen atom can form a first bond with the silicon atom, and can form a second bond with the silicon atom or another linking group (for example, C 6-20 an arylene group, or C 1-5 an alkylene group.

[0041] For example, the number average molecular weight of the compound of Chemical Formula 1 described above can be 1000 g / mol to 15000 g / mol, and the weight average molecular weight can be 1000 g / mol to 30000 g / mol. In the present application, the molecular weight is calculated or measured by GPC analysis (based on polystyrene).

[0042] The trialkoxysilane comprising an alkenyl group can comprise at least one of the compounds represented by the following Chemical Formula 2-1.

[0043] [Chemical Formula 2-1]

[0044]

[0045] In Chemical Formula 2-1, R1 includes a linear or branched C 2-20 alkenyl group, and R4 includes a C 1-5 alkoxy group.

[0046] The dialkoxysilane including at least one aryl group can include at least one of compounds represented by the following Chemical Formulas 3-1 and 3-2.

[0047] [Chemical Formula 3-1]

[0048]

[0049] [Chemical Formula 3-2]

[0050]

[0051] In Chemical Formulas 3-1 and 3-2, R2 includes a linear or branched C 6-20 aryl group, R3 includes a linear or branched C 6-20 aryl group, C 1-20 alkyl group, or C 2-20 alkenyl group, R4 includes a C 1-5 alkoxy group, and R5 includes a C 6-20 arylene group, or C 1-5 alkylene group.

[0052] For example, the trialkoxysilane including an alkenyl group can include vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, trimethoxy(4-vinylphenyl)silane, triethoxy(4-vinylphenyl)silane, or a combination thereof.

[0053] For example, the dialkoxysilane including at least one aryl group can include methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,4-bis(methoxydimethylsilyl)benzene, 1,4-bis(ethoxydimethylsilyl)benzene, 4-vinylphenyldimethoxysilane, 4-vinylphenyldiethoxysilane, or a combination thereof.

[0054] The siloxane resin obtained from the hydrolytic condensation reaction of the mixture of the trialkoxysilane having an alkenyl group, the dialkoxysilane having at least one aryl group, and the catalyst is advantageous in simultaneously having properties suitable for an insulating material for an ultra-high frequency / ultra-high speed electronic device, such as a low dielectric constant and a dielectric loss tangent, a low water absorption, a high glass transition temperature, a low thermal expansion, a low ratio of a loss modulus to a storage modulus, etc.

[0055] In particular, a siloxane resin obtained by a hydrolysis condensation reaction of a mixture of trialkoxysilane having an alkenyl group, dialkoxysilane having at least one aryl group, and a catalyst can have a significantly increased condensation degree of siloxane bonds, and a rigidness of a molecular structure can also be enhanced. Thus, a dielectric constant and a dielectric loss tangent of a cured material of the siloxane resin composition can be significantly reduced, and a water absorption can also be significantly reduced due to a reduction in the number of hydroxyl groups. For example, the condensation degree of the siloxane resin can be equal to or greater than 95%, and preferably equal to or greater than 99%.

[0056] For example, a resin obtained by a non-hydrolytic condensation reaction of an organoalkoxysilane and an organosilanol can have a low condensation degree and a high proportion of hydroxyl groups. Thus, the resin can have a high dielectric constant and a high dielectric loss tangent, and a high water absorption. For example, the condensation degree of the resin obtained by a non-hydrolytic condensation reaction of an organoalkoxysilane and an organosilanol can be 80% or less, or 85% or less.

[0057] For example, a siloxane resin obtained by a hydrolysis condensation reaction of a mixture of trialkoxysilane having an alkenyl group, dialkoxysilane having at least one aryl group, and a catalyst can have a reduced dipole moment of the entire molecule due to the presence of the alkenyl group and the aryl group, and thus a dielectric constant and a dielectric loss tangent of the siloxane resin can be expected to be reduced.

[0058] For example, a siloxane resin obtained by a hydrolysis condensation reaction of a mixture of trialkoxysilane having an alkenyl group, dialkoxysilane having at least one aryl group, and a catalyst can have a highly connected siloxane bond, and thus an increase in the glass transition temperature and a reduction in the thermal expansion can be expected. In addition, since a ratio of a loss modulus to a storage modulus of the siloxane resin is reduced due to the highly connected siloxane bond, the siloxane resin can not be fluid at room temperature. Thus, the siloxane resin composition can form a film without an additional curing process. Therefore, the siloxane resin composition can be advantageous in applications for low dielectric insulating materials for ultra-high frequency / ultra-high speed electronic devices. In addition, since the siloxane resin can have increased symmetry due to the dialkoxysilane, an additional effect of reducing the dielectric constant and the dielectric loss tangent can be expected.

[0059] For example, since a siloxane resin obtained only by a hydrolysis condensation reaction of a dialkoxysilane has maximized symmetry due to a high proportion of linear siloxane structures, an excellent effect of reducing a dielectric constant and a dielectric loss tangent is expected. However, since the siloxane resin has a relatively high proportion of connected siloxane bonds, the proportion of a loss modulus to a storage modulus can be relatively high. Thus, since the siloxane resin composition can not form a film without an additional curing process, the siloxane resin composition can be disadvantageous in application to a low dielectric insulating material for ultra-high frequency / ultra-high speed electronic devices. In addition, since the siloxane resin obtained only by a hydrolysis condensation reaction of a dialkoxysilane can be high in cost, the siloxane resin composition can be disadvantageous in application to a low dielectric insulating material for ultra-high frequency / ultra-high speed electronic devices.

[0060] The siloxane resin or the siloxane resin composition (without a large amount of an additional solvent) can have a ratio of a loss modulus to a storage modulus of less than or equal to 1, which can be a solid according to E3277 of the American Society for Testing and Materials (ASTM). Thus, such a film-forming ability can be suitable for application to a low dielectric insulating material for ultra-high frequency / ultra-high speed electronic devices.

[0061] Preferably, the molar ratio of the dialkoxysilane having at least one aryl group to the trialkoxysilane having an alkenyl group can be equal to or greater than 1. More preferably, the siloxane resin can have a structure of Chemical Formula 1, and the ratio of a and b (i.e., the molar ratio of the trialkoxysilane having an alkenyl group to the dialkoxysilane having at least one aryl group) can be 1:3 to 1:1. In one embodiment, the number average molecular weight of the compound of Chemical Formula 1 can be 1000 g / mol to 15000 g / mol, and the weight average molecular weight thereof can be 1000 g / mol to 30000 g / mol.

[0062] A cured material of the siloxane resin composition having the above-described combination can have a low dielectric constant and a low dielectric loss tangent, thereby achieving excellent insulating properties.

[0063] To synthesize the siloxane resin, the reaction conditions, such as a reaction temperature, a reaction condition, a material, an amount or a concentration of an acid or a base aqueous solution, can be adjusted in a hydrolysis condensation reaction of a mixture of the trialkoxysilane having an alkenyl group, the dialkoxysilane having at least one aryl group, and a catalyst.

[0064] The acid aqueous solution as a catalyst can include hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, toluenesulfonic acid, acetic acid, butyric acid, palmitic acid, oxalic acid, tartaric acid, or a combination thereof.

[0065] The base aqueous solution as a catalyst can include an alkali metal compound, an alkaline earth metal compound, a quaternary ammonium compound, ammonia, an amine compound aqueous solution, or a combination thereof.

[0066] For example, the aqueous alkali solution can include an alkali metal compound selected from the group consisting of sodium hydroxide, potassium hydroxide, and lithium hydroxide, an alkaline earth metal compound selected from the group consisting of barium hydroxide monohydrate, barium hydroxide octahydrate, calcium hydroxide, and magnesium hydroxide, a quaternary ammonium compound selected from the group consisting of silanol tetraalkylammonium, tetraethylammonium, hydroxide, tetramethylammonium chloride, and tetrabutylammonium fluoride, ammonia, an amine compound aqueous solution, or a combination thereof.

[0067] Although the concentration of the aqueous acid or alkali solution can be 0.01N to 10N, embodiments of the present application are not limited thereto.

[0068] For example, when the siloxane resin is synthesized by a hydrolysis condensation reaction of a mixture of trialkoxysilane having an alkenyl group, dialkoxysilane having at least one aryl group, and a catalyst, the mixture of trialkoxysilane having an alkenyl group, dialkoxysilane having at least one aryl group, and a catalyst can be stirred in an inert gas atmosphere at 40°C to 300°C for 2 to 48 hours. When the content of the organosilane compound as a whole is 1 mole, the content of the aqueous acid or alkali solution can be 1 mole to 10 moles.

[0069] After the siloxane resin is synthesized by a hydrolysis condensation reaction of a mixture of trialkoxysilane having an alkenyl group, dialkoxysilane having at least one aryl group, and a catalyst, the aqueous acid or alkali solution can be removed by a conventionally known physical or chemical method to prevent an increase in water absorption. For example, after a ketone is added to dissolve the siloxane resin, the ketone in which the siloxane resin is dissolved can be separated from the remaining portion including the aqueous acid or alkali solution by a solvent extraction method.

[0070] The siloxane resin composition can include a radical initiator for polymerization of the alkenyl group of the siloxane resin.

[0071] The radical initiator can include at least one selected from the group consisting of 2,3-dimethyl-2,3-diphenylbutane, 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexyne, 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-triperoxonane, di(t-butyl) peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di(t-butylperoxy isopropyl)benzene, t-butyl cumyl peroxide, di(t-amyl) peroxide, diisopropylbenzene peroxide, 4,4-di(t-butylperoxy)butyl valerate, t-butyl peroxybenzoate, 2,2-di(t-butylperoxy)butane, t-amyl peroxybenzoate, t-butyl peroxyacetate, t-butyl peroxy-(2-ethylhexyl) carbonate, t-butyl peroxyisopropylcarbonate, t-butyl peroxy-3,5,5-trimethylhexanoate, 1,1-di(t-butylperoxy)cyclohexane, t-amyl peroxyacetate, t-amyl peroxy-(2-ethylhexyl) carbonate, 1,1-di(t-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(t-amylperoxy)cyclohexane, t-butyl monoperoxymaleate, 1,1'-azobis(hexahydrobenzocinnamate), t-butyl peroxyisobutyrate, t-butyl peroxydiethylacetate, t-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, t-amyl peroxy-2-ethylhexanoate, di(3-methylbenzoyl) peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, ammonium persulfate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, t-amyl peroxy-pivalate, t-butyl peroxyneoheptanoate, 1,1,3,3-tetramethylbutyl peroxy-pivalate, t-butyl peroxy-pivalate, dicetyl peroxydicarbonate, ditetradecyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, t-butyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, t-amyl peroxyneodecanoate, cumyl peroxyneodecanoate, di(3-methoxybutyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, diisobutyryl peroxide, b-benzoin, benzoin ethyl ether, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, an oxime ester compound, and combinations thereof.

[0072] The content of the radical initiator can be 0.01 parts by weight to 5 parts by weight with respect to 100 parts by weight of the siloxane resin.

[0073] The initiation of the radical initiator can be performed by heat or light according to known methods and conditions, but can not be limited thereto.

[0074] The silicone resin composition can be cured by the radical initiator, thereby forming a cured material thereof.

[0075] The cured material of the silicone resin composition can have a dielectric constant of 3.3 or less at a frequency of 10 GHz and a dielectric loss tangent of 0.003 or less at a frequency of 10 GHz, which is suitable for a low dielectric insulating material for ultra-high frequency / ultra-high speed electronic devices.

[0076] When the silicone resin composition is cured after removing an acid or base catalyst by a physical or chemical method, the water absorption of the cured material can be 0.1% or less, which is suitable for a low dielectric insulating material for ultra-high frequency / ultra-high speed electronic devices.

[0077] The cured material can have a glass transition temperature of 300°C or more, which is suitable for a low dielectric insulating material for ultra-high frequency / ultra-high speed electronic devices.

[0078] The cured material can have a thermal expansion of less than 100 ppm / °C at 20°C to 300°C, which is suitable for a low dielectric insulating material for ultra-high frequency / ultra-high speed electronic devices.

[0079] One embodiment of the present application can provide a film manufactured from the silicone resin composition. The film can have a shape of a self-supporting thin film, a sheet, or a roll.

[0080] When the film formed at a high temperature from the silicone resin composition is cooled to room temperature, a self-supporting thin film that is easy to handle can be obtained without an additional curing or semi-curing process due to a low ratio of loss modulus to storage modulus of the silicone resin composition. In view of the manufacturing process, the above-described low dielectric insulating material for ultra-high frequency / ultra-high speed electronic devices.

[0081] One embodiment of the present application can provide a composite film or a composite sheet including at least one of a glass cloth and an inorganic filler in addition to the cured material of the silicone resin composition. The glass cloth or the inorganic filler can be dispersed in the cured material.

[0082] The glass cloth can include a woven glass fabric, a nonwoven glass fabric, or a mixture thereof woven with glass fibers including at least one selected from the group consisting of A glass, C glass, D glass, E glass, AR glass, R glass, S glass, S-2 glass, T glass, NE glass, E-CR glass, quartz, and combinations thereof, but is not limited thereto.

[0083] The inorganic filler can include at least one selected from the group consisting of silicon dioxide (SiO2), silsesquioxane, aluminum oxide (Al2O3), boron oxide (B2O3), titanium oxide (TiO2), zirconium oxide (ZrO2), silicon carbide (SiC), aluminum carbide (Al4C3), boron carbide (B4C), titanium carbide (TiC), zirconium carbide (ZrC), aluminum nitride (AIN), silicon nitride (Si3N4), boron nitride (BN), titanium nitride (TiN), zirconium nitride (ZrN), and combinations thereof, but is not limited thereto.

[0084] A composite film or composite sheet including at least one of a glass cloth and an inorganic filler, in addition to a cured material of a siloxane resin composition, can have very small thermal expansion, which can be advantageous in a subsequent heating process.

[0085] One embodiment of the present application can provide a copper-clad laminate (CCL) including a composite film or composite sheet, which is a cured material of a siloxane resin composition.

[0086] One embodiment of the present application can provide a printed circuit board including a copper-clad laminate.

[0087] One embodiment of the present application can provide an ultra-high frequency / ultra-high speed electronic device including a printed circuit board.

[0088] The siloxane resin composition according to the embodiments can achieve low dielectric constant and dielectric loss tangent, low water absorption, high glass transition temperature, low thermal expansion, film-forming ability, etc., thereby providing the characteristics of a low dielectric insulating material suitable for use in an ultra-high frequency / ultra-high speed electronic device.

[0089] Hereinafter, the present application will be described in more detail through examples, but the following examples are merely exemplary embodiments of the present application, and the present application is not limited to the examples.

[0090] Example 1

[0091] Vinyltrimethoxysilane (Gelset, USA) and diphenyldimethoxysilane (Gelset, USA) were mixed in a molar ratio of 1:1. To this, an aqueous ammonia solution (NH4OH(aq), 0.1N) was added, and then stirred at 80°C for 12 hours under a nitrogen atmosphere. In order to remove the basic catalyst from the siloxane resin obtained after stirring, the mixture was mixed with methyl isobutyl ketone (MIBK, Samchun Chemical, Korea) and water (H2O) in a weight ratio of 1:5:4. Due to the difference in solubility, the MIBK layer in which the siloxane resin was dissolved was separated from the water layer in which the basic catalyst was dissolved. After only the MIBK layer was obtained, the MIBK was evaporated using a reduced pressure evaporator, and finally a siloxane resin having a number average molecular weight of 4960 g / mol and a weight average molecular weight of 9280 g / mol was obtained.

[0092] The degree of condensation (D.O.C) of the siloxane resin was about 100% calculated using nuclear magnetic resonance spectroscopy and the following formula.

[0093]

[0094] A curable siloxane resin composition was prepared by adding 1 part by weight of di(tert-butyl) peroxide (DTBP, Sigma Aldrich) based on 100 parts by weight of the siloxane resin.

[0095] A cured material was prepared by heat treating (4 hours, 250°C) the prepared siloxane resin composition.

[0096] Example 2

[0097] A siloxane resin, a curable siloxane resin composition, and a cured material thereof were prepared by the same method as in Example 1, except that vinyltrimethoxysilane and diphenyldimethoxysilane were mixed in a molar ratio of 2:3. The number average molecular weight and the weight average molecular weight of the siloxane resin were 2170 g / mol and 4327 g / mol, respectively.

[0098] The degree of condensation (D.O.C) of the siloxane resin was about 100% calculated using nuclear magnetic resonance spectroscopy and the following formula.

[0099] Example 3

[0100] A siloxane resin, a curable siloxane resin composition, and a cured material thereof were prepared by the same method as in Example 1, except that vinyltrimethoxysilane and diphenyldimethoxysilane were mixed in a molar ratio of 3:7. The number average molecular weight and the weight average molecular weight of the siloxane resin were 1608 g / mol and 3527 g / mol, respectively.

[0101] The degree of condensation (D.O.C) of the siloxane resin calculated using nuclear magnetic resonance spectroscopy and the above formula was about 100%.

[0102] Example 4

[0103] A siloxane resin, a curable siloxane resin composition, and a cured material thereof were prepared by the same method as in Example 1, except that an aqueous hydrochloric acid solution (HC1(aq), 0.1 N) was used instead of an aqueous ammonia solution. The number average molecular weight and the weight average molecular weight of the siloxane resin were 4130 g / mol and 8830 g / mol, respectively.

[0104] Example 5

[0105] A curable siloxane resin composition prepared in Example 1 was impregnated in a glass cloth (NE-glass, NEA1035, Nittobo Co.), and then cured in the same manner as in Example 1, thereby forming a composite film.

[0106] Example 6

[0107] Silica (FB, Denka Co., Japan) was added to a curable siloxane resin composition prepared in Example 1, and then cured in the same manner as in Example 1, thereby forming a composite film.

[0108] Comparative Example 1

[0109] A siloxane resin, a curable siloxane resin composition, and a cured material thereof were prepared in the same manner as in Example 1, except that vinylmethyldimethoxysilane and diphenyldimethoxysilane were mixed in a molar ratio of 2:3.

[0110] Comparative Example 2

[0111] A siloxane resin, a curable siloxane resin composition, and a cured material thereof were prepared in the same manner as in Example 1, except that vinyltriethoxysilane and methyldiethoxysilane were mixed in a molar ratio of 1:1.

[0112] Comparative Example 3

[0113] A cured material of a curable siloxane resin composition was prepared in the same manner as in Example 1, except that the step of removing the catalyst was omitted.

[0114] Comparative Example 4

[0115] The curable silicone resin composition prepared in Comparative Example 1 was impregnated in a glass cloth, and then cured in the same manner as in Example 1, thereby forming a composite film.

[0116] Comparative Example 5

[0117] The curable silicone resin composition prepared in Comparative Example 1 was impregnated in a glass cloth, and then cured in the same manner as in Example 1, thereby forming a composite film.

[0118] Experiment 1 - Measurement of Dielectric Constant and Dielectric Loss Tangent

[0119] The dielectric constant and dielectric loss tangent (Dk / Df) of the cured silicone resin compositions and composite films prepared according to Examples 1 to 6 and Comparative Examples 1 to 5 at 10 GHz were measured using a vector network analyzer (N5222B, Keysight Technologies, USA) and a split post dielectric resonator (QWED, Poland) of 10 GHz, and the results are shown in Table 1.

[0120] Experiment 2 - Measurement of Water Absorption Experiment 3 - Measurement of Glass Transition Temperature

[0121] The water absorption of the cured silicone resin compositions and composite films prepared according to Examples 1 to 6 and Comparative Examples 1 to 5 was measured according to the ASTM D570 standard, and the results are shown in Table 1.

[0122] Experiment 4 - Measurement of Thermal Expansion

[0123] The glass transition temperature of the cured silicone resin compositions and composite films prepared according to Examples 1 to 6 and Comparative Examples 1 to 5 was measured according to the ASTM E1545 standard using a thermal mechanical analyzer (TMA, SS6100, SII Co., Japan), and the results are shown in Table 1.

[0124] Experiment 5 - Measurement of Ratio of Loss Modulus to Storage Modulus

[0125] The thermal expansion of the cured silicone resin compositions and composite films prepared according to Examples 1 to 6 and Comparative Examples 1 to 5 was measured according to the ASTM E831 using a thermal mechanical analyzer (TMA, SS6100, SII Co., Japan), and the results are shown in Table 1 below.

[0126] Table 1

[0127] The ratio of loss modulus to storage modulus (tand, tangent of loss angle) of the silicone resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 5 was measured with a rheometer (MCR 302, Anton Paar, Austria) according to ASTM E277, and the measurement results are shown in Table 1 below.

[0128] ​

[0129] Referring to Table 1, the cured silicone resin compositions and composite films prepared according to Examples 1 to 6 had a dielectric constant of 3.3 or less and a dielectric loss tangent of 0.003 or less at 10 GHz. Thus, it can be confirmed that they have dielectric properties suitable for low dielectric insulating materials used in ultra-high frequency / super-high speed electronic devices.

[0130] Referring to Table 1, the cured silicone resin compositions and composite films prepared according to Examples 1 to 6 had a water absorption of 0.1% or less. Thus, it can be confirmed that they have water absorption properties suitable for low dielectric insulating materials used in ultra-high frequency / super-high speed electronic devices.

[0131] Referring to Table 1, the cured silicone resin compositions and composite films prepared according to Examples 1 to 6 did not show a glass transition at 300℃ or less, which means that the glass transition temperature of the cured silicone resin compositions and composite films is greater than or equal to 300℃. Thus, it can be confirmed that they have thermal properties suitable for low dielectric insulating materials used in ultra-high frequency / super-high speed electronic devices.

[0132] Referring to Table 1, the cured silicone resin compositions and composite films prepared according to Examples 1 to 6 had a thermal expansion of less than 100 ppm / ℃. Thus, it can be confirmed that they have thermal expansion properties suitable for low dielectric insulating materials used in ultra-high frequency / super-high speed electronic devices.

[0133] On the contrary, referring to Table 1, the cured silicone resin composition prepared according to Comparative Example 2 had a dielectric loss tangent of more than 0.003 at 10 GHz, which is not suitable for low dielectric insulating materials used in ultra-high frequency / super-high speed electronic devices.

[0134] Referring to Table 1, the cured silicone resin composition prepared according to Comparative Example 3 had a water absorption of more than 0.1%, which is not suitable for low dielectric insulating materials used in ultra-high frequency / super-high speed electronic devices.

[0135] Referring to Table 1, the cured silicone resin compositions and composite films prepared according to the comparative examples 1 to 5 have a 'tand' greater than 1, which means flowability at room temperature. Thus, they cannot form a film before the curing process, which is not suitable for low dielectric insulating materials for ultra-high frequency / ultra-high speed electronic devices.

[0136] Referring to Table 1, although the cured silicone resin compositions and composite films prepared according to the comparative examples 1 to 5 show some suitable properties, they are not completely suitable for low dielectric insulating materials for ultra-high frequency / ultra-high speed electronic devices.

[0137] Although the preferred embodiments of the present application have been disclosed in detail above, the scope of the present application is not limited to the above, and various modifications and improvements of the present application which are made by those skilled in the art based on the basic concept of the present application defined by the following claims belong to the scope of the present application.

Claims

1. A curable silicone resin composition comprising: a silicone resin and a radical initiator, the silicone resin is obtained by a hydrolytic condensation reaction of a mixture of a trialkoxysilane having a vinyl group and a dialkoxysilane having at least one aryl group, the silicone resin is represented by the following Chemical Formula 1, [Chemical Formula 1] In Chemical Formula 1, R1 includes straight-chain or branched C 2-20 alkyl, R2 includes straight-chain or branched C 6-20 alkyl, R3 includes straight-chain or branched C 6-20 aryl, C 1-20 alkyl or C 2-20 alkyl, a and b are natural numbers, and b is greater than or equal to a. 2.The curable silicone resin composition according to claim 1, wherein the number average molecular weight of the silicone resin is 1000 g / mol to 15000 g / mol, and the weight average molecular weight of the silicone resin is 1000 g / mol to 30000 g / mol. 3.The curable silicone resin composition according to claim 1, wherein the trialkoxysilane comprises at least one of the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, trimethoxy(4-vinylphenyl)silane, and triethoxy(4-vinylphenyl)silane. 4.The curable silicone resin composition according to claim 1, wherein the dialkoxysilane comprises at least one of the group consisting of methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,4-bis(methoxydimethylsilyl)benzene, 1,4-bis(ethoxydimethylsilyl)benzene, 4-vinylphenyldimethoxysilane, and 4-vinylphenyldiethoxysilane.

5. The curable siloxane resin composition of claim 1, wherein the free radical initiator comprises at least one of the group consisting of 2,3-dimethyl-2,3-diphenylbutane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3-hexyne, 3,6,9-triethyl-3,6,9-trimethyl-l,4,7-triperoxonane, di(tert-butyl) peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di(tert-butylperoxy isopropyl)benzene, tert-butyl cumyl peroxide, di(tert-amyl) peroxide, di-cumyl peroxide, 4,4-di(tert-butylperoxy)butyl valerate, tert-butyl peroxybenzoate, 2,2-di(tert-butylperoxy)butane, tert-amyl peroxybenzoate, tert-butyl peroxyacetate, tert-butyl peroxy-(2-ethylhexyl) carbonate, tert-butyl peroxyisopropyl carbonate, tert-butyl peroxy-3,5,5-trimethylhexanoate, 1,1-di(tert-butylperoxy)cyclohexane, tert-amyl peroxyacetate, tert-amyl peroxy-(2-ethylhexyl) carbonate, 1,1-di(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, tert-butyl monoperoxymaleate, 1,1'-azobis(hexahydrobenzocinnamate), tert-butyl peroxyisobutyrate, tert-butyl diethylperoxy dicarbonate, tert-butyl peroxy-2-ethylhexanoate, benzoyl peroxide, tert-amyl peroxy-2-ethylhexanoate, di(3-methylbenzoyl) peroxide, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate, ammonium persulfate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(isobutyronitrile), didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, tert-amyl peroxypivalate, tert-butyl peroxyneoheptanoate, 1,1,3,3-tetramethylbutyl peroxy pivalate, tert-butyl peroxy pivalate, dicetyl peroxydicarbonate, ditetradecyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, bis(4-tert-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, tert-butyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, tert-amyl peroxyneodecanoate, cumyl peroxyneodecanoate, di(3-methoxybutyl) peroxydicarbonate, 1,1,3,3-tetramethylbutyl peroxyneodecanoate, cumyl peroxyneodecanoate, diisobutyryl peroxide, benzoin, benzoin ethyl ether, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, and an oxime ester compound.

6. The curable siloxane resin composition of claim 1, wherein the ratio of loss modulus to storage modulus of the curable siloxane resin composition is 1 or less.

7. A film comprising a cured material of the curable siloxane resin composition of claim 1.

8. The film according to claim 7, wherein the cured material has a dielectric constant of 3.3 or less and a dielectric loss tangent of 0.003 or less at a frequency of 10 GHz.

9. A composite film comprising a cured material of the curable siloxane resin composition according to claim 1, and at least one of a glass cloth and an inorganic filler.

10. A copper-clad laminate comprising the composite film according to claim 9.

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