Curable siloxane resin composition and film containing the same

Abstract

To be capable of forming a cured material having physical properties suitable for a material for a low-dielectric insulation layer of ultra-high frequency / ultra-high speed electronic devices, such as a low dielectric constant / dielectric loss tangent in gigahertz frequency bands, a low water absorption, a high glass-transition temperature, a low coefficient of thermal expansion, and a low ratio of loss modulus to storage modulus.SOLUTION: The disclosed curable siloxane resin composition includes a hydrolytic condensation product of a trialkoxysilane having an alkenyl group and a dialkoxysilane having at least one allyl group.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable siloxane resin composition having properties suitable as a low-dielectric insulating layer material for high-frequency and ultra-high-speed electronic devices, and a film containing the same. [Background technology]

[0002] Ultra-high frequency and ultra-high-speed electronic devices, exemplified by 5G / 6G communications, virtual reality (VR), artificial intelligence (AI), autonomous vehicles, and high-performance computing (HPC), enable rapid transmission, reception, and processing of large amounts of data, and can build ultra-connectivity between numerous devices, resulting in rapid market growth. Ultra-high frequency and ultra-high-speed electronic devices operate in frequency bands of gigahertz (GHz) and above, and in order to maintain the performance of these electronic devices under such conditions, transmission losses occurring in internal circuits, including printed circuit boards, integrated circuits, and semiconductor packaging redistribution layers (RDLs), must be minimized. Therefore, various research and development efforts are being undertaken to reduce circuit transmission losses in ultra-high frequency and ultra-high-speed electronic devices.

[0003] Transmission loss is expressed as the sum of conductor loss and dielectric loss, and in the high-frequency band, dielectric loss accounts for a very large portion of this loss. Since such dielectric loss is determined by the dielectric constant and dielectric loss tangent of the insulating layer that makes up the circuit, it is a commonly used method to minimize the transmission loss of ultra-high frequency and ultra-high-speed electronic elements by applying a material with a low dielectric constant / dielectric loss tangent as the insulating layer material.

[0004] To date, many materials have been proposed as low-dielectric insulating layer materials for ultra-high frequency and ultra-high-speed electronic devices, but these have limitations in practical application while simultaneously satisfying appropriate thermal, mechanical, and dielectric reliability. For example, the polyimide resin composition proposed in International Publication Patent 2022-163335 does not have sufficient dielectric properties. Also, the polyphenylene resin composition proposed in US Publication Patent 2023-0312912 A1 has a low glass transition temperature, making it difficult to expect thermal reliability. On the other hand, the filler-containing liquid crystal crystalline resin proposed in US Registered Patent 11760932 B2 has excellent dielectric properties, but it does not solve the problem of reduced reliability in via holes due to the anisotropy of the chemical structure of the liquid crystal resin. Furthermore, the methacrylic resin proposed in U.S. Published Patent 2022-0169769A1 does not use a commonly used dielectric property measurement method, the bismaleimide resin proposed in U.S. Registered Patent 11678432 B2 does not clearly present the results of examples regarding thermomechanical reliability such as glass transition temperature, and the epoxy resin composition proposed in Japanese Registered Patent 6867459B2 does not clearly present the results of examples regarding dielectric constant and its reliability. Therefore, it is difficult to determine whether the materials presented in each document are suitable as low-dielectric insulating layer materials for ultra-high frequency and ultra-high-speed electronic devices.

[0005] On the other hand, Korean published patent 10-2023-0039848A proposed a siloxane resin with low dielectric constant / dielectric loss tangent, low moisture absorption rate, and excellent thermomechanical reliability in the high-frequency range, demonstrating its potential as a low-dielectric insulating layer material for ultra-high frequency and ultra-high-speed electronic devices. However, this siloxane resin has a high ratio of loss modulus to storage modulus at room temperature, making it fluid and difficult to form into a free-standing film, thus making it difficult to easily apply to the insulating material lamination process for high-integrated circuit construction. Furthermore, the precursors required for resin production are also significantly less price-competitive if the resin is used across its entire range. Therefore, there is a need for a new resin that has low dielectric constant / dielectric loss tangent in the frequency band above gigahertz, as well as appropriate thermal and mechanical properties and reliability, the possibility of forming a free-standing film, and price competitiveness. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication Patent 2022-163335 [Patent Document 2] U.S. Published Patent 2023-0312912 [Patent Document 3] U.S. Registered Patent 11760932 [Patent Document 4] U.S. Published Patent 2022-0169769 [Patent Document 5] U.S. Registered Patent 11678431 [Patent Document 6] Japanese Registered Patent No. 6867459 [Patent Document 7] Korean Published Patent 10-2023-0039848A [Overview of the project] [Problems that the invention aims to solve]

[0007] The present invention aims to solve the aforementioned problems by providing a curable siloxane resin composition that has suitable properties (low dielectric constant / dielectric loss tangent, low moisture absorption rate, high glass transition temperature, low thermal expansion coefficient, low loss modulus to storage modulus ratio, price competitiveness, etc.) as a low dielectric insulating layer material for ultra-high frequency and ultra-high speed electronic devices. [Means for solving the problem]

[0008] A curable siloxane resin composition according to one embodiment of the present invention comprises a siloxane resin and a radical polymerization initiator. The siloxane resin is a trialkoxysilane having an alkenyl group, and at least one Ariel It is produced by a hydrolysis condensation reaction of a mixture containing a dialkoxysilane having a group, and is represented by the following formula 1.

[0009] [Chemical]

[0010] In the formula, R1 contains a linear or branched C 2-20 alkenyl group, R2 contains a linear or branched C 6-20 Ariel group, R3 is a linear or branched C 6-20 Ariel group, a C1-C 20 alkyl group, or a C 2-20 alkenyl group, a and b are each natural numbers, and b is greater than or equal to a.

[0011] The number average molecular weight of the siloxane resin is 1,000 g / mol to 15,000 g / mol, and the weight average molecular weight is 1,000 g / mol to 30,000 g / mol.

[0012] The trialkoxysilane contains at least one selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, trimethoxy(4-vinylphenyl)silane, and triethoxy(4-vinylphenyl)silane.

[0013] The dialkoxysilane contains at least one selected from the group consisting of methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,4-bis(methoxydimethylsilyl)benzene, 1,4-bis(ethoxydimethylsilyl)benzene, 4-vinyldiphenyldimethoxysilane, and 4-vinyldiphenyldiethoxysilane.

[0014] The radical polymerization initiators are 2,3-dimethyl-2,3-diphenylbutane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexine-3,3,6,9-triethyl-3,6,9-trimethyl-1,4,7-tripeloxonane, di(tert-butyl)-peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di(tert-butylperoxy-isopropyl)benzene, tert-butylcumylperoxide, di-(tert-amyl)-peroxide, dicumylperoxide, butyl4,4-di( tert-butylperoxy)valerate, tert-butylperoxybenzoate, 2,2-di(tert-butylperoxy)butane, tert-amylperoxy-benzoate, tert-butylperoxy-acetate, tert-butylperoxy-(2-ethylhexyl)carbonate, tert-butylperoxyisopropylcarbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, 1,1-di(tert-butylperoxy)cyclohexane, tert-amylperoxyacetate, tert- Milperoxy-(2-ethylhexyl) carbonate, 1,1-di(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, tert-butyl-monoperoxymalate, 1,1'-azodi(hexahydrobenzonitrile), tert-butylperoxy-isobutyrate, tert-butylperoxydiethylacetate, tert-butylperoxy-2-ethylhexanoic acid, dibenzoyl peroxide, tert-amylperoxy-2-ethylhexanoic acid, di( 3-methylbenzoyl)peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoic acid, ammonium peroxodisulfate, 2,5,-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,2'-azodi(2-methylbutyronitelyl), 2,2'-azodi(isobutyronitelyl), didecanoylperoxide, dilauroylperoxide, di(3,5,5-trimethylhexanoyl)peroxide, tert-amylperoxypivalate, tert-butylperoxyneoheptanoate, 1,1,3,3,-Tetramethylbutylperoxypivalate, tert-butylperoxypivalate, dicetylperoxydicarbonate, dimyristylperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxycarbonate, diisopropylperoxydicarbonate, tert-butylperoxyneodecanoate, di-sec-butylperoxydicarbonate, tert-amylperoxyneodecanoate, cumylperoxy It comprises at least one selected from the group consisting of oheptanoates, di(3-methoxybutyl)peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, cumylperoxyneodecanoate, diisobutyryl peroxide, benzoin, benzoin ethyl ether, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, and oxime ester compounds.

[0015] The curable siloxane resin composition has a ratio of loss modulus to storage modulus of 1 or less.

[0016] Another embodiment of the present invention includes a cured product of the curable siloxane resin composition.

[0017] The cured product has a dielectric constant of 3.3 or less and a dielectric loss tangent of 0.003 or less at 10 GHz.

[0018] Another embodiment of the present invention provides a composite film comprising a film containing a cured product of the curable siloxane resin composition, and at least one of glass cloth or an inorganic filler.

[0019] Another embodiment of the present invention, a copper-clad laminate (CCL), includes the composite film. [Effects of the Invention]

[0020] The curable siloxane resin composition according to the present invention has low dielectric constant / dielectric loss tangent, low moisture absorption rate, high glass transition temperature, low thermal expansion coefficient, and price competitiveness in the frequency band of gigahertz or higher, thus providing properties suitable for low dielectric insulating layer materials in ultra-high frequency and ultra-high-speed electronic devices.

[0021] Furthermore, the curable siloxane resin composition according to the present invention has a very high storage modulus at room temperature and a very small ratio of loss modulus to storage modulus. Therefore, it can behave like a solid without any additional curing process, can be manufactured in film, sheet, and roll forms without stickiness, is easy to handle, and provides convenience for subsequent processing steps. In particular, it can provide properties suitable for low-dielectric insulating layer materials for ultra-high frequency and ultra-high-speed electronic devices. [Modes for carrying out the invention]

[0022] Embodiments of the present invention will be described in detail so that they can be easily implemented by a person with ordinary skill in the art to which the invention pertains. However, the present invention can be embodied in a variety of different forms and is not limited to the embodiments described herein. Furthermore, in the case of widely known prior art, specific descriptions thereof will be omitted.

[0023] In the entire specification of the present invention, when a part of it is said to "include" a certain component, this means that, unless otherwise stated to the contrary, it may include other components as well, rather than excluding them.

[0024] Terms such as “abbreviated” and “substantially” used throughout the specification of this invention are used to mean, or nearly to mean, the numerical values ​​of the manufacturing and material tolerances inherent to the meaning referred to, when such values ​​are presented, in order to aid in the understanding of the invention and to prevent unscrupulous infringers from unfairly exploiting disclosures that refer to precise or absolute numerical values.

[0025] As used throughout the specification of this invention, the terms "step" or "step" do not mean "step for".

[0026] Throughout the specification of the present invention, if one part is described as being "connected" to another part, this includes not only cases where they are "directly connected," but also cases where they are "electrically connected" with other elements in between.

[0027] Throughout the specification of the present invention, when a member is said to be located "on" another member, this includes not only cases where one member is in contact with another member, but also cases where there is yet another member between the two members.

[0028] Throughout the specification of the present invention, the term “these combinations” as included in the Marcoush expression means one or more mixtures or combinations selected from the group of components described in the Marcoush expression, and means including one or more selected from the group of components.

[0029] Throughout the specification of the present invention, the term “alkyl group” includes, for example, linear or branched C1-7 alkyl groups or C1-20 alkyl groups, including, but not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, hebutyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, hebutadecyl, octadecyl, nonadecyl, eicosanyl, or all possible isomers thereof.

[0030] Throughout the specification of this invention, the term “alkenyl group” means a monovalent hydrocarbon group in which an alkyl group having two or more carbon atoms contains at least one carbon-carbon double bond, and includes, but is not limited to, linear or branched C2-20 alkenyl groups.

[0031] Throughout the specification of this invention, the term " ArielThe term "group" refers to a monovalent working group formed by the removal of hydrogen atoms present in one or more rings of an allene, and is C6-20. Ariel Allenes include, but are not limited to, groups such as phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, or all possible isomers thereof. Allenes are hydrocarbon groups having aromatic rings, including single-ring or multi-ring hydrocarbon groups, where the multi-ring hydrocarbon group includes one or more aromatic rings, and additional rings may include aromatic or non-aromatic rings.

[0032] Throughout the specification of the present invention, the term "alkoxy group or alkoxy" means a C1-20 alkoxy group in which an alkyl group and an oxygen atom are bonded, and includes, but is not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, hebutyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, hebutadecyloxy, octadecyloxy, nonadecyloxy, eicosanyloxy, or all possible isomers thereof.

[0033] Throughout the specification of the present invention, the term "curable siloxane resin composition" means a composition comprising a curable siloxane resin or a radical polymerization initiator for curing a curable siloxane resin.

[0034] The following describes in detail a method for producing a curable siloxane resin composition according to one embodiment of the present invention.

[0035] A curable siloxane resin composition according to one embodiment of the present invention comprises a siloxane resin and a radical polymerization initiator. The siloxane resin is a trialkoxysilane having an alkenyl group, at least one ArielIt is obtained by the hydrolysis and condensation reaction of a mixture of a dialkoxysilane containing a base and an aqueous acid or base solution, and is represented by the following formula 1.

[0036] [Chemical formula]

[0037] In the formula, R1 contains a linear or branched C 2-20 alkenyl group, R2 contains a linear or branched C 6-20 Ariel group, R3 contains a linear or branched C 6-20 Ariel group, a C1-C 20 alkyl group, or a C 2-20 alkenyl group, and a and b are each natural numbers, and b is greater than or equal to a.

[0038] The oxygen atom forms a first bond with the silicon atom and a second bond with the silicon atom or another linking group (e.g., a C 6-20 Ariren group or a C 1-5 alkylene group).

[0039] For example, the number average molecular weight of the compound of Chemical formula 1 is 1,000 g / mol to 15,000 g / mol, and the weight average molecular weight is 1,000 g / mol to 30,000 g / mol. In this application, the molecular weight is calculated or measured by GPC analysis (polystyrene standard).

[0040] The trialkoxysilane containing the alkenyl group contains at least one compound represented by the following formula 2-1.

[0041] [Chemical formula]

[0042] In the formula, R1 contains a linear or branched C 2-20It contains an alkenyl group, and R4 is C 1-5 Contains an alkoxy group.

[0043] The at least one of the above Ariel Dialkoxysilanes containing the group include at least one compound represented by the following formulas 3-1 and 3-2.

[0044] [ka]

[0045] [ka]

[0046] In equations 3-1 and 3-2, R2 is linear or branched C 6-20 Ariel The group contains R3, which is linear or branched C 6-20 Ariel Group, C1-C 20 Alkyl alkyl group, or C 2-20 It contains an alkenyl group, and R4 is C 1-5 It contains an alkoxy group, and R5 is C 6-20 Ariel Base, or C 1-5 Contains an Achillene group.

[0047] For example, the trialkoxysilane containing the alkenyl group includes vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, trimethoxy(4-vinylphenyl)silane, and triethoxy(4-vinylphenyl)silane, or combinations thereof.

[0048] For example, the above ArielDialkoxysilanes containing the group include methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,4-bis(methoxydimethylsilyl)benzene, 1,4-bis(ethoxydimethylsilyl)benzene, and 4-vinyldiphenyldimethoxysilane, 4-vinyldiphenyldiethoxysilane, or combinations thereof.

[0049] Trialkoxysilane containing the aforementioned alkenyl group, and at least one Ariel When producing siloxane resins by hydrolysis condensation reaction of an organic dialkoxysilane containing a group and an aqueous acid or base solution, it is highly advantageous to simultaneously possess properties suitable for low-dielectric insulating layer materials in ultra-high frequency and ultra-high-speed electronic devices, namely, a low dielectric constant / dielectric loss tangent, low moisture absorption rate, high glass transition temperature, low thermal expansion coefficient, and a low ratio of loss modulus to storage modulus.

[0050] More specifically, for example, trialkoxysilane in an acid or base aqueous solution, and at least one Ariel When a siloxane resin is produced by the hydrolysis condensation reaction of an organic dialkoxysilane containing a hydroxyl group, the degree of condensation of the siloxane bond increases significantly, and the rigidity of the molecular structure increases. As a result, the dielectric constant / dielectric loss tangent of the siloxane resin composition decreases sharply, and the moisture absorption rate also decreases sharply due to the decrease in hydroxyl groups. For example, the degree of condensation of the siloxane resin is 95% or higher, preferably 99% or higher.

[0051] For example, when a resin is produced by a non-hydrolysis condensation reaction of an organic alkoxysilane and an organic silanol, the degree of condensation deteriorates, resulting in a higher proportion of hydroxyl groups. This leads to a higher dielectric constant / dielectric loss and moisture absorption rate compared to the siloxane resin composition. For instance, the degree of condensation of a resin obtained by a non-hydrolysis condensation reaction of an organic alkoxysilane and an organic silanol is 80% or less, or 85% or less.

[0052] For example, trialkoxysilane and at least one acid or base aqueous solution Ariel When producing siloxane resin by hydrolysis condensation reaction of organic dialkoxysilanes containing a group, the alkenyl group and Ariel The dipole moment of the entire molecule decreases, and this can be expected to reduce the dielectric constant and dielectric loss tangent of the siloxane resin.

[0053] For example, trialkoxysilanes containing alkenyl groups in aqueous solutions of acid or base, and at least one Ariel When producing siloxane resins by hydrolysis condensation reaction of organic dialkoxysilanes containing a specific group, there is a high probability of obtaining even stronger siloxane bonds, which can be expected to increase the glass transition temperature and decrease the coefficient of thermal expansion. Furthermore, the strong siloxane bonds reduce the ratio of the loss modulus to the storage modulus of the siloxane resin, resulting in no fluidity of the siloxane resin at room temperature. This allows for the formation of a film from the siloxane resin composition itself without further curing processes, which is extremely advantageous in terms of the process of applying it as a low-dielectric insulating layer material for ultra-high frequency and ultra-high-speed electronic devices. Moreover, the dialkoxysilane provides a highly symmetrical structure, which can be expected to further reduce the dielectric constant / dielectric loss tangent.

[0054] For example, when producing siloxane resin by hydrolysis condensation reaction of only dialkoxysilane, the high proportion of linear siloxane structures makes it highly likely to obtain a structure with maximized symmetry, and a very high reduction in dielectric constant / dielectric loss tangent can be expected. However, the rigidity of the siloxane bonds decreases, and if a further curing process is not performed due to the high ratio of loss modulus and storage modulus, the film formation effect of the siloxane resin composition itself cannot be expected, which is very disadvantageous in terms of the process for subsequent application as a low-dielectric insulating layer material for ultra-high frequency and ultra-high-speed electronic devices. Furthermore, when producing siloxane resin by hydrolysis condensation reaction of only dialkoxysilane, the overall production cost becomes very high due to the cost of producing dialkoxysilane, which is very disadvantageous for application as a low-dielectric insulating layer material for ultra-high frequency and ultra-high-speed electronic devices.

[0055] The ratio of the loss modulus to the storage modulus of the siloxane resin composition is less than or equal to 1, which can be specified for solids according to the American Society for Testing and Materials (ASTM) standard E3277. Therefore, this is a suitable film-forming characteristic for low-dielectric insulating layer materials in ultra-high frequency and ultra-high-speed electronic devices.

[0056] Preferably, the trialkoxysilane containing the alkenyl group Ariel The molar ratio of the dialkoxysilanes containing the group is the same or greater. More preferably, the siloxane resin may have the structure of formula 1, where the ratio of a to b (trialkoxysilane containing an alkenyl group and at least one other group) Ariel The molar ratio of the dialkoxysilane containing the group is 1:3 to 1:1. According to one embodiment, the number-average molecular weight of the compound of formula 1 is 1,000 g / mol to 15,000 g / mol, and the weight-average molecular weight is 1,000 g / mol to 30,000 g / mol.

[0057] The cured siloxane resin obtained by this combination possesses both a low dielectric constant and a dielectric loss tangent, thus achieving excellent insulating performance.

[0058] When producing the siloxane resin, a trialkoxysilane containing an alkenyl group is dissolved in an acid or a basic aqueous solution, and at least one Ariel The hydrolysis condensation reaction of organic dialkoxysilanes containing the group is carried out by adjusting reaction conditions such as reaction temperature, reaction atmosphere, and the type, amount, and concentration of the acid or base aqueous solution.

[0059] The acidic aqueous solution includes hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid, toluenesulfonic acid, butyric acid, palmitic acid, oxalic acid, tartaric acid aqueous solution, or a combination thereof.

[0060] The basic aqueous solution contains alkali metal compounds, alkaline earth metal compounds, quaternary ammonium compounds, ammonia, aqueous solutions of amine compounds, or combinations thereof. For example, it contains one or more selected from the group consisting of alkali metal compounds selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide; alkaline earth metal compounds selected from barium hydroxide monohydrate, barium hydroxide octahydrate, potassium hydroxide, and magnesium hydroxide; quaternary ammonium compounds selected from tetraalkylammonium silanolate, tetraethylammonium hydroxide, tetramethylammonium chloride, and tetrabutylammonium fluoride; ammonia; aqueous solutions of amine compounds; and combinations thereof.

[0061] The concentration of the acid or base aqueous solution is 0.01 N to 10 N, respectively, but is not limited to this range.

[0062] For example, trialkoxysilanes containing alkenyl groups in aqueous solutions of acid or base, and at least one Ariel When producing a siloxane resin by hydrolysis condensation reaction of an organic dialkoxysilane containing a group, the trialkoxysilane having an alkenyl group and at least one Ariel A mixture of a dialkoxysilane containing the group and an aqueous acid or base solution is stirred under a non-reactive gas atmosphere at 40-300°C for 2-48 hours. Here, the aqueous acid or base solution in the mixture is present in an amount of 1-10 moles per mole of the total organosilicon compound, but is not limited to this.

[0063] Trialkoxysilane containing an alkenyl group in an aqueous solution of acid or base, and at least one ArielWhen producing siloxane resin by hydrolysis condensation reaction of an organodialkoxysilane containing a group, the acid or base catalyst can usually be removed by well-known physical or chemical methods to prevent an increase in the moisture absorption rate of the siloxane resin due to the acid or base catalyst contained in the acid or base aqueous solution, but is not limited thereto. For example, to remove the acid or base catalyst, a ketone can be added to dissolve the siloxane, and then the ketone in which the siloxane is dissolved can be separated from the base catalyst by a layer separation method.

[0064] The siloxane resin composition may contain a radical polymerization initiator for the polymerization of alkenyl groups in the siloxane resin.

[0065] Radical polymerization initiators: 2,3-dimethyl-2,3-diphenylbutane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexine-3,3,6,9-triethyl-3,6,9-trimethyl-1,4,7-tripeloxonane, di(tert-butyl)-peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di(tert-butylperoxy-isopropyl)benzene, tert-butylcumylperoxide, di-(tert-amyl)-peroxide, dicumylperoxide, butyl 4,4-di(te rt-butylperoxy)valerate, tert-butylperoxybenzoate, 2,2-di(tert-butylperoxy)butane, tert-amylperoxybenzoate, tert-butylperoxyacetate, tert-butylperoxy-(2-ethylhexyl)carbonate, tert-butylperoxyisopropylcarbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, 1,1-di(tert-butylperoxy)cyclohexane, tert-amylperoxyacetate, 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'-azodi(hexahydrobenzonitrile), tert-butylperoxy-isobutyrate, tert-butylperoxydiethylacetate, tert-butylperoxy-2-ethylhexanoic acid, dibenzoyl peroxide, tert-amylperoxy-2-ethylhexanoic acid, di(3- Methylbenzoyl) peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoic acid, ammonium peroxodisulfate, 2,5,-dimethyl-2,5-di(2-ethylhexanoyl peroxide)hexane, 2,2'-azodi(2-methylbutyronitelyl), 2,2'-azodi(isobutyronitelyl), didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, tert-amyl peroxypivalate, tert-butylperoxyneoheptanoate, 1,1,3,3,-Tetramethylbutylperoxypivalate, tert-butylperoxypivalate, dicetylperoxydicarbonate, dimyristylperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxycarbonate, diisopropylperoxydicarbonate, tert-butylperoxyneodecanoate, di-sec-butylperoxydicarbonate, tert-amylperoxyneodecanoate, cumylperoxyneoheptanoate, This includes, but is not limited to, one or more compounds selected from the group consisting of di(3-methoxybutyl)peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, cumylperoxyneodecanoate, diisobutyryl peroxide, benzoin, benzoin ethyl ether, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, oxime ester compounds, and combinations thereof.

[0066] The radical polymerization initiator is included in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the siloxane resin.

[0067] The initiation of radical polymerization initiators for curing siloxane resin compositions is carried out by light or heat, by commonly known methods and conditions, but is not limited thereto.

[0068] By using a radical polymerization initiator, a siloxane resin composition can be cured to produce a cured product of the siloxane resin composition.

[0069] The cured product of the siloxane resin composition has a dielectric constant of 3.3 or less at a frequency of 10 GHz and a dielectric loss of 0.003 or less at a frequency of 10 GHz. These dielectric properties are suitable for low-dielectric insulating layer materials in ultra-high frequency and ultra-high-speed electronic devices.

[0070] When a siloxane resin composition is cured after removing an acid or base catalyst added to the siloxane resin by physical and chemical methods, the cured product of the siloxane resin composition has a moisture absorption rate of 0.1% or less, which is a moisture absorption rate characteristic suitable for low-dielectric insulating layer materials for ultra-high frequency and ultra-high-speed electronic devices.

[0071] The cured product of the siloxane resin composition has a glass transition temperature of 300°C or higher, which is a suitable glass transition temperature characteristic for low-dielectric insulating layer materials in ultra-high frequency and ultra-high-speed electronic devices.

[0072] The cured product of the siloxane resin composition has a thermal expansion coefficient of less than 100 ppm / °C at 20-300°C, which is a suitable thermal expansion coefficient characteristic for low-dielectric insulating layer materials in ultra-high frequency and ultra-high-speed electronic devices.

[0073] One embodiment can provide a film made using a curable siloxane resin composition. The film may be in the form of a freestanding film, sheet, or roll.

[0074] When manufacturing freestanding films, sheets, and rolls, if a fluid curable siloxane resin composition is formed into a film under high-temperature conditions and then cooled to room temperature, as mentioned above, the low ratio of loss modulus to storage modulus of the curable siloxane resin composition allows for the production of a freestanding film that is easy to handle without further curing or radiating processes. From an overall process perspective, this is a suitable property for low-dielectric insulating layer materials for ultra-high frequency and ultra-high-speed electronic devices.

[0075] One embodiment can provide a composite film or sheet comprising a cured product of a curable siloxane resin composition and at least one of glass cloth or an inorganic filler. The glass cloth or inorganic filler is dispersed within the cured product.

[0076] Glass cloth includes, but is not limited to, woven glass fabric, non-woven glass fabric, or mixtures thereof, made from glass fibers containing one or more 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, guartz, and combinations thereof.

[0077] Inorganic fillers include, but are not limited to, one or more selected from the group consisting of silica (SiO2), silsesquioxane alumina (Al2O3), boria (B2O3), titania (TiO2), zirconia (ZrO2), silicon carbide (SiC), aluminum carbide (Al4C3), boron carbide (B4C), titanium carbide (TiC), zirconium carbide (ZrC), aluminum nitride (AlN), silicon nitride (Si3N4), boron nitride (BN), titanium nitride (TiN), zirconium nitride (ZrN), and combinations thereof.

[0078] When a composite film or sheet is manufactured by including at least one of glass cloth or an inorganic filler in the cured product of a siloxane composition, an extreme reduction in the coefficient of thermal expansion is obtained, which is very advantageous in subsequent thermal processing processes.

[0079] One embodiment can provide a copper-clad laminate including a film or composite film or sheet containing a cured product of a curable siloxane resin composition.

[0080] One embodiment provides a printed circuit board including a copper-clad laminate.

[0081] One embodiment provides an ultra-high frequency, ultra-high-speed electronic element including a printed circuit board.

[0082] The curable siloxane resin composition possesses a low dielectric constant / dielectric loss tangent, low moisture absorption rate, high glass transition temperature, low thermal expansion coefficient, and film formation capability, thus achieving a well-balanced set of properties suitable for low-dielectric insulating layer materials in ultra-high frequency and ultra-high-speed electronic devices. [Examples]

[0083] The present invention will be described in more detail below with reference to examples, but the following examples are merely examples of the present invention and the present invention is not limited to these examples.

[0084] Example 1 Vinyltrimethoxysilane (Gelest, USA) and diphenyldimethoxysilane (Gelest, USA) were mixed in a 1:1 molar ratio. After adding a 0.1N aqueous ammonia solution (NH4OH(aq)) to the mixture, it was stirred under a nitrogen atmosphere at 80°C for 12 hours. To remove the ammonia water, which acts as a catalyst, from the siloxane resin obtained after stirring, the mixture was mixed with methyl isobutyl ketone (MIBK, SAMCHUN CHEMICALS, Korea) and water (H2O) in a weight ratio of 1:5:4. Due to the difference in solubility, the MIBK layer containing dissolved siloxane and the aqueous layer containing dissolved catalyst were separated, and only the MIBK layer was obtained. Subsequently, MIBK and siloxane resin were separated using vacuum distillation to obtain siloxane resin (number-average molecular weight (Mn): 4960 g / mol, weight-average molecular weight (Mw): 9280 g / mol).

[0085] The degree of condensation of the obtained siloxane resin, calculated by NMR (Nuclear Magnetic Resonance) spectroscopy, was approximately 100%, and the degree of condensation was calculated as follows.

[0086]

number

[0087] [ka]

[0088] A curable siloxane resin composition was prepared by adding 1 part by weight of di(tert-butyl)-peroxide (DTBP, Sigma Aldrich, USA) to 100 parts by weight of the manufactured siloxane resin.

[0089] The manufactured siloxane resin composition was heat-treated (4 hours, 250°C) to produce a cured product of the curable siloxane resin composition.

[0090] Example 2 A siloxane resin and a cured product of the curable siloxane resin composition were prepared in the same manner as in Example 1, except that vinyltrimethoxysilane and diphenyldimethoxysilane were mixed in a molar ratio of 2:3 (number average molecular weight (Mn): 2170 g / mol, weight average molecular weight (Mw): 4327 g / mol of the siloxane resin before curing).

[0091] The degree of condensation of the obtained siloxane resin, calculated by NMR (Nuclear Magnetic Resonance) spectroscopy, was approximately 100%.

[0092] Example 3 A siloxane resin and a cured product of the curable siloxane resin composition were prepared in the same manner as in Example 1, except that vinyltrimethoxysilane and diphenyldimethoxysilane were mixed in a molar ratio of 3:7 (number average molecular weight (Mn): 1608 g / mol, weight average molecular weight (Mw): 3527 g / mol of the siloxane resin before curing).

[0093] The degree of condensation of the obtained siloxane resin, calculated by NMR (Nuclear Magnetic Resonance) spectroscopy, was approximately 100%.

[0094] Example 4 A siloxane resin and a cured product of the curable siloxane resin composition were prepared in the same manner as in Example 1, except that a 0.1N aqueous hydrochloric acid solution (HCl(aq)) was used instead of an aqueous solution of 0.1N aqueous ammonia. (Number average molecular weight (Mn): 4130 g / mol, weight average molecular weight (Mw): 8830 g / mol of the siloxane resin before curing)

[0095] Example 5 The siloxane composition prepared in Example 1 was impregnated into glass cloth (NE-glass, NEA1035, Nittobo), and then cured in the same manner as in Example 1 to produce a composite film.

[0096] Example 6 A composite film was produced by curing the siloxane composition prepared in Example 1 in the same manner as in Example 1, except that silica (FB, Denka, Japan) was added as an inorganic filler.

[0097] Comparative Example 1 A curable siloxane resin composition was prepared in the same manner as in Example 1, except that vinylmethyldimethoxysilane (Gelest, USA) and diphenyldimethoxysilane were mixed in a molar ratio of 2:3, and a cured product of the curable siloxane resin composition was produced.

[0098] Comparative Example 2 A curable siloxane resin composition was prepared in the same manner as in Example 1, except that vinyltriethoxysilane and methyldiethoxysilane were mixed in a 1:1 molar ratio, and a cured product of the curable siloxane resin composition was produced.

[0099] Comparative Example 3 Except for the catalyst removal process, a cured product of the curable siloxane resin composition was produced using the same method as in Example 1.

[0100] Comparative Example 4 The siloxane composition prepared in Comparative Example 1 was impregnated into a glass cloth, and then cured in the same manner as in Example 1 to produce a composite film.

[0101] Comparative Example 5 A composite film was produced by curing the siloxane composition prepared in Comparative Example 1 in the same manner as in Example 1, except that silica was added as an inorganic filler.

[0102] Experiment Example 1 - Measurement Experiment of Dielectric Constant / Dielectric Loss Tangent The dielectric constant / dielectric loss tangent (Dk / Df) at 10 GHz of the cured products of the curable siloxane resin compositions produced in Examples 1-6 and Comparative Examples 1-5, and of the composite films containing the cured products, was measured using a vector network analyzer (N5222B, Keysight, USA) and a split post dielectric resonator (10 GHz, QWED, Poland). The measurement results are shown in Table 1 below.

[0103] Experiment Example 2 - Experiment to measure moisture absorption rate The moisture absorption rates of the cured products of the curable siloxane resin compositions produced in Examples 1-6 and Comparative Examples 1-5, and the composite films containing the cured products, were measured according to ASTM D570 standards, and the measurement results are shown in Table 1 below.

[0104] Experimental Example 3 - Measurement Experiment of Glass Transition Temperature The glass transition temperatures of the cured products of the curable siloxane resin compositions produced in Examples 1-6 and Comparative Examples 1-5, and of the composite films containing the cured products, were measured using a Thermo Mechanical Analyzer (SS6100, SII Co., Ltd., Japan) according to ASTM E1545 standards, and the measurement results are shown in Table 1 below.

[0105] Experiment Example 4 - Measurement Experiment of Thermal Expansion Coefficient The thermal expansion coefficients of the cured products of the curable siloxane resin compositions produced in Examples 1-6 and Comparative Examples 1-5, and the composite films containing the cured products, were measured using a Thermo Mechanical Analyzer (SS6100, SII Co., Ltd., Japan) in accordance with ASTM E831, and the measurement results are shown in Table 1 below.

[0106] Experimental Example 5 - Measurement Experiment of the Ratio of Loss Modulus to Storage Modulus The ratio (tand) of the storage modulus to the loss factor of the curable siloxane resin compositions produced in Examples 1-6 and Comparative Examples 1-5 was measured using a rheometer (MCR302, Anton Paar, Austria) according to ASTM E277 standards, and the measurement results are shown in Table 1 below.

[0107] [Table 1]

[0108] Table 1 shows that the cured products of the curable siloxane resin compositions according to Examples 1 to 6, as well as the composite films containing the cured products, all have a dielectric constant of 3.3 or less and a dielectric loss tangent of 0.003 or less at 10 GHz. Therefore, they possess dielectric constant / dielectric loss tangent characteristics suitable for low dielectric insulating layer materials for ultra-high frequency and ultra-high-speed electronic devices.

[0109] Table 1 shows that the cured products of the curable siloxane resin compositions according to Examples 1 to 6, and the composite films containing the cured products, all have a moisture absorption rate of 0.1% or less, indicating that they possess moisture absorption characteristics suitable for low-dielectric insulating layer materials for ultra-high frequency and ultra-high-speed electronic devices.

[0110] Table 1 shows that the glass transition temperatures of the cured products of the curable siloxane resin compositions from Examples 1 to 6 were not below 300°C when measured according to Experimental Example 3. Therefore, it can be confirmed that the glass transition temperatures of the cured products of all curable siloxane resin compositions, and the composite films containing the cured products, are 300°C or higher. Accordingly, it can be seen that the cured products of the curable siloxane resin compositions from Examples 1 to 5 have glass transition temperature characteristics suitable for low-dielectric insulating layer materials for ultra-high frequency and ultra-high-speed electronic devices.

[0111] Table 1 shows that the thermal expansion coefficients of the cured products of the curable siloxane resin compositions according to Examples 1 to 6, and the composite films containing the cured products, are all less than 100 ppm / °C. Therefore, it can be seen that they have thermal expansion coefficient characteristics suitable for low-dielectric insulating layer materials for ultra-high frequency and ultra-high-speed electronic devices.

[0112] On the other hand, referring to Table 1, the cured product of the curable siloxane resin composition according to Comparative Example 2 has a dielectric loss tangent of 0.003 or more at 10 GHz, which is not a suitable dielectric property for a low-dielectric insulating layer material for ultra-high frequency and ultra-high-speed electronic devices.

[0113] Referring to Table 1, the cured product of the curable siloxane resin composition according to Comparative Example 3 has a moisture absorption rate of 0.1% or more, which is not a suitable moisture absorption characteristic for low-dielectric insulating layer materials for ultra-high frequency and ultra-high-speed electronic devices.

[0114] Referring to Table 1, the cured products of the curable siloxane resin compositions from Comparative Examples 1-5, and the composite films containing the cured products, have a tand greater than 1 and are fluid at room temperature, making film formation impossible. Therefore, these properties are not suitable for materials used as low-dielectric insulating layers in ultra-high frequency and ultra-high-speed electronic devices.

[0115] Referring to Table 1, the glass transition temperature and thermal expansion coefficient characteristics of the cured products of the curable siloxane resin compositions of Comparative Examples 1 to 5, and the composite films containing the cured products, each exhibit characteristics suitable for low-dielectric insulating layers in ultra-high frequency and ultra-high-speed electronic devices. However, overall, for the reasons stated above, they are ultimately not suitable for low-dielectric insulating layers in ultra-high frequency and ultra-high-speed electronic devices.

[0116] Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto. Many modifications and improvements made by those skilled in the art, utilizing the basic concepts of the present invention as defined in the following claims, also fall within the scope of the present invention.

Claims

1. A siloxane resin represented by the following formula 1 is produced by a hydrolysis condensation reaction of a mixture containing a trialkoxysilane having an alkenyl group and a dialkoxysilane having at least one aryl group, It contains a radical polymerization initiator, A curable siloxane resin composition having a ratio of loss modulus to storage modulus of 1 or less. 【Chemistry 1】 (In the formula, R1 is linear or branched C ２－２０ It contains an alkenyl group, and R2 is linear or branched C ６－２０ It contains an aryl group, and R3 is linear or branched C ６－２０ Aryl group, C １ -C ２０ Alkyl alkyl group, or C ２－２０ (It contains an alkenyl group, and a and b are natural numbers, where b is greater than or equal to a.)

2. The curable siloxane resin composition according to claim 1, wherein the number average molecular weight of the siloxane resin is 1,000 g / mol to 15,000 g / mol, and the weight average molecular weight is 1,000 g / mol to 30,000 g / mol.

3. The curable siloxane resin composition according to claim 1, wherein the trialkoxysilane comprises at least one selected from the group consisting of vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, trimethoxy(4-vinylphenyl)silane, and triethoxy(4-vinylphenyl)silane.

4. The curable siloxane resin composition according to claim 1, wherein the dialkoxysilane comprises at least one selected from the group consisting of methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,4-bis(methoxydimethylsilyl)benzene, 1,4-bis(ethoxydimethylsilyl)benzene, 4-vinyldiphenyldimethoxysilane, and 4-vinyldiphenyldiethoxysilane.

5. The radical polymerization initiators are 2,3-dimethyl-2,3-diphenylbutane, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexine-3,3,6,9-triethyl-3,6,9-trimethyl-1,4,7-tripeloxonane, di(tert-butyl)-peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, di(tert-butylperoxy-isopropyl)benzene, tert-butylcumylperoxide, di-(tert-amyl)-peroxide, dicumylperoxide, butyl4,4-di( tert-butylperoxy)valerate, tert-butylperoxybenzoate, 2,2-di(tert-butylperoxy)butane, tert-amylperoxy-benzoate, tert-butylperoxy-acetate, tert-butylperoxy-(2-ethylhexyl)carbonate, tert-butylperoxyisopropylcarbonate, tert-butylperoxy-3,5,5-trimethylhexanoate, 1,1-di(tert-butylperoxy)cyclohexane, tert-amylperoxyacetate, tert- Milperoxy-(2-ethylhexyl) carbonate, 1,1-di(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, tert-butyl-monoperoxymalate, 1,1'-azodi(hexahydrobenzonitrile), tert-butylperoxy-isobutyrate, tert-butylperoxydiethylacetate, tert-butylperoxy-2-ethylhexanoic acid, dibenzoyl peroxide, tert-amylperoxy-2-ethylhexanoic acid, di( 3-methylbenzoyl)peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoic acid, ammonium peroxodisulfate, 2,5,-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,2'-azodi(2-methylbutyronideyl), 2,2'-azodi(isobutyronideyl), didecanoylperoxide, dilauroylperoxide, di(3,5,5-trimethylhexanoyl)peroxide, tert-amylperoxypivalate, tert-butylperoxyneoheptanoate, 1,1,3,3,-Tetramethylbutylperoxypivalate, tert-butylperoxypivalate, dicetylperoxydicarbonate, dimyristylperoxydicarbonate, di(2-ethylhexyl)peroxydicarbonate, di(4-tert-butylcyclohexyl)peroxycarbonate, diisopropylperoxydicarbonate, tert-butylperoxyneodecanoate, di-sec-butylperoxydicarbonate, tert-amylperoxyneodecanoate, cumylperoxyneoheptanoate, di( A curable siloxane resin composition according to claim 1, comprising at least one selected from the group consisting of 3-methoxybutyl)peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, cumylperoxyneodecanoate, diisobutyryl peroxide, benzoin, benzoin ethyl ether, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, and oxime ester compounds.

6. A film comprising a cured product of a curable siloxane resin composition according to any one of claims 1 to 5.

7. The film according to claim 6, wherein the cured product has a dielectric constant of 3.3 or less at 10 GHz and a dielectric loss tangent of 0.003 or less.

8. A composite film comprising a cured product of a curable siloxane resin composition according to any one of claims 1 to 5, and at least one of glass cloth or an inorganic filler.

9. A copper-clad laminate comprising the composite film described in claim 8.

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