Curable siloxane resin composition and film including 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 for use as a low-dielectric insulating layer material in 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, which are used in 5G / 6G communications, virtual reality (VR), artificial intelligence (AI), autonomous vehicles, and high-performance computing (HPC), are capable of transmitting and processing large amounts of data at high speed, enabling the creation of ultra-connectivity between numerous devices, resulting in rapid market growth. Ultra-high-frequency and ultra-high-speed electronic devices operate at frequencies above gigahertz (GHz). To maintain the performance of electronic devices under these conditions, transmission loss 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 conducted to reduce circuit transmission loss in ultra-high-frequency and ultra-high-speed electronic devices.

[0003] Transmission loss is expressed as the sum of conductor loss and dielectric loss, of which dielectric loss accounts for a very large portion in the high frequency band.Since this dielectric loss is determined by the dielectric constant and dielectric loss tangent of the insulating layer that makes up the circuit, a common method for minimizing transmission loss in ultra-high frequency and ultra-high speed electronic devices is to use materials with 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 terms of practical application while simultaneously satisfying appropriate thermal, mechanical, and dielectric reliability. For example, International Patent Publication No. 2022-163335 proposes a polyimide resin composition, but its dielectric properties are insufficient. Furthermore, the polyphenylene resin composition proposed in U.S. Patent Publication No. 2023-0312912 A1 has a low glass transition temperature, making it difficult to expect thermal reliability. Meanwhile, the filler-containing liquid crystal crystalline resin proposed in U.S. Patent Publication No. 11760932 B2 has excellent dielectric properties, but does not resolve the problem of reduced reliability in via holes due to the anisotropy of the liquid crystal resin's chemical structure. In addition, the methacrylic resin proposed in U.S. Patent Publication No. 2022-0169769A1 does not provide a commonly used method for measuring dielectric properties, the bismaleimide resin proposed in U.S. Patent Registration No. 11678432 B2 does not provide clear examples of thermomechanical reliability such as glass transition temperature, and the epoxy resin composition proposed in Japanese Patent Registration No. 6867459B2 does not provide clear examples of dielectric constant and its reliability, making it difficult to determine whether the materials proposed in each document are suitable as low-dielectric insulating layer materials for ultra-high frequency and ultra-high speed electronic devices.

[0005] Meanwhile, in Korean Patent Publication No. 10-2023-0039848A, we proposed a siloxane resin with low dielectric constant / dielectric dissipation factor (DTF), low moisture absorption, 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 and is fluid, making it difficult to form into a free-standing film and difficult to apply to insulating material lamination processes for highly integrated circuit configurations. Furthermore, the precursors required for resin production are not cost-competitive enough to fully utilize this resin. Therefore, a new resin is needed that has low DTF / DTF in the gigahertz and higher frequency ranges, as well as suitable thermal and mechanical properties and reliability, the ability to form into a free-standing film, and cost competitiveness. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] International Patent Publication No. 2022-163335 [Patent Document 2] U.S. Patent Publication 2023-0312912 [Patent Document 3] US Patent 11760932 [Patent Document 4] U.S. Patent Publication 2022-0169769 [Patent Document 5] US Patent 11678431 [Patent Document 6] Japanese Patent Registration No. 6867459 [Patent Document 7] Korean Patent Publication No. 10-2023-0039848A Summary of the Invention [Problem to be solved by the invention]

[0007] In order to solve the above problems, the present invention aims to provide a curable siloxane resin composition having properties (low dielectric constant / dielectric dissipation factor, low moisture absorption rate, high glass transition temperature, low thermal expansion coefficient, low loss modulus / storage modulus ratio, price competitiveness, etc.) suitable for use as a low dielectric insulating layer material in ultra-high frequency / 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 produced by a hydrolysis and condensation reaction of a mixture containing a trialkoxysilane having an alkenyl group and a dialkoxysilane having at least one allyl group, and is represented by the following formula 1:

[0009] [ka]

[0010] In the formula, R1 is a linear or branched C 2-20 R2 is a linear or branched C 6-20 R3 is a linear or branched C 6-20 Allyl group, C1-C 20 Alkyl group or C 2-20 It includes an alkenyl group, wherein a and b are each a natural number, 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 includes 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 includes 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 initiator may be 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-butylcumyl peroxide, di-(tert-amyl)-peroxide, dicumyl peroxide, butyl 4,4-di( tert-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- peroxy-(2-ethylhexyl)carbonate, 1,1-di(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, tert-butyl-monoperoxy-maleate, 1,1'-azodi(hexahydrobenzonitrile), tert-butylperoxy-isobutyrate, tert-butylperoxydiethyl acetate, tert-butylperoxy-2-ethylhexanoic acid, dibenzoyl peroxide, tert-amylperoxy-2-ethylhexanoic acid, di( 3-methylbenzoyl) peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, ammonium peroxodisulfate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,2'-azodi(2-methylbutyronitolyl), 2,2'-azodi(isobutyronitolyl), didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, tert-amyl peroxypivalate, tert-butyl peroxyneoheptanoate, 1,1,3,3,-Tetramethylbutyl peroxypivalate, tert-butyl peroxypivalate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxycarbonate, diisopropyl peroxydicarbonate, tert-butyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, tert-amyl peroxyneodecanoate, cumyl peroxyne The compound includes at least one selected from the group consisting of butyl peroxyneodecanoate, di(3-methoxybutyl)peroxydicarbonate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, cumyl peroxyneodecanoate, 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] A film according to another aspect of the present invention comprises a cured product of the curable siloxane resin composition.

[0017] 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.

[0018] A composite film according to another embodiment of the present invention includes a film containing the cured product of the curable siloxane resin composition, and at least one of a glass cloth and an inorganic filler.

[0019] A copper clad laminate (CCL) according to another aspect of the present invention 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 above gigahertz, and therefore can provide properties suitable for use as a low-dielectric insulating layer material 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, so it can behave like a solid without a separate curing process, is non-sticky, and can be produced in the form of a film, sheet, or roll. It is easy to handle and provides convenience for subsequent processing steps, making it particularly suitable for use as a low-dielectric insulating layer material in ultra-high frequency and ultra-high speed electronic devices. DETAILED DESCRIPTION OF THE INVENTION

[0022] The present invention will be described in detail below so that those skilled in the art can easily practice the present invention. However, the present invention may be embodied in various different forms and is not limited to the embodiments described herein. Furthermore, detailed descriptions of well-known techniques will be omitted.

[0023] Throughout the specification of the present invention, when a part "comprises" a certain element, this does not mean that it excludes other elements, but that it can also include other elements, unless otherwise specified to the contrary.

[0024] The terms "approximately," "substantially," and the like used throughout the specification of the present invention are used to mean a numerical value or a value close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are given, and are used to prevent unscrupulous infringers from unfairly taking advantage of the disclosure in which precise or absolute numerical values ​​are stated to aid in the understanding of the present invention.

[0025] To the extent used throughout the present specification, the term "step of" or "step of" does not mean "a step for."

[0026] Throughout the specification of the present invention, when a part is said to be "connected" to another part, this includes not only when they are "directly connected" to each other, but also when they are "electrically connected" to each other via another element therebetween.

[0027] Throughout the present specification, when an element is said to be "on" another element, this does not only include when the element is in contact with the other element, but also when there is another element between the two elements.

[0028] Throughout the present specification, the term "combination thereof" contained in a Markush expression means a mixture or combination of one or more selected from the group of elements described in the Markush expression, and means including one or more selected from the group of elements.

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

[0030] Throughout the present specification, the term "alkenyl group" refers to a monovalent hydrocarbon group in the form of an alkyl group having two or more carbon atoms and containing at least one carbon-carbon double bond, and includes, but is not limited to, linear or branched C2-20 alkenyl groups.

[0031] Throughout the present specification, the term "aryl group" refers to a monovalent functional group formed by the removal of a hydrogen atom present in one or more rings of an arene, including C6-20 aryl groups such as, but not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, or all possible isomers thereof. Arenes are hydrocarbon groups having an aromatic ring, including single-ring or multi-ring hydrocarbon groups, where multi-ring hydrocarbon groups contain one or more aromatic rings and additional rings, either aromatic or non-aromatic.

[0032] Throughout the present specification, the term "alkoxy group or alkoxy" refers to an alkyl group bonded to an oxygen atom and includes a C1-20 alkoxy group, such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, eicosanyloxy, or any possible isomers thereof, but is not limited thereto.

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

[0034] A method for producing a curable siloxane resin composition according to one embodiment of the present invention will now be described in detail.

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

[0036] [ka]

[0037] In the formula, R1 is a linear or branched C 2-20 R2 is a linear or branched C 6-20 R3 is a linear or branched C 6-20 Allyl group, C1-C 20 Alkyl group or C 2-20 It includes an alkenyl group, wherein a and b are each a natural number, and b is greater than or equal to a.

[0038] The oxygen atom forms a first bond with the silicon atom, and the silicon atom or another linking group (e.g., C 6-20 Arylene group or C 1-5 It forms a second bond with the 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 alkenyl group-containing trialkoxysilane includes at least one compound represented by the following formula 2-1.

[0041] [ka]

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

[0043] The dialkoxysilane containing at least one allyl group includes at least one of the compounds represented by the following formulas 3-1 and 3-2.

[0044] [ka]

[0045] [ka]

[0046] In formulas 3-1 and 3-2, R2 is a linear or branched C 6-20 R3 is a linear or branched C 6-20 Allyl group, C1-C 20 Alkyl group or C 2-20 alkenyl group, and R4 is C 1-5 R5 is C 6-20 Allyl group or C 1-5 Contains an akylene group.

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

[0048] For example, the allyl group-containing dialkoxysilane includes methylphenyldimethoxysilane, methylphenyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 1,4-bis(methoxydimethylsilyl)benzene, 1,4-bis(ethoxydimethylsilyl)benzene, 4-vinyldiphenyldimethoxysilane, 4-vinyldiphenyldiethoxysilane, or a combination thereof.

[0049] When a siloxane resin is prepared by the hydrolysis and condensation reaction of a mixture of the alkenyl group-containing trialkoxysilane, the organodialkoxysilane containing at least one allyl group, and an aqueous acid or base solution, it is advantageous in simultaneously possessing properties suitable for low-dielectric insulating layer materials in ultra-high frequency and ultra-high speed electronic devices, such as a low dielectric constant / dielectric dissipation factor, a low moisture absorption rate, a high glass transition temperature, a low thermal expansion coefficient, and a low ratio of loss modulus to storage modulus.

[0050] Specifically, when a siloxane resin is prepared by the hydrolysis and condensation reaction of a trialkoxysilane and an organodialkoxysilane containing at least one allyl group in an acid or base aqueous solution, the degree of condensation of the siloxane bond increases significantly, resulting in an increased rigidity of the molecular structure, and not only a sharp decrease in the dielectric constant / dielectric loss tangent of the siloxane resin composition, but also a sharp decrease in moisture absorption rate due to the decrease in hydroxyl groups. For example, the degree of condensation of the siloxane resin is 95% or more, preferably 99% or more.

[0051] For example, when a resin is produced by the non-hydrolytic condensation reaction of an organic alkoxysilane and an organic silanol, the degree of condensation is reduced, resulting in a high proportion of hydroxy groups, resulting in a higher dielectric constant / dielectric loss and moisture absorption rate than the siloxane resin composition. For example, the degree of condensation of the resin obtained by the non-hydrolytic condensation reaction of an organic alkoxysilane and an organic silanol is 80% or less, or 85% or less.

[0052] For example, when a siloxane resin is produced by the hydrolysis and condensation reaction of a trialkoxysilane and an organodialkoxysilane containing at least one allyl group in an acid or base aqueous solution, the dipole moment of the entire molecule is reduced by the alkenyl and allyl groups, which can be expected to reduce the dielectric constant and dielectric loss tangent of the siloxane resin.

[0053] For example, when a siloxane resin is prepared by the hydrolysis and condensation reaction of an alkenyl-containing trialkoxysilane and an organodialkoxysilane containing at least one allyl group in an acid or base aqueous solution, a stronger siloxane bond is likely to be obtained, which can be expected to increase the glass transition temperature and reduce the thermal expansion coefficient. Furthermore, the stronger siloxane bond reduces the ratio of the loss modulus to the storage modulus of the siloxane resin, which eliminates the fluidity of the siloxane resin at room temperature. This allows the siloxane resin composition to form a film without the need for a further curing process, which is highly advantageous in terms of processing for use as a low-dielectric insulating layer material in ultra-high frequency and ultra-high speed electronic devices. Furthermore, the dialkoxysilane provides a highly symmetrical structure, which can be expected to further reduce the dielectric constant / dielectric loss tangent.

[0054] For example, when siloxane resins are produced by the hydrolysis and condensation reaction of only dialkoxysilanes, the high proportion of linear siloxane structures makes it highly likely that a structure with maximized symmetry can be obtained, which can lead to extremely low dielectric constants and dielectric dissipation factors. However, the rigidity of the siloxane bonds is reduced, and the ratio of loss modulus to storage modulus is high. Therefore, without a further curing process, the film-forming effect of the siloxane resin composition itself cannot be expected, which is very disadvantageous in terms of processing for application as a low-dielectric insulating layer material for ultra-high frequency and ultra-high speed electronic devices. Furthermore, when siloxane resins are produced by the hydrolysis and condensation reaction of only dialkoxysilanes, the overall production costs due to the dialkoxysilane production costs are very high, making it very disadvantageous for application as a low-dielectric insulating layer material for ultra-high frequency and ultra-high speed electronic devices.

[0055] The siloxane resin composition has a loss modulus to storage modulus ratio of 1 or less, which can be defined for solids according to the American Society for Testing and Materials (ASTM) E3277 standard. This is therefore a film-forming property suitable for use as a low-dielectric insulating layer material in ultra-high-frequency and ultra-high-speed electronic devices.

[0056] Preferably, the molar ratio of the dialkoxysilane containing at least one allyl group to the trialkoxysilane containing an alkenyl group is the same or larger. More preferably, the siloxane resin may have a structure of Formula 1, and the ratio of a to b (the molar ratio of the trialkoxysilane containing an alkenyl group to the dialkoxysilane containing at least one allyl 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] A cured product of the siloxane resin obtained by such a combination has both a low dielectric constant and a low dielectric loss tangent, and therefore can achieve excellent insulating performance.

[0058] The siloxane resin is produced by a hydrolysis and condensation reaction of an alkenyl-containing trialkoxysilane and at least one allyl-containing organodialkoxysilane using an acid or base aqueous solution, and the reaction conditions, such as reaction temperature, reaction atmosphere, and the type, amount, and concentration of the acid or base aqueous solution, are adjusted.

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

[0060] The aqueous base solution contains an alkali metal compound, an alkaline earth metal compound, a quaternary ammonium compound, ammonia, an aqueous amine compound, or a combination thereof, such as one or more selected from the group consisting of an alkali metal compound selected from sodium hydroxide, potassium hydroxide, and lithium hydroxide, an alkaline earth metal compound selected from barium hydroxide monohydrate, barium hydroxide octahydrate, potassium hydroxide, and magnesium hydroxide, a quaternary ammonium compound selected from tetraalkylammonium silanolate, tetraethylammonium hydroxide, tetramethylammonium chloride, and tetrabutylammonium fluoride, ammonia, an aqueous amine compound, and a combination thereof.

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

[0062] For example, when preparing a siloxane resin by the hydrolysis and condensation reaction of an alkenyl-containing trialkoxysilane and an organodialkoxysilane containing at least one allyl group using an aqueous acid or base solution, a mixture of the alkenyl-containing trialkoxysilane, the dialkoxysilane containing at least one allyl group, and the aqueous acid or base solution is stirred in 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 thereto.

[0063] When preparing a siloxane resin by the hydrolysis and condensation reaction of an alkenyl-containing trialkoxysilane and at least one allyl-containing organodialkoxysilane in an acid or base aqueous solution, the acid or base catalyst contained in the acid or base aqueous solution can be removed by a known physical or chemical method 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 this 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 phase separation method.

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

[0065] The radical polymerization initiators are 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-butylcumyl peroxide, di-(tert-amyl)-peroxide, dicumyl peroxide, butyl 4,4-di(te tert-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-monoperoxy-maleate, 1,1'-azodi(hexahydrobenzonitrile), tert-butylperoxy-isobutyrate, tert-butylperoxydiethyl acetate, tert-butylperoxy-2-ethylhexanoic acid, dibenzoyl peroxide, tert-amylperoxy-2-ethylhexanoic acid, di(3- Methylbenzoyl) peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, ammonium peroxodisulfate, 2,5-dimethyl-2,5-di(2-ethylhexanoyl peroxide)hexane, 2,2'-azodi(2-methylbutyronitolyl), 2,2'-azodi(isobutyronitolyl), didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, tert-amyl peroxypivalate, tert-butyl peroxyneoheptanoate, 1,1,3,3,-tetramethylbutyl peroxypivalate, tert-butyl peroxypivalate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxycarbonate, diisopropyl peroxydicarbonate, tert-butyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, tert-amyl peroxyneodecanoate, cumyl peroxyneoheptanoate, The peroxygenating agent may include, but is not limited to, one or more 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 contained in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the siloxane resin.

[0067] The initiation of the radical polymerization initiator for curing the siloxane resin composition is usually carried out by light or heat using well-known methods and conditions, but is not limited thereto.

[0068] By using a radical polymerization initiator, the 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, which are dielectric properties suitable for use as low-dielectric insulating layer materials in ultra-high frequency and ultra-high speed electronic devices.

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

[0071] The cured product of the siloxane resin composition is characterized by a glass transition temperature of 300°C or higher, which is a glass transition temperature characteristic suitable for use as a low-dielectric insulating layer material 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 to 300°C, which is a thermal expansion coefficient characteristic suitable for use as a low-dielectric insulating layer material in ultra-high frequency and ultra-high speed electronic devices.

[0073] One embodiment may provide a film made using the curable siloxane resin composition, the film having a free-standing film, sheet, or roll form.

[0074] In the production of freestanding films, sheets, and rolls, when a fluid curable siloxane resin composition is formed into a film at high temperatures and then cooled to room temperature, a freestanding film that is easy to handle can be obtained without further curing or curing processes due to the low ratio of loss modulus to storage modulus of the curable siloxane resin composition as described above. Considering the overall process, this is a property that is suitable for use as a low-dielectric insulating layer material in ultra-high frequency and ultra-high speed electronic devices.

[0075] In one embodiment, a composite film or sheet may be provided that includes a cured product of a curable siloxane resin composition and at least one of glass cloth and an inorganic filler, wherein the glass cloth or inorganic filler is dispersed within the cured product.

[0076] Examples of the glass cloth include, but are not limited to, woven glass fabrics made of 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, non-woven glass fabrics, and mixtures thereof.

[0077] The inorganic filler includes, but is 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 cured product of a siloxane composition is mixed with at least one of glass cloth and inorganic filler to produce a composite film or sheet, the effect of extremely reducing the coefficient of thermal expansion is obtained, which is very advantageous in the subsequent thermal processing steps.

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

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

[0081] One embodiment provides an ultra-high frequency, ultra-high speed electronic device that includes a printed wiring board.

[0082] The curable siloxane resin composition has low dielectric constant / dielectric loss tangent, low moisture absorption rate, high glass transition temperature, low thermal expansion coefficient, and film formability, and can realize a well-balanced set of properties suitable for use as a low-dielectric insulating layer material in ultra-high frequency and ultra-high speed electronic devices. [Example]

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

[0084] Example 1 Vinyltrimethoxysilane (Gelest, USA) and diphenyldimethoxysilane (Gelest, USA) were mixed in a 1:1 molar ratio. After adding 0.1N aqueous ammonia solution (NHOH(aq)), the mixture was stirred at 80°C for 12 hours under a nitrogen atmosphere. To remove the aqueous ammonia, which acts as a catalyst, from the resulting siloxane resin, the mixture was mixed with methyl isobutyl ketone (MIBK, SAMCHUN CHEMICALS, Korea) and water (HO) in a weight ratio of 1:5:4. Due to differences in solubility, the MIBK layer containing the dissolved siloxane and the aqueous layer containing the dissolved catalyst separated, yielding only the MIBK layer. Thereafter, the MIBK and the siloxane resin were separated using vacuum distillation to obtain a 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 about 100%, and the degree of condensation was calculated as follows.

[0086]

number

[0087] [ka]

[0088] To the prepared siloxane resin, 1 part by weight of di(tert-butyl)-peroxide (DTBP, Sigma Aldrich, USA) was added per 100 parts by weight of the siloxane resin to prepare a curable siloxane resin composition.

[0089] The prepared siloxane resin composition was heat-treated (4 hours, 250° C.) to prepare 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) of the siloxane resin before curing: 2170 g / mol, weight average molecular weight (Mw): 4327 g / mol).

[0091] The degree of condensation of the resulting 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) of the siloxane resin before curing: 1608 g / mol, weight average molecular weight (Mw): 3527 g / mol).

[0093] The degree of condensation of the resulting 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 0.1 N aqueous hydrochloric acid (HCl(aq)) was used instead of 0.1 N aqueous ammonia. (Number average molecular weight (Mn) of the siloxane resin before curing: 4130 g / mol, weight average molecular weight (Mw): 8830 g / mol)

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

[0096] Example 6 A composite film was prepared 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 also prepared.

[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 molar ratio of 1:1, and a cured product of the curable siloxane resin composition was also prepared.

[0099] Comparative Example 3 A cured product of the curable siloxane resin composition was prepared in the same manner as in Example 1, except for the catalyst removal process.

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

[0101] Comparative Example 5 A composite film was prepared 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] Experimental Example 1 - Dielectric constant / dielectric loss tangent measurement experiment 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 to 6 and Comparative Examples 1 to 5, and of composite films containing the cured products, were measured using a vector network analyzer (N5222B, Keysight, USA) and a split post dielectric resonator (for 10 GHz, QWED, Poland), and the measurement results are shown in Table 1 below.

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

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

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

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

[0107] [Table 1]

[0108] From Table 1, it can be seen that the cured products of the curable siloxane resin compositions of Examples 1 to 6 and the composite films containing the cured products all have a dielectric constant of 3.3 or less and a dielectric dissipation factor of 0.003 or less at 10 GHz, and therefore have dielectric constant / dielectric dissipation factor characteristics suitable for use as low-dielectric insulating layer materials in ultra-high frequency and ultra-high speed electronic devices.

[0109] From Table 1, it can be seen that the cured products of the curable siloxane resin compositions of Examples 1 to 6 and the composite films containing the cured products all have moisture absorption rates of 0.1% or less, and therefore have moisture absorption properties suitable for use as low-dielectric insulating layer materials in ultra-high frequency and ultra-high speed electronic devices.

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

[0111] From Table 1, it can be seen that the thermal expansion coefficients of the cured products of the curable siloxane resin compositions of Examples 1 to 6 and the composite films containing the cured products are all less than 100 ppm / °C, and therefore have thermal expansion coefficient properties suitable for use as low-dielectric insulating layer materials in 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 in ultra-high frequency / 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 moisture absorption rate characteristic suitable for a low-dielectric insulating layer material for ultra-high frequency and ultra-high speed electronic devices.

[0114] Referring to Table 1, the cured products of the curable siloxane resin compositions of Comparative Examples 1 to 5 and composite films containing the cured products had a tangent greater than 1 and were fluid at room temperature, making them impossible to form into films. These properties are therefore not suitable for use as materials for low-dielectric insulating layers in ultra-high-frequency and ultra-high-speed electronic devices.

[0115] Referring to Table 1, the glass transition temperatures and thermal expansion coefficients of the cured products of the curable siloxane resin compositions and composite films containing the cured products according to Comparative Examples 1 to 5 each exhibit properties suitable for use as low-dielectric insulating layer materials in ultra-high frequency and ultra-high speed electronic devices. However, overall, for the reasons described above, they are ultimately not suitable as low-dielectric insulating layer materials in ultra-high frequency and ultra-high speed electronic devices.

[0116] Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and many variations and improvements made by those skilled in the art using the basic concept of the present invention 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, which is produced by a hydrolysis and condensation reaction of a mixture containing a trialkoxysilane having an alkenyl group and a dialkoxysilane having at least one allyl group; and a radical polymerization initiator. 【Chemistry 1】 (Wherein R1 is a linear or branched C ２－２０ R2 is a linear or branched C ６－２０ R3 is a linear or branched C ６－２０ Allyl group, C １ -C ２０ an alkyl group or C ２－２０ It contains an alkenyl group, and a and b are each a natural number, and b is greater than or equal to a.

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

3. 2. 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. 2. 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 initiator may be 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-butylcumyl peroxide, di-(tert-amyl)-peroxide, dicumyl peroxide, butyl 4,4-di( tert-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- peroxy-(2-ethylhexyl)carbonate, 1,1-di(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-di(tert-amylperoxy)cyclohexane, tert-butyl-monoperoxy-maleate, 1,1'-azodi(hexahydrobenzonitrile), tert-butylperoxy-isobutyrate, tert-butylperoxydiethyl acetate, tert-butylperoxy-2-ethylhexanoic acid, dibenzoyl peroxide, tert-amylperoxy-2-ethylhexanoic acid, di( 3-methylbenzoyl) peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, ammonium peroxodisulfate, 2,5-dimethyl-2,5-di(2-ethylhexanoylperoxy)hexane, 2,2'-azodi(2-methylbutyronitolyl), 2,2'-azodi(isobutyronitolyl), didecanoyl peroxide, dilauroyl peroxide, di(3,5,5-trimethylhexanoyl) peroxide, tert-amyl peroxypivalate, tert-butyl peroxyneoheptanoate, 1,1,3,3,-Tetramethylbutyl peroxypivalate, tert-butyl peroxypivalate, dicetyl peroxydicarbonate, dimyristyl peroxydicarbonate, di(2-ethylhexyl) peroxydicarbonate, di(4-tert-butylcyclohexyl) peroxycarbonate, diisopropyl peroxydicarbonate, tert-butyl peroxyneodecanoate, di-sec-butyl peroxydicarbonate, tert-amyl peroxyneodecanoate, cumyl peroxyneoheptanoate, di( The curable siloxane resin composition according to claim 1, comprising at least one selected from the group consisting of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, and oxime ester compounds.

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

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

8. The film according to claim 7, wherein 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.

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

10. A copper clad laminate comprising the composite film of claim 9.

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