Composition for low dielectric member

Abstract

To provide a composition which enables formation of a low dielectric member that has low dielectric characteristics and has high heat resistance.SOLUTION: A composition for a low dielectric member enables manufacture of a low dielectric resin composition holding an extremely low dielectric constant even in a high frequency region of 10 GHz or more by curing a polymerizable silsesquioxane compound having a specific structure with a polymer or a monomer that is polymerizable with the silsesquioxane by copolymerization, and thereby reducing a resin component amount that causes a dielectric constant in a curable resin by a large volume and large porosity of the silsesquioxane.SELECTED DRAWING: Figure 1

Description

Technical field

[0001] The present invention relates to a composition capable of forming a low dielectric member used in resins for electronic substrates and semiconductor packages. In particular, the present invention relates to a low dielectric material that has both a low dielectric constant and high heat resistance, and enables high-speed and low-loss signal transmission in electronic devices, which are increasingly using higher frequencies. [Background technology]

[0002] In recent years, with the shift to 5G and beyond5G and 6G in communication equipment, the frequency of electrical signals on electronic devices and circuit boards such as information and communication equipment and computers has become higher, and the radio waves transmitted and received by antennas have also become higher frequency. The problem is that the transmission speed cannot be increased within the device, or that the signal is attenuated (loss) on the circuit board or antenna board. Therefore, resin materials used for these applications are required to have low dielectric constants and dielectric loss tangents, and instead of conventional epoxy resins, acrylic resins, polyimide (PI) sheets, and polyethylene terephthalate (PET) sheets, liquid crystal Polymer (LCP), polyphenylene ether (PPE), cycloolefin polymer (COP), fluororesin (PTFE), and other resins that have not been used much so far, as well as improved polyimide (mPI) that can be utilized with conventional production processes. It is starting to be used. Curable low dielectric resins have a dielectric constant of 3.0 or less, and materials containing silica or high thermal conductivity fillers have a dielectric constant of 3.5 or less, and there is a need to develop materials with a dielectric constant lower than these. has been developed and is being advanced. (Non-patent document 1)

[0003] In order to achieve such a low dielectric constant, studies are being conducted on introducing bulky hydrocarbon molecules into polymer chains (Patent Documents 1 and 2) and using silicone resins (Patent Documents 3 and 4). It is progressing. In addition, in recent years, studies have been underway to use resins with low dielectric constants in combination in order to satisfy various properties required for products such as water absorption and processability. For example, mixing polyphenylene ether resin and maleimide resin Many studies have been reported (Patent Documents 5 and 6).

[0004] On the other hand, polysilsesquioxane (PSQ) is being developed as a material with a low dielectric constant and high heat resistance, although it is not in the 10GHz to 100THz region for the current beyond5G and 6G (Patent Document 7). Those that have been given functional groups to enable thermal polymerization (Patent Document 8), those that have been incorporated into polyimide (Patent Document 9), those that are compatible with radical reactivity (Patent Document 10), and those that have been combined with fillers to achieve high thermal conductivity. (Patent Document 11) has been developed. In an attempt to apply PSQ, which has been developed for various uses, to electronic devices used in the region of 10 GHz or higher, Patent Document 12 discloses that cage-shaped PSQ is used as a resin for low dielectric substrates using chain siloxane. Polymerized polymers are being considered. However, unlike low dielectric constant epoxy resins and acrylic resins that have traditionally been used in electronic devices and semiconductor elements, it is not possible to mix them with other resins to form electronic devices, so PSQ is used in the same way as conventional resins. We have developed a resin and a composition for forming the resin that can be used in applications with a dielectric constant of less than 3.0 at frequencies above 10 GHz. [Prior art documents] [Patent document]

[0005] [Patent Document 1] International Publication No. 2008 / 114880 [Patent Document 2] Japanese Patent Application Publication No. 2009-149528 [Patent Document 3] Japanese Patent Application Publication No. 2005-290155 [Patent Document 4] Japanese Patent Application Publication No. 2019-081951 [Patent Document 5] Patent No. 7031774 [Patent Document 6] Japanese Patent Application Publication No. 2020-169273 [Patent Document 7] International Publication No. 2003 / 024870 [Patent Document 8] Japanese Patent Application Publication No. 2007-332211 [Patent Document 9] Japanese Patent Application Publication No. 2010-152332 [Patent Document 10] International Publication No. 2018 / 131565 [Patent Document 11] Patent No. 6902193 [Patent Document 12] Japanese Patent Application Publication No. 2022-49915 [Non-patent literature]

[0006] [Non-patent document 1] Hiroyuki Fukunaga / Yoshiyuki Hamato, "Basics and how to choose high-speed / high-frequency boards", RF World, CQ Publishing, 2017, No.40, p.p.97-111 [Summary of the invention] [Problem to be solved by the invention]

[0007] As mentioned above, information communication equipment and computers used in beyond 5G and 6G are driven at high frequencies, so it is desirable for peripheral materials to have a low dielectric constant. Furthermore, since the current semiconductor manufacturing process is based on the accumulation of past technologies, it is preferable to use materials that can be used in conventional molding processes. Therefore, an object of the present invention is to provide a composition that can form a member that has a low dielectric constant and can be cured in the same manner as conventional epoxy. [Means to solve the problem]

[0008] The present inventor has discovered that the present invention contains at least one silsesquioxane compound having a polymerizable group, and by studying its structure and curing method, it has a low dielectric constant of less than 3.0 and high heat resistance. The present invention was completed by discovering a composition that can be cured at a temperature of 200°C or lower, similar to the curing temperature of the resins for electronic components up until now.

[0009] The composition for a low dielectric member according to the first aspect of the present invention is a cage-shaped silsesquioxane (hereinafter, bifunctional or more functional silsesquioxane) having two or more thermosetting or photocurable polymerizable groups. ) and a curing component, and a cured product obtained by curing without adding a filler to the composition is characterized in that the dielectric constants of the cured resin at 10 GHz and 28 GHz are both lower than 3.0. A composition for low dielectric materials.

[0010] In the composition for a low dielectric member according to the second aspect of the present invention, the difunctional or higher functional silsesquioxane is selected from the group of compounds represented by formula (1) and formula (2). is a compound, A composition for a low dielectric member according to a first aspect. TIFF2023170310000002.tif53150 [wherein R is independently alkyl having 1 to 45 carbons, cycloalkyl having 4 to 8 carbons, aryl having 6 to 16 carbons, or arylalkyl having 7 to 16 carbons; In alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine and at least one -CH 2 - may be replaced by -O- or -CH=CH-; in the benzene ring in aryl having 6 to 16 carbon atoms and arylalkyl having 7 to 16 carbon atoms, at least one hydrogen is a halogen or ~10 alkyl may be substituted; in this C1-10 alkyl, at least one hydrogen may be replaced by fluorine and at least one -CH 2 - may be replaced by -O- or -CH=CH-; in alkylene in arylalkyl having 7 to 16 carbon atoms, the number of carbon atoms is 1 to 10 and at least one -CH 2 - may be replaced by -O-; and Y 1 are each independently a group represented by formula (a). ] TIFF2023170310000003.tif24150 [where X is independently cyclopentyl, cyclohexyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 Alkyl having 1 to 10 carbon atoms, where - may be replaced with -O-, phenyl, where at least one hydrogen may be replaced with halogen or alkyl having 1 to 10 carbon atoms, at least one hydrogen having halogen or carbon number Phenyl alkyl composed of phenyl which may be substituted with 1 to 10 alkyl and alkylene having 1 to 4 carbon atoms, or oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, succinimide residue, acrylic, A group having methacryl, a maleimide residue, vinyl or allyl; in the alkyl having 1 to 10 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced by -O-; in alkylene of phenylalkyl, at least one -CH 2 - may be replaced by -O-; and at least one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride, succinimide, acrylic, methacrylic, maleimide, vinyl or allyl It is a group having ] TIFF2023170310000004.tif53150[Here, R has the same definition as R in equation (1), and Y 2 is a group represented by formula (b) or a group represented by formula (c). ] TIFF2023170310000005.tif47150 [where, in each of formula (b) and formula (c), X has the same definition as X in formula (a), and Z in formula (c) is -O-, -CH 2 - or a single bond. ]

[0011] In the composition for a low dielectric member according to the third aspect of the present invention, the difunctional or higher-functional silsesquioxane is such that in the formula (1) and formula (2) according to the second aspect, R is independent. cyclohexyl, phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms, or phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms; Phenylalkyl composed of alkylene having 1 to 4 carbon atoms; In the alkyl having 1 to 4 carbon atoms, which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced by -O-; X is independently alkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms; Phenylalkyl consisting of phenyl and alkylene having 1 to 4 carbon atoms, in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms, or oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride A group having a residue, acrylic, methacrylic, maleimide residue, vinyl or allyl, and in the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least 1-CH 2 - may be replaced by -O-; and In each of formula (a), formula (b) and formula (c) according to the second aspect, at least one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide. The composition for a low dielectric member according to the first or second embodiment, which is a group having a residue, vinyl or allyl.

[0012] In the composition for a low dielectric member according to the fourth aspect of the present invention, the difunctional or higher functional silsesquioxane is formed by R being cyclohexyl in the formula (1) and formula (2) according to the second aspect. , phenyl in which at least one hydrogen may be replaced with a halogen or an alkyl having 1 to 4 carbon atoms, or phenyl in which at least one hydrogen may be replaced with a halogen or an alkyl having 1 to 4 carbon atoms; 4 is a phenylalkyl composed of alkylene; In the alkyl having 1 to 4 carbon atoms, which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced by -O-; In each of formula (a), formula (b) and formula (c) according to the second embodiment, one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue. group, vinyl or allyl, where the remaining phenyl which may be replaced with an alkyl group, phenyl which may have at least one hydrogen replaced with a halogen or an alkyl group having 1 to 4 carbon atoms, and phenylalkyl consisting of alkylene having 1 to 4 carbon atoms; In the alkyl having 1 to 4 carbon atoms, which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced by -O-, A composition for a low dielectric member according to any one of the first to third aspects.

[0013] In the composition for a low dielectric member according to the fifth aspect of the present invention, the bifunctional or more functional silsesquioxane is represented by the formula (1) and formula (2) according to the second aspect, and R is cyclohexyl or is phenyl; In each of formula (a), formula (b) and formula (c) according to the second embodiment, one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue. group, vinyl or allyl, and the remaining X is methyl, ethyl, t-butyl, cyclopentyl, cyclohexyl or phenyl, A composition for a low dielectric member according to any one of the first to fourth aspects.

[0014] In the composition for a low dielectric member according to the sixth aspect of the present invention, the bifunctional or higher functional silsesquioxane is represented by the formula (1) and formula (2) according to the second aspect, and R is phenyl. can be; In each of formula (a), formula (b) and formula (c), one of X has oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue, vinyl or allyl and the remaining X is methyl or phenyl, A composition for a low dielectric member according to any one of the first to fifth aspects.

[0015] The composition for a low dielectric member according to the seventh aspect of the present invention is any one of the first to sixth compositions, wherein the difunctional or higher functional silsesquioxane is a compound represented by formula (1-1). A composition for a low dielectric member according to an embodiment. Here, in formula (1-1), Me represents methyl and Ph represents phenyl. TIFF2023170310000006.tif39150

[0016] The composition for a low dielectric member according to the eighth aspect of the present invention is any one of the first to sixth compositions, wherein the difunctional or higher functional silsesquioxane is a compound represented by formula (1-2). A composition for a low dielectric member according to an embodiment. Here, in formula (1-2), Me represents methyl and Ph represents phenyl. TIFF2023170310000007.tif41150

[0017] The composition for a low dielectric member according to the ninth aspect of the present invention is any one of the first to sixth compositions, wherein the difunctional or higher functional silsesquioxane is a compound represented by formula (2-1). A composition for a low dielectric member according to an embodiment. Here, in formula (2-1), Me represents methyl and Ph represents phenyl. TIFF2023170310000008.tif40150

[0018] The composition for a low dielectric member according to the tenth aspect of the present invention is any one of the first to sixth compositions, wherein the difunctional or higher functional silsesquioxane is a compound represented by formula (2-2). A composition for a low dielectric member according to an embodiment. Here, in formula (2-2), Me represents methyl and Ph represents phenyl. TIFF2023170310000009.tif41150

[0019] The composition for a low dielectric member according to the eleventh aspect of the present invention is any one of the first to sixth compositions, wherein the difunctional or higher functional silsesquioxane is a compound represented by formula (2-3). A composition for a low dielectric member according to an embodiment. Here, in formula (2-3), Me represents methyl. TIFF2023170310000010.tif53170

[0020] The composition for a low dielectric member according to the twelfth aspect of the present invention is any one of the first to sixth compositions, wherein the difunctional or more functional silsesquioxane is a compound represented by formula (2-4). A composition for a low dielectric member according to an embodiment. Here, in formula (2-4), Me represents methyl. TIFF2023170310000011.tif65153

[0021] The composition for a low dielectric member according to the thirteenth aspect of the present invention is the composition according to any one of the first to sixth aspects, wherein the difunctional or higher functional silsesquioxane is a compound represented by formula (2-5). A composition for a low dielectric member according to an embodiment. Here, in formula (2-5), Me represents methyl and Ph represents phenyl. TIFF2023170310000012.tif3481

[0022] In the composition for a low dielectric member according to the fourteenth aspect of the present invention, the curing component is an amine curing agent, an active ester curing agent, a phenol / novolac curing agent, an acid generator, a phosphorus curing accelerator, or an azo curing agent. The composition for a low dielectric member according to any one of the first to thirteenth embodiments, which is a system polymerization initiator.

[0023] A low dielectric member according to a fifteenth aspect of the present invention is a low dielectric member obtained by curing the composition for a low dielectric member according to any one of the first to fourteenth aspects.

[0024] An electronic device according to a sixteenth aspect of the present invention includes a low dielectric member according to the fifteenth aspect; an electronic device having at least one capability selected from the group consisting of the capability of transmitting, converting, transmitting, and processing radio frequencies; Electronics.

Effect of the invention

[0025] A low dielectric member formed from the composition for a low dielectric member of the present invention has an extremely low dielectric constant and high heat resistance in a high frequency region of 10 GHz or higher. Furthermore, it has excellent properties such as controllability of thermal expansion coefficient, chemical stability, hardness, and mechanical strength. The composition for a low dielectric member and the low dielectric member are suitable for, for example, a low dielectric substrate, a low dielectric resin component, a low dielectric insulating film, a varnish serving as a raw material thereof, a low dielectric adhesive, and the like. [Brief explanation of drawings]

[0026]

Figure 1

Figure 2

[0027] Embodiments of the present invention will be described below. Further, the present invention is not limited to the following embodiments.

[0028] The terms used in the present invention will be explained. The compound represented by formula (1) may be referred to as compound (1). Compounds represented by other formulas may also be referred to in a simplified manner. The expression "at least one A may be replaced by B or C" means that at least one A may be replaced by B or C, in addition to the case where at least one A is replaced by B or C. This means that at the same time that B is substituted, at least one other A may be substituted with C. In the chemical formulas described herein, Me is methyl and Ph is phenyl. In the examples, the display data of the electronic balance is shown using g (gram), which is a mass unit. Weight % and weight ratio are data based on such numerical values.

[0029] [Composition for low dielectric materials] The composition for a low dielectric member of the present invention is produced by copolymerizing a polymerizable silsesquioxane compound (a bifunctional or higher functional silsesquioxane) and a polymer or monomer that can be polymerized with the silsesquioxane. By curing, the large volume and large porosity of the silsesquioxane reduce the amount of resin components that cause dielectric constant in the cured resin, resulting in an extremely low dielectric constant even in the high frequency range of 10 GHz or higher. It becomes possible to produce a composition for a low dielectric member that maintains the properties.

[0030] The composition for a low dielectric member according to the first embodiment of the present invention has a basic skeleton having a cage structure in which a plurality of cyclic siloxanes form a closed space, and a specific structure having a polymerizable functional group. This is a curable resin composition with a low dielectric constant, which is produced by applying a polymerizable silsesquioxane compound and producing a cured product with a low density of resin components.

[0031] <Difunctional or higher functional silsesquioxane> Difunctional or higher functional silsesquioxanes include oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residues, succinimide residues, acrylic, methacrylic, maleimide residues, and cage-shaped structures having two or more vinyl or allyl groups. At least one of silsesquioxanes. This cage-type structure is a structure in which a plurality of cyclic siloxanes form a closed space, and the shape of the closed space is not particularly limited. Furthermore, the present invention also includes silsesquioxanes having a structure in which at least one part of the cage structure is not blocked (for example, a double decker type).

[0032] Specific examples of bifunctional or more functional silsesquioxanes having such a structure include Compound (1) and Compound (2). TIFF2023170310000013.tif117168

[0033] In formula (1) and formula (2), R is independently from alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl having 6 to 16 carbon atoms, and arylalkyl having 7 to 16 carbon atoms. is the group of choice. That is, in each of formula (1) and formula (2), the eight R's may be composed of two or more different groups, but it is preferable that all of them are the same group. In this alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced by -O- or -CH=CH-, but adjacent -CH 2 - is never replaced with -O-. This alkyl preferably has 1 to 10 carbon atoms.

[0034] When R is cycloalkyl having 4 to 8 carbon atoms, it may be a group with a crosslinked structure. Preferred examples of cycloalkyl are cyclopentyl and cyclohexyl, with cyclohexyl being more preferred.

[0035] When R is aryl having 6 to 16 carbon atoms or arylalkyl having 7 to 16 carbon atoms, at least one hydrogen in the benzene ring in these groups may be replaced with halogen or alkyl having 1 to 10 carbon atoms. good. Examples of halogens are fluorine, chlorine and bromine. In this alkyl having 1 to 10 carbon atoms, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced by -O- or -CH=CH-, but adjacent -CH 2 - is never replaced with -O-. This alkyl preferably has 1 to 4 carbon atoms. In alkylene in arylalkyl having 7 to 16 carbon atoms, the number of carbon atoms is 1 to 10, and at least one -CH 2 - may be replaced by -O-, but adjacent -CH 2 - is never replaced with -O-. The alkylene preferably has 1 to 4 carbon atoms.

[0036] Examples of such aryl having 6 to 16 carbon atoms are phenyl, halogenated phenyl, 4-methylphenyl, 4-ethylphenyl, 4-butylphenyl, 4-octylphenyl, 2,4-dimethylphenyl, 4-methoxy Phenyl, 4-butoxyphenyl, 4-trifluoromethylphenyl, 4-trifluoromethoxyphenyl, 3-chloro-4-methylphenyl, 3,5-dichloro-4-methylphenyl, and 2,3-difluoro-4- It is methoxyphenyl. Among these, phenyl is particularly preferred.

[0037] Examples of the above-mentioned arylalkyl having 7 to 16 carbon atoms include phenylmethyl, phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 4-chlorophenylmethyl, 4-fluorophenylmethyl, 2-(4-fluorophenyl )propyl, 2-(4-chlorophenyl)ethyl, 4-methylphenylmethyl, 2-(4-methylphenyl)ethyl, 2-(2,5dimethylphenyl)ethyl, 4-trifluoromethylphenylmethyl, 2-( 4-Trifluoromethylphenyl)ethyl, 2-(4-ethenylphenyl)ethyl, 4-methoxyphenylmethyl, 4-ethoxyphenylmethyl, 2-(4-methoxyphenyl)ethyl, 3-(4-methoxyphenyl) propyl, 2-chloro-4-methylphenylmethyl, and 2,5-dichloro-4-methylphenylmethyl.

[0038] Y in equation (1) 1 is a group represented by formula (a), and Y in formula (2) 2 is a group represented by formula (b) or formula (c). When considering manufacturing costs, the two Y in equation (2) 2 are preferably the same group, but may be different groups. TIFF2023170310000014.tif79168

[0039] In each of formula (a), formula (b) and formula (c), X is independently cyclopentyl, cyclohexyl, at least one hydrogen optionally replaced by fluorine, and one -CH 2 Alkyl having 1 to 10 carbon atoms, where - may be replaced with -O-, phenyl, where at least one hydrogen may be replaced with halogen or alkyl having 1 to 10 carbon atoms, at least one hydrogen having halogen or carbon number Phenylalkyl consisting of phenyl which may be substituted with 1 to 10 alkyl and alkylene having 1 to 4 carbon atoms, or oxiranyl, 3,4-epoxycyclohexyl succinic anhydride residue, succinimide residue, acrylic, methacryl , a group having a maleimide residue, vinyl or allyl. At this time, in the alkyl having 1 to 10 carbon atoms, which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and at least one -CH 2 - may be replaced by -O-, one -CH in alkylene of phenylalkyl 2 - may be replaced with -O-. In each of formula (a), formula (b) and formula (c), at least one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, succinimide residue, acrylic, methacryl, maleimide. A group having a residue, vinyl or allyl.

[0040] In each of formula (a), formula (b) and formula (c), one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide residue, vinyl or allyl. , where the remaining X is cyclopentyl, cyclohexyl, at least one hydrogen may be replaced by fluorine, and one -CH 2 alkyl having 1 to 10 carbon atoms in which - may be replaced with -O-, phenyl in which at least one hydrogen may be replaced with a halogen or alkyl having 1 to 10 carbon atoms, and at least one hydrogen in which at least one hydrogen is a halogen or carbon The group is preferably selected from phenylalkyl, which is composed of phenyl which may be substituted with alkyl having 1 to 10 carbon atoms, and alkylene having 1 to 4 carbon atoms.

[0041] The preferred ranges of formula (1) and formula (2) are expressed as follows with respect to R and X. That is, R is independently cyclohexyl, phenyl, in which at least one hydrogen may be replaced with a halogen or an alkyl having 1 to 4 carbon atoms, or at least one hydrogen is replaced with a halogen or an alkyl having 1 to 4 carbon atoms. phenylalkyl composed of optional phenyl and alkylene having 1 to 4 carbon atoms; at least one hydrogen in the alkyl having 1 to 4 carbon atoms, which is a substituent of phenyl, may be replaced with fluorine; and one -CH 2 - may be replaced by -O-; phenyl which may be replaced with ~4 alkyl, phenylalkyl consisting of phenyl where at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms, and alkylene having 1 to 4 carbon atoms, or A group having oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacryl, maleimide residue, vinyl or allyl; at least one alkyl having 1 to 4 carbon atoms as a substituent of phenyl Hydrogen may be replaced by fluorine, and at least one -CH 2 - may be replaced by -O-; and in each of formula (a), formula (b) and formula (c), at least one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride A group having a residue, an acrylic, methacrylic, maleimide residue, vinyl or allyl.

[0042] More preferable ranges of formula (1) and formula (2) are expressed as follows with respect to R and X. That is, R is cyclohexyl, phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms, or phenyl in which at least one hydrogen may be replaced with halogen or alkyl having 1 to 4 carbon atoms. and alkylene having 1 to 4 carbon atoms; in the alkyl having 1 to 4 carbon atoms, which is a substituent of phenyl, at least one hydrogen may be replaced with fluorine, and one - CH 2 - may be replaced by -O-; in each of formula (a), formula (b) and formula (c), one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic , methacryl, a maleimide residue, a group having vinyl or allyl, in which the remaining Phenyl which may be replaced with alkyl having 1 to 4 carbon atoms, phenyl which may have at least one hydrogen replaced with halogen or alkyl having 1 to 4 carbon atoms, and phenyl consisting of alkylene having 1 to 4 carbon atoms. alkyl; in the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced by fluorine, and at least one -CH 2 - may be replaced with -O-.

[0043] More preferable ranges of formula (1) and formula (2) are expressed as follows with respect to R and X. That is, R is cyclohexyl or phenyl; in each of formula (a), formula (b), and formula (c), one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic , a maleimide residue, vinyl or allyl, and the remaining X is methyl, ethyl, t-butyl, cyclopentyl, cyclohexyl or phenyl.

[0044] Particularly preferred ranges of formula (1) and formula (2) are expressed as follows with respect to R and X. That is, R is phenyl; in each of formula (a), formula (b), and formula (c), one of X is oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acrylic, methacrylic, maleimide. a group having a residue, vinyl or allyl, and the remaining X is methyl or phenyl.

[0045] Preferred examples of groups having oxiranyl, 3,4-epoxycyclohexyl or succinic anhydride residues are shown below. TIFF2023170310000015.tif23168In these expressions, R 2 and R 4 is alkylene having 1 to 6 carbon atoms. One -CH in this alkylene 2 - may be replaced with -O- or 1,4-phenylene. And R 3 is hydrogen or alkyl having 1 to 6 carbon atoms.

[0046] Among these, a group having any one of oxiranyl, succinic anhydride residue, and 3,4-epoxycyclohexyl is more preferred.

[0047] Particularly preferred examples of X are groups represented by formula (3), formula (4), and formula (5), respectively. TIFF2023170310000016.tif81168

[0048] Preferred examples of groups having acrylic, methacrylic, maleimide residues, vinyl or allyl are shown below. TIFF2023170310000017.tif9654 TIFF2023170310000018.tif10351

[0049] In formulas (6) to (11), R b is hydrogen, halogen, -CF 3 , or alkyl having 1 to 5 carbon atoms, and in the formula R b If there are multiple , they may be the same or different.

[0050] Among these, a group having any one of methacryl, maleimide residue, vinyl, and allyl is more preferred.

[0051] Specific examples of compound (1) and compound (2) are shown below. In formulas (1-1) to (2-5), Me represents methyl and Ph represents phenyl. TIFF2023170310000019.tif44168

[0052] TIFF2023170310000020.tif45168

[0053] TIFF2023170310000021.tif45168

[0054] TIFF2023170310000022.tif45168

[0055] TIFF2023170310000023.tif52168

[0056] TIFF2023170310000024.tif60143

[0057] TIFF2023170310000025.tif3481

[0058] These bifunctional or higher functional silsesquioxanes are (1-1):Patent No. 5013127 (1-2):Patent No. 4470738 (2-1):Patent No. 5408597 (2-2)(2-5):Patent No. 4379120 (2-3)(2-4):Patent No. 5018065 It can be easily obtained by referring to .

[0059] The difunctional or higher functional silsesquioxane used in the present invention has a difunctional or higher functional group in order to form a polymer chain in combination with a curing component (hereinafter sometimes referred to as a curing agent) or a reactive elastomer. It is preferable to have one, including cases where it has trifunctionality or more, or tetrafunctionality or more. Further, a compound having functional groups at both ends of the long side of the bifunctional or more functional silsesquioxane is preferable because it can form a linear bond.

[0060] <Polymerizable compound> The composition for a low dielectric member of the present invention is a polymer having a polymerizable group capable of reacting with a polymerizable group imparted to the difunctional or more functional silsesquioxane, as well as a difunctional or more functional silsesquioxane. Alternatively, a low molecular compound may be used as a constituent element. For example, when the functional group of bifunctional or higher functional silsesquioxane is an epoxy group or oxetane group, reactive polyphenylene ether oligomers, reactive polyimide oligomers, reactive polyimide oligomers, reactive polyimide oligomers, etc., which have an amino group, hydroxyl group, or active ester structure at the terminal By combining maleimide oligomers, reactive biphenyl oligomers, reactive bisphenol oligomers, etc., it is possible to construct resins with low dielectric constant, high heat resistance, and adhesive properties, and in combination with reactive polyalkyl ether compounds, reactive EPDM compounds, etc. It is possible to construct a flexible resin with a low dielectric constant. If the functional group of the silsesquioxane having two or more functionalities is radically polymerizable such as an acrylic group, methacrylic group, maleimide residue, vinyl group, or allyl group, the terminal may contain an acrylic group, methacrylic group, maleimide residue, vinyl group, By combining reactive polyphenylene ether oligomers, reactive polyimide oligomers, reactive polymaleimide oligomers, reactive biphenyl oligomers, reactive bisphenol oligomers, etc. that have an allyl group, a resin with a lower dielectric constant and higher heat resistance can be constructed. I can do it.

[0061] <Liquid crystalline polymerizable compound> In the composition for a low dielectric member of the present invention, a liquid crystalline polymerizable compound may be used as a dielectric constant component in addition to the bifunctional or higher functional silsesquioxane. Liquid crystalline polymerizable compounds (hereinafter sometimes referred to as polymerizable liquid crystal compounds) have good molecular linearity and high regularity, so their thermal conductivity due to conduction of phonon vibrations in the direction of molecular orientation is low. Since the development of dielectric constant and dielectric loss caused by molecular vibration caused by the softness of molecular chains is suppressed, low dielectric constant and low dielectric loss can be expected. For example, polymerizable liquid crystal compounds described in Japanese Patent No. 5084148, Japanese Patent No. 6653793, and Japanese Patent No. 6902193 are preferred.

[0062] <Other components> An organic compound (such as a polymerizable compound or a polymer compound), a polymerization initiator, a solvent, etc.

[0063] <Unbonded polymer compound> The polymer compound that is not directly bonded to the difunctional or higher functional silsesquioxane in the composition for a low dielectric member of the present invention is preferably a compound that does not reduce film-forming properties and mechanical strength. This polymer compound may be any polymer compound that does not react with the difunctional or higher functional silsesquioxane or the curing agent. For example, if the difunctional or higher functional silsesquioxane has an oxiranyl group and the curing agent has an amino group, , polyolefin resin, polyvinyl resin, silicone resin, wax, etc. In low dielectric materials, it is preferable to have voids between molecular chains in the sense that the dielectric constant decreases, but if moisture is adsorbed due to capillarity and deteriorates dielectric properties, it is preferable to use a material with a low dielectric constant and water absorption that does not bond directly. It is preferable to fill the voids by adding a low molecular weight compound. The content can be determined by first preparing a composition for a low dielectric component that does not contain unbound polymerizable compounds, measuring its porosity, and adding an amount of the polymer compound that can fill the porosity. desirable.

[0064] <Polymerization initiator> The composition for a low dielectric member of the present invention may include a polymerization initiator as a component. The polymerization initiator may be, for example, a photo-radical polymerization initiator, a photo-cationic polymerization initiator, a thermal radical polymerization initiator, etc., depending on the polymerization method of the composition for a low dielectric member.

[0065] The photoradical polymerization initiator is not particularly limited, and known ones can be used. For example, 4-methoxyphenyl-2,4-bis(trichloromethyl)triazine, 2-(4-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, 9-phenylacridine, 9,10 -Benzphenazine, benzophenone / Michler's ketone mixture, azobisisobutyronitrile (AIBN), hexaarylbiimidazole / mercaptobenzimidazole mixture, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one , benzyl dimethyl ketal, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2,4-diethylxanthone / methyl p-dimethylaminobenzoate mixture, benzophenone / methyltriethanol Examples include amine mixtures. Commercially available products include, for example, products manufactured by Ciba Specialty Co., Ltd. under the trade name "DaroCure Series 1173, 4265" and "IrgaCure Series 184, 369, 500, 651, 784, 819, 907, 1300, 1700, 1800. , 1850, 2959'', product names manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., ``V-59, V-65, V-70, V-601, AIBN-HP'', etc.

[0066] The photocationic polymerization initiator is not particularly limited, and known ones can be used.For example, the product name "Silacure UVI-6990, 6974" manufactured by UCC Co., Ltd., and the product name manufactured by ADEKA Co., Ltd. "ADEKA Optomer SP-150, 152, 170, 172", product name "Photoinitiator 2074" manufactured by Rhodia Co., Ltd., product name "Irgacure 250" manufactured by Ciba Specialty Co., Ltd., product manufactured by Midori Kagaku Co., Ltd. Examples include the name "DTS-102".

[0067] Preferred examples of thermal radical polymerization initiators include benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, di-t-butylperoxydicarbonate, oxide (DTBPO), t-butylperoxydiisobutyrate, lauroyl peroxide, dimethyl 2,2'-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN), etc. Can be mentioned.

[0068] Preferred initiators for anionic, coordination and living polymerizations include, for example, n-C 4 H 9 Li, t-C 4 H 9 Li, R 3 Examples include alkali metal alkyl compounds such as Al, aluminum compounds, and transition metal compounds. <Curing agent> When the composition for a low dielectric member contains a compound having a cyclic ether group as a constituent element, it may contain a curing agent as a constituent element. Examples of preferred curing agents are shown below.

[0069] As an amine curing agent, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, o-xylenediamine, m-xylenediamine, p-xylenediamine, trimethylhexamethylenediamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine , 1,3-bisaminomethylcyclohexane, bis(4-amino-3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, norbornenediamine, 1,2-diaminocyclohexane, 3,9-dipropanamine- 2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, o-phenylenediamine, m-phenylenediamine, Examples include p-phenylene diamine, 4,4'-diaminodiphenylsulfone, polyoxypropylene diamine, polyoxypropylene triamine, polycyclohexyl polyamine, and N-aminoethylpiperazine.

[0070] As acid anhydride curing agents, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride Acid, methylcyclohexenetetracarboxylic dianhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, ethylene glycol bisanhydrotrimethylate, glycerin bis(anhydrotrimellitate) ) monoacetate, dedecenyl succinic anhydride, chlorendic anhydride, etc.

[0071] As a phenolic curing agent, phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, m-ethylphenol, p-ethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, o-isopropylphenol, p-tert-butylphenol, o-sec-butylphenol, p-octylphenol, 2 ,6-di-tert-butylphenol, resorcinol, 1-naphthol, 2-naphthol, bisphenol A, phenol novolak, xylylene novolak, bisphenol A novolak, and the like. In addition to the above, curing agents described in JP-A No. 2004-256687, JP-A No. 2002-226550, etc. can also be used.

[0072] The active ester curing agent is not particularly limited and any known one can be used. For example, as an active ester compound containing a dicyclopentadiene type diphenol structure, DIC Corporation's product name "HPC-8000H-" is used. 65T", an active ester compound containing a naphthalene structure under the trade name "EXB-8150-65T" manufactured by DIC Corporation; an active ester compound containing an acetylated product of phenol novolac under the trade name "DC808" manufactured by Mitsubishi Chemical Corporation; phenol An active ester compound containing a benzoylated novolac is the product name "YLH1026" manufactured by Mitsubishi Chemical Corporation, an active ester curing agent that is an acetylated product of phenol novolac is "DC808" manufactured by Mitsubishi Chemical Corporation, and a product name of "DC808" manufactured by Mitsubishi Chemical Corporation Examples of the active ester curing agent which is a benzoylated product include the product name "YLH1026" manufactured by Mitsubishi Chemical Corporation.

[0073] In addition, as a curing accelerator, 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), 1,5-diazabicyclo[4.3.0]-5-nonene, 5,6-dibutylamino-1,8 - Cyclamidine compounds such as diazabicyclo[5.4.0]-7-undecene; the cycloamidine compounds include maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone , quinone compounds such as 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, diazophenyl Compounds with intramolecular polarization obtained by adding compounds with π bonds such as methane and phenol resins; Tertiary amine compounds such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; Derivatives of tertiary amine compounds; imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole; derivatives of said imidazole compounds; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris(4 -Organic phosphine compounds such as methylphenyl)phosphine, diphenylphosphine, and phenylphosphine; In molecules formed by adding a compound having a π bond such as maleic anhydride, the above-mentioned quinone compounds, diazophenylmethane, and phenol resin to the organic phosphine compound. Phosphorus compounds with polarization; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate; the tetraphenylboron Salt derivatives; adducts of phosphine compounds such as triphenylphosphonium-triphenylborane, N-methylmorpholinetetraphenylphosphonium-tetraphenylborate and the tetraphenylboron salt; and the like.

[0074] <Solvent> The composition for a low dielectric member may contain a solvent. When the composition contains components that need to be polymerized, the polymerization may be carried out in a solvent or without a solvent. The composition containing a solvent may be applied onto a substrate by, for example, a spin coating method, and then the solvent may be removed and then photopolymerized. Further, after photocuring, post-treatment may be performed by heating to an appropriate temperature and thermally curing. Preferred solvents include, for example, benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, cyclohexane, methylcyclohexane, cyclopentanone. , 2-butanone, cyclohexanone, 2-methoxy-1-methylethyl acetate (PGMEA), etc. The above solvents may be used alone or in combination of two or more. Note that it is not very meaningful to limit the proportion of the solvent used during polymerization, and it may be determined for each individual case, taking into account polymerization efficiency, solvent cost, energy cost, and the like.

[0075] <Others> A stabilizer may be added to the composition for a low dielectric member in order to facilitate handling. As such stabilizers, known stabilizers can be used without limitation, and examples thereof include hydroquinone, 4-ethoxyphenol, and 3,5-di-t-butyl-4-hydroxytoluene (BHT). Furthermore, additives (oxides, etc.) may be added to adjust the viscosity and color of the composition for low dielectric members. Examples include titanium oxide to make it white, carbon black to make it black, and fine silica powder to adjust viscosity. Additionally, additives may be added to further increase mechanical strength. For example, inorganic fibers and cloths such as glass fibers, carbon fibers, and carbon nanotubes, and polymer additives include fibers and polymers such as polyvinyl formal, polyvinyl butyral, polyester, polyamide, and polyimide.

[0076] <Inorganic filler as filler> A filler (inorganic filler) can be added to the composition for a low dielectric member in order to improve thermal conductivity, improve mechanical strength, adjust viscosity, and the like. For example, fillers with high thermal conductivity are not particularly limited, and any known filler can be used, such as metal nitrides such as aluminum nitride, boron nitride, and silicon nitride, and carbides such as diamond, graphite, and silicon carbide. , metal oxides such as magnesium oxide, aluminum oxide, zinc oxide, silicon oxide, titanium oxide, tin oxide, forminium oxide, calcium oxide, metal hydroxides such as magnesium hydroxide, aluminum hydroxide, and cordierite, Alternatively, it may be a silicate compound such as mullite, or a metal filler such as gold, silver, copper, platinum, iron, tin, lead, nickel, aluminum, magnesium, tungsten, molybdenum, or stainless steel. Preferred are boron nitride and silicon oxide, which have a low dielectric constant, and hexagonal boron nitride (h-BN) is particularly preferred because it has a low dielectric constant and high thermal conductivity. Commercially available powder fillers with low dielectric loss tangents include Denka Fused Silica FB-5D, GT130MC, GT5SDC, Denka Boron Nitride SGP, SP-2, manufactured by Denka Co., Ltd. ) Admatex product name “SO-C2, SO-E1”, MOMENTIVE product name “MOMENTIVETM PTX25”, low dielectric glass cloth for imparting mechanical strength is Nitto Boseki Co., Ltd. product name “NE Glass” 2116, 3313'', etc.

[0077] Examples of the shape of the filler include spherical, amorphous, fibrous, rod-like, cylindrical, plate-like, and hollow spherical shapes. The shape of the filler is preferably one that does not interfere with the orientation of the polymerizable liquid crystal compound when it develops a liquid crystal phase. The type, shape, size, amount added, etc. of the filler can be appropriately selected depending on the purpose. If the obtained low dielectric molded body requires insulation, a filler having electrical conductivity may be used as long as the desired insulation, dielectric constant, and dielectric loss are maintained. It is preferable to use boron nitride in the form of plate-like crystals, or because the polymerizable liquid crystal compound is likely to be oriented perpendicularly to the plate-like structure, or the polymerizable liquid crystal compound is likely to be oriented along the plate-like structure. Whether to align vertically or along a flat plate depends on the affinity between the polymerizable liquid crystal compound and the filler. It is preferable to use a polymerizable liquid crystal compound and a spherical silicon oxide having a fine particle size to increase the viscosity of the melt or solution, and to use a silicate compound to reduce the coefficient of thermal expansion of the molded product. In order to lower the dielectric constant, increasing the air content even a little lowers the relative dielectric constant, so it is preferable to use hollow silica, porous silica, silicate, or the like. Further, in order to adjust the viscosity and thixotropy, it is preferable to use spherical or spherical silica. When increasing mechanical strength, it is preferable to use fibrous silica or silicate glass.

[0078] The average particle size of the spherical or irregularly shaped filler is preferably 0.1 to 200 μm. More preferably, it is 1 to 100 μm. When it is 0.1 μm or more, the thermal conductivity is good, and when it is 200 μm or less, the filling rate can be increased. Regarding the fibrous filler, the longer the fiber length, the better the tensile strength, but it may be difficult to knead and disperse, so it is preferable to select it depending on the application. When dispersed, the average particle size of the fibrous filler is preferably 0.01 to 200 μm. More preferably, it is 0.1 to 100 μm. If it is 0.1 μm or more, the thermal conductivity is good, and if it is 200 μm or less, the mechanical strength can be increased. In this specification, the average particle diameter is based on particle size distribution measurement using a laser diffraction / scattering method. In other words, when a powder is divided into two parts based on a certain particle size using the wet method using analysis based on Frahnhofer diffraction theory and Mie's scattering theory, the diameter at which the larger and smaller sides are equal (based on volume) is determined. was taken as the median diameter. The amount of the filler is preferably such that the low dielectric molded article after curing contains 5 to 90% by volume of the filler. More preferably, it is 20 to 80% by volume. If it is 20% by volume or more, the thermal conductivity will be high in the case of a high thermal conductivity filler, and the dielectric loss tangent will be low in the case of a low dielectric loss tangent filler, which is preferable. When the content is 80% by volume or less, the low dielectric molded body does not become brittle, which is preferable.

[0079] [Low dielectric resin] The low dielectric resin, which is another embodiment of the present invention, is a cured product of the above-mentioned composition for low dielectric members, and is used as a low dielectric member in the form of sheets, films, plates, fibers, three-dimensional shapes ( In addition to being used as insulation parts of connectors, etc., it can also be used as is as a coating agent, adhesive, or filler. The low dielectric resin has a low dielectric constant because it is a cured product of the above-mentioned composition, and when a polymer of a polymerizable liquid crystal compound is used as the polymer, it has good thermal conductivity, heat resistance, rigidity, elasticity, It also has excellent molding fluidity, chemical resistance, and dimensional stability.

[0080] <Manufacturing method> Hereinafter, a method for producing a composition for a low dielectric member, and a method for producing a low dielectric, high heat resistant substrate and a low dielectric, high heat resistant insulating layer from the composition will be specifically described.

[0081] The composition for a low dielectric member of the present invention can also be used as it is dissolved in a solvent. To prepare the solution, add difunctional or higher functional silsesquioxane, curing component, polymerizable liquid crystal compound, solvent, filler, additives, etc. as necessary, and stir and remove using a stirrer until the composition is uniform. foam. For example, using a rotation / revolution mixer, after stirring for 10 minutes at a rotation speed of 2000 rpm, defoaming is performed for 10 minutes at a rotation speed of 2200 rpm. In addition to the rotation and revolution mixer, the dispersion can be carried out using a stirring motor, a sieve machine, a three-roll mill, a ball mill, a rotation and revolution mill, a planetary mill, a bead mill, a jet mill, and the like.

[0082] As the coating method, it is preferable to use a wet coating method in order to uniformly coat the composition for a low dielectric member. Among the wet coating methods, when producing a small amount, the spin coating method is preferable because it is simple and allows formation of a homogeneous film. When productivity is important, gravure coating method, die coating method, bar coating method, reverse coating method, roll coating method, slit coating method, dipping method, spray coating method, kiss coating method, reverse kiss coating method, air knife coating Preferred methods include method, curtain coating method, inkjet method, flexo printing method, screen printing method, and rod coating method. The wet coating method can be appropriately selected from these methods depending on the required film thickness, viscosity, curing conditions, etc.

[0083] When manufacturing sheets, a casting method is used, in which a composition solution for low dielectric members is coated on a base material that has been subjected to mold release treatment using the method described above, and then peeled off, and when manufacturing structures. Resin molding methods such as press molding method, injection method, various 3D printer molding methods (discharge lamination method), etc., using a mold to make a mixture of raw material powder or a prepolymerized resin by reacting some polymerizable groups in advance. can be used. After molding, it is possible to remove the mold and carry out the main curing, or to carry out the main curing while remaining in the mold.

Example

[0084] The present invention will be explained in detail below using examples. However, the present invention is not limited to what is described in the following examples.

[0085] The materials constituting the low dielectric member used in the examples of the present invention are as follows.

[0086] <Polymerizable silsesquioxane compound (bifunctional or higher functional silsesquioxane)> ·Silsesquioxane 1: Compound represented by the following formula (1-1) (manufactured by JNC Co., Ltd.) In formula (1-1), Me represents methyl and Ph represents phenyl. TIFF2023170310000026.tif39150

[0087] ·Silsesquioxane 3: Compound represented by the following formula (2-1) (manufactured by JNC Co., Ltd.) In formula (2-1), Me represents methyl and Ph represents phenyl. TIFF2023170310000027.tif45168

[0088] ·Silsesquioxane 5: Compound represented by the following formula (2-3) (manufactured by JNC Co., Ltd.) In formula (2-3), Me represents methyl. TIFF2023170310000028.tif51163

[0089] ·Silsesquioxane 6: Compound represented by the following formula (2-4) (manufactured by JNC Co., Ltd.) In formula (2-4), Me represents methyl. TIFF2023170310000029.tif54127

[0090] ·Silsesquioxane 7: Compound represented by the following formula (2-5) (manufactured by JNC Co., Ltd.) In formula (2-5), Me represents methyl and Ph represents phenyl. TIFF2023170310000030.tif3481

[0091] <Curing accelerator, initiator> ·Imidazole curing agent: 2-ethyl-4-methylimidazole (2E4MZ) (trade name manufactured by Tokyo Kasei Kogyo Co., Ltd.) ·Phosphorus curing accelerator: TBP-3S (trade name manufactured by Hokuko Chemical Industry Co., Ltd.) ·Azo photocuring initiator: V-601 (product name manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ·Peroxide crosslinking agent: Perbutyl P (trade name manufactured by NOF Corporation)

[0092] <Other polymerizable compounds> ·Amine curing agent: 4,4’-diamino-1,2-diphenylethane (DDM) (product name manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) ·Active ester curing agent: HPC-8000-65T (product name manufactured by DIC Corporation) ·Reactive polyphenylene ether oligomer (hydroxyl groups at both ends): Noryl SA90 (product name manufactured by SABIC (G)) ·Reactive polyphenylene ether oligomer (methacrylic groups at both ends): Noryl SA9000 (product name manufactured by SABIC (G)) ·Bismaleimide compound: BМI-80 (product name manufactured by K-I Kasei Co., Ltd.) ·Biphenyl 1: Compound represented by the following formula (H-1) (manufactured by JNC Co., Ltd.) TIFF2023170310000031.tif2395·Biphenyl-type epoxy resin: Epicote YX4000H (product name manufactured by Mitsubishi Chemical Corporation) ·Bisphenol F type epoxy resin: jER807 (product name manufactured by Mitsubishi Chemical Corporation)

[0093] [Example 1] <Preparation of low dielectric material> An example of preparing a low dielectric member is shown below. ·Preparation of composition solution for low dielectric materials Assuming that oxiranyl is not ring-opened, weigh 0.4503 g of silsesquioxane 1 and 0.8530 g of SA90 so that the equivalent weight of the oxiranyl group and the hydroxyl group of the curing agent match, and place them in a 20 ml glass screw cap bottle. I put it in. 1.38 g of ethyl acetate was added to the bottle so that the solid content concentration was approximately 50% by weight, the bottle was capped, and the bottle was heated at 50° C. for 3 hours in a dry incubator. After standing overnight at room temperature, a 10% by weight solution of 2E4MZ in ethyl acetate was added so that the amount of initiator was 2 parts by weight per 100 parts by weight of the solid content, and the mixture was stirred by rotation for 1 hour using a small ball mill stand. , as a raw material solution.

[0094] ·Preparation of samples for permittivity measurement As shown in Figure 2, a spacer made of two layers of heat-resistant masking tape with a width of 10 mm and a thickness of 130 μm is pasted in a 10 cm square shape on a polyimide film (J-2 manufactured by Nipper Co., Ltd.) that has been subjected to mold release treatment as shown in Figure 2. The sample was placed on a hot plate set at 50° C., and the entire amount of the solution was dropped onto an area of ​​5 cm×5 cm inside the spacer using a dropper. After leaving this as it was on a hot plate for 1 hour, it was further dried in a vacuum dryer at 50°C for 3 hours, and further dried in a hot air dryer at 50°C overnight.

[0095] ·The sample for dielectric constant measurement needs to be 50 to 200 μm thick, so it has to be much thicker than a normal insulating film. Therefore, in this study, the thickness before drying was approximately 500 μm, so the solvent dried from the surface of the liquid and remained inside, resulting in foaming in a carme-like shape during vacuum drying. A polyimide film with a mold release agent was placed on the top of the foamed state, and the top and bottom were sandwiched between 2 mm thick aluminum plates, and the film was placed in a mini test press made by Toyo Seiki Co., Ltd. set at 120°C, and the final product was degassed. After applying pressure to 10 MPa and heating to 175°C, it was cured for 60 minutes. When increasing the temperature from 120°C to 200°C, as the dried sample melts or softens, the resin flows inside the simple mold, reducing its apparent thickness and resulting in a drop in pressure. After confirming melting or softening, the resin was degassed by repeating pressurization and then depressurization. In the study of Example 1, foaming occurred because a thick sample had to be made to measure dielectric properties. When an insulating film several μm thick is formed on an aluminum substrate using the spin coating method, this bubbling phenomenon is not observed and a clean film is obtained.

[0096] <Evaluation method of dielectric properties> Using an AET cavity resonator (TE mode 10 GHz, 28 GHz) connected to a vector network analyzer (Anritsu MS46522B-043), we measured the resonant frequency shift and attenuation of the measurement sample. The dielectric constant (Dk) and dielectric loss tangent (Df) were calculated using the company's software. To reduce the influence of moisture content in the strips when comparing data, the strips were left standing in an electronic desiccator set at 10% relative humidity for one day, and the dielectric properties were evaluated in a laboratory with an air conditioner set at a temperature of 20℃. , started after the sample had been allowed to stand for at least 60 minutes. In addition, when this sample was larger than about 1 cm square, the film cracked due to curing shrinkage, so we measured it without removing it from the polyimide film, and separately measured the dielectric properties of the polyimide film alone. The dielectric properties of only the sample layer were determined using . In addition, some samples with low flexibility due to their thick films had cracks, but if there were no gaps, there was almost no effect on the measurement of dielectric properties, so measurements were carried out as they were. On the other hand, samples with large voids or samples with remaining powder parts have a large effect on the evaluation of dielectric properties, so these parts were avoided during measurement.

[0097] [Example 2]~[Example 9] As shown in Table 1, samples were prepared in the same manner as in Example 1, except that the difunctional or higher functional silsesquioxane, curing agent, initiator, and solvent were changed, and the dielectric properties were evaluated.

[0098] [Example 10] In order to carry out the main curing by UV curing, the solution was prepared in the same manner as in Example 1, except that the difunctional or higher functional silsesquioxane, curing agent, initiator, and solvent were changed, as shown in Table 1. A film was formed using a bar coater so that the film thickness in a wet state was 100 μm, and vacuum drying was performed. At this time, in order to prevent thermal decomposition of the azo initiator from starting, drying and preliminary curing of the solvent was performed using a vacuum dryer so as not to exceed 50°C. The obtained polyimide film with an uncured film was placed in a stainless steel container for photocuring experiments with a quartz glass lid, and after replacing the container with nitrogen for 5 minutes, it was irradiated with 100 mJ of UV light and cured. The dielectric properties of the sample after curing were evaluated and designated as Example 10.

[0099] [Comparative example 1]~[Comparative example 4] As shown in Table 1, samples were prepared in the same manner as in Example 1, except that the difunctional or higher functional silsesquioxane was replaced with an organic monomer or oligomer, and the curing agent, initiator, and solvent were changed as appropriate. was evaluated.

[0100]

table 1

[0101] <Dielectric property evaluation results> Table 2 summarizes the curing conditions and dielectric property measurement results for each sample.

[0102] [Table 2]

[0103] Comparing Examples 1 to 3 and Comparative Example 1, it is found that when a curing agent with an OH group at the end is used, the composition containing a bifunctional or higher functional silsesquioxane of the present invention is a commercially available biphenyl-type epoxy resin. It can be seen that both the dielectric constant (Dk) and the dielectric loss tangent (Df) are significantly lower than the above. The samples of Example 1 and Example 2 tend to have a void structure, and even if they are re-created, there are some voids, and the dielectric constant is based on the air contained therein, but in applications where voids can be included, It can be used as a material with extremely low dielectric constant. Comparing Examples 4 to 5 and Comparative Example 2, even when an amine curing agent is used, the composition containing the bifunctional or more functional silsesquioxane of the present invention has a lower dielectric constant, and especially a lower dielectric loss tangent. is found to be low. It is generally said that the combination of epoxy and amine curing agents is not suitable for low dielectric and low loss resins, but even when using general DDM, quite low numbers have been obtained, and it is suitable for low dielectric materials. It is believed that the use of a curing agent would further improve the properties. However, in this example, only the bifunctional or higher functional silsesquioxane and the curing agent are polymerized, so there is no composition that exhibits flexibility. As a result, the film was not flexible, and in some samples, when processing for 28 GHz measurement after 10 GHz measurement, the film cracked and peeled off from the base material, making measurements impossible. . There is no problem when forming a film on a hard substrate, but for applications that require flexibility, it is better to copolymerize a compound with a flexible structure such as an alkyl, ether, or butadiene-based elastomer as the third component. . Therefore, we tried active ester curing agents, which are attracting attention as curing agents for low dielectric applications (Examples 8 and 9 and Comparative Example 4). The polymerization conditions for active ester-based curing agents are difficult. For example, when comparing Example 4 and Example 9 using the same silsesquioxane 5, DDM has a higher absolute value of dielectric constant, but In Example 9, the dielectric properties are better at 28 GHz than at 10 GHz, and it can be said that the material is more resistant to high frequencies. It is generally said that dielectric properties deteriorate as the frequency increases, and this is a characteristic that deserves special mention. Furthermore, in order to lower the dielectric constant, radical curing resins are said to have better properties than epoxy resins, and polymerizable groups with double bonds such as maleimide and methacrylate are attracting attention. ing. As an example, in Example 6, a bismaleimide compound (BМI-80) having a maleimide group at both ends was used, and in Example 7, a radical-reactive silsesquioxane 7 having a vinyl group and a reactive compound having a methacrylic group were used. When combined with polyphenylene ether oligomer (SA9000), a resin with lower dielectricity than Examples 4 and 5, which does not contain bubbles, was obtained. In addition, UV curing is also possible due to radical reactivity, and even in Example 10, in which the silsesquioxane component was reduced and the initiator was changed for transparency from Example 7, the amount of silsesquioxane component was reduced. Although the dielectric constant is a little high, a sufficiently low dielectric composition has been obtained.

[0104] As described above, the cage-shaped silsesquioxane having two or more thermosetting or photocurable polymerizable groups of the present invention and the composition for a low dielectric member containing a curing component can withstand high frequencies of 10 GHz or more. It can be suitably used as an insulating member for electronic devices and equipment handled. [Explanation of symbols]

[0105] 11 Silsesquioxane unit (constituent unit) 12 Polymer chains 13 Polymerizable site 21 Polyimide sheet with mold release agent (A5 size) 22 Heat-resistant masking tape (2 layers)

Claims

1. A composition for low dielectric members, comprising a cage-type silsesquioxane having two or more thermosetting or photocurable polymerizable groups (hereinafter, sometimes referred to as a bifunctional or higher functional silsesquioxane), and a curing component, wherein the composition is cured without adding a filler, and the cured resin has a relative dielectric constant at 10 GHz and 28 GHz both of which are lower than 3.

0.

2. The di- or higher functional silsesquioxane is a compound selected from the group of compounds represented by formula (1) and formula (2), The composition for low dielectric members according to claim 1 . [wherein R is independently alkyl having 1 to 45 carbon atoms, cycloalkyl having 4 to 8 carbon atoms, aryl having 6 to 16 carbon atoms, or arylalkyl having 7 to 16 carbon atoms; in the alkyl having 1 to 45 carbon atoms, at least one hydrogen may be replaced by fluorine, and at least one —CH ２ - may be replaced by -O- or -CH=CH-; in the benzene ring in the aryl having 6 to 16 carbon atoms and the arylalkyl having 7 to 16 carbon atoms, at least one hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms; in the alkyl having 1 to 10 carbon atoms, at least one hydrogen may be replaced by fluorine, and at least one -CH ２ - may be replaced by -O- or -CH=CH-; the alkylene in the arylalkyl having 7 to 16 carbon atoms has 1 to 10 carbon atoms and at least one -CH ２ - may be replaced by -O-; and Y １ are each independently a group represented by formula (a). [wherein X is independently cyclopentyl, cyclohexyl, at least one hydrogen may be replaced by fluorine, and at least one —CH ２ alkyl having 1 to 10 carbon atoms, where - may be replaced by -O-; phenyl, where at least one hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms; phenylalkyl composed of phenyl, where at least one hydrogen may be replaced by halogen or alkyl having 1 to 10 carbon atoms, and alkylene having 1 to 4 carbon atoms; or a group having oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, succinimide residue, acryl, methacryl, maleimide residue, vinyl, or allyl; in the alkyl having 1 to 10 carbon atoms which is the phenyl substituent, at least one hydrogen may be replaced by fluorine, and at least one -CH ２ - may be replaced by -O-; in the alkylene of phenylalkyl, at least one -CH ２ - may be replaced by -O-; and at least one of X is a group having oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, succinimide residue, acryl, methacryl, maleimide residue, vinyl, or allyl. [wherein R has the same definition as R in formula (1), and Y ２ is a group represented by formula (b) or a group represented by formula (c). [wherein, in each of formula (b) and formula (c), X has the same definition as X in formula (a), and Z in formula (c) is —O—, —CH ２ - or a single bond.]

3. The bifunctional or higher functional silsesquioxane is represented by the formula (1) and the formula (2) according to claim 2, wherein R is independently cyclohexyl, phenyl in which at least one hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms, or phenylalkyl composed of phenyl in which at least one hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms and alkylene having 1 to 4 carbon atoms; In the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced by fluorine, and at least one -CH ２ - may be replaced by -O-; X is independently alkyl having 1 to 4 carbon atoms, fluorinated alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, phenyl in which at least one hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms, phenylalkyl composed of phenyl in which at least one hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms and alkylene having 1 to 4 carbon atoms, or a group having oxiranyl, 3,4-epoxycyclohexyl, succinic anhydride residue, acryl, methacryl, maleimide residue, vinyl or allyl, and in the alkyl having 1 to 4 carbon atoms which is the phenyl substituent, at least one hydrogen may be replaced by fluorine, and at least one -CH ２ - may be replaced by -O-; and In each of the formulas (a), (b) and (c) according to claim 2, at least one of X is a group having oxiranyl, 3,4-epoxycyclohexyl, a succinic anhydride residue, an acryl group, a methacryl group, a maleimide residue, a vinyl group or an allyl group. The composition for low dielectric members according to claim 1 .

4. The bifunctional or higher functional silsesquioxane is represented by the formula (1) and the formula (2) according to claim 2, wherein R is cyclohexyl, phenyl in which at least one hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms, or phenylalkyl composed of phenyl in which at least one hydrogen may be replaced by halogen or alkyl having 1 to 4 carbon atoms and alkylene having 1 to 4 carbon atoms; In the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced by fluorine, and at least one -CH ２ - may be replaced by -O-; In each of formulas (a), (b) and (c) according to claim 2, one of X is a group having oxiranyl, 3,4-epoxycyclohexyl, a succinic anhydride residue, an acryl, a methacryl, a maleimide residue, vinyl or allyl, and the remaining X is an alkyl having 1 to 4 carbon atoms, a fluorinated alkyl having 1 to 4 carbon atoms, cyclopentyl, cyclohexyl, phenyl in which at least one hydrogen may be replaced by halogen or an alkyl having 1 to 4 carbon atoms, or a phenylalkyl composed of phenyl in which at least one hydrogen may be replaced by halogen or an alkyl having 1 to 4 carbon atoms and an alkylene having 1 to 4 carbon atoms; In the alkyl having 1 to 4 carbon atoms which is a substituent of phenyl, at least one hydrogen may be replaced by fluorine, and at least one -CH ２ - may be replaced by -O-; The composition for low dielectric members according to claim 1 .

5. The bifunctional or higher functional silsesquioxane is represented by the formula (1) and the formula (2) according to claim 2, wherein R is cyclohexyl or phenyl; In each of the formulas (a), (b) and (c) according to claim 2, one of X is a group having oxiranyl, 3,4-epoxycyclohexyl, a succinic anhydride residue, an acryl, a methacryl, a maleimide residue, vinyl or allyl, and the remaining X is methyl, ethyl, t-butyl, cyclopentyl, cyclohexyl or phenyl. The composition for low dielectric members according to claim 1 .

6. The bifunctional or higher functional silsesquioxane is represented by the formula (1) or (2) according to claim 2, wherein R is phenyl; In each of the formulas (a), (b) and (c) according to claim 2, one of X is a group having oxiranyl, 3,4-epoxycyclohexyl, a succinic anhydride residue, an acryl, a methacryl, a maleimide residue, a vinyl or an allyl, and the remaining X is methyl or phenyl. The composition for low dielectric members according to claim 1 .

7. The difunctional or higher functional silsesquioxane is a compound represented by formula (1-1):

2. A composition for low dielectric members according to claim 1, wherein in formula (1-1), Me represents methyl and Ph represents phenyl.

8. The di- or higher functional silsesquioxane is a compound represented by formula (1-2):

2. The composition for low dielectric members according to claim 1, wherein in formula (1-2), Me represents methyl and Ph represents phenyl.

9. The di- or higher functional silsesquioxane is a compound represented by formula (2-1):

2. A composition for low dielectric members according to claim 1, wherein in formula (2-1), Me represents methyl and Ph represents phenyl.

10. The di- or higher functional silsesquioxane is a compound represented by formula (2-2):

2. The composition for low dielectric members according to claim 1, wherein in formula (2-2), Me represents methyl and Ph represents phenyl.

11. The di- or higher functional silsesquioxane is a compound represented by formula (2-3):

2. The composition for low dielectric members according to claim 1, wherein in formula (2-3), Me represents methyl.

12. The di- or higher functional silsesquioxane is a compound represented by formula (2-4):

2. The composition for low dielectric members according to claim 1, wherein in formula (2-4), Me represents methyl.

13. The di- or higher functional silsesquioxane is a compound represented by formula (2-5):

2. The composition for low dielectric members according to claim 1, wherein in formula (2-5), Me represents methyl and Ph represents phenyl.

14. 2. The composition for low dielectric members according to claim 1, wherein the curing component is an amine-based curing agent, an active ester curing agent, a phenol-novolac curing agent, an acid generator, a phosphorus-based curing accelerator, or an azo-based polymerization initiator.

15. A low dielectric component obtained by curing the composition for low dielectric components according to claim 1.

16. The low dielectric member according to claim 15; an electronic device having at least one capability selected from the group consisting of capabilities to generate, convert, transmit, and process radio frequency signals; electronic equipment.

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